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(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) 



(19) World Intellectual Property Organization 

International Bureau 




IIIIIIIIIIH 



(43) International Publication Date (10) International Publication Number 

23 January 2003 (23.01.2003) PCT WO 03/007296 Al 



(51) International Patent Classification 7 : G11B 7/24, 

C07C 251/20, C07D 231/38, C09B 11/02, C09D 11/18, 
C09B 11/18, 11/28 

(21) International Application Number: PCT/EP02/07434 

(22) International Filing Date: 4 July 2002 (04.07.2002) 
(25) Filing Language: English 



(26) Publication Language: 



English 



(30) Priority Data: 

2001 1297/01 
2001 1516/01 



13 July 2001 (13.07.2001) CH 
17 August 2001 (17.08.2001) CH 



(71) Applicant (for all designated States except US): CIBA 
SPECIALTY CHEMICALS HOLDING INC. [CH/CH]; 
Klybeckstrasse 141, CH-4057 Basel (CH). 

(72) Inventors; and 

(75) Inventors/Applicants (for US only): LEHMANN, 
Urs [CH/CH]; Unterer Rheinweg 50, CH-4057 Basel 
(CH). AESCHLIMANN, Peter [CH/CH]; Sandweg 16, 
CH-4123 Allschwil (CH). SUTTER, Peter [CH/CH]; 
Seemattlistrasse 14/2, CH-4132 Muttenz (CH). SCHMID- 
HALTER, Beat [CH/CH]; Dahlienstrasse 25, CH-4416 
Bubcndorf (CH). BUDRY, Jean-Luc [CH/CH]; Rue des 
Oeuches 52, CH-2842 Rossemaison (CH). SPAHNI, 
Heinz [CH/CH]; Eggstrasse 23, CH-4402 Frenkendorf 
(CH). 



(74) Common Representative: CIBA SPECIALTY CHEMI- 
CALS HOLDING INC.; Patentabteilung, Klybeckstrasse 
141, CH-4057 Basel (CH). 

(81) Designated States (national): AE, AG, AL, AM, AT, AU, 

AZ, BA, BB, BG, BR, BY, BZ, CA, CH, CN, CO, CR, CU, 
CZ, DE, DK, DM, DZ, EC, EE, ES, FT, GB, GD, GE, GH, 
GM, HR, HIT, TD, TL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, 
LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, 
MX, MZ, NO, NZ, OM, PH, PL, PT, RO, RU, SD, SE, SG, 
SI, SK, SL, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, 
VN, YU, ZA, ZM, ZW. 

(84) Designated States (regional): ARIPO patent (GH, GM, 
KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZM, ZW), 
Eurasian patent (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), 
European patent (AT, BE, BG, CH, CY, CZ, DE, DK, EE, 
ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, SK, 
TR), OAPI patent (BE, BJ, CF, CG, CI, CM, GA, GN, GQ, 
GW, ML, MR, NE, SN, TD, TG). 

Published: 

— with international search report 

before the expiration of the time limit for amending the 
claims and to be republished in the event of receipt of 
amendments 

For two-letter codes and other abbreviations, refer to the "Guid- 
ance Notes on Codes and Abbreviations" appearing at the begin- 
ning of each regular issue of the PCT Gazette. 



(54) Title: FAST- WRITABLE AND PRECISION- WRITABLE HIGH-CAPACITY OPTICAL STORAGE MEDIA 



O 




(x m -) D 



(Y n+ ) a 



(I) 



(57) Abstract: The invention relates to an optical 
recording medium, comprising a substrate and a recording 
layer, wherein the recording layer comprises a compound 
of formula (I), wherein R ls R 2 , R 3 , R4, R 5 , Rg, R7, R 8 , 
R9,Rio, Rn, R12 and R13 are each independently of the 
others hydrogen, Gi or Ci-C 2 4alkyl, C 2 -C24alkenyl, 
C 2 -C 2 4alkynyl, C 3 -C 24 cycloalkyl, C 3 -C 24 cycloalkenyl, 
C 7 -C 24 aralkyl, C6-C 24 aryl, C 4 -C 12 heteroaryl or 
Ci-Ci 2 heterocycloalkyl, each unsubstituted or substituted 
by one or more identical or different substituents Gi, 
wherein Ri and R 2 , Ri and R13, R 2 and R 3 , R 3 and R^, R4 and R 5 , R 5 and R 6 , Re and R 7 , R7 and R 8 , R 8 and R 9 , R 9 and Ri 0 , Rio 
and Rll, R u and R 12 and/or R 12 and R 13 can independently of one another be bonded to one another in pairs separately or, when 
they contain substitutable sites, via a direct bond or via a -CH 2 -, -O-, -S-, -NH- or -NCi-C 24 alkyl -bridge in such a manner that, 
together with the atoms and bonds indicated in formula (I), five- or six-membered, saturated, unsaturated or aromatic, unsubstituted 
or Ga-substituted rings are formed, Gi is any desired substituent,? x m-^ is an inorganic, organic or organometallic anion, Y n+ is a 
proton or a metal, ammonium or phosphonium cation, and m and n arc each independently of the other a number from 1 to 5, and 
p and q are each independently of the other O or a number from 0.2 to 6, the ratio of p and q to one another, depending upon m 
and n and, as applicable, the number of charged Gi, being such that in formula (I) there is no excess positive or negative charge. 
Generally the optical recording medium according to the invention additionally comprises a reflecting layer. The recording media 
according to the invention exhibit high sensitivity and good playback characteristics, especially at high recording and playback 
speeds. The light stability is also excellent 



WO 03/007296 



PCT/EP02/07434 



- 1 ■ 

Fast-writable and precision-writable high-capacity optical storage media 

The field of the invention is the optical storage of information on write-once 
storage media, the information pits being differentiated by the different optical 
properties of a colorant at written and unwritten sites. This technology is 
usually termed "WORM" (for example "CD-R" or "DVD-R"); those terms have been 
retained herein. 

Compact discs that are writable at a wavelength of from 770 to 830 nm are 
known from "Optical Data Storage 1989", Technical Digest Series, Vol. 1, 45 
(1989). They are read at a reduced readout power. According to the Orange 
Book Standard, at the recording wavelength the medium must have a base 
reflectivity of 65% or more. As recording media it is possible to use, for 
example, cyanine dyes (JP-58/125246), phthalocyanines (EP-A-676 751, 
EP-A-712 904), azo dyes (US-5 441 844), double salts (US-4 626 496), 
dithioethene metal complexes (JP-A-63/288785, JP-A-63/288786), azo metal 
complexes (US-5 272 047, US-5 294 471, EP-A-649 133, EP-A-649 880) or 
mixtures thereof (EP-A-649 884). 

By using more recent compact high-performance red diode lasers that emit in 
the range of from 600 to 700 nm it is possible in principle to achieve a 6- to 8- 
fold improvement in data packing density, in that the track spacing (distance 
between two turns of the information track) and the size of the pits as well as 
the redundancy can each be reduced to approximately half the value in 
comparison with conventional CDs. 

This imposes extraordinarily high demands on the recording layer to be used, 
however, such as high refractive index, high light stability in daylight and under 
laser radiation of low power density (readout) with, at the same time, high 
sensitivity under laser radiation of high power density (writing), uniformity of 
script width at different length pulse durations and also high contrast. The 
known recording layers still do not possess these properties to an entirely 
satisfactory extent. 

EP-A-0 805 441 describes an optical recording medium comprising xanthene 
dyes, which can be both recorded and read at from 600 to 700 nm. In the 
Examples, good results are achieved with a 10 mW laser diode of wavelength 



WO 03/007296 



PCT/EP02/07434 



- 2 - 

635 nm. It has been found, however, that under practical conditions the 
results for the dyes disclosed in EP-A-0 805 441 are not able fully to satisfy the 
demands (which have increased in the interim) in respect of sensitivity, record- 
ing speed and mark accuracy and reproducibility, especially in the range from 
640 to 680 nm. 

US-3 781 711 discloses laser dye compositions comprising dyes having a rigid 
structure, including 9,9-dimethyl-2-dimethylamino-7H,9H-anthracene-7- 
dimethyliminium nitrate. Such compounds are used in high dilution. 

WO-A-00/64986 describes carbopyronine fluorescent dyes and their use as 
marker groups in diagnostics. The absorption maxima and the fluorescent 
yield are not appreciably altered by coupling such compounds to carriers and 
biomolecules. 

The aim of the invention is to provide an optical recording medium, the record- 
ing layer of which has high storage capacity combined with excellent other 
properties. The recording medium should be both writable and readable, with 
a minimum of errors, at the same wavelength in the range of from 600 to 
700 nm (preferably from 630 to 690 nm) at high speed. 

Very surprisingly, by the use of certain carbopyronine dyes as recording layer it 
has been possible to provide an optical recording medium having properties 
that are astonishingly better than those of recording media known hitherto. 

The invention accordingly relates to an optical recording medium comprising a 
substrate and a recording layer, wherein the recording layer comprises a com- 
pound of formula (I) 









R 7 














.R 8 




N 
i 










(Y" + ) q 


R 2 




R 13 R 12 Rn 


i 

R 10 





(I) 



wherein R x , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9) R 10) R n , R 12 and R 13 are each 
independently of the others hydrogen, G lf or C r C 2 4alkyl, C 2 -C 2 4alkenyl, 



WO 03/007296 



PCT/EP02/07434 



• 3 - 

C 2 -C 24 alkynyl, C3-C 24 cycloalkyl, C 3 -C 2 4cyc[oalkenyl, C 7 -C 24 aralkyl, C 6 -C 24 aryl, 
C 4 -C 12 heteroaryl or C r Ci 2 heterocycloalkyl, each unsubstituted or substituted 
by one or more identical or different substituents Gi, 

wherein Rj and R 2 , R 2 and R 13 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 5 and R 6 , 
R 6 and R 7j R 7 and R 8 , R 8 and R 9 , R 9 and Ri 0 , Rio and R n , R n and R 12 
and/or R 12 and R i3 can independently of one another be bonded to one 
another in pairs separately or, when they contain substitutable sites, via a 
direct bond or via a -CH 2 - -0-, -S-, -N H- or -NC r C 24 alkyl- bridge in such 
a manner that, together with the atoms and bonds indicated in formula (I), 
five- or six-membered, saturated, unsaturated or aromatic, unsubstituted 
or G r substituted rings are formed, 

Gi is any desired substituent, 

X m_ is an inorganic, organic or organometallic anion, 

Y n+ is a proton or a metal, ammonium or phosphonium cation, and 

m and n are each independently of the other a number from 1 to 5, and p and 
q are each independently of the other 0 or a number from 0.2 to 6, 
the ratio of p and q to one another, depending upon m and n and, as 
applicable, the number of charged Gi substituents, being such that in 
formula (I) there is no excess positive or negative charge. 

Generally the optical recording medium according to the invention additionally 
comprises a reflecting layer, but this is not absolutely necessary perse and it 
can be omitted depending upon the type of detector. 

Each Gi is, where applicable independently of any other Gi, any desired sub- 
stituent, for example halogen, -OH, -0~, -OA, =0, -SH, -S~, -SA, =S, -N0 2 , -CN, 
-NH 2 , -NHA, -N(A) 2 , -N + H 3 , -N + H 2 A, -N + H(A 2 ), -N + (A) 3 , -NHCOA, -N(A)COA, -CHO, 
-C(A)=0, -CH(OA) 2 , -C(A)(0A) 2 , -C(OA) 3 , -CH=N-A, -C(A)=N-A, -N=CH-A, 
-N=C(A) 2 , -N=N-A, -COO", -COOH, -COOA, -C0NH 2 , -CONHA, -CON(A) 2 , 
-NHCONH 2 , -NHCONHA, -NHCON(A) 2 , -N(A)CONH 2 , -N(A)CONHA, 
-N(A)CON(A) 2 , -S0 2 A, -S0 3 ~, -S0 3 H, -S0 3 A, -P0 3 ", -PO(OA) 2 , -Si(A) 3 , -0Si(A) 3 , 
-Si(OA) 2 (A) or -Si(0A) 3 , each A being independently of the others alkyl, alkenyl, 



WO 03/007296 PCT/EP02/07434 



alkynyl, cycloalkyl, cycloalkenyl, aralkyl, aryl or heteroaryl, each of which can 
be uninterrupted or interrupted by one or more hetero atoms, such as N, 0, P 
and S, for example in the form of a polyalkylene glycol chain, pyrrolidinyl, 
piperidyl, piperazinyl, morpholinyl, oxybisphenylene or heteroaryl, such as 
pyridyl, furyl, thienyl or phenothiazinyl. 

A is typically Ci-C 24 alkyl, C 2 -C 24 alkenyl, C 2 -C 24 alkynyl, C 3 -C 24 cycloalkyl, 
C 3 -C 24 cycloalkenyl, C 7 -C 24 aralkyl, C 6 -C 24 aryl or C 4 -C 12 heteroaryl. 

It will be understood that different As can also be combined, such as, for 
example, in chromanyl, phosphindolinyl or l-phenyl-2-pyrazolinyl, that is to 
say, for example, in substituted form azo-3-methyl-5-oxo-l-phenyl-2-pyrazolin- 
(4)-yl. It is also possible for alkylene, arylene or aralkylene to be used in place 
of two As, for example morpholino in place of methyl-3-oxabutyl-amino or 
4-methyl-piperidino in place of ethyl-3-azabutyl-amino. 

When Gx contains a radical A, that radical can be unsubstituted or substituted 
by from 1 to 5 identical or different substituents G 2 , each G 2 being as defined 
for Gi, except that G 2 can only be unsubstituted or mono-substituted by G 3 , 
where G 3 likewise is as defined for Gi, except that G 3 is not further substituted. 

Especially the following substituents may be mentioned as Gi: -CH 2 -CH 2 -OH, 
■CH 2 -0-CH 3 , -CH 2 -0-(CH 2 ) 7 -CH 3 , -CH 2 -CH 2 -0-CH 2 -CH 3 , -CH 2 -CH(0CH 3 ) 2 , 
-CH 2 -CH 2 -CH(OCH 3 ) 2 , -CH 2 -C(OCH 3 ) 2 -CH 3 , -CH 2 -CH 2 -0-CH 2 -CH 2 -0-CH 3 , 
-(CH 2 ) 3 -OH, -(CH 2 ) 6 -0H, -(CH 2 ) 7 -0H, <CH 2 ) 8 -OH, -(CH 2 ) 9 -OH, -(CH 2 ) 10 -OH, 
-(CH 2 ) n -OH, -(CH 2 ) 12 -OH, -CH 2 -Si(CH 3 ) 3 , -CH 2 -CH 2 -0-Si(CH 3 ) 2 -C(CH 3 ) 3 , 
■(CH 2 ) 3 -0-Si(CH 3 ) 2 -C(CH 3 ) 3 , -(CH 2 ) 4 -0-Si(C 6 H 5 ) 2 -C(CH 3 ) 3 , 
-(CH 2 ) 5 -0-Si(CH(CH 3 ) 2 ) 3 , -CH 2 -CH 2 -CH(CH 3 )-CH 2 -CH 2 -CH(OH)-C(CH 3 ) 2 -OH, 
•CH 2 -CH(CH 3 )-CH 2 -OH, -CH 2 -C(CH 3 ) 2 -CH 2 -OH, -CH 2 -C(CH 2 -OH) 3) 

-CH 2 -CH(OH)-CH 3 , -CH 2 -CH(OH)-CH 2 -OH, -CH 2 CH 2 0-T]) , -(CH 2 ) 3 0-T]> , 
and -(CH 2 ) 2 CH=N-R 14 , wherein R 14 is C r C 24 alkyl, C 2 -C 24 a)kenyl, C 2 -C 24 alkynyl, 



WO 03/007296 



PCT/EP02/07434 



- 5 - 



C 3 -C 24 cycloaikyI, C 3 -C 24 cycloalkenyl, C 7 -C 2 4aralkyl f C 6 -C 24 aryl, C 4 -Ci 2 heteroaryl 
or Ci"Ci 2 heterocycloalkyI, each unsubstituted or substituted by one or more 
identical or different substituents G 2 , or is a metal complex. When R 14 is 
C r C 24 alkyl, it may be uninterrupted or interrupted by from 1 to 3 oxygen 
and/or silicon atoms. G 2 or G 3 may especially advantageously be alkyl unsub- 
stituted or substituted by one or two hydroxy substituents or by a metallocenyl 
or azo metal complex radical. Such radicals G x are of very special importance 
as R 6 . 



The compound of formula (I) may optionally also be a dimer of formula 




wherein R{ to Ri 3 ' have the same meanings as Ri to R i3 and an R substituent 
selected from Ri to R x3 is bonded to an R 1 substituent selected from Ri' to Ri 3 \ 
for example via a direct bond, an alkylene group or a hetero atom, or an R' 
substituent selected from Ri' to Ri 3 ' is a direct bond to an R substituent 
selected from Ri to R i3 . 

Great importance is attached especially to compounds of formula (II) wherein 
R 6 is bonded to R 6 \ or R 6 ' is a direct bond to R 6 . 

When the numbers p and q are not whole numbers, it is to be understood by 
formulae (I) and (II) that there is a mixture of a certain molar composition, the 
individual components of which may also have different stoichiometry. 

Alkyl, alkenyl or alkynyl may be straight-chain or branched. Aikenyl is alkyl that 
is mono- or poly-unsaturated, wherein two or more double bonds may be 
isolated or conjugated. Alkynyl is alkyl or alkenyl that is double-unsaturated 
one or more times, wherein the triple bonds may be isolated or conjugated with 
one another or with double bonds. Cycloalkyl or cycloalkenyi is monocyclic or 
polycyclic alkyl or alkenyl, respectively. 



WO 03/007296 PCT/EP02/07434 



C r C 24 Alkyl can therefore be, for example, methyl, ethyl, n-propyl, isopropyl, 
n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methyl-butyl, n-pentyl, 2-pentyl, 3- 
pentyl, 2,2-dimethylpropyl, n-hexyl, heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 
2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, 
hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl or 
tetracosyl. 

C 3 -C 2 4Cycloalkyl can therefore be, for example, cyclopropyl, cyclopropyl- 
methyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexyl-methyl, trimethyl- 
cyclohexyl, thujyl, norbomyl, bornyl, norcaryl, caryl, menthyl, norpinyl, pinyl, 

1- adamantyl, 2-adamantyl, 5a-gonyl or 5^-pregnyl. 

C 2 -C 24 Alkenyl is, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-l-yl; 3-buten-l- 
yl, l,3-butadien-2-yl, 2-penten-l-yl, 3-penten-2-yl, 2-methyl-l-buten-3-yl, 

2- methyl-3-buten-2-yl, 3-methyl-2-buten-l-yl, l,4-pentadien-3-yl, or any desired 
isomer of hexenyl, octenyl, nonenyl, decenyl, dodecenyl, tetradecenyl, hexa- 
decenyl, octadecenyl, eicosenyl, heneicosenyl, docosenyl, tetracosenyl, hexa- 
dienyl, octadienyl, nonadienyl, decadienyl, dodecadienyl, tetradecadienyl, hexa- 
decadienyl, octadecadienyl or eicosadienyl. 

C 3 -C 24 Cycloalkenyl is, for example, 2-cyclobuten-l-yl, 2-cyclopenten-l-yl, 
2-cyclohexen-l-yl, 3-cyclohexen-l-yl, 2,4-cyclohexadien-l-yl, l-p-menthen-8-yl, 
4(10)-thujen-10-yl, 2-norbornen-l-yl, 2,5-norbornadien-l-yl, 7,7-dimethyl-2,4- 
norcaradien-3-yl or camphenyl. 

Ci-C 24 Alkoxy is 0 — C r C 2 4alkyl, and C 1 -C 24 alkylthio is S — Ci-C^alkyl. 

C 2 -C 24 Alkynyl is, for example, l-propyn-3-yl, l-butyn-4-yl, l-pentyn-5-yl, 

2- methyl-3-butyn-2-yl, l,4-pentadiyn-3-yl, l,3-pentadiyn-5-yl, l-hexyn-6-yl, 
cis-3-methyl-2-penten-4-yn-l-yi, trans-3-methyl-2-penten-4-yn-l-yl, 1,3-hexa- 
diyn-5-yl, l-octyn-8-yl, l-nonyn-9-yl, l-decyn-10-yl or l-tetracosyn-24-yl. 

C 7 -C 24 Aralkyl is, for example, benzyl, 2-benzyl-2-propyl, p-phenyl-ethyl, 
9-fluorenyl, a,a-dimethylbenzyl, co-phenyl -butyl, o-phenyl-octyl, co-phenyl- 
dodecyl or S-methyl-S-Cl'^'^'.S'-tetramethyl-butyO-benzyl. C 7 -C 24 Aralkyl can 
also be, for example, 2,4,6-tri-tert-butyl-benzyl or l-(3,5-dibenzyl-phenyl> 

3- methyl-2-propyl. When C 7 -C 24 aralkyl is substituted, either the alkyl moiety or 



WO 03/007296 



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- 7 ■ 



the aryl moiety of the aralkyl group can be substituted, the latter alternative 
being preferred. 

C6-C 2 4Aryl is, for example, phenyl, naphthyl, biphenylyl, 2-fluorenyl, phen- 
anthryl, anthracenyl or terphenylyl. 

Halogen is chlorine, bromine, fluorine or iodine, preferably chlorine or bromine. 

C 4 -C 12 Heteroaryl is an unsaturated or aromatic radical having 4n+2 conjugated 
7t-electrons, for example 2-thienyl, 2-furyl, 1-pyrazolyl, 2-pyridyl, 2-thiazolyl, 
2-oxazolyl, 2-imidazolyl, isothiazolyl, triazolyl or any other ring system consist- 
ing of thiophene, furan, pyridine, thiazole, oxazole, imidazole, isothiazole, thia- 
diazole, triazole, pyridine and benzene rings and unsubstituted or substituted 
by from 1 to 6 ethyl, methyl, ethylene and/or methylene substituents. 

Furthermore, aryl and aralkyl can also be aromatic groups bonded to a metal, 
for example in the form of metallocenes of transition metals known perse, more 
especially 



wherein R 1S is CH 2 OH, CH 2 0A, COOH, COOA or COO-. 

C r Ci 2 Heterocycloalkyl is an unsaturated or partially unsaturated ring system 
radical, for example tetrazolyl, pyrrolidyl, piperidyl, piperazinyl, imidazolinyl, 
pyrazolidinyl, pyrazolinyl, morpholinyl, quinuclidinyl or another C 4 -Ci 2 hetero- 
aryl that is mono- or poly-hydrogenated. 

Y n+ as a metal, ammonium or phosphonium cation is, for example, Li + , Na + , 
K + , Mg 2+ , Ca 2+ , Cu 2+ , Ni 2+ , Fe 2+ , Co 2+ , Zn 2+ , Sn 2+ , Cr 3+ , La 3+ , methyl- 
ammonium, ethylammonium, pentadecylammonium, isopropylammonium, 
dicyclohexylammonium, tetramethylammonium, tetraethylammonium, tetra- 
butylammonium, benzyltrimethylammonium, benzyltriethylammonium, 
methyltrioctylammonium, tridodecylmethylammonium, tetrabutylphos- 
phonium, tetraphenylphosphonium, butyltriphenylphosphonium or ethyl- 




WO 03/007296 



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- 8 - 



triphenylphosphonium, or protonated Primen 81 R™ or Rosin Amin D™. 

X m ' as an inorganic, organic or organometallic anion is, for example, the anion 
of a mineral acid, the conjugate base of an organic acid or an organometai 
complex anion, for example fluoride, chloride, bromide, iodide, perchlorate, 
periodate, nitrate, l /z carbonate, hydrogen carbonate, C r C 4 alkyl sulfate, 
Vz sulfate, hydrogen sulfate, 1/3 phosphate, Vz hydrogen phosphate, dihydrogen 
phosphate,,^ C r C 4 alkanephosphonate, Ci-C 4 alkane-C r Ci 2 alkyl-phosphonate, 
di-C r C 4 a!kylphosphinate, tetrafluoroborate, hexafluorophosphate, hexafluoro- 
antimonate, acetate, trifluoroacetate, heptafluorobutyrate, Vz oxalate, methane- 
sulfonate, trifluoromethanesulfonate, tosylate, benzenesulfonate, p-chloro- 
benzenesulfonate, p-nitrobenzenesulfonate, an alcoholate, phenolate (e.g. 
phenolate itself), carboxylate (also e.g. benzoate), sulfonate or phosphonate) or 
a negatively charged metal complex. 

The person skilled in the art will readily recognise that it is also possible to use 
other anions with which he is familiar. It will be self-evident to him that — of 

an inorganic, organic or organometallic anion having x negative charges, for 
example Vz'SOa 2 ', is a multiply charged anion which neutralises several singly 
charged cations or a cation having x charges, as the case may be. 

Phenolates or carboxyfates are, for example, anions of Ci-C^alkylated, 
especially tert-C 4 -C 8 alkyiated, phenols or benzoic acids, such as 



When X m " is an organometallic anion, it is preferably a metal complex of 
formula [(Li)Mi(L 2 )] m " (III) or [(L 3 )M 2 (L 4 )]" (IV), wherein M a and M 2 are a 
transition metal, preferably Mi being Cr 3+ or Co 3+ and M 2 being Ni 2+ , Co 2+ or 
Cu 2+ , m is a number from 1 to 6, Li and L 2 are each independently of the other 
a ligand of formula 




WO 03/007296 



PCT/EP02/07434 




Ri6, R17, Ri8r R197 R20 and R21 are each independently of the others hydrogen, 
halogen, cyano, R 24 , N0 2 , NR 24 R 25 , NHC0-R 24 , NHC00R 24 , S0 2 -R 24 , S0 2 NH 2 , 



WO 03/007296 



PCT/EP02/07434 



- 10 - 



S0 2 N.HR 2 4, SO2NR24R25, S0 3 ~or SO3H, preferably hydrogen, chlorine, S0 2 NH 2 
or S0 2 NHR 2 4, and R22 and R 2 3 are each independently of the other CN, CONH 2 , 
CONHR24, CONR24R25, COOR24 or C0R 24 , wherein R 2 4 and R 25 are each 
independently of the other C r Ci 2 alkyl, C 1 -Ci2alkoxy-C 2 -Ci 2 alkyl, C 7 -C 12 aralkyl 
or C 6 -C 12 aryl, preferably Ci-C 4 alkyl, each unsubstituted or substituted by 
hydroxy, halogen, sulfato, C r C 6 aIkoxy, Ci-C 6 alkylthio, C r C 6 alkylamino or by 
di-C r C 6 alkylamino, or R 2 4 and R 2 5 together are C4-C 10 heterocycloalkyl; it also 
being possible for R i6 and R17, Ris and R 19 , and/or R 20 and R 2 i to be bonded 
together in pairs in such a manner that a 5- or 6-membered ring is formed. 

Reference is made by way of illustration, but on no account as a limitation, to 

the individual compounds disclosed in US-5 219 707, US-6 168 843, 

US-6 242 067, WO-01/19923, WO-01/62853, EP-A-1 125 987, 

EP-A-1 132 902, JP-A-06/199045, JP-A-07/262604, J P-A-2000/ 190642 and 

JP-A-2000/198273. 

It is also possible, however, to use any other known transition metal complex 
anion that contains, for example, a phenolic or phenylcarboxylic azo compound 
as ligand U or L 2 . 

Preference is given to compounds of formula (I) wherein R 1( R 4( R 5 , R 7 , R 8 and 
Rn are hydrogen; R 2 , R3, R9, Rio, R12 and Ri 3 are each independently of the 
others methyl, ethyl or R 14 , it being possible for R 2 and R 3 , R 9 and R 10 , R12 and 
R 13 and/or R 9 and Ri 0 also to be bonded together in pairs via a direct bond, 
methylene, -O- or -N(Ci-C 4 alkyl); and R 6 is hydrogen or C 1 -Ci 2 alkyl, C 6 -C 12 aryl 
or C 7 -C 13 aralkyl, each unsubstituted or mono- to tetra-substituted by halogen, 
-Or, -OR 26 , -CN, -NR26R27, -N + R 26 R 2 7R28, -N(R 26 )COR 27 , -COO", -COOR 26) 
-CONR 25 R 27 , R14 or by -N(R 26 )COR 27 R28, wherein R 26 , R 27 and R 28 are each 
independently of the others C r Ci 2 alkyl, C 6 -C 12 aryl or C 7 -C 13 aralkyl; 

all the bridging possibilities, limitations and definitions indicated above 
otherwise remaining unchanged. 



When R 6 is unsubstituted or substituted C 6 -C 12 aryl, it is preferably -\^-R 31 , 




R. 



'30 



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wherein R 29 , R30 and R 31 are each independently of the others hydrogen, 
halogen, COOR 32 , 0R 32 or NR 32 R 33 , wherein R 32 and R 33 are each independently 
of the other hydrogen or C r Ci 2 alky!, C 2 -Ci 2 alkenyl, C r C i2 cycloalkyl, 
C 2 -Ci 2 cycloalkenyl, C 6 -C 12 aryl or C 7 -C 13 aralkyl, each unsubstituted or sub- 
stituted by one or two hydroxy substituents or by a metallocenyl or azo metai 
complex radical and uninterrupted or interrupted by 1, 2, 3, 4 or 5 oxygen 
and/or silicon atoms. R 29 is preferably hydrogen, carboxy or C00-C r C 8 alkyl, 
R 30 is hydrogen or halogen, and R 31 is hydrogen, C r C 8 alkoxy or di-C r C 8 alkyl- 
amino. 



R34, R35 and R 36 are each independently of the others hydrogen or R 37 . 

When R 6 is substituted by R 37 , then it is preferably substituted by a single R 37 . 
The total number of radicals R 37 in formula (I) is preferably 0, 1 or 2, especially 
0 or 1. The total number of radicals R 37 in formula (II) is preferably 0, 1, 2, 3 
or 4, especially 0 or 2. 

R 37 is preferably alkyl uninterrupted or interrupted by from 1 to 3 oxygen 
and/or silicon atoms and unsubstituted or substituted by one or two hydroxy 
substituents or by a metallocenyl or azo metal complex radical, especially 
C r C 8 alkyl, CH 2 -CH 2 -OH, -CH 2 -0-CH 3 , -CH 2 -0-(CH 2 ) 7 -CH 3 , -CH 2 -CH 2 -0-CH 2 -CH 3 , 
-CH 2 -CH(OCH 3 ) 2 , -CH 2 -CH 2 -CH(OCH 3 ) 2 , -CH 2 -C(OCH 3 ) 2 -CH 3 , 
-CH 2 -CH 2 -0-CH 2 -CH 2 -0-CH 3l -(CH 2 ) 3 -OH, -(CH 2 ) 6 -0H, -(CH 2 ) 7 -OH, -(CH 2 ) 8 -OH, 
-(CH 2 ) 9 -OH, -(CH 2 ) 10 -OH, <CH 2 )n-OH, -(CH 2 ) 12 -OH, -CH 2 -Si(CH 3 ) 3 , 
-CH 2 -CH 2 -0-Si(CH 3 ) 2 -C(CH 3 ) 3 , <CH 2 ) 3 -0-Si(CH 3 ) 2 -C(CH 3 ) 3 , 
■(CH 2 ) 4 -0-Si(C 6 H 5 ) 2 -C(CH 3 ) 3 , -(CH 2 ) 5 -0-Si(CH(CH 3 ) 2 ) 3 , 
-CH 2 -CH 2 -CH(CH 3 )-CH 2 -CH 2 -CH(OH)-C(CH 3 ) 2 -OH, -CH 2 -CH(CH 3 )-CH 2 -OH, 
-CH 2 -C(CH 3 ) 2 -CH 2 -OH, -CH 2 -C(CH 2 -OH) 3 , -CH 2 -CH(OH)-CH 3 , 

-CH 2 -CH(OH)-CH 2 -OH, -C^CHp-^ • -<CH 2 ) 3 0-^) , -CH 2 CH 2 -< 0 [) , 



Special preference is given to compounds of formula (I) wherein R 6 is 





OR„ or R 37 , and 



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p 

OR 



14 



_ (C H 2 ^- N 0-^ Rl4 ' " (CH2)3 °"r i4 ' " (CH2)2 °"r 14 ' C 2 -C 8 alkylene-0-CO-D, 
C 2 -C 8 alkylene-C00-D or C 2 -C 8 alkylene-N=CH-0, wherein D is 






or -ch 




Azo metal complex radicals have, for example, the formula -[(Li)Mi(L 2 )] m -. 

Metallocenyl radicals preferably contain as metal Ni, Co, Cu, Ti or especially 
Fe. For example, R 37 in formula (I) or (II) as a metallocenyl radical may be 



-(CH 2 ) 6 -Q 



^CH 2 -^f> 



2* , -(CH 2 ) 2 -0 



2+ 



Fe 



, -(CH 2 ) 3 -< 



pcH 2 -^r> 



O 



"(CH 2 ) 3 




CH 2 OH 



-(CH 2 ) 3 -i , -(CH 2 ) r O ^ 

[-C2-C 8 alkylene-SO 2 ]2-0-S, [-C 2 -C 8 alkylene-O-C 2 -C 8 alkylene-NHSO 2 ]2-0-S ; 
[-C 2 -C 8 alkylene-NHSO 2 ] 2 -0-S, [-C 2 -C 8 alkylene-NH-C 2 -C 8 alkylene-SO2]2-0-$ or 
[-C 2 -C 8 alkylene-N(Ci-C 8 alkyl)-C2-C 8 alkylene-SO 2 ] 2 -0-S; or in formula (II) as an 
azo metal complex radical may be [-C 2 -Caalkylene-SO 2 ]2-0-, 
[-C 2 -C 8 alkylene-NHSO 2 ]2-0-, [-C 2 -C 8 alkylene-O-C 2 -C 8 alkylene-NHSO2]2-0-, 
[-C2-C 8 alkylene-NH-C2-C 8 alkylene-SO 2 ]2-0- or 

[-C 2 -C 8 alkylene-N(C 1 -Csalkyl)-C2-C 8 alkylene-SO 2 ] 2 -0-, wherein S is S0 3 - 
S0 2 -C 1 -C 8 alkyl, S0 2 NR 3 9R4o, R39 and R 40 are each independently of the other 
hydrogen or Ci-Ci 2 alkyl, C 2 -Ci 2 alkenyl, Ci-Ci 2 cycloalkyl, C 2 -Ci 2 cycloalkenyl, 
C6-Ci 2 aryl or C 7 -Ci 3 aralkyl, each uninterrupted or interrupted by from 1 to 5 
oxygen and/or silicon atoms and unsubstituted or substituted by one or two 
hydroxy substituents, and 0 is the bivalent radical of an organometallic anion 
selected from the group consisting of 



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and those of the formulae Ql, Q2, Q3, Q4, Q5, Q6, Q7, 08, Q9, Q10, Qll, 
Q12, Q13, Q14, Q15, Q16, Q17, Q18, Q19, Q20, Q21, Q22, Q23, Q24 and 
Q25 given hereinbelow. 

-Alky!ene-SO 2 -0, -alkylene-NHSO 2 -0, -alkylene-O-alky!ene-NHSO 2 -0, 



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PCT/EP02/07434 



-alkylene-NH-alkylene-SO 2 -0 or -alkylene-N(alkyl)-alkylene-SO 2 -0 are preferably 
-(CH 2 ) 2 -SO 2 -0, ■(CH 2 ) 2 -NHSO2-0, -(CH 2 ) 2 -O-(CH 2 ) 2 -NHSO 2 -0, 
-(CH 2 ) 2 -NH-(CH 2 ) 2 -SO 2 -0, -(CH 2 ) 6 -NHSO 2 -0 or •(CH 2 )2-N(C 4 H 9 )-(CH 2 ) 2 -SO 2 -0. 

Of special interest are compounds of formula (I) substituted by azo metal 

-<ch 2 ) 2 nh(ch 2 ) 2 so 2 

complex radicals such as, for example, \ > and 

\ : -o 

Cu 

also compounds of formula (II) wherein two radicals of formula (I) are linked via 

\ 




a bridge of formula ° k^^^lf***) o 



0 K /^(CH^- 




— (CH 2 ) 2 0(CH 2 ) 2 NHS0 2 ^v s .N, 0 



O N"^^S0 2 NH(CH 2 ) 2 0(CH 2 ) 2 - 



CH 3 



-(CH 2 ) 2 0(CH 2 ) 2 NHS0 2 ^v_N.^ O 

Ujl ^Cp-'°>^ 



O , NI^^S0 2 NH(CH 2 ) 2 0(CH 2 ) 2 - 
N 



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Those preferences apply to each of the sub-structures contained in formula (I) 
or (II), in each case independently of any other sub-structures which may be 
present, provided that the condition inherent in formula (I) or (II) is fulfilled, 



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i.e. that the resulting compound does not have an excess positive or negative 
charge. Sub-structures of formula (I) or (II) are to be understood as including 
their three components carbopyronine, (X m_ ) p and (Y n+ ) q that are not bonded to 
one another. 

Special preference is given also to compounds of formula (I) or (II) wherein Y n+ 
is [NH 2 R 38 R 3g ] + , R38 being hydrogen or C r Ci 2 alkyl and R 39 being C r C 24 alkyl or 
C 7 -C 24 aralkyl, and R 38 and R 39 together having from 8 to 25 carbon atoms. 

Special preference is given also to compounds of formula (I) or (II) wherein m 
and n are each the number 1, p is a number from 1 to 2 x / 2 , and q is a number 
from 0 to IV2, the sum of positive charges in formula (I) or (II) being equal to 
the sum of negative charges. 

Very special preference is given to the compounds of formula [G + ]i -[Q~]i (V) or 
[G + ]i(F)r(CI) s ■ [Q~]i (VI), wherein G + is a cation selected from the group 
consisting of 




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- 17 



HoC^H^CHo 




CH 3 H 3 C CH 3 



..CH, (G9) ' «,C 
N 3 

CH, 



H 3 C. 




(Gil), 



+.CH, 



(G13), 



N 

CH 3 H 3 C CH 3 CH 



+.CH, 




(G10), 



(G12), 



CH,CH. 



+-CH 9 CH. 



2 W1 '3 



CH 2 CH 3 



(G14), 



3 



CH 3 CH 2 . n ^> , ^>^^ N+ .CH 2 CH3 
CH 3 CH 2 H 3 C CH 3 CH 2 CH 3 



CH 3 CH 2 



H 3 C. 




(G15), 



CH 3 CH 2 



CH 2 CH 3 



CH 3 CH 2 . 



CH 3 H 3 C CH 3 CH 3 




(G16), 



N+ -CH 2 CH 3 
i 



CH 3 CH 2 H 3 C CH 3 CH,CH 



2 W '3 



H n 



H 3 C. 




(G17), 




(G19), 



CH 3 CH 2 . 



H 3 C CH 3 



CH 3 CH 2 



(G18), 



•wCH^CHg 



CH 3 CH 2 H 3 C CH 3 CH,CH, 




(G20), 



•t^CHgCHg 



H 3 C CH 3 



CH 2 CH 3 



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- 18- 




(G21), 



H 3 C 



H 3 C. 



CH 3 CH 2 . 



H 3 C CH 3 C H 2 CH 3 



(G23), 




(G22), 



+*CH2CH 3 



(G24), 



CH 3 CH 2 . N 



H 3 C. 



CH 3 H 3 C-C C-CH 3 CH 



N - CH 3 (G25), ^ 

CH 3 H 3 C-C C-CH 3 



+-CH 2 CH 3 



CH 2 CH 3 




OH 



(G26), 




3 ° H 2 H 2 



..ch, (G27), 



CH, H 3 C-C C-CH 3 ch. 




CH 3 CH ? >^ 

CH 3 CH 2 H 3 C-C C-CH 3 6h 2 CH 3 




(G28), 



N+ .CH 2 CH 3 (G29)? 



+ , CH , (G30), 



CH3H3C-CJ-CH3 CH. 



CH3C1-L 

1 




CH2CH2 



CH,CH H 3 C-C C-CH 3 C H 0 CH 



N+ .CH 2 CH 3 (G31), CH 3 CH 2 . N 




+ .ch,ck (G32), 




2 WI *3 



(G33), h 3 c. 

I 



CH 3 CH 2 H 3 C-C C-CH 3 C H 2 CH 3 
n-?4 H 9 



+ . CH (G34), 

N 3 
1 




CH H 3 C-C C-CH 3 CH, 



' 3 3 H 2 H 2 3 *" " 3 



CH 3 H 3 C -S 2 f CH3 



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H 3 C. 




(G45), 



CH 3 CH 2 ., 



CH.H.C-C^C-CH, CH ' 




(G46), 



N + ' CH 2 CH 3 
I 



CH 3 CH 2 H 3 C-C C— CH 3 CH ,CH 



r 1 '3 



H 3 C. 




(G47) , 



CH 3 CH 2 



CH H 3 C-C C-CH 3 CH 




(G48), 



H 2 H 2 



CH 3 CH 2 H 3 C-C C-CH 3 cH 2 CH 3 



H 3 C. 




H 2 H 2 

CH 2 CH 2 OH 



-CH 2 CH 3 (G49), 



CH-, H 3 C CH 3 ChLCI-L 



H 3 C. 




+-CH q 



(G50), 



CH 2 OCH 3 




T ^ "X" ^ ^ N 

CH 3 H 3 C CH 3 CH 3 
CH 2 0(CH 2 ) 7 CH 3 



H 3 C. 
3 N 

CH, H 3 C CH 3 CH. 



+ .CH, < G51 >' H,C. 




(G52), 



CH 2 CH 2 OCH 2 CH 3 



H 3 C. 




CH 3 H 3 C CH 3 CH 
CH 2 CH(OCH 3 ) 2 



+ .CH 3 < G53 >' H 3 C. 



H 3 C. 



CH 3 H 3 C CH 3 C H 3 

CH 2 CH 2 CH(OCH 3 ) 2 

+ .CH 3 < G55 >' 

CH, H 3 C CH 3 CH 3 

CH 2 ) 2 0(CH 2 ) 2 OCH 3 




(G54), 




CH 3 H 3 C CH 3 CH 3 

CH 2 C(OCH 3 ) 2 CH 3 



H,C. 




+.CH, 



(G56), 



H 3 C. 




CH, H 3 C CH 3 C H 3 
CH 2 ) 3 OH 



.ch, CG57), H 



CH 3 H 3 C CH 3 CH 3 
(CH 2 ) 8 OH 




+ -CH 3 
N 3 

CH 3 H 3 C CH 3 CH 3 



(G58), 



H 3 C, 




CH 2 ) 7 OH 



CH 3 H 3 C CH 3 CH 3 



N|+ .CH 3 < G59 >> H 3 C. 
N N 
1 i 




(G60), 



CH, H 3 C CH 3 CH, 



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- 21 - 



H,C. 



H 3 C. 



CH 2 ) 3 OH 




CHA.OH 



+ .CH, 



(G61), 



H 3 C. 



H 3 C CH 3 CH 3 
CH 2 ) 10 OH 




(G62), 



CH 3 H 3 C CH 3 ch. 




CH^OH 



+ .CH 3 < G63 >' H 3 C. 
N 3 3 N 

i i 




+-CH, 
N 3 

CH 3 H 3 C CH 3 CH. 



(G64), 



(G65), 



H 3 C. 




(G66), 



CH 3 H 3 C CH 3 cH 



CH 2 ) 2 OSi(CH 3 ) 2 C(CH 3 ) 3 



(G67), 



H 3 C CH 3 C H 3 

CH 2 ) 4 OSi(C 6 H 5 ) 2 C(CH 3 ) 3 




CH 2 ) 3 OSi(CH 3 ) 2 C(CH 3 ) 3 

(G68), 




CH 3 H 3 C CH 3 CH 3 

(CH 2 ) 5 OSi(CH(CH 3 ) 2 ) 3 



H 3 C CH 3 CH 



.CH, (GG9). Hj0 . n 

I 



3 3 ull 3 '3 

(CH 2 ) 2 CH(CH 3 ) 2 )(CH 2 ) 2 CH(OH)C(CH 3 ) 2 OH 




(G70), 



CH, H 3 C CH 3 CH 




N 3 
H 3 C CH 3 CH 3 
CH 2 CH(CH 3 )CH,0H 




+ .CH 3 ^ G72 >' H 3 C, 
N 3 N 
i i 




N 3 

CH 3 H 3 C CH 3 C H 3 
CH 2 CH(OH)CH 3 



(G73), 



+ .CH, < G74 >> H,C. 



H 3 C CH 3 CH, 




(G75), 



CH, H 3 C CH 3 CH. 



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and tautomers thereof, r is a number from 1 to 6, s is a number from 1 to 4, 
and Q~ is an organometallic anion selected from the group consisting of 



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In formula (VI), preferably r is 0 and s is 1 or 2, or especially r is 1 and s is 0, 



for example compounds wherein G + is 




(G84), 



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- 29 - 



COOH 




(G85), 



n+ ,CH 2 CH 3 
CH 2 CH 3 



(G87). 



H 3 C. 




(GS6) or 



The compounds of formulae (I) and (II) are in some cases known compounds 
which can be found, for example, in the prior art mentioned above. Some of 
them are new, but they can be prepared analogously to the known compounds 
by methods known perse, for example by methods disclosed in J, Chem. Soc. 
Ill 1963 / 2655-2662, J. Chem. Soc. (B) 1967 / 91-92, J. Chem. Soc. (B) 
1969 / 1068-1071, J. Chem. Soc. (B) 1971 / 319-324, J. Chem. Soc. (B) 
1971 / 1468-1471 or Heterocycles 21/1, 167-190 [1984]. The compounds 
used according to the invention can also be prepared from their leuco forms, 
some of which are known for photographic and electrophotographic appli- 
cations, according to methods known to the person skilled in the art. Metal 
complexes, preferably those of formula (III), are well known from the specialist 
literature. In particular, they may be those metal complexes described in 
GB 1 599 812 or EP 450 421, and reference is made expressly to the teaching 
contained therein. 



Compounds of formula (I) or their precursors are preferably prepared by 



oxidation of a compound of formula 




(X), it having 



v 2 R t K 13 K 12 R 11 R 10 

been found, most surprisingly, that liquid acids, for example acetic acid, are 
especially advantageous solvents and (meta)periodate is an especially 
advantageous oxidising agent, especially in combination. The reaction 



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proceeds more selectively and the compounds in question are obtained in 
better yield and better purity, which results in better application-related 
properties in optical storage media. Ammonium (meta)periodates, especially 
tetrabutylammonium (meta)periodate, and acetic acid, especially glacial acetic 
acid, are particularly advantageous. 

The invention accordingly relates also to a process for the preparation of a 
compound of formula (I), wherein a compound of structure 





i 5 


R 6 












I 7 


„R 8 


1 










R 2 




R 13 R 12 


R ii 


i 

R 10 



(X) 



is oxidised in the presence of a Ci-C 18 carboxylic acid. The amount of 
Ci-Ciscarboxylic acid is advantageously from 0.1 to 10 000 parts by weight, 
based on (X). 

The carbopyronine dyes used according to the invention have in ethanolic 
solution a narrow absorption band having its maximum at from 540 to 640 nm. 
Very surprisingly, they also have a comparatively weak tendency towards 
agglomeration in the solid state, so that the absorption curve remains advanta- 
geously narrow also in the solid state. This is true especially in the presence of 
metal-containing anions (X m ") p , for example the metal complex anions indicated 
above. 

The carbopyronine dyes used according to the invention also have, in the form 
of a solid film, as used in optical storage media, at the longer wavelength flank 
of the absorption band a high refractive index which preferably achieves a peak 
value of from 2.0 to 3.0 in the range of from 600 to 700 nm, so that a medium 
having high reflectivity as well as high sensitivity and good playback character- 
istics in the desired spectral range is achieved. 

The substrate, which functions as support for the layers applied thereto, is 
advantageously semi-transparent (T>10%) or preferably transparent (T>90%). 
The support can have a thickness of from 0.01 to 10 mm, preferably from 0.1 



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to 5 mm. 

The recording layer is preferably arranged between the transparent substrate 
and the reflecting layer. The thickness of the recording layer is from 10 to 
1000 nm, preferably from 30 to 300 nm, especially about 80 nm, for example 
from 60 to 120 nm. The absorption of the recording layer is typically from 0.1 
to 1.0 at the absorption maximum. The layer thickness is very especially 
chosen in known manner depending upon the respective refractive indices in 
the non-written state and in the written state at the reading wavelength, so that 
in the non-written state constructive interference is obtained, but in the written 
state destructive interference is obtained, or vice versa. 

The reflecting layer, the thickness of which can be from 10 to 150 nm, prefer- 
ably has high reflectivity (R>45%, especially R>60%), coupled with low trans- 
parency (T< 10%). In further embodiments, for example in the case of media 
having a plurality of recording layers, the reflector layer may likewise be semi- 
transparent, that is to say may have comparatively high transparency (for 
example T>50%) and low reflectivity (for example R<30%). 

The uppermost layer, for example the reflective layer or the recording layer, 
depending upon the layer structure, is advantageously additionally provided 
with a protective layer having a thickness of from 0.1 to 1000 jam, preferably 
from 0.1 to 50 jam, especially from 0.5 to 15 fim. Such a protective layer can, 
if desired, serve also as adhesion promoter for a second substrate layer 
applied thereto, which is preferably from 0.1 to 5 mm thick and consists of the 
same material as the support substrate. 

The reflectivity of the entire recording medium is preferably at least 15%, 
especially at least 40%. 

The main features of the recording layer according to the invention are the very 
high initial reflectivity in the said wavelength range of the laser diodes, which 
can be modified with especially high sensitivity; the high refractive index; the 
narrow absorption band in the solid state; the good uniformity of the script 
width at different pulse durations; the good light stability; and the good 
solubility in polar solvents. 



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The recording medium according to the invention is neither writable nor read- 
able using the infra-red laser diodes of customary CD apparatus in accordance 
with the requirements of the Orange Book Standard, because at 780 nm the 
refractive indices (n) characteristically lie between 1.4 and 1.9 and their imag- 
inary components (k) between 0 and a maximum of 0.04. As a result, the risk 
of damage in the event of an erroneous attempt at writing using an apparatus 
not capable of high resolution is largely averted, which is of advantage. The use 
of dyes of formula (I) results in advantageously homogeneous, amorphous and 
low-scatter recording layers having a high refractive index, and the absorption 
edge is surprisingly especially steep even in the solid phase. Further advant- 
ages are high light stability in daylight and under laser radiation of low power 
density with, at the same time, high sensitivity under laser radiation of high 
power density, uniform script width, high contrast, and also good thermal 
stability and storage stability. 

At a relatively high recording speed, the results obtained are surprisingly better 
than with previously known recording media. The marks are more precisely 
defined relative to the surrounding medium, and thermally induced deforma- 
tions do not occur. The error rate (BLER) and the statistical variations in mark 
length (jitter) are also low both at normal recording speed and at relatively high 
recording speed, so that an error-free recording and playback can be achieved 
over a large speed range. There are virtually no rejects even at high recording 
speed, and the reading of written media is not slowed down by the correction 
of errors. The advantages are obtained in the entire range of from 600 to 
700 nm (preferably from 630 to 690 nm), but are especially marked at from 
640 to 680 nm, more especially from 650 to 670 nm, particularly at 
658±5nm. 

Suitable substrates are, for example, glass, minerals, ceramics and thermo- 
setting or thermoplastic plastics. Preferred supports are glass and homo- or 
co-polymeric plastics. Suitable plastics are, for example, thermoplastic poly- 
carbonates, polyamides, polyesters, polyacrylates and polymethacrylates, 
polyurethanes, polyolefins, polyvinyl chloride, polyvinylidene fluoride, poly- 
imides, thermosetting polyesters and epoxy resins. The substrate can be in 
pure form or may also comprise customary additives, for example UV 
absorbers or dyes, as proposed e.g. in JP 04/167 239 as light-stabilisers for 



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the recording layer. In the latter case it may be advantageous for the dye 
added to the support substrate to have an absorption maximum 
hypsochromically shifted relative to the dye of the recording layer by at least 
10 nm, preferably by at least 20 nm. 

The substrate is advantageously transparent over at least a portion of the 
range from 600 to 700 nm (preferably as indicated above), so that it is 
permeable to at least 90% of the incident light of the writing or readout 
wavelength. The substrate has preferably on the coating side a spiral guide 
groove having a groove depth of from 50 to 500 nm, a groove width of from 
0.2 to 0.8 jam and a track spacing between two turns of from 0.4 to 1.6 nm, 
especially having a groove depth of from 100 to 200 nm, a groove width of 
0.3 jam and a spacing between two turns of from 0.6 to 0.8 jam. The storage 
media according to the invention are therefore suitable especially advanta- 
geously for the optical recording of DVD media having the currently customary 
pit width of 0.4 jam and track spacing of 0.74 jam. The increased recording 
speed relative to known media allows synchronous recording or, for special 
effects, even accelerated recording of video sequences with excellent image 
quality. 

The recording layer, instead of comprising a single compound of formula (1) or 
(II), may also comprise a mixture of such compounds having, for example, 2, 3, 
4 or 5 carbopyronine dyes according to the invention. By the use of mixtures, 
for example mixtures of isomers or homologues as well as mixtures of different 
structures, the solubility can often be increased and/or the amorphous content 
improved. If desired, mixtures of ion pair compounds may have different 
anions, different cations or both different anions and different cations. 

For a further increase in stability it is also possible, if desired, to add known 
stabilisers in customary amounts, for example a nickel dithiolate described in 
JP 04/025 493 as light stabiliser. 

The recording layer comprises a compound of formula (I) or (II) or a mixture of 
such compounds advantageously in an amount sufficient to have a substantial 
influence on the refractive index, for example at least 30% by weight, prefer- 
ably at least 60% by weight, especially at least 80% by weight. The recording 
layer can especially valuably comprise a compound of formula (I) or a mixture 



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-34- 

of a plurality of such compounds as main component, or may consist exclusive- 
ly or substantially of one or more compounds of formula (I). 

Further customary constituents are possible, for example other chromophores 
(for example those disclosed in WO-01/75873, or others having an absorption 
maximum at from 300 to 1000 nm), stabilisers, 1 0 2 - ? triplet- or luminescence- 
quenchers, melting-point reducers, decomposition accelerators or any other 
additives that have already been described in optical recording media. Prefer- 
ably, stabilisers or fluoresence-quenchers are added if desired. 

When the recording layer comprises further chromophores, they may in 
principle be any dye that can be decomposed or modified by the laser radiation 
during the recording, or they may be inert towards the laser radiation. When 
the further chromophores are decomposed or modified by the laser radiation, 
this can take place directly by absorption of the laser radiation or can be 
induced indirectly by the decomposition of the compounds of formula (I) or (II) 
according to the invention, for example thermally. 

Naturally, further chromophores or coloured stabilisers may influence the 
optical properties of the recording layer. It is therefore preferable to use further 
chromophores or coloured stabilisers, the optical properties of which conform 
as far as possible to those of the compounds formula (I) or (II) or are as 
different as possible, or the amount of further chromophores is kept small. 

When further chromophores having optical properties that conform as far as 
possible to those of compounds formula (I) or (II) are used, preferably this 
should be the case in the range of the longest-wavelength absorption flank. 
Preferably the wavelengths of the inversion points of the further chromophores 
and of the compounds of formula (I) or (II) are a maximum of 20 nm, especially 
a maximum of 10 nm, apart. In that case the further chromophores and the 
compounds of formula (I) or (II) should exhibit similar behaviour in respect of 
the laser radiation, so that it is possible to use as further chromophores known 
recording agents the action of which is synergistically enhanced or heightened 
by the compounds of formula (I) or (II). 

When further chromophores or coloured stabilisers having optical properties 
that are as different as possible from those of compounds of formula (I) or (II) 



WO 03/007296 



PCT/EP02/07434 



- 35 - 



are used, they advantageously have an absorption maximum that is hypso- 
chromically or bathochromically shifted relative to the dye of formula (I) or (II). 
In that case the absorption maxima are preferably at least 50 nm, especially at 
least 100 nm, apart. Examples thereof are UV absorbers that are hypso- 
chrornic to the dye of formula (I) or (II), or coloured stabilisers that are batho- 
chromic to the dye of formula (I) or (II) and have absorption maxima lying, for 
example, in the NIR or IR range. Other dyes can also be added for the purpose 
of colour-coded identification, colour-masking ("diamond dyes") or enhancing 
the aesthetic appearance of the recording layer. In all those cases, the further 
chromophores or coloured stabilisers should preferably exhibit behaviour 
towards light and laser radiation that is as inert as possible. 

When another dye is added in order to modify the optical properties of the 
compounds of formula (I) or (II), the amount thereof is dependent upon the 
optical properties to be achieved. The person skilled in the art will find little 
difficulty in varying the ratio of additional dye to compound of formula (I) or (II) 
until he obtains his desired result. 

When chromophores or coloured stabilisers are used for other purposes, the 
amount thereof should preferably be small so that their contribution to the 
total absorption of the recording layer in the range of from 600 to 700 nm is a 
a maximum of 20%, preferably a maximum of 10%. In such a case, the amount 
of additional dye or stabiliser is advantageously a maximum of 50% by weight, 
preferably a maximum of 10% by weight, based on the recording layer. 

Most preferably, however, no additional chromophore is added, unless it is a 
coloured stabiliser. 

Further chromophores that can be used in the recording layer in addition to the 
compounds of formula (I) or (II) are, for example, cyanines and cyanine metal 
complexes (US 5 958 650), styryl compounds (US-6 103 331), oxonol dyes 
(EP-A-833 314), azo dyes and azo metal complexes (JP-A-1 1/028865), 
phthalocyanines (EP-A-232 427, EP-A-337 209, EP-A-373 643, EP-A-463 550, 
EP-A-492 508, EP-A-509 423, EP-A-511 590, EP-A-513 370, EP-A-514 799, 
EP-A-518 213, EP-A-519 419, EP-A-519 423, EP-A-575 816, EP-A-600 427, 
EP-A-676 751, EP-A-712 904, WO-98/14520, WO-00/09522, PCT/EP- 
02/03945), porphyrins and azaporphyrins (EP-A-822 546, US-5 998 093), 



WO 03/007296 



PCT/EP02/07434 



- 36 - 

dipyrromethene dyes and metal chelate compounds thereof (EP-A-822 544, 
EP-A-903 733), xanthene dyes and metal complex salts thereof (US-5 851 621) 
or quadratic acid compounds (EP-A-568 877), or oxazines, dioxazines, diaza- 
styryls, formazans, anthraquinones or phenothiazines; this list is on no account 
exhaustive and the person skilled in the art will interpret the list as including 
further known dyes. 

Stabilisers, 1 0 2 - 7 triplet- or luminescence-quenchers are, for example, metal 
complexes of N- or S-containing enolates, phenolates, bisphenolates, thiolates 
or bisthiolates or of azo, azomethine or formazan dyes, such as bis(4-dimethyl- 
aminodithiobenzil)nickel [CAS N° 38465-55-3], ®Irgalan Bordeaux EL, ®Cibafast 
N or similar compounds, hindered phenols and derivatives thereof (optionally 
also as counter-ions X), such as ®Cibafast AO, o-hydroxyphenyl-triazoles or 
-triazines or other UV absorbers, such as ®Cibafast W or ®Cibafast P or hinder- 
ed amines (TEMPO or HALS, also as nitroxides or NOR-HALS, optionally also as 
counter-ions X), and also as cations diimmoniurn, Paraquat™ or Orthoquat™ 
salts, such as ®Kayasorb IRG 022, ®Kayasorb IRG 040, optionally also as 
radical ions, such as N,N,N',N , -tetrakis(4-dibutylaminophenyl>p-phenylene- 
amine-ammonium hexafluorophosphate, hexafluoroantimonate or perchlorate. 
The latter are available from Organica (Wolfen / DE); ®Kayasorb brands are 
available from Nippon Kayaku Co. Ltd., and ®lrgalan and ®Cibafast brands are 
available from Ciba Spezialitatenchemie AG. 

Many such structures are known, some of them also in connection with optical 
recording media, for example from US-5 219 707, JP-A-06/199045, 
JP-A-07/76169, JP-A-07/262604 or JP-A-2000/272241. They may be, for 
example, salts of the metal complex anions disclosed above with any desired 
cations, for example the cations disclosed above. 

Also suitable are neutral metal complexes, for example those metal complexes 
disclosed in EP 0 822 544, EP 0 844 243, EP 0 903 733, EP 0 996 123, 
EP 1 056 078, EP 1 130 584 or US 6 162 520, for example 



WO 03/007296 



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- 37 - 




H 3 C H 3 C 



of the formula (L 3 )M 2 (L 5 ) (VII), (L 6 )M 2 (L 7 ) (VIII) or M 2 (L 8 ) (IX), wherein L 5 is 
C r Ci 2 alkyl-OH, C 6 -C 12 aryl-OH, C 7 -C 12 aralkyl-OH, C r C 12 alkyl-SH, C 6 -C 12 aryl-SH, 
C 7 -Ci 2 aralkyl-SH, C r C 12 alkyl-NH 2 , C 6 -C 12 aryl-NH 2 , C 7 -Ci 2 aralkyl-NH 2 , 
di-C r C 12 alkyl-NH, di-C 6 -C 12 aryl-NH, di-C 7 -Ci 2 aralkyl-NH, tri-C r C 12 alkyl-N, 
tri-C 6 -C 12 aryl-N or tri-C 7 -C 12 aralkyl-N, 




M 2 and R 16 to R 21 being as defined above. 



A particular example of an additive of formula (IX) that may be mentioned is a 



WO 03/007296 PCT/EP02/07434 

■ 38 - 



copper complex, illustrated e.g. by a compound of formula 




A particular example of an additive of formula (VII) that may be mentioned is a 
nickel bisphenolate, illustrated e.g. by the compound of formula 




The person skilled in the art will know from other optical information media, or 
will easily identify, which additives in which concentration are best suited to 
which purpose. Suitable concentrations of additives are, for example, from 
0.001 to 1000% by weight, preferably from 1 to 50% by weight, based on the 
recording medium of formula (I) or (II). 

The recording medium according to the invention, in addition to comprising 
compounds of formula (I) or (II), may additionally comprise salts, for example 
ammonium chloride, pentadecylammonium chloride, sodium chloride, sodium 
sulfate, sodium methyl sulfonate or sodium methyl sulfate, the ions of which 
may originate e.g. from the components used. The additional salts, if present, 
may be present preferably in amounts of up to 20% by weight, based on the 
total weight of the recording layer. 



Reflecting materials suitable for the reflective layer include especially metals, 
which provide good reflection of the laser radiation used for recording and 



WO 03/007296 



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- 39 - 

playback, for example the metals of Main Groups III, IV and V and of the Sub- 
Groups of the Periodic Table of the Elements. Al, In, Sn, Pb, Sb, Bi, Cu, Ag, Au, 
Zn, Cd, Hg, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Pd, 
Os, Ir, Pt, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu and 
alloys thereof are especially suitable. Special preference is given to a reflective 
layer of aluminium, silver, copper, gold or an alloy thereof, on account of their 
high reflectivity and ease of production. 

Materials suitable for the protective layer include chiefly plastics, which are 
applied in a thin layer to the support or the uppermost layer either directly or 
with the aid of adhesive layers. It is advantageous to select mechanically and 
thermally stable plastics having good surface properties, which may be 
modified further, for example written. The plastics may be thermosetting 
plastics and thermoplastic plastics. Preference is given to radiation-cured (e.g 
using UV radiation) protective layers, which are particularly simple and 
economical to produce. A wide variety of radiation-curable materials are 
known. Examples of radiation-curable monomers and oligomers are acrylates 
and methacrylates of diols, triols and tetrols, polyimides of aromatic tetra- 
carboxylic acids and aromatic diamines having d-C 4 alkyl groups in at least two 
ortho-positions of the amino groups, and oligomers with dialkylmaleinimidyl 
groups, e.g. dimethylmaleinimidy! groups. 

The recording media according to the invention may also have additional 
layers, for example interference layers. It is also possible to construct 
recording media having a plurality of (for example two) recording layers. The 
structure and the use of such materials are known to the person skilled in the 
art. Preferred, if present, are interference layers that are arranged between the 
recording layer and the reflecting layer and/or between the recording layer and 
the substrate and consist of a dielectric material, for example as described in 
EP 353 393 of Ti0 2 , Si 3 N 4 , ZnS or silicone resins. 

The recording media according to the invention can be produced by processes 
known perse, various methods of coating being employable depending upon 
the materials used and their function. 

Suitable coating methods are, for example, immersion, pouring, brush-coating, 
blade-application and spin-coating, as well as vapour-deposition methods 



WO 03/007296 



-40 - 



PCT/EP02/07434 



carried out under a high vacuum. When pouring methods are used, for 
example, solutions in organic solvents are generally used. When solvents are 
employed, care should be taken that the supports used are insensitive to those 
solvents. Suitable coating methods and solvents are described, for example, in 
EP-A-401 791. 

The recording layer is preferably applied by spin-coating with a dye solution, 
solvents that have proved satisfactory being especially alcohols, e.g. 
2-methoxyethanol, n-propanol, isopropanol, isobutanol, n-butanol, amyl alcohol 
or 3-methyl-l-butanol or preferably fluorinated alcohols, e.g. 2,2,2-trifluoro- 
ethanol or 2,2,3,3-tetrafluoro-l-propanol, and mixtures thereof. It will be 
understood that other solvents or solvent mixtures can also be used, for 
example those solvent mixtures described in EP-A-511 598 and EP-A-833 316. 
Ethers (dibutyt ether), ketones (2,6-dimethyl-4-heptanone, 5-methyl-2- 
hexanone) or saturated or unsaturated hydrocarbons (toluene, xylene) can also 
be used, for example in the form of mixtures (e.g. dibutyl ether / 2,6-dimethyl- 
4-heptanone) or mixed components. 

The person skilled in the art of spin-coating will in general routinely try out all 
the solvents with which is he is familiar, as well as binary and ternary mixtures 
thereof, in order to discover the solvents or solvent mixtures which result in a 
high-quality and, at the same time, cost-effective recording layer containing the 
solid components of his choice. Known methods of process engineering can 
also be employed in such optimisation procedures, so that the number of 
experiments to be carried out can be kept to a minimum. 

The invention therefore relates also to a method of producing an optical 
recording medium, wherein a solution of a compound of formula (I) in an 
organic solvent is applied to a substrate having pits. The application is 
preferably carried out by spin-coating. 

The application of the metallic reflective layer is preferably effected by 
sputtering, vapour-deposition in vacuo or by chemical vapour deposition (CVD). 
The sputtering technique is especially preferred for the application of the 
metallic reflective layer on account of the high degree of adhesion to the 
support. Such techniques are known and are described in specialist literature 
(e.g. J.L. Vossen and W. Kern, "Thin Film Processes", Academic Press, 1978). 



WO 03/007296 



PCT/EP02/07434 



-41 - 

The structure of the recording medium according to the invention is governed 
primarily by the readout method; known function principles include the 
measurement of the change in the transmission or, preferably, in the reflection, 
but it is also known to measure, for example, the fluorescence instead of the 
transmission or reflection. 

When the recording material is structured for a change in reflection, the follow- 
ing structures, for example, can be used: transparent support / recording layer 
(optionally multilayered) / reflective layer and, if expedient, protective layer 
(not necessarily transparent); or support (not necessarily transparent) / 
reflective layer / recording layer and, if expedient, transparent protective layer. 
In the first case, the light is incident from the support side, whereas in the 
latter case the radiation is incident from the recording layer side or, where 
applicable, from the protective layer side. In both cases the light detector is 
located on the same side as the light source. The first-mentioned structure of 
the recording material to be used according to the invention is generally 
preferred. 

When the recording material is structured for a change in light transmission, 
the following different structure, for example, comes into consideration: 
transparent support/ recording layer (optionally multilayered) and, if 
expedient, transparent protective layer. The light for recording and for readout 
can be incident either from the support side or from the recording layer side 
or, where applicable, from the protective layer side, the light detector in this 
case always being located on the opposite side. 

Suitable lasers are those having a wavelength of 600-700 nm, for example 
commercially available lasers having a wavelength of 602, 612, 633, 635, 647, 
650, 670 or 680 nm, especially semi-conductor lasers, such as GaAsAI, 
InGaAlP or GaAs laser diodes having a wavelength especially of about 635, 650 
or 658 nm. The recording is effected, for example, point for point in a manner 
known perse, by modulating the laser in accordance with the mark lengths and 
focussing its radiation onto the recording layer. It is known from the specialist 
literature that other methods are currently being developed which may also be 
suitable for use. 

The process according to the invention allows the storage of information with 



WO 03/007296 



PCT/EP02/07434 



- 42 - 

great reliability and stability, distinguished by very good mechanical and 
thermal stability and by high light stability and by sharp boundary zones of the 
pits. Special advantages include the high contrast, the low jitter and the 
surprisingly high signal/noise ratio, so that excellent readout is achieved. The 
high storage capacity is especially valuable in the field of video. 

The readout of information is carried out according to methods known perse by 
registering the change in absorption or reflection using laser radiation, for 
example as described in "CD-Player und R-DAT Recorder" (Claus Biaesch- 
Wiepke, Vogel Buchverlag, WUrzburg 1992). 

The information-containing medium according to the invention is especially an 
optical information material of the WORM type. It may be used, for example, 
as a playable DVD (digital versatile disk), as storage material for a computer or 
as an identification and security card or for the production of diffractive optical 
elements, for example holograms. 

The invention accordingly relates also to a method for the optical recording, 
storage and playback of information, wherein a recording medium according to 
the invention is used. The recording and the playback advantageously take 
place in a wavelength range of from 600 to 700 nm. 

The following Examples illustrate the invention in greater detail: 

Example 1 : 98.22 g of N-[7-(dimethylamino)-9,9-dimethyl-2(9H)-anthracenyl- 
idene]-N-methyl-perchlorate are dissolved in 25 litres of ethanol. Separately, 
256.25 g of the sodium salt of the metal complex of formula Q20 (in each case 
based on dry weight) are then dissolved in 40 litres of ethanol, with heating to 
65°C. After cooling to 23°C, the two solutions are combined (for example by 
pumping the second solution into the first), stirred for 30 minutes to complete 
the reaction and clarified by filtration. The solution is concentrated by evap- 
oration under a low vacuum using a rotary evaporator with a water bath at a 
temperature of about 65°C, yielding 353.63 g of crude product. 15 litres of 
water are added to the crude product and the mixture is treated mechanically 
and/or by ultrasound for 30 minutes at 10-20°C in order to dissolve the 
inorganic salts. After filtration and washing with 10 litres of water, the 
filtration residue is dried at 80°C / 1.6-10 3 Pa , yielding 322.30 g of the 



WO 03/007296 



PCT/EP02/07434 




Example 2 : The procedure is as in Example 1, but instead of N -[7 -(dim ethyl - 
amino)-9,9-dimethyl-2(9H)-anthracenylidene]-N-methyl-perchlorate there is 
used an equimolar amount of the product of formula 




(Gil). 



Example 3 : The procedure is as in Example 1, but instead of N-[7-(dimethyl- 
amino)-9,9-dimethyl-2(9H)-anthracenylidene]-N-methyl-perchlorate there is 
used an equimolar amount of the product of formula 




(G88). 



Example 4 : The procedure is as in Example 1, but instead of N-[7-(dimethyl- 
amino)-9,9-dimethyl-2(9H)-anthracenylidene]-N-methyl-perch!orate there is 
used an equimolar amount of the product of formula 



WO 03/007296 



PCT/EP02/07434 



■44 - 




(G89). 



Example 5 : The procedure is as in Example 1, but instead of N- [7 -(dimethyl- 
amino)-9,9-dimethyl-2(9H)-anthracenylidene]-N-methyl-perchlorate there is 
used an equimolar amount of the product of formula 



(G90). 




Example 6 : The procedure is as in Example 1, but instead of the metal 
complex of formula Q20 there is used an equimolar amount of the metal 
complex of formula Q3. 

Example 7 : 2% by weight of the product according to Example 1 are dissolved 
in 2,2,3,3-tetrafluoro-l-propanol and the solution is filtered through a Teflon 
filter of pore size 0.2 p,m and applied by spin-coating at 1000 rev/min to the 
surface of a 0.6 mm thick, grooved polycarbonate disc (groove depth: 170 nm, 
groove width: 350 nm, track spacing: 0.74 jam) of 120 mm diameter. The 
excess solution is spun off by increasing the rotational speed. On evaporation 
of the solvent, the dye remains behind in the form of a uniform, amorphous 
solid layer. After drying in a circulating-air oven at 70°C (10 min), the solid 
layer exhibits an absorption of 0.45 at 625 nm. In a vacuum coating apparatus 
(Twister™, Balzers Unaxis), a 60 nm thick silver layer is then applied to the 
recording layer by atomisation. Then a 6 \im thick protective layer of a UV- 
curable photopolymer (650-020, DSM) is applied thereto by means of spin- 
coating. The recording support exhibits a reflectivity of 47% at 658 nm. The 
optical constants (absorption maximum X max , refractive index at 658 nm n 558 , 



WO 03/007296 



PCT/EP02/07434 



-45- 



absorption coefficient at 658 nm k 658 ) are determined reflectometrically 
(ETA-RT™, ETA-Optik Steag-Hamatech): 

A. max = 624 nm ; n 65 s = 2.29 ; k 658 = 0.21 . 



Using a commercial test apparatus (DVDT-R 650™, Expert Magnetics), marks 
are written into the active layer at a speed of 3.5 m/sec using a laser diode of 
wavelength 658 nm and laser power of 9.2 mW. Then, using the same test 
apparatus, the dynamic parameters are determined, there being obtained good 
measured values: 

DTC Jitter = 8.8% ; R14H = 47% ; I14/I14H = 0.72 . 

Example 8 : The procedure is as in Example 7, but the product according to 
Example 6 is used instead of the product according to Example 1. The optical 
constants are determined reflectometrically as in Example 7: 

W = 626 nm ; n 658 = 2.55 ; k 658 = 0.33 . 

Comparison Example 9 : The procedure is as in Examples 7 and 8, but the 
product according to Example A8 of EP-A-0 805 441 is used instead of the 
products according to Examples 1 and 6. The optical constants are determined 
reflectometrically in the same way: 

A, max = 581 nm ; n 658 = 1.94 ; k 65S = 0.016 . 

This disc cannot be written using commercial recording apparatus (Pioneer 
A03 DVD-R(G)) on account of insufficient sensitivity. 

Examples 10-2094 : The procedure is as in Examples 7-9, but the following 
compounds of formula [G + ]-[X~], which can be prepared analogously to 
Examples 1-6, are used: 



Ex. 




[X-] 


10 


Gl 


Q2 


11 


G2 


Q2 


12 


G3 


Q2 


13 


G4 


Q2 


14 


G5 


Q2 


15 


G6 


Q2 


16 


G7 


Q2 


17 


G8 


Q2 


18 


G9 


Q2 



19 


G10 


02 


20 


Gil 


Q2 


21 


G12 


Q2 


22 


G13 


Q2 


23 


G14 


Q2 


24 


G15 


Q2 


25 


G16 


Q2 


26 


G17 


Q2 


27 


G18 


Q2 


28 


G19 


Q2 



29 


G20 


Q2 


30 


G21 


Q2 


31 


G22 


02 


32 


G23 


Q2 


33 


G24 


Q2 


34 


G25 


Q2 


35 


G26 


Q2 


36 


G27 


Q2 


37 


G28 


Q2 


38 


G29 


Q2 



WO 03/007296 



PCT/EP02/07434 



39 


G30 


Q2 


40 


G31 


Q2 


41 


G32 


Q2 


42 


G33 


Q2 


43 


G34 


Q2 


44 


G35 


Q2 


45 


G36 


Q2 


46 


G37 


Q2 


47 


G38 


Q2 


48 


G39 


Q2 


49 


G40 


Q2 


50 


G41 


02 


51 


G42 


Q2 


52 


G43 


Q2 


53 


G44 


Q2 


54 


G45 


Q2 


55 


G46 


Q2 


56 


G47 


Q2 


57 


G48 


Q2 


58 


G49 


Q2 


59 


G50 


Q2 


60 


G51 


Q2 


61 


G52 


Q2 


62 


G53 


Q2 


63 


G54 


Q2 


64 


G55 


Q2 


65 


G56 


Q2 


66 


G57 


Q2 


67 


G58 


Q2 


68 


G59 


Q2 


69 


G60 


Q2 


70 


G61 


Q2 


71 


G62 


Q2 


72 


G63 


Q2 


73 


G64 


Q2 


74 


G65 


Q2 


75 


G66 


Q2 


76 


G67 


Q2 


77 


G68 


Q2 


78 


G69 


Q2 


79 


G70 


Q2 


80 


G71 


Q2 


81 


G72 


Q2 



-46 - 



82 


G73 


02 

Tt.TT. 


83 


G74 


02 

^1 


84 


G75 


Q2 


85 


G76 


Q2 


86 


G77 


Q2 


87 


G78 


Q2 

Xn 


88 


G79 


Q2 


89 


G80 


Q2 


90 


G81 


Q2 


91 


G82 


Q2 

Jfs 


92 


G83 


02 


93 


G84 


Q2 


94 


G85 


Q2 


95 


G86 


Q2 


96 


G87 


Q2 


97 


G2 


Q3 


98 


G3 


Q3 


99 


G4 


Q3 


100 


G5 


Q3 


101 


G6 


Q3 


102 


G7 


03 


103 


G8 


Q3 


104 


G9 


Q3 

S: 


105 


G10 


Q3 


106 


Gil 


Q3 


107 


G12 


Q3 


108 


G13 


Q3 


109 


G14 


Q3 


110 


G15 


Q3 


111 


G16 


03 


112 


G17 


03 


113 


G18 


Q3 


114 


G19 


Q3 


115 


G20 


03 

X 


116 


G21 


Q3 


117 


G22 


Q3 


118 


G23 


Q3 


119 


G24 


Q3 


120 


G25 


Q3 


121 


G26 


Q3 


122 


G27 


Q3 


123 


G28 


Q3 


124 


G29 


Q3 



125 


G30 


03 

Si ^ 


126 


G31 


03 


127 


G32 


03 


128 


G33 


03 


I 129 


G34 


03 

Si 


130 


G35 


03 


131 


G36 


03 

Si 


132 


G37 


03 

Si w 


133 


G38 


Q3 

Si 


134 


G39 


03 

Sr 


135 


G40 


03 

Si ^ 


136 


G41 


03 

Si v -' 


137 


G42 


03 


138 


G43 


03 

Si ^ 


139 


G44 


03 


140 


G45 


03 


141 


G46 


03 


142 


G47 


03 


143 


G48 


03 

Sr w 


144 


G49 


03 


145 


G50 


03 


146 


G51 


03 


147 


G52 


03 

Si w 


148 


G53 


03 


149 


G54 


03 

S; ^ 


150 


G55 


03 

Si *^ 


151 


G56 


03 

Si ^ 


152 


G57 


03 


153 


G58 


03 


154 


G59 


03 


155 


G60 


03 


156 


G61 


03 


157 


G62 ! 


03 

Si ^ 


158 


G63 


03 


159 


G64 


Q3 

Si w 


160 


G65 


Q3 


161 


G66 


Q3 


162 


G67 


Q3 


163 


G68 


Q3 


164 


G69 


Q3 


165 


G70 


Q3 


166 


G71 


Q3 


167 


G72 


Q3 



WO 03/007296 



PCT/EP02/07434 



168 


G73 


03 


169 


G74 


03 


170 


G75 


03 


171 


G76 


03 


172 


G77 


03 


173 


G78 


03 


174 


G79 


03 


175 


G80 


03 


176 


G81 


03 


177 


G82 


03 


178 


G83 


03 


179 


G84 


03 


180 


G85 

V^l V»/ 


03 


181 


G86 


03 


182 


G87 


03 


183 


Gl 


04 


184 


G2 


04 
x^ 


185 


G3 


04 


186 


G4 


04 


187 


G5 


04 


188 


G6 


04 


189 


G7 


04 


190 


G8 


04 


191 


G9 


04 


192 


G10 


04 


193 


Gil 

\-A JL JL 


04 


194 


G12 

\-A JL e_ 


04 


195 


G13 


04 


196 


G14 


04 


197 


G15 


04 
x^ 


198 

JL ~/ v — * 


G16 


04 


199 

JL —J «—/ 


G17 


04 


200 


G18 


04 


201 


G19 


04 


202 

C_ 


G20 

V_-l V-/ 


04 


203 


G21 


04 


204 


G22 


04 


205 


G23 


Q4 


206 


G24 


Q4 


207 


G25 


Q4 


208 


G26 


Q4 


209 


G27 


Q4 


210 


G28 


04 



-47 - 



211 


G29 


04 


212 


G30 


04 


213 


G31 


04 


214 


G32 


04 

x*+ 


215 


G33 


04 


216 


G34 


04 


217 


G35 


04 


218 


G36 

V>4 -v-^ v 


! 04 


219 


G37 


1 04 


220 


G38 

W V./ 


04 


221 


G39 


04 


222 


G40 


04 


223 


G41 


04 


224 


G42 


04 


225 


G43 


04 


226 


I G44 


04 


1 227 


G45 


04 


228 


G46 


04 


229 


G47 


04 


230 

b> vJ* v/ 


G48 


04 


231 


G49 


04 


232 


G50 


04 


233 


G51 


04 


234 


G52 


04 


235 


G53 


04 


236 


G54 


04 


237 


G55 


04 


238 


G56 

v V/ 


04 


239 


G57 


04 


1 240 


G58 


04 


241 


G59 


04 
y^ 


i ?42 


G60 


04 
x^ 


243 


G61 


04 


244 


G62 


04 


245 


G63 


04 


246 


G64 


04 


247 


G65 


Q4 


248 


G66 


Q4 


249 


G67 


Q4 


250 


G68 


Q4 


251 


G69 


04 


252 


G70 


Q4 


253 


G71 


04 



254 


G7? 


OA 


255 

L— 


0/0 


OA 


256 

t— v-/ VJ 


G74 


OA 


257 


G7^ 


OA 


258 


G76 


OA 
y^ 


259 


G77 


DA 
X^ 


260 


G78 


OA 


261 


G79 


OA 


262 


vJOu 


OA 


263 


GR1 

UUl 


OA 
X^ 


264 


G82 


OA 


265 




OA 


266 


GR4 


OA 


267 




OA 


268 


UOU 


OA 


269 


G87 


OA 


270 






271 






272 








HA 


yo 


91 A 

C. i Hr 




OR 


27R 




OR 


976 


C1-7 

\Zk / 




977 






27R 




OR 


27Q 




OR 


9R0 


ftl 1 
ul J. 


OR 


£_0 X 


O JL ^1 


OR 






go 


9R1 




go 




O JL O 


go 






go 




ft 1 7 


go 


9R7 


ft 1 R 


go 


6,00 


ft 1 Q 


g-> 


289 


G20 


05 


! 290 


G21 


Q5 


291 


G22 


Q5 


292 


G23 


Q5 


293 


G24 


Q5 


294 


G25 


Q5 


295 


G26 


Q5 


296 


G27 


Q5 



WO 03/007296 



PCT/EP02/07434 



297 


G28 


Q5 


298 


G29 


Q5 


299 


G30 


Q5 


300 


G31 


Q5 


301 


G32 


Q5 


302 


G33 


Q5 


303 


G34 


Q5 


304 


G35 


Q5 


305 


G36 


Q5 


306 


G37 


Q5 


307 


G38 


Q5 


308 


G39 


Q5 


309 


G40 


Q5 


310 


G41 


Q5 


1 311 


G42 


Q5 


312 


G43 


05 


313 


G44 


05 


314 


G45 


Q5 

s 


315 


G46 


Q5 


316 


G47 


Q5 


317 


G48 


Q5 


318 


G49 


Q5 


319 


G50 


Q5 


320 


G51 


Q5 


321 


G52 


05 


322 


G53 


Q5 


323 


G54 


05 


324 


G55 


Q5 


325 


G56 


05 


326 


G57 


05 


327 


G58 


05 


328 


G59 


Q5 


329 


G60 


Q5 


330 


G61 


05 


331 


G62 


05 


332 


G63 


Q5 


333 


G64 


Q5 


334 


G65 


Q5 


335 


G66 


Q5 


336 


G67 


Q5 


337 


G68 


Q5 


338 


G69 


Q5 


339 


G70 


Q5 



-48 - 



340 


G71 


Q5 


341 


G72 


Q5 


342 


G73 


Q5 


343 


G74 


Q5 


344 


G75 


Q5 


345 


G76 


Q5 


346 


G77 


Q5 


L 347 


G78 


Q5 


348 


G79 


05 


349 


G80 


Q5 


350 


G81 


Q5 


351 


G82 


Q5 

^ 


352 


G83 


Q5 


353 


G84 


Q5 


354 


G85 


Q5 


355 


G86 


05 


356 


G87 


05 

X, 


357 


Gl 


06 


358 


G2 


06 


359 


G3 


06 


360 


G4 


06 


361 


G5 


06 


362 


G6 


Q6 


363 


G7 


Q6 

> 


364 


G8 


06 


365 


G9 


06 


366 


G10 


06 


367 


Gil 


06 


368 


G12 


06 


369 


G13 


Q6 

...... X^ 


370 


G14 


06 


371 


G15 


Q6 


372 


G16 


06 


373 


G17 


06 


374 


G18 


06 


375 


G19 


Q6 


376 


G20 


Q6 


377 


G21 


Q6 


378 


G22 


Q6 


379 


G23 


Q6 


380 


G24 


Q6 


381 


G25 


Q6 


382 


G26 


Q6 



383 


G27 


06 


! 384 


G28 


06 


1 385 


G29 


06 


386 


G30 


06 


387 


G31 


06 


388 


G32 


06 


389 


G33 


06 


390 


G34 


06 


391 


G35 


06 


392 


G36 


06 


393 


G37 


06 


394 


G38 


06 


395 


G39 


06 


396 


G40 


06 


397 


G41 


06 


398 


G42 


06 


399 


G43 


06 


400 


G44 


06 


401 


G45 


06 


402 


G46 


06 


403 


G47 


06 


404 


G48 


06 


405 


G49 


06 


406 


G50 


06 


407 


G51 


06 


408 


G52 


06 


409 


G53 


06 


410 


G54 


06 


411 


G55 


06 


412 


G56 


06 


413 


G57 


06 


414 


G58 


06 


415 


G59 


06 


416 


G60 


06 


417 


G61 


06 


418 


G62 


Q6 


419 


G63 


Q6 


420 


G64 


06 


421 


G65 


Q6 


422 


G66 


Q6 


423 


G67 


06 


424 


G68 


Q6 


425 


G69 


06 



WO 03/007296 



PCT/EP02/07434 



426 


G70 


Q6 


427 


G71 


Q6 


428 


G72 


Q6 


429 


G73 


Q6 


430 


G74 


Q6 


431 


G75 


Q6 


432 


G76 


Q6 


433 


G77 


Q6 


434 


G78 


Q6 


435 


G79 


Q6 


436 


G80 


Q6 


437 


G81 


Q6 


438 


G82 


Q6 


439 


G83 


Q6 


440 


G84 


Q6 


441 


G85J 


Q6 


442 


G86 


Q6 


443 


G87 


Q6 


444 


Gl 


Q7 


445 


G2 


07 


446 


G3 


Q7 


447 


G4 


Q7 


448 


G5 


Q7 


449 


G6 


Q7 


450 


G7 


Q7 


451 


G8 


Q7 


452 


G9 


Q7 


453 


G10 


Q7 


454 


Gil 


Q7 


455 


G12 


Q7 


456 


G13 


Q7 


457 


G14 


Q7 


458 


G15 


Q7 


459 


G16 


Q7 


460 


G17 


Q7 


461 


G18 


Q7 


462 


G19 


07 


463 


G20 


Q7 


464 


G21 


Q7 


465 


G22 


Q7 


466 


G23 


Q7 


467 


G24 


Q7 


468 


G25 


Q7 



-49 - 



469 


G26 


Q7 


470 


G27 


Q7 


471 


G28 


Q7 


472 


G29 


Q7 


473 


G30 


Q7 


474 


G31 


Q7 


475 


G32 


Q7 


476 


G33 


Q7 


477 


G34 


Q7 


478 


G35 


Q7 


479 


G36 


Q7 


480 


G37 


Q7 


481 


G38 


Q7 


482 


G39 


Q7 


483 


G40 


Q7 


484 


G41 


Q7 


485 


G42 


Q7 


486 


G43 


Q7 


487 


G44 


Q7 


488 


G45 


Q7 


489 


G46 


Q7 


490 


G47 


Q7 


491 


G48 


Q7 


492 


G49 


Q7 


493 


G50 


Q7 


494 


G51 


Q7 


495 


G52 


Q7 


496 


G53 


Q7 


497 


G54 


Q7 


498 


G55 


Q7 


499 


G56 


Q7 


500 


G57 


Q7 


501 


G58 


Q7 


502 


G59 


Q7 

3L- 


503 


G60 


Q7 


504 


G61 


Q7 


505 


G62 


Q7 


506 


G63 


Q7 


507 


G64 


Q7 


508 


G65 


Q7 


509 


G66 


Q7 


510 


G67 


Q7 


511 


G68 


Q7 



512 


G69 


Q7 


513 


G70 


Q7 


514 


G71 


07 


515 


G72 


07 


516 


G73 


Q7 


517 


G74 


07 


518 


G75 


07 


519 


G76 


07 


520 


G77 


Q7 

x. ' 


521 


G78 


Q7 


522 


G79 


07 


523 


G80 


Q7 


524 


G81 


Q7 


525 


G82 


07 


526 


G83 


07 


527 


G84 


07 


528 


G85 


07 


529 


G86 


Q7 


530 


G87 


07 


531 


Gl 


08 


532 


G2 


08 


533 


G3 


Q8 


534 


G4 


08 


535 


G5 


08 


536 


G6 


Q8 


537 


G7 


08 


538 


G8 


08 


539 


G9 


08 


540 


G10 


08 


541 


Gil 


Q8 


542 


G12 


Q8 


543 


G13 


Q8 


544 


G14 


Q8 


545 


G15 


Q8 


546 


G16 


Q8 


547 


G17 


Q8 


548 


G18 


Q8 


549 


G19 


Q8 


550 


G20 


Q8 


551 


G21 


Q8 


552 


G22 


08 


553 


G23 


Q8 


554 


G24 


Q8 



WO 03/007296 



PCT/EP02/07434 



555 


G25 


08 


556 


G26 


08 


557 


G27 


08 


558 


G28 


08 


559 


G29 


08 

.re" 


560 


G30 


08 


561 


G31 


08 


562 


G32 


08 


563 


G33 


08 


564 


G34 


08 


565 


G35 


08 


566 


G36 


08 


567 


G37 


08 


568 


G38 


08 


569 


G39 


08 


570 


G40 


OR 


571 


G41 


08 


572 


G42 


08 


573 


G43 


08 


574 


G44 


08 


575 


G45 


08 


576 


G46 


08 


577 


G47 


08 


578 


G48 


08 


579 


G49 


08 


580 


G50 


08 


581 


G51 


08 


582 


G52 


08 


583 


G53 


08 


584 


G54 


08 


585 


G55 


08 


586 


G56 

W 


08 


587 


G57 


08 


588 


G^R 

V-40O 


OR 


589 


G59 


OR 


590 


G60 


08 


591 


G61 


Q8 


592 


G62 


Q8 


593 


G63 


Q8 


594 


G64 


Q8 


595 


G65 


Q8 


596 


G66 


08 


597 


G67 


08 



- 50 - 



598 


G68 


OR 


599 


G69 


OR 


600 


G70 


OR 


601 


G71 


OR 


602 


G72 


08 


603 


G73 


08 


604 


G74 


OR 


605 


G75 


08 


606 

V-/ w \y 


G76 


08 


607 


Gil 


OR 


608 


G78 


OR 


609 


G79 


OR 


610 


G80 

Vw4 1_> W 


OR 


611 


G81 


OR 


! 612 


G82 


OR 
y° 


613 


GR3 


OR 

y° 




GR4 


OR 


615 


G85 


OR 
y° 


616 


GR6 


OR 
y° 


617 


G87 


OR 
y° 


618 


Gl 


09 
x^ 


619 


G2 


09 


620 


G3 


09 


621 


G4 


OQ 


i 622 

Kj L— C— 


G5 


OQ 


623 


G6 


09 
x^ 


624 


G7 


09 


625 ! 


GR 


OQ 


626 


G9 


09 


627 


G10 


09 


! 628 


Gl 1 


OQ 


1 629 
\-j c~ -j 


G12 

\J X Cm 


09 


630 


G13 


09 


631 


Gl 4 


OQ 




Gl *=> 


OQ 


633 


G16 


09 


634 


G17 


Q9 


635 


G18 


Q9 


636 


G19 


Q9 


637 


G20 


Q9 


638 


G21 


Q9 


639 


G22 


Q9 


640 


G23 


Q9 



AA1 

vJH- x 


G9A 


no 


AA9 




no 




H9A 




AAA 


G97 


gy 


AAR 


09R 


gy 


AAA 




no 

gy 


AA7 
o*+ / 


UOU 


V 9 


AAR 


uO X 




AAQ 




no 

gy 


UJU 




OQ 

gy 






OQ 

gy 






OQ 

gy 


UJO 




OQ 

gy 




bo / 


OQ 

gy 


OOO 


boo 


OQ 

gy 


OjO 




OQ 

gy 


OO / 




OQ 

Qy 


ceo 
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OQ 

gy 






OQ 

gy 


uou 




OQ 

gy 


OO X 




OQ 

gy 




HAR 


OQ 

gy 




nAA 


OQ 

gy 






OQ 

gy 


OOO 


r^AP 

VJIH-O 


OQ 

gy 


AAA 

OOO 




OQ 

gy 


AA7 




OQ 

gy 


AA£2 
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bO 1 


OQ 

gy 


AAQ 


r^R9 


OQ 

gy 


A7H 
O / \J 


uOj 


OQ 

gy 


\ A7 1 
O / 1 




OQ 

gy 


A79 

O / i£L 


bOO 


OQ 

gy 


A7^ 
O / o 


ORA 

UJU 


OQ 

gy 


A7A 
o / *+ 


f^R7 

UJ / 


OQ 

gy 


A7R 
o / 


boo 


OQ 

gy 


676 


G59 


OQ 


677 


G60 


Q9 


678 


G61 


Q9 


679 


G62 


Q9 


680 


G63 


Q9 


681 


G64 


Q9 


682 


G65 


Q9 


683 


G66 


Q9 



WO 03/007296 



PCT/EP02/07434 



684 


G67 


Q9 


685 


G68 


Q9 


686 


G69 


Q9 


687 


G70 


Q9 


688 


G71 


Q9 


689 


G72 


Q9 


690 


G73 


Q9 


691 


G74 


Q9 


692 


G75 


Q9 


693 


G76 


Q9 


694 


G77 


Q9 


695 


G78 


Q9 


696 


G79 


Q9 


697 


G80 


Q9 


698 


G81 


Q9 


699 


G82 


Q9 


700 


G83 


Q9 


701 


G84 


Q9 


702 


G85 


Q9 


703 


G86 


Q9 


704 


G87 


Q9 


705 


Gl 


Q10 


706 


G2 


Q10 


707 


G3 


Q10 


708 


G4 


Q10 


709 


G5 


Q10 


710 


G6 


Q10 


711 


G7 


Q10 


712 


G8 


Q10 


713 


G9 


Q10 


714 


G10 


Q10 


715 


Gil 


Q10 


716 


G12 


Q10 


717 


G13 


Q10 


718 


G14 


010 


719 


G15 


Q10 


720 


G16 


Q10 


721 


G17 


Q10 


722 


G18 


Q10 


723 


G19 


Q10 


724 


G20 


Q10 


725 


G21 


Q10 


726 


G22 


Q10 



- 51 - 



727 


G23 


Q10 


728 


G24 


Q10 


729 


G25 


Q10 


730 


G26 


Q10 


731 


G27 


Q10 


732 


G28 


Q10 


733 


G29 


Q10 


734 


G30 


Q10 


735 


G31 


Q10 


736 


G32 


Q10 


737 


G33 


Q10 


738 


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812 


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WO 03/007296 



PCT/EP02/07434 



813 


G22 


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814 


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815 


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816 


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855 


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- 52 - 



856 


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857 


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859 


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910 


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911 


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WO 03/007296 



PCT/EP02/07434 



942 


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943 


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944 


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- 53 - 



985 


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994 


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995 


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013 


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G33 


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013 


1000 


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1001 


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WO 03/007296 



PCT/EP02/07434 



1 D71 

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WO 03/007296 



PCT/EP02/07434 



1200 


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015 


1214 


G75 


Q15 


1215 


G76 


Q15 


1216 


G77 


Q15 


1217 


G78 


Q15 


1218 


G79 


Q15 


1219 


G80 


Q15 


1220 


G81 


Q15 


1221 


G82 


Q15 


1222 


G83 


Q15 


1223 


G84 


Q15 


1224 


G85 


Q15 


1225 


G86 


Q15 


1226 


G87 


Q15 


1227 


Gl 


Q16 


1228 


G2 


Q16 


1229 


G3 


Q16 


1230 


G4 


Q16 


1231 


G5 


Q16 


1232 


G6 


016 


1233 


G7 


Q16 


1234 


G8 


Q16 


1235 


G9 


Q16 


1236 


G10 


Q16 


1237 


Gil 


Q16 


1238 


G12 


Q16 


1239 


G13 


Q16 


1240 


G14 


Q16 


1241 


G15 


Q16 


1242 


G16 


Q16 



- 55 - 



1243 


G17 


Q16 


1244 


G18 


Q16 


1245 


G19 


Q16 


1246 


G20 


Q16 


1247 


G21 


Q16 


1248 


G22 


Q.16 


1249 


G23 


Q16 


1250 


G24 


Q16 


1251 


G25 


Q16 


1252 


G26 


Q16 


1253 


G27 


Q16 


1254 


G28 


Q16 


1255 


G29 


Q16 


1256 


G30 


Q16 


1257 


G31 


Q16 


1258 


G32 


Q16 


1259 


G33 


Q16 


1260 


G34 


Q16 


1261 


G35 


Q16 


1262 


G36 


Q16 


1263 


G37 


Q16 


1264 


G38 


Q16 


1265 


G39 


Q16 


1266 


G40 


Q16 


1267 


G41 


Q16 


1268 


G42 


Q16 


1269 


G43 


Q16 


1270 


G44 


Q16 


1271 


G45 


Q16 


1272 


G46 


Q16 


1273 


G47 


Q16 


1274 


G48 


Q16 


1275 


G49 


Q16 


1276 


G50 


Q16 


1277 


G51 


Q16 


1278 


G52 


Q16 


1279 


G53 


Q16 


1280 


G54 


Q16 


1281 


G55 


Q16 


1282 


G56 


Q16 


1283 


G57 


Q16 


1284 


G58 


Q16 


1285 


G59 


Q16 



1286 


G60 


Q16 


1287 


G61 


Q16 


1288 


G62 


Q16 


1289 


G63 


Q16 


1290 


G64 


Q16 


1291 


G65 


Q16 


1292 


G66 


Q16 


1293 


G67 


Q16 


1294 


G68 


Q16 


1295 


G69 


Q16 


1296 


G70 


Q16 


1297 


G71 


Q16 


1298 


G72 


Q16 


1299 


G73 


Q16 


1300 


G74 


Q16 


1301 


G75 


Q16 


1302 


G76 


Q16 


1303 


G77 


Q16 


1304 


G78 


Q16 


1305 


G79 


Q16 


1306 


G80 


Q16 


1307 


G81 


Q16 


1308 


G82 


Q16 


1309 


G83 


Q16 


1310 


G84 


Q16 


1311 


G85 


Q16 


1312 


G86 


Q16 


1313 


G87 


Q16 


1314 


Gl 


Q17 


1315 


G2 


Q17 


1316 


G3 


Q17 


1317 


G4 


Q17 


1318 


G5 


Q17 


1319 


G6 


Q17 


1320 


G7 


Q17 


1321 


G8 


Q17 


1322 


G9 


Q17 


1323 


G10 


Q17 


1324 


Gil 


Q17 


1325 


G12 


Q17 


1326 


G13 


Q17 


1327 


G14 


Q17 


1328 


G15 


Q17 



WO 03/007296 



PCT/EP02/07434 



1329 


G16 


Q17 


1330 


G17 


Q17 


1331 


G18 


Q17 


1332 


G19 


Q17 


1333 


G20 


Q17 


1334 


G21 


Q17 


1335 


G22 


Q17 


1336 


G23 


Q17 


1337 


G24 


Q17 


1338 


G25 


Q17 


1339 


G26 


Q17 


1340 


G27 


Q17 


1341 


G28 


Q17 


1342 


G29 


Q17 


1343 


G30 


Q17 


1344 


G31 


Q17 


1345 


G32 


Q17 


1346 


G33 


Q17 


1347 


G34 


Q17 


1348 


G35 


Q17 ! 


1349 


G36 


Q17 


1350 


G37 


Q17 


1351 


G38 


Q17 


1352 


G39 


Q17 


1353 


G40 


Q17 


1354 


G41 


Q17 


1355 


G42 


Q17 


1356 


G43 


Q17 


1357 


G44 


Q17 


1358 


G45 


Q17 


1359 


G46 


Q17 


1360 


G47 


Q17 


1361 


G48 


Q17 


1362 


G49 


Q17 


1363 


G50 


Q17 


1364 


G51 


Q17 


1365 


G52 


Q17 


1366 


G53 


Q17 


1367 


G54 


Q17 


1368 


G55 


Q17 


1369 


G56 


Q17 


1370 


G57 


Q17 


1371 


G58 


017 



- 56 - 



1372 


G59 


Q17 


1373 


G60 


Q17 


1374 


G61 


Q17 


1375 


G62 


Q17 


1376 


G63 


Q17 


1377 


G64 


Q17 


1378 


G65 


Q17 


1379 


G66 


Q17 


1380 


G67 


Q17 


1381 


G68 


017 


1382 


G69 


Q17 


1383 


G70 


Q17 


1384 


G71 


Q17 


1385 


G72 


Q17 


1386 


G73 


Q17 


1387 


G74 


Q17 


1388 


G75 


Q17 


1389 


G76 


Q17 


1390 


G77 


017 


1391 


G78 


Q17 


1392 


G79 


Q17 


1393 


G80 


Q17 


1394 


G81 


Q17 


1395 


G82 


Q17 


1396 


G83 


Q17 


1397 


G84 


Q17 


1398 


G85 


Q17 


1399 


G86 


Q17 


1400 


G87 


Q17 


1401 


Gl 


Q18 


1402 


G2 


Q18 


1403 


G3 


Q18 


1404 


G4 


Q18 


1405 


G5 


Q18 


1406 


G6 


Q18 


1407 


G7 


Q18 


1408 


G8 


Q18 


1409 


G9 


Q18 


1410 


G10 


Q18 


1411 


Gil 


Q18 


1412 


G12 


Q18 


1413 


G13 


Q18 


1414 


G14 


Q18 



1415 


G15 


Q18 


1416 


G16 


Q18 


1417 


G17 


Q18 


1418 


G18 


Q18 


1419 


G19 


Q18 


1420 


G20 


Q18 


1421 


G21 


Q18 


1422 


G22 


Q18 


1423 


G23 


Q18 


1424 


G24 


Q18 


1425 


G25 


Q18 


1426 


G26 


Q18 


1427 


G27 


Q18 


1428 


G28 


Q18 


1429 


G29 


Q18 


1430 


G30 


Q18 


1431 


G31 


Q18 


1432 


G32 


Q18 


1433 


G33 


018 


1434 


G34 


Q18 


1435 


G35 


Q18 


1436 


G36 


Q18 


1437 


G37 


Q18 


1438 


G38 


Q18 


1439 


G39 


Q18 


1440 


G40 


Q18 

-S 


1441 


G41 


Q18 


1442 


G42 


Q18 


1443 


G43 


Q18 


1444 


G44 


Q18 


1445 


G45 


Q18 


1446 


G46 


Q18 


1447 


G47 


Q18 


1448 


G48 


Q18 


1449 


G49 


018 


1450 


G50 


Q18 


1451 


G51 


018 


1452 


G52 


Q18 


1453 


G53 


Q18 


1454 


G54 


Q18 


1455 


G55 


Q18 


1456 


G56 


Q18 


1457 


G57 


Q18 



WO 03/007296 



PCT/EP02/07434 



1458 


G58 


Q18 


1459 


G59 


018 


1460 


G60 


Q18 


1461 


G61 


Q18 


1462 


G62 


Q18 


1463 


G63 


Q18 


1464 


G64 


Q18 


1465 


G65 


Q18 


1466 


G66 


Q18 


1467 


G67 


Q18 


1468 


G68 


Q18 


1469 


G69 


Q18 


1470 


G70 


Q18 


1471 


G71 


Q18 


1472 


G72 


Q18 


1473 


G73 


Q18 


1474 


G74 


Q18 


1475 


G75 


Q18 


1476 


G76 


Q18 


1477 


G77 


Q18 


1478 


G78 


Q18 


1479 


G79 


Q18 


1480 


G80 


Q18 


1481 


G81 


Q18 


1482 


G82 


Q18 


1483 


G83 


018 


1484 


G84 


Q18 


1485 


G85 


Q18 


1486 


G86 


Q18 


1487 


G87 


Q18 


1488 


Gl 


Q19 


1489 


G2 


Q19 


1490 


G3 


Q19 


1491 


G4 


Q19 


1492 


G5 


Q19 


1493 


G6 


Q19 


1494 


G7 


Q19 


1495 


G8 


Q19 


1496 


G9 


Q19 


1497 


G10 


Q19 


1498 


Gil 


Q19 


1499 


G12 


Q19 


1500 


G13 


Q19 



- 57 - 



1501 


G14 


Q19 


1502 


G15 


Q19 


1503 


G16 


Q19 


1504 


G17 


Q19 


1505 


G18 


Q19 


1506 


G19 


Q19 


1507 


G20 


Q19 


1508 


G21 


Q19 


1509 


G22 


Q19 


1510 


G23 


Q19 


1511 


G24 


Q19 


1512 


G25 


Q19 


1513 


G26 


Q19 


1514 


G27 


Q19 


1515 


G28 


Q19 


1516 


G29 


Q19 


1517 


G30 


Q19 


1518 


G31 


Q19 


1519 


G32 


Q19 


1520 


G33 


Q19 


1521 


G34 


Q19 


1522 


G35 


Q19 


1523 


G36 


Q19 


1524 


G37 


Q19 


1525 


G38 


Q19 


1526 


G39 


Q19 


1527 


G40 


Q19 


1528 


G41 


Q19 


1529 


G42 


Q19 


1530 


G43 


Q19 


1531 


G44 


Q19 


1532 


G45 


Q19 


1533 


G46 


Q19 


1534 


G47 


Q19 


1535 


G48 


Q19 


1536 


G49 


Q19 


1537 


G50 


Q19 


1538 


G51 


Q19 


1539 


G52 


Q19 


1540 


G53 


Q19 


1541 


G54 


Q19 


1542 


G55 


Q19 


1543 


G56 


Q19 



1544 


G57 


Q19 


1545 


G58 


Q19 


1546 


G59 


Q19 


1547 


G60 


Q19 


1548 


G61 


Q19 


1549 


G62 


Q19 


1550 


G63 


Q19 


1551 


G64 


Q19 


1552 


G65 


Q19 


1553 


G66 


Q19 


1554 


G67 


Q19 


1555 


G68 


Q19 


1556 


G69 


Q19 


1557 


G70 


Q19 


1558 


G71 


Q19 


1559 


G72 


Q19 


1560 


G73 


Q19 


1561 


G74 


Q19 


1562 


G75 


Q19 


1563 


G76 


Q19 


1564 


G77 


Q19 


1565 


G78 


Q19 


1566 


G79 


Q19 


1567 


G80 


Q19 


1568 


G81 


Q19 


1569 


G82 


Q19 


1570 


G83 


Q19 


1571 


G84 


Q19 


1572 


G85 


Q19 


1573 


G86 


Q19 


1574 


G87 


Q19 


1575 


G2 


Q20 


1576 


G3 


020 


1577 


G4 


Q20 


1578 


G5 


Q20 


1579 


G6 


Q20 


1580 


G7 


Q20 


1581 


G8 


Q20 


1582 


G9 


Q20 


1583 


G10 


020 


1584 


G12 


Q20 


1585 


G13 


Q20 


1586 


G14 


Q20 



WO 03/007296 



PCT/EP02/07434 



1587 


G15 


Q20 


1588 


G16 


Q20 


1589 


G17 


Q20 


1590 


G18 


Q20 


1591 


G19 


Q20 


1592 


G20 


Q20 


1593 


G21 


Q20 


1594 


G22 


Q20 


1595 


G23 


Q20 


1596 


G24 


Q20 


1597 


G25 


Q20 


1598 


G26 


Q20 

_L 


1599 


G27 


Q20 


1600 


G28 


Q20 


1601 


G29 


Q20 


1602 


G30 


Q20 


1603 


G31 


Q20 


1604 


G32 


Q20 


1605 


G33 


Q20 


1606 


G34 


Q20 


1607 


G35 


Q20 


1608 


G36 


Q20 


1609 


G37 


Q20 


1610 


G38 


Q20 


1611 


G39 


Q20 


1612 


G40 


Q20 


1613 


G41 


Q20 

_S 


1614 


G42 


Q20 


1615 


G43 


Q20 


1616 


G44 


020 


1617 


G45 


1 Q20 

"""" 


1618 


G46 


Q20 


1619 


G47 


Q20 


1620 


G48 


020 

Ml, 7^ , 


1621 


G49 


Q20 

— X 


1622 


G50 


Q20 


1623 


G51 


Q20 


1624 


G52 


Q20 


1625 


G53 


Q20 


1626 


G54 


Q20 


1627 


G55 


Q20 


1628 


G56 


Q20 


1629 


G57 


Q20 



- 58 - 



1630 


G58 


Q20 


1631 


G59 


Q20 


1632 


G60 


Q20 


1633 


G61 


Q20 


1634 


G62 


Q20 


1635 


G63 


Q20 


1636 


G64 


Q20 


1637 


G65 


Q20 


1638 


G66 


Q20 


1639 


G67 


Q20 


1640 


G68 


Q20 


1641 


G69 


Q20 


1642 


G70 


Q20 


1643 


G71 


Q20 


1644 


G72 


Q20 


1645 


G73 


Q20 


1646 


G74 


Q20 


1647 


G75 


Q20 


1648 


G76 


Q20 


1649 


G77 


Q20 


1650 


G78 


Q20 


1651 


G79 


Q20 


1652 


G80 


Q20 


1653 


G81 


Q20 


1654 


G82 


Q20 


1655 


G83 


Q20 


1656 


G84 


020 


1657 


G85 


Q20 


1658 


G86 


020 


1659 


G87 


020 


1660 


Gl 


021 


1661 


G2 


Q2'l 


1662 


G3 


021 


1663 


G4 


Q21 


1664 


G5 


Q21 - 


1665 


G6 


Q21 


1666 


G7 


Q21 


1667 


G8 


Q21 


1668 


G9 


021 


1669 


G10 


Q21 


1670 


Gil 


Q21 


1671 


G12 


Q21 


1672 


G13 


Q21 



1673 


G14 


Q21 


1674 


G15 


Q21 


1675 


G16 


Q21 


1676 


G17 


Q21 


1677 


G18 


Q21 


1678 


G19 


Q21 


1679 


G20 


Q21 


1680 


G21 


Q21 


1681 


G22 


Q21 


1682 


G23 


Q21 


1683 


G24 


Q21 


1684 


G25 


Q21 


1685 


G26 


Q21 


1686 


G27 


Q21 


1687 


G28 


Q21 


1688 


G29 


Q21 


1689 


G30 


Q21 


1690 


G31 


Q21 


1691 


G32 


Q21 


1692 


G33 


Q21 


1693 


G34 


Q21 


1694 


G35 


Q21 


1695 


G36 


Q21 


1696 


G37 


Q21 


1697 


G38 


Q21 


1698 


G39 


Q21 ; 


1699 


G40 


Q21 


1700 


G41 


Q21 


1701 


G42 


Q21 


1702 


G43 


Q21 


1703 


G44 


021 


1704 


G45 


Q21 


1705 


G46 


Q21 


1706 


G47 


Q21 


1707 


G48 


Q21 


1708 


G49 


Q21 


1709 


G50 


Q21 


1710 


G51 


Q21 


1711 


G52 


Q21 


1712 


G53 


Q21 


1713 


G54 


Q21 


1714 


G55 


Q21 


1715 


G56 


Q21 



WO 03/007296 



PCT/EP02/07434 



1716 


G57 


Q21 


1717 


G58 


Q21 


1718 


G59 


Q21 


1719 


G60 


Q21 


1720 


G61 


Q21 


1721 


G62 


Q21 


1722 


G63 


Q21 


1723 


G64 


Q21 


1724 


G65 


Q21 


1725 


G66 


Q21 


1726 


G67 


Q21 


1727 


G68 


Q21 


1728 


G69 


Q21 


1729 


G70 


Q21 


1730 


G71 


Q21 


1731 


G72 


Q21 


1732 


G73 


_Q21 


1733 


G74 


Q21 


1734 


G75 


Q21 


1735 


G76 


Q21 


1736 


G77 


Q21 


1737 


G78 


Q21 


1738 


G79 


Q21 


1739 


G80 


Q21 


1740 


G81 


Q21 


1741 


G82 


Q21 


1742 


G83 


Q21 


1743 


G84 


Q21 


1744 


G85 


Q21 


1745 


G86 


Q21 


1746 


G87 


Q21 


1747 


Gl 


Q22 


1748 


G2 


022 


1749 


G3 


Q22 


1750 


G4 


Q22 


1751 


G5 


Q22 


1752 


G6 


Q22 


1753 


G7 


Q22 


1754 


G8 


Q22 


1755 


G9 


Q22 


1756 


G10 


Q22 


1757 


Gil 


Q22 


1758 


G12 


Q22 



- 59 - 



1759 


G13 


Q22 


1760 


G14 


Q22 


1761 


G15 


Q22 


1762 


G16 


Q22 


1763 


G17 


Q22 


1764 


G18 


Q22 


1765 


G19 


Q22 


1766 


G20 


Q22 


1767 


G21 


Q22 


1768 


G22 


022 


1769 


G23 


022 


1770 


G24 


Q22 


1771 


G25 


Q22 


1772 


G26 


Q22 


1773 


G27 


Q22 


1774 


G28 


Q22 


1775 


G29 


Q22 


1776 


G30 


Q22 


1777 


G31 


Q22 


1778 


G32 


Q22 


1779 


G33 


Q22 


1780 


G34 


Q22 


1781 


G35 


Q22 


1782 


G36 


Q22 


1783 


G37 


Q22 


1784 


G38 


Q22 


1785 


G39 


Q22 


1786 


G40 


Q22 


1787 


G41 


Q22 


1788 


G42 


Q22 


1789 


G43 


Q22 


1790 


G44 


Q22 


1791 


G45 


022 


1792 


G46 


Q22 


1793 


G47 


Q22 


1794 


G48 


Q22 


1795 


G49 


Q22 


1796 


G50 


Q22 


1797 


G51 


Q22 


1798 


G52 


Q22 


1799 


G53 


Q22 


1800 


G54 


Q22 


1801 


G55 


Q22 



1802 


G56 


Q22 


1803 


G57 


Q22 


1804 


G58 


Q22 


1805 


G59 


Q22 


1806 


G60 


Q22 


1807 


G61 


Q22 


1808 


G62 


Q22 


1809 


G63 


Q22 


1810 


G64 


Q22 


1811 


G65 


Q22 


1812 


G66 


Q22 


1813 


G67 


Q22 


1814 


G68 


Q22 


1815 


G69 


022 


1816 


G70 


Q22 


1817 


G71 


Q22 


1818 


G72 


Q22 


1819 


G73 


Q22 


1820 


G74 


Q22 


1821 


G75 


Q22 


1822 


G76 


Q22 


1823 


G77 


Q22 


1824 


G78 


Q22 


1825 


G79 


Q22 


1826 


G80 


Q22 


1827 


G81 


Q22 


1828 


G82 


Q22 


1829 


G83 


Q22 


1830 


G84 


Q22 


1831 


G85 


Q22 


1832 


G86 


Q22 


1833 


G87 


Q22 


1834 


Gl 


Q23 


1835 


G2 


Q23 


1836 


G3 


Q23 


1837 


G4 


Q23 


1838 


G5 


Q23 


1839 


G6 


Q23 


1840 


G7 


Q23 


1841 


G8 


Q23 


1842 


G9 


Q23 


1843 


G10 


Q23 


1844 


Gil 


Q23 



WO 03/007296 



PCT/EP02/07434 



1845 


G12 


Q23 


1846 


G13 


Q23 


1847 


G14 


Q23 


1848 


G15 


Q23 


1849 


G16 


Q23 


1850 


G17 


Q23 


1851 


G18 


Q23 


1852 


G19 


Q23 


1853 


G20 


Q23 


1854 


G21 


Q23 


1855 


G22 


Q23 


1856 


G23 


Q23 


1857 


G24 i 


Q23 


1858 


G25 


Q23 


1859 


G26 


Q23 


1860 


G27 ! 


Q23 


1861 


G28 


Q23 


1862 


G29 


Q23 


1863 


G30 


023 


1864 


G31 ! 


Q23 


1865 


G32 


Q23 


1866 


G33 


Q23 


1867 


G34 


Q23 


1868 


G35 


Q23 


1869 


G36 


Q23 


1870 


G37 


Q23 


1871 


G38 


Q23 


1872 


G39 


Q23 


1873 


G40 


Q23 


1874 


G41 


Q23 


1875 


G42 


Q23 


1876 


G43 


Q23 


1877 


G44 


Q23 


1878 


G45 


Q23 


1879 


G46 


Q23 


1880 


G47 


Q23 


1881 


G48 


023 


1882 


G49 


Q23 


1883 


G50 


Q23 


1884 


G51 


Q23 


1885 


G52 


Q23 


1886 


G53 


Q23 


1887 


G54 


Q23 



- 60 - 



1888 


G55 


Q23 


1889 


G56 


Q23 


1890 


G57 


Q23 


1891 


G58 


Q23 


1892 


G59 


Q23 


1893 


G60 


Q23 


1894 


G61 


Q23 


1895 


G62 


Q23 


1896 


G63 


Q23 


1897 


G64 


Q23 


1898 


G65 


Q23 


1899 


G66 


Q23 


1900 


G67 


Q23 


1901 


G68 


Q23 


1902 


G69 


Q23 


1903 


G70 


Q23 


1904 


G71 


Q23 


1905 


G72 


Q23 


1906 


G73 


Q23 

JS - 


1907 


G74 


Q23 


1908 


G75 


Q23 


1909 


G76 


Q23 


1910 


G77 


Q23 


1911 


G78 


Q23 


1912 


G79 


Q23 


1913 


G80 


Q23 


1914 


G81 


Q23 


1915 


G82 


Q23 


1916 


G83 


Q23 


1917 


G84 


Q23 


1918 


G85 


Q23 


1919 


G86 


Q23 


1920 


G87 


Q23 


1921 


Gl 


Q24 


1922 


G2 


Q24 


1923 


G3 


Q24 


1924 


G4 


Q24 


1925 


G5 


Q24 


1926 


G6 


Q24 


1927 


G7 


Q24 


1928 


G8 


Q24 


1929 


G9 


Q24 


1930 


G10 


Q24 



1931 


Gil 


Q24 


1932 


G12 


024 


1933 


G13 


024 


1934 


G14 


Q24 


1935 


G15 


Q24 


1936 


G16 


Q24 


1937 


G17 


Q24 


1938 


G18 


Q24 


1939 


G19 


Q24 


1940 


G20 


_Q24 


1941 


G21 


024 


1942 


G22 


Q24 


1943 


G23 


Q24 


1944 


G24 


024 


1945 


G25 


024 

-S 


1946 


G26 


024 


1947 


G27 


024 


1948 


G28 


024 


1949 


G29 


024 


1950 


G30 


024 


1951 


G31 


024 


1952 


G32 


Q24 


1953 


G33 


024 


1954 


G34 


Q24 


1955 


G35 


024 


1956 


G36 


Q24 1 


1957 


G37 


024 


1958 


G38 


024 


1959 


G39 


Q24 


1960 


G40 


Q24 


1961 


G41 


024 


1962 


G42 


024 


1963 


G43 


024 


1964 


G44 


024 


1965 


G45 


Q24 


1966 


G46 


Q24 


1967 


G47 


Q24 


1968 


G48 


Q24 


1969 


G49 


Q24 


1970 


G50 


Q24 


1971 


G51 


Q24 


1972 


G52 


Q24 


1973 


G53 


Q24 



WO 03/007296 



PCT/EP02/07434 



1974 


G54 


024 


1975 


G55 


024 


1976 


G56 


Q24 


1977 


G57 


024 


1978 


G58 


Q24 


1979 


G59 


Q24 


1980 


G60 


Q24 


1981 


G61 


Q24 


1982 


G62 


Q24 


1983 


G63 


Q24 


1984 


G64 


Q24 


1985 


G65 


Q24 


1986 


G66 


Q24 


1987 


G67 


Q24 


1988 


G68 


Q24 


1989 


G69 


Q24 


1990 


G70 


Q24 


1991 


G71 


Q24 


1992 


G72 


Q24 


1993 


G73 


024 


1994 


G74 


Q24 


1995 


G75 


Q24 


1996 


G76 


Q24 


1997 


G77 


Q24 


1998 


G78 


Q24 


1999 


G79 


024 


2000 


G80 


Q24 


2001 


G81 


Q24 


2002 


G82 


Q24 


2003 


G83 


Q24 


2004 


G84 


Q24 


2005 


G85 


Q24 


2006 


G86 


Q24 


2007 


G87 


Q24 


2008 


Gl 


Q25 


2009 


G2 


Q25 


2010 


G3 


Q25 


2011 


G4 


Q25 


2012 


G5 


Q25 


2013 


G6 


Q25 


2014 


G7 


Q25 



- 61 - 



2015 


G8 


Q25 


2016 


G9 


Q25 


2017 


G10 


Q25 


2018 


Gil 


Q25 


2019 


G12 


Q25 


2020 


G13 


Q25 


2021 


G14 


Q25 


2022 


G15 


Q25 


2023 


G16 


Q25 


2024 


G17 


Q25 


2025 


G18 


Q25 


2026 


G19 


Q25 


2027 


G20 


Q25 


2028 


G21 


Q25 


2029 


G22 


Q25 


2030 


G23 


Q25 


2031 


G24 


Q25 


2032 


G25 


Q25 


2033 


G26 


Q25 


2034 


G27 


Q25 


2035 


G28 


Q25 


2036 


G29 


Q25 


2037 


G30 


Q25 


2038 


G31 


Q25 


2039 


G32 


Q25 


2040 


G33 


Q25 


2041 


G34 


Q25 


2042 


G35 


Q25 


2043 


G36 


Q25 


2044 


G37 


Q25 


2045 


G38 


Q25 


2046 


G39 


Q25 


2047 


G40 


Q25 


2048 


G41 


Q25 


2049 


G42 


Q25 


2050 


G43 


Q25 


2051 


G44 


Q25 


2052 


G45 


Q25 


2053 


G46 


Q25 


2054 


G47 


Q25 


2055 


G48 


Q25 



2056 


G49 


Q25 


2057 


G50 


Q25 


2058 


G51 


Q25 


2059 


G52 


Q25 


2060 


G53 


Q25 


2061 


G54 


Q25 


2062 


G55 


Q25 


2063 


G56 


Q25 


2064 


G57 


Q25 


2065 


G58 


Q25 


2066 


G59 


Q25 


2067 


G60 


Q25 


2068 


G61 


Q25 


2069 


G62 


Q25 


2070 


G63 


Q25 


2071 


G64 


Q25 


2072 


G65 


Q25 


2073 


G66 


Q25 


2074 


G67 


Q25 


2075 


G68 


Q25 


2076 


G69 


Q25 


2077 


G70 


Q25 


2078 


G71 


Q25 


2079 


G72 


Q25 


2080 


G73 


Q25 


2081 


G74 


Q25 


2082 


G75 


Q25 


2083 


G76 


Q25 


2084 


G77 


Q25 


2085 


G78 


Q25 


2086 


G79 


Q25 


2087 


G80 


Q25 


2088 


G81 


Q25 


2089 


G82 


Q25 


2090 


G83 


Q25 


2091 


G84 


Q25 


2092 


G85 


Q25 


2093 


G86 


Q25 


2094 


G87 


Q25 



WO 03/007296 



PCT/EP02/07434 



-62- 



Examples 2095-2442 : The procedure is 
compounds of formula [G + ] ■ [X m "] p ■ [Y n+ ] ( 
analogously to Examples 1-6, are used: 



L_ A . 


VJi 


vm- 




vn+ 
i 


n 
M 


POQ5 


V_* X 


ni 


/2 




n 

vJ 


P096 


GP 


ni 


Vo 

/2 




o 




G3 




Vo 
/2 




n 

VJ 


POQR 




m 


Vd 
/2 




n 

VJ 




G5 
Vj| >J 


oi 


/2 




o 

VJ 


pi no 

c~ JL \J\J 


VJlVj 


Ol 


Vo 
/2 




n 

vJ 


pi m 


G7 

V3 / 


Ol 


Vo 
/2 




vy 


pi op 


GR 


Ol 


Vo 
/2 




0 

vy 


PI 03 


GQ 


Ol 


Vo 
/2 




n 

vy 


PI 04 




Ol 


/2 




n 


PI 05 


VJJ J. X 


Ol 


/2 




n 

VJ 


PI Ofi 

X VJvj 


RIP 


Ol 


Vo 
/2 




vj 


PI D7 

c~ X\J J 


G1 3 

vj x o 


Ol 


Vo 
/2 




o 

VJ 


PI OR 


Gl 4 
VJI J. «+ 


Ol 


/2 




o 


PI OQ 

JL VJ 3/ 


m 5 


Ol 


/2 




0 
\j 


pi i n 


Gift 

vJI X vJ 


Ol 

V^x 


Vo 
/2 




o 


PI 1 1 

£- X X X 


Gl 7 


Ol 

\JX 


1/ 
/2 




n 

VJ 


PI 1 P 


Gl R 


Ol 


/2 




n 

VJ 


O 1 1 *3 

J. x O 


ul^ 


Ol 


Vo 
72 




o 

VJ 


PI 1 A 


gpo 

VJ /C.VJ 


Ol 


Vo 

/2 




VJ 


Ol IK 
J. 1 ZJ 


(IP 1 

V3*l 1 


Ol 


1A 
72 




n 


<c J. xO 






1/ 
72 






PI 1 7 


GP3 
VjJ 


Ol 


V> 
/2 




n 

vj 


2118 


G24 


Qi 


% 




0 


2119 


G25 


Ql 


y 2 




0 


2120 


G26 


Ql 


y 2 




0 


2121 


G27 


Ql 


y 2 




0 


2122 


G28 


Ql 


y 2 




0 


2123 


G29 


Ql 


y 2 




0 


2124 


G30 


Ql 


y 2 




0 


2125 


G31 


Ql 


y 2 




0 


2126 


G32 


Ql 


y 2 




0 


2127 


G33 


Ql 


y 2 




0 


2128 


G34 


Ql 


y 2 




0 


2129 


G35 


Ql 


y 2 




0 


2130 


G36 


Ql 


y 2 




0 



as in Examples 7-9, but the following 
i (XI), which can be prepared 



PI 31 




Ol ! 
y x 


Vo 

/2 






2132 

C— X nJ £_ 


Q3R 

^>y(j 


Ol 








2133 

C. — L J J 


G39 

uj ~y 


Ol 


Vo 
/2 




n 

w 


PI 34 


040 


Ol ' 


Vo 
/2 




0 

vJ 


2135 

X O *J 


041 

V-3"-r JL 


Ol 


Vo 
/2 




n 


2136 


Q4P 


Ol 


/2 




n 


PI 37 

C.1 J/ 


043 


Ol i 


Vo 
/2 






21 3R 

ill JO 


Q44 


Ol 


/2 




n 

VJ 


PI 3Q 


045 


Ol 


l/ 0 
/2 




n 

VJ 


PI 40 


046 


Ol 


/2 




0 

VJ 


PI 41 


047 


Ol 


/2 




n 

VJ 


PI 4? 


04R 


Ol 

Vx 


/2 




n 

VJ 


P143 


04Q 


01 


Vo 
/2 




n 


PI 44 


O50 


Ol 


v> 

/2 




n 

VJ 


PI 45 


051 

v3J X 


Ol 


/2 




VJ 


PI 4fi 


05P 


01 


/2 




n 

VJ 


PI 47 


G53 

V3JJ 


Ol 






VJ 


PI 4R 

C- X tU 


054 


Ol 


/2 




n 

VJ 


PI 4Q 

x *-r Zy 


055 


Ol 


l/ 0 
/2 




VJ 


PI 50 


VJ300 


Ol 

\c X 


Vo 

/2 




o 

VJ 


PI 51 

£.1 ji 


057 


Ol 


l/ 0 

/2 




O 

VJ 


PI 5P 


05R 


O! 


Vo 

/2 




VJ 


PI 53 

Z_ X JO 


05Q 

vj Jy 


Ol 


/2 




VJ 


2154 

x »-y 


G60 

>j w vy 


01 


Vo 
/2 




n 

VJ 


2155 


G61 


Ql 


y 2 




0 


2155 


G62 


Ql 


y 2 




0 


2157 


G63 


Ql 


y 2 




0 


2158 


G64 


Ql 


y 2 




0 


2159 


G65 


Ql 


y 2 




0 


2160 


G66 


Ql 


y 2 




0 


2161 


G67 


Ql 


y 2 




0 


2162 


G68 


Ql 


y 2 




0 


2163 


G69 


Ql 


y 2 




0 


2164 


G70 


Ql 


y 2 




0 


2165 


G71 


Ql 


y 2 




0 


2166 


G72 


Ql 


y 2 




0 


2167 


G73 


Ql 


y 2 




0 



WO 03/007296 



PCT/EP02/07434 



- 63 - 



2168 


G74 


Ql 


y 2 




0 


2169 


G75 


Ql 


Vz 




0 


2170 


G76 


Ql 


Vz 




0 


2171 


G77 


Ql 


Vz 




0 


2172 


G78 


Ql 


Vz 




0 


2173 


G79 


Ql 


Vz 




0 


2174 


G80 


Ql 


Vz 




0 


2175 


G81 


Ql 


Vz 




0 


2176 


G82 


Ql 


Vz 




0 


2177 


G83 


Ql 


Vz 




0 


2178 


G84 


Ql 


Vz 




0 


2179 


G85 


Ql 


Vz 




0 


2180 


G86 


Ql 


Vz 




0 


2181 


G87 


Ql 


Vz 




0 


2182 


Gl 


Q26 


Vz 




0 


2183 


G2 


Q26 


Vz 




0 


2184 


G3 


Q26 


Vz 




0 


2185 


G4 


Q26 


Vz 




0 


2186 


G5 


Q26 


Vz 




0 


2187 


G6 


Q26 


Vz 




0 


2188 


G7 


Q26 


Vz 




0 


2189 


G8 


Q26 


Vz 




0 


2190 


[ G9 


Q26 


Vz 




0 


2191 


G10 


Q26 


Vz 




0 


2192 


Gil 


Q26 


Vz 




0 


2193 


G12 


Q26 


Vz 




0 


2194 


G13 


Q26 


Vz 




0 


2195 


G14 


Q26 


Vz 




0 


2196 


G15 


Q26 


Vz 




0 


2197 


G16 


Q26 


Vz 




0 


2198 


G17 


Q26 


Vz 




0 


2199 


G18 


Q26 


Vz 




0 


2200 


G19 


Q26 


Vz 




0 


2201 


G20 


Q26 


Vz 




0 


2202 


G21 


Q26 


Vz 




! 0 


2203 


G22 


Q26 


Vz 




0 


2204 


G23 


Q26 


Vz 




0 


2205 


G24 


Q26 


Vz 




0 


2206 


G25 


Q26 


Vz 




0 


2207 


G26 


Q26 


Vz 




0 


2208 


G27 


Q26 


Vz 




0 


2209 


G28 


Q26 


Vz 




0 


2210 


G29 


Q26 


Vz 




0 



2211 


G30 


Q26 


Vz 




0 


2212 


G31 


Q26 


Vz 




0 


2213 


G32 


Q26 


Vz 




0 


2214 


G33 


Q26 


Vz 




0 


2215 


G34 


Q26 


Vz 




0 


2216 


G35 


Q26 


Vz 




0 


2217 


G36 


Q26 


Vz 




0 


2218 


G37 


Q26 


Vz 




0 


2219 


G38 


Q26 


Vz 




0 


2220 


G39 


Q26 


Vz 




0 


2221 


G40 


Q26 


Vz 




0 


2222 


G41 


Q26 


Vz 




0 


2223 


G42 


Q26 


Vz 




0 


2224 


G43 


Q26 


Vz 




0 


2225 


G44 


Q26 


Vz 




0 


2226 


G45 


Q26 


Vz 




0 


2227 


G46 


Q26 


Vz 




0 


2228 


G47 


Q26 


Vz 




0 


2229 


G48 


Q26 


Vz 




0 


2230 


G49 


Q26 


Vz 




0 


2231 


G50 


Q26 


Vz 




0 


2232 


G51 


Q26 


Vz 




0 


2233 


G52 


Q26 


Vz 




0 


2234 


G53 


Q26 


Vz 




0 


2235 


G54 


Q26 


Vz 




0 


2236 


G55 


Q26 


Vz 




0 


2237 


G56 


Q26 


Vz 




0 


2238 


G57 


Q26 


Vz 




0 


2239 


G58 


Q26 


Vz 




0 


2240 


G59 


Q26 


Vz 




0 


2241 


G60 


Q26 


Vz 




0 


2242 


G61 


Q26 


Vz 




0 


2243 


G62 


Q26 


Vz 




0 


2244 


G63 


026 


Vz 




0 


2245 


G64 


Q26 


Vz 




0 


2246 


G65 


Q26 


Vz 




0 


2247 


G66 


Q26 


Vz 




0 


2248 


G67 


Q26 


Vz 




0 


2249 


G68 


026 


Vz 




0 


2250 


G69 


Q26 


Vz 




0 


2251 


G70 


Q26 


Vz 




0 


2252 


G71 


Q26 


Vz 




0 


2253 


G72 


Q26 


Vz 




0 



WO 03/007296 



PCT/EP02/07434 



■ 64 - 



2254 


G73 


Q26 


y 2 




0 


2255 


G74 


Q26 


Vz 




0 


2255 


G75 


Q26 


Vz 




0 


2257 


G76 


Q26 


Vz 




0 


2258 


G77 


Q26 


Vz 




0 


2259 


G78 


Q26 


Vz 




0 


2260 


G79 


Q26 


Vz 




0 


2261 


G80 


Q26 


Vz 




0 


2262 


G81 


Q26 


Vz 




0 


2263 


G82 


Q26 


Vz 




0 


2264 


G83 


Q26 


Vz 




0 


2265 


G84 


Q26 


Vz 




0 


2266 


G85 


Q26 


Vz 




0 


2267 


G86 


Q26 


Vz 




0 


2268 


G87 


Q26 


Vz 




0 


2269 


Gl 


Ql 


1 


NH 4 + 


1 


2270 


G2 


Ql 


1 


NH 4 + 


1 


2271 


G3 


Ql 


1 


NH 4 + 


1 


2272 


G4 


Ql 


1 


NH 4 + 


1 


2273 


G5 


Ql 


1 


NH 4 + 


1 


2274 


G6 


Ql 


1 


NH 4 + 


1 


2275 


G7 


Ql 


1 


NH 4 + 


1 


2276 


G8 


Ql 


1 


NH 4 + 


1 


2277 


G9 


Ql 


1 


NH 4 + 


1 


2278 


G10 


Ql 


1 


NH 4 + 


1 


2279 


Gil 


Ql 


1 


NH 4 + 


1 


2280 


G12 


Ql 


1 


NH 4 + 


1 


2281 


G13 


Ql 


1 


NH 4 + 


1 


2282 


G14 


Ql 


1 


NH 4 + 


1 


2283 


G15 


Ql 


1 


NH 4 + 


1 


2284 


G16 


Ql 


1 


NH 4 + 


1 


2285 


G17 


Ql 


1 


NH 4 + 


1 


2286 


G18 


Ql 


1 


NH 4 + 


1 


2287 


G19 


• Ql 


1 


NH 4 + 


1 


2288 


G20 


Ql 


1 


NH 4 + 


1 


2289 


G21 


Ql 


1 


NH 4 + 


1 


2290 


G22 


Ql 


1 


NH 4 + 


1 


2291 


G23 


Ql 


1 


NH 4 + 


1 


2292 


G24 


Ql 


1 


NH 4 + 


1 


2293 


G25 


Ql 


1 


NH 4 + 


1 


2294 


G26 


Ql 


1 


NH 4 + 


1 


2295 


G27 


Ql 


1 


NH 4 + 


1 


2296 


G28 


Ql 


1 


NH 4 + 


1 



2297 


G29 


Ql 


l 


NH 4 + 


1 


2298 


G30 


Ql 


l 


NH 4 + 


1 


2299 


G31 


Ql 


1 


NH 4 + 


1 


2300 


G32 


Ql 


1 


NH 4 + 


1 


2301 


G33 


Ql 


1 


NH 4 + 


1 


2302 


G34 


Ql 


l 


NH 4 + 


1 


2303 


G35 


Ql 


1 


NH 4 + 


1 


2304 


G36 


Ql 


l 


NH 4 + 


1 


2305 


G37 


Ql 


l 


NH 4 + 


1 


2306 


G38 


Ql 


l 


NH 4 + 


1 


2307 


G39 


Ql 


l 


NH 4 + 


1 


2308 


G40 


Ql 


l 


NH 4 + 


1 


2309 


G41 


Ql 


l 


NH 4 + 


1 


2310 


G42 


Ql 


l 


NH 4 + 


1 


2311 


G43 


Ql 


l 


NH 4 + 


1 


2312 


G44 


Ql 


1 


NH 4 + 


1 


2313 


G45 


Ql 


l 


NH 4 + 


1 


2314 


G46 


Ql 


l 


NH 4 + 


1 


2315 


G47 


Ql 


l 


NH 4 + 


1 


2316 


G48 


Ql 


1 


NH 4 + 


1 


2317 


G49 


Ql 


1 


NH 4 + 


1 


2318 


G50 


Ql 


l 


NH 4 + 


1 


2319 


G51 


Ql 


1 


NH 4 + 


1 


2320 


G52 


Ql 


l 


NH 4 + 


1 


2321 


G53 


Ql 


l 


NH 4 + 


1 


2322 


G54 


Ql 


l 


NH 4 + 


1 


2323 


G55 


Ql 


l 


NH 4 + 


1 


2324 


G56 


Ql 


l 


NH 4 + 


1 


2325 


G57 


Ql 


l 


NH 4 + 


1 


2326 


G58 


Ql 


l 


NH 4 + 


1 


2327 


G59 


Ql 


l 


NH 4 + 


1 


2328 


G60 


Ql 


l 


NH 4 + 


1 


2329 


G61 


Ql 


l 


NH 4 + 


1 


2330 


G62 


Ql 


l 


NH 4 + 


1 


2331 


G63 


Ql 


l 


NH 4 + 


1 


2332 


G64 


Ql 


l 


NH 4 + 


1 


2333 


G65 


Ql 


l 


NH 4 + 


1 


2334 


G66 


Ql 


l 


NH 4 + 


1 


2335 


G67 


Ql 


1 


NH 4 + 


1 


2336 


G68 


Ql 


l 


NH 4 + 


1 


2337 


G69 


Ql 


1 


NH 4 + 


1 


2338 


G70 


Ql 


l 


NH 4 + 


1 


2339 


G71 


Ql 


l 


NH 4 + 


1 



WO 03/007296 



PCT/EP02/07434 



- 65 - 



2340 


G72 


Ql 


1 


NH 4 + 


1 


2341 


G73 


Ql 


1 


NH 4 + 


1 


2342 


G74 


Ql 


1 


NH 4 + 


1 


2343 


G75 


Ql 


1 


NH 4 + 


1 


2344 


G76 


Ql 


1 


NH 4 + 


1 


2345 


G77 


Ql 


1 


NH 4 + 


1 


2346 


G78 


Ql 


1 


NH 4 + 


1 


2347 


G79 


Ql 


1 


NH 4 + 


1 


2348 


G80 


Ql 


1 


NH 4 + 


1 


2349 


G81 


Ql 


1 


NH 4 + 


1 


2350 


G82 


Ql 


1 


NH 4 + 


1 


2351 


G83 


Ql 


1 


NH 4 + 


1 


2352 


G84 


Ql 


1 


NH 4 + 


1 


2353 


G85 


Ql- 


1 


NH 4 + 


1 


2354 


G86 


Ql 


1 


NH 4 + 


1 


2355 


G87 


Ql 


1 


NH 4 + 


1 


2355 


Gl 


Q26 


1 


NH 4 + 


1 


2357 


G2 


Q26 


1 


NH 4 + 


1 


2358 


G3 


Q26 


1 


NH 4 + 


1 


2359 


G4 


Q26 


1 


NH 4 + 


1 


2360 


G5 


Q26 


1 


NH 4 + 


1 


2361 


G6 


Q26 


1 


NH 4 + 


1 


2362 


G7 


Q26 


1 


NH 4 + 


1 


2363 


G8 


Q26 


1 


NH 4 + 


1 


2364 


G9 


Q26 


1 


NH 4 + 


1 


2365 


G10 


Q26 


1 


NH 4 + 


1 


2366 


Gil 


Q26 


1 


NH 4 + 


1 


2367 


G12 


Q26 


1 


NH 4 + 


1 


2368 


G13 


Q26 


1 


NH 4 + 


1 


2369 


G14 


Q26 


1 


NH 4 + 


1 


2370 


G15 


Q26 


1 


NH 4 + 


1 


2371 


G16 


Q26 


1 


NH 4 + 


1 


2372 


G17 


Q26 


1 


NH 4 + 


1 


2373 


G18 


Q26 


1 


NH 4 + 


1 


2374 


G19 


Q26 


1 


NH 4 + 


1 


2375 


G20 


Q26 


1 


NH 4 + 


1 


2376 


G21 


Q26 


1 


NH 4 + 


1 


2377 


G22 


Q26 


1 


NH 4 + 


1 


2378 


G23 


Q26 


1 


NH 4 + 


1 


2379 


G24 


Q26 


1 


NH 4 + 


1 


2380 


G25 


Q26 


1 


NH 4 + 


1 


2381 


G26 


Q26 


1 


NH 4 + 


1 


2382 


G27 


Q26 


1 


NH 4 + 


1 



2383 


G28 


Q26 


1 


NH 4 + 


1 


2384 


G29 


Q26 


1 


NH 4 + 


1 


2385 


G30 


Q26 


1 


NH 4 + 


1 


2386 


G31 


Q26 


1 


NH 4 + 


1 


2387 


G32 


Q26 


1 


NH 4 + 


1 


2388 


G33 


Q26 


1 


NH 4 + 


1 


2389 


G34 


Q26 


1 


NH 4 + 


1 


2390 


G35 


Q26 


1 


NH 4 + 


1 


2391 


G36 


Q26 


1 


NH 4 + 


1 


2392 


G37 


Q26 


1 


NH 4 + 


1 


2393 


G38 


Q26 


1 


NH 4 + 


1 


2394 


G39 


Q26 


1 


NH 4 + 


1 


2395 


G40 


Q26 


1 


NH 4 + 


1 


2396 


G41 


Q26 


1 


NH 4 + 


1 


2397 


G42 


Q26 


1 


NH 4 + 


1 


2398 


G43 


Q26 


1 


NH 4 + 


1 


2399 


G44 


Q26 


1 


NH 4 + 


1 


2400 


G45 


Q26 


1 


NH 4 + 


1 


2401 


G46 


Q26 


1 


NH 4 + 


1 


2402 


G47 


Q26 


1 


NH 4 + 


1 


2403 


G48 


Q26 


1 


NH 4 + 


1 


2404 


G49 


Q26 


1 


NH 4 + 


1 


2405 


G50 


Q26 


1 


NH 4 + 


1 


2406 


G51 


Q26 


1 


NH 4 + 


1 


2407 


G52 


Q26 


1 


NH 4 + 


1 


2408 


G53 


Q26 


1 


NH 4 + 


1 


2409 


G54 


Q26 


1 


NH 4 + 


1 


2410 


G55 


Q26 


1 


NH 4 + 


1 


2411 


G56 


Q26 


1 


NH 4 + 


1 


2412 


G57 


Q26 


1 


NH 4 + 


1 


2413 


G58 


Q26 


1 


NH 4 + 


1 


2414 


G59 


Q26 


1 


NH 4 + 


1 


2415 


G60 


Q26 


1 


NH 4 + 


1 


2416 


G61 


Q26 


1 


NH 4 + 


1 


2417 


G62 


Q26 


1 


NH 4 + 


1 


2418 


G63 


Q26 


1 


NH 4 + 


1 


2419 


G64 


Q26 


1 


NH 4 + 


1 


2420 


G65 


Q26 


1 


NH 4 + 


1 


2421 


G66 


Q26 


1 


NH 4 + 


1 


2422 


G67 


Q26 


1 


NH 4 + 


1 


2423 


G68 


Q26 


1 


NH 4 + 


1 


2424 


G69 


Q26 


1 


NH 4 + 


1 


2425 


G70 


Q26 


1 


NH 4 + 


1 



WO 03/007296 



PCT/EP02/07434 



2426 


G71 


Q26 


1 


NH 4 + 


1 


2427 


G72 


Q26 


1 


NH 4 + 


1 


2428 


G73 


Q26 


1 


NH 4 + 


1 


2429 


G74 


Q26 


1 


NH 4 + 


1 


2430 


G75 


Q26 


1 


NH 4 + 


1 


2431 


G76 


Q26 


1 


NH 4 + 


1 


2432 


G77 


Q26 


1 


NH 4 + 


1 


2433 


G78 


Q26 


1 


NH 4 + 


1 


2434 


G79 


Q26 


1 


NH 4 + 


1 



2435 


G80 


Q26 


1 


NH 4 + 


1 


2436 


G81 


Q26 


1 


NH 4 + 


1 


2437 


G82 


Q26 


1 


NH 4 + 


1 


2438 


G83 


026 


1 


NH 4 + 


1 


2439 


G84 


Q26 


1 


NH 4 + 


1 


2440 


G85 


Q26 


1 


NH 4 + 


1 


2441 


G86 


Q26 


1 


NH 4 + 


1 


2442 


G87 


Q26 


1 


NH 4 + 


1 




Example 2443 : The procedure is as in Examples 7-9, but the product of 
formula G89 according to Example 4 is used together with 20% by weight 
(based on the product according to Example G89) of the product of formula 

Example 2444 : The procedure is as in Example 2443, but the product of 
formula G89 according to Example 4 is used together with 20% by weight 
(based on the product according to Example G89) of the product of formula 



ho- 




Example 2445 : The procedure is as in Example 2443, but the product of 
formula G89 according to Example 4 is used together with 20% by weight 
(based on the product according to Example G89) of the product of formula 




Example 2446 : The procedure is as in Example 2443, but the product of 
formula G89 according to Example 4 is used together with 20% by weight 
(based on the product according to Example G89) of the product of formula 



WO 03/007296 



PCT/EP02/07434 



-67 - 




Example 2447 : The procedure is as in Example 2443, but the product of 
formula G89 according to Example 4 is used together with 20% by weight 
(based on the product according to Example G89) of the product of formula 




Examples 2448-2452 : The procedure is as in Examples 2443-2447, but the 
product of formula G90 according to Example 5 is used instead of the product 
of formula G89 according to Example 4. 

Example 2453 : 12.1 g of N-ethylaniline are stirred in 22 ml of 2-chloro- 
propionic acid ethyl ester in the presence of 10.6 ml of sodium carbonate and 
0.2 g of potassium iodide until the N-ethylaniline can no longer be detected in 
thin-layer chromatography. The chloropropionic acid ester is distilled off, and 
the oil that remains is taken up in ethyl acetate and extracted with water until 
salt-free. The dried organic phase is concentrated, yielding 20 g of an oily mass 
of formula: 




Example 2454 : 7.1 g of the compound according to Example 2453 are 
introduced into 20 ml of N,N-dimethylformamide and cooled in an ice bath. 
3.2 ml of phosphorus oxytrichloride are then slowly added dropwise and the 
mixture is stirred first at 20°C, and then for a further 4 hours at 60°C. The 
cooled reaction mass is discharged into a small amount of ice-water and 



WO 03/007296 



PCT/EP02/07434 



-68- 



neutralised with dilute sodium hydroxide solution. The resulting oil is taken up 
in ethyl acetate and washed with sodium chloride solution. The organic phase 
is dried and concentrated, yielding 6.7 g of the product of formula: 



Example 2455 : 6.7 g of the compound according to Example 2454 are 
dissolved in 50 ml of methanol, and 0.43 g of sodium borohydride is added. 
After 30 minutes at 20°C, the starting material can no longer be detected. The 
reaction solution is freed of methanol by distillation and the residue is taken up 
in ethyl acetate and washed with concentrated sodium chloride solution. The 
dried ethyl acetate phase is concentrated by evaporation; yielding 4.6 g of an 



Example 2456 : 4.25 g of the compound according to Example 2455 are 
dissolved in 25 ml of dichloromethane, and 2.6 ml of 3-isopropenyl-N,N- 
dimethylaniline are added. While cooling with an ice bath, 16 ml of a 1M boron 
trichloride solution in dichloromethane are added and the mixture is left to 
react overnight in the initial ice-bath to complete the reaction. Then, while 
cooling in an ice bath, 16 ml of concentrated sulfuric acid are added dropwise. 
The resulting reaction mixture is discharged onto ice, neutralised with sodium 
hydroxide solution and taken up in dichloromethane. After being washed, the 
organic phase is dried and the dichloromethane is distilled off, leaving behind 
5.8 g of a blue-green, very oxygen-senstive oil of formula 



Example 2457 : 5.8 g of the compound according to Example 2456 are 
dissolved in 40 ml of 100% acetic acid, and 150 drops of 60% perchloric acid 
are added. 1.65 g of tetrabutylammonium (meta)periodate are added to the 
resulting mixture. Stirring is carried out for 3 hours at 40°C, and the reaction 



o. 






WO 03/007296 



PCT/EP02/07434 



■ 69 - 

mass is discharged into 250 ml of water and 25 g of sodium perchiorate 
monohydrate and the oily mass obtained is treated with a potassium per- 
chiorate solution. After working up, 3.4 g of crude product are obtained. 
Repeated chromatographic purification of the crude product yields the 
analytically pure compound of the following formula: 

H C 

CH 3 H 3 C CH 3 3 ^ O 

h /ySVt t °' Ch3 c, ° 4 ~- 

X^^^k^ CH 3 

Example 2458 : 1.33 g of analytically pure product according to Example 
2457 are dissolved in acetone with 2.78 g of the cobalt complex of structure 
Q20 and the solution is concentrated by evaporation. The residue is taken up in 
methylene chloride, extracted by shaking repeatedly with deionised water and, 
without drying of the organic phase, concentrated to dryness without residue, 
yielding 3.13 g of compound of formula: 




Example 2459 : The procedure is as in Example 7, but instead of the product 
according to Example 1 there is used an equal amount of the product accord- 
ing to Example 2458. The absorption maximum of a recording support pro- 
duced analogously to Example 7 is at 623 nm. 

Example 2460 : 2.7 g of 4-fluorobenzaldehyde are stirred at 1 10°C in 20 ml of 
dimethyl sulfoxide with 3.74 g of morpholine and 3 g of potassium carbonate 
for 6 hours. Customary working-up yields 0.95 g of crystalline product of 
formula 



WO 03/007296 



- 70 - 



PCT/EP02/07434 



O. 




H 

That product is processed further analogously to Examples 2455 to 2458; 
yielding the compound of formula: 



Example 2461 : The procedure is as in Example 7, but instead of the product 
according to Example 1 there is used an equal amount of the product accord- 
ing to Example 2460. The absorption maximum of a recording support pro- 
duced analogously to Example 7 is at 626 nm. 

Example 2462 : The procedure is as in Example 7, but instead of the product 
according to Example 1 there is used an equal amount of the product accord- 
ing to Example 3. The absorption maximum of the recording support is at 
625 nm. 

Example 2463 : The procedure is as in Example 3, but instead of the metal 
complex of formula Q20 there is used an equimolar amount of the metal 
complex of formula Q16. The absorption maximum of a recording support 
produced analogously to Example 7 is at 631 nm. 

Example 2464 : The procedure is as in Example 1, but instead of the sodium 
salt of the metal complex of formula Q20 there is used the same amount of the 

product of formula r=( cu /=\ - The absorption maximum of a 





recording support analogous to Example 7 is at about 630 nm. 



WO 03/007296 



-71 - 



PCT/EP02/07434 



Examples 2465-2470 : Analogously to Example 7, recording supports are 
produced using the products of other Examples. The following absorption 
maxima are obtained: 



txampie 


LO r\ o» o» r ol ! r~» or o i it*\r\ a ^*4" o ov. kyi i"\ ncm or 

Kecoraing suppon comprising 
product according to 
Example: 


ADsorpiion maximum 


2465 


98 


623 nm 


2466 


183 


636 nm 


2467 


1227 


632 nm 


2468 


1576 


621 nm 


2469 


1583 


625 nm 


2470 


1921 


633 nm 



WO 03/007296 



PCT/EP02/07434 



-72- 

What is claimed is: 

1. An optical recording medium, comprising a substrate and a recording layer, 
wherein the recording layer comprises a compound of formula (I) 

1 

R 2 

wherein R 1; R 2 , R3, R 4 , R5, Re, R7, Rs, R9, Rio, R11, R12 and R i3 are each 
independently of the others hydrogen, Gi, or C r C 24 alkyl, C 2 -C 24 alkenyl, 
C 2 -C 24 alkynyl, C 3 -C 24 cycloalkyl, C 3 -C 24 cycloalkenyl, C 7 -C 24 aralkyl, C 6 -C 24 aryl, 
C 4 -C i2 heteroaryl or Ci-Ci 2 heterocycloalkyl, each unsubstituted or substituted 
by one or more identical or different substituents Gi, 

wherein Ri and R 2 , Ri and R X3 , R 2 and R 3 , R 3 and R 4? R 4 and R 5 , R 5 and R 6 , 
R 6 and R 7 , R 7 and R 8 , Rs and R 9 , R 9 and R 10 , Rio and R n , R n and R i2 
and/or R i2 and R i3 can independently of one another be bonded to one 
another in pairs separately or, when they contain substitutable sites, via a 
direct bond or via a -CH 2 - -0-, -S-, -NH- or -NCi-C 24 alkyk bridge in such 
a manner that, together with the atoms and bonds indicated in formula (I), 

five- or six-membered, saturated, unsaturated or aromatic, unsubstituted 
or G r substituted rings are formed, 

Gi is any desired substituent, 

X m ~ is an inorganic, organic or organometallic anion, 

Y n+ is a proton or a metal, ammonium or phosphonium cation, and 

m and n are each independently of the other a number from 1 to 5, and p and 
q are each independently of the other 0 or a number from 0.2 to 6, 
the ratio of p and q to one another, depending upon m and n and, as 
applicable, the number of charged Gi, being such that in formula (I) there is no 
excess positive or negative charge. 




(Y n+ ) q 



(I) 



R 1 R13R12 R 1C 



WO 03/007296 



PCT/EP02/07434 



-73 - 



2. A recording medium according to claim 1, which additionally comprises a 
reflecting layer. 



R 29 



3. A recording medium according to claim 1 or 2, wherein R 6 is 



R 30 



and R 29 , R30 and R 31 are each independently of the others hydrogen, halogen, 
COOR32, OR 32 or NR32R33, wherein R 32 and R 33 are each independently of the 
other hydrogen or C r Ci 2 alkyl, C 2 -C 12 alkenyi, C r Ci 2 cycloalkyl, C 2 -Ci 2 cyclo- 
alkenyl, C 6 -C 12 aryl or C 7 -Ci 3 aralkyl, each unsubstituted or substituted by one or 
two hydroxy substituents or by a metallocenyl or azo metal complex radical 
and uninterrupted or interrupted by 1, 2, 3, 4 or 5 oxygen and/or silicon 
atoms. 

4. A recording medium according to claim 1, 2 or 3, wherein R lf R 4 , R 5 , R 7 , R 8 
and Rn are hydrogen; R 2 , R 3 , R 9 , Ri 0 , R12 and R 13 are each independently of 
the others methyl, ethyl or R i4 , it being possible for R 2 and R 3 , R 9 and R 10 , R12 
and R13 and/or R9 and Ri 0 also to be bonded together in pairs via a direct 
bond, methylene, -O- or -N(C r C4alkyl); and R 6 is hydrogen or C r C 12 alkyl, 
C 6 -Ci 2 aryl or C 7 -Ci 3 aralkyl, each unsubstituted or mono- to tetra-substituted by 
halogen, -Cr, -OR 26 , -CN, -NR 25 R 2 7, -N + R 26 R 2 7R28, -N(R 26 )COR 27 , -COO", 
-COOR 26 , -CONR 26 R27, Ri4 or by -N(R 26 )COR 2 7R28, wherein R 26 , R 27 and R 28 are 
each independently of the others C r Ci 2 alkyl, C 6 -Ci 2 aryl or C 7 -Ci 3 aralkyl. 

5. A recording medium according to claim 3 or 4, wherein R 6 is > 

hQ , hQ-NR 35 R 36 , ~O- 0R 3a' -p^ OR 35 ° r R37 ' and 

COOR 34 COOR 34 36 COOR 34 

R34; R35 and R 36 are each independently of the others hydrogen or R 37 , 
R 37 being alkyl uninterrupted or interrupted by from 1 to 3 oxygen and/or 
silicon atoms and unsubstituted or substituted by one or two hydroxy 
substituents or by a metallocenyl or azo metal complex radical. 

6. A recording medium according to claim 1, 2, 3, 4 or 5, wherein X m " is a 
metal complex of formula [(Li)Mi(L 2 )] m " (III) or [(L 3 )M 2 (L 4 )]" (IV), wherein Mi 
and M 2 are a transition metal, preferably M x being Cr 3+ or Co 3+ and M 2 being 



WO 03/007296 



PCT/EP02/07434 



-74- 

Ni 2+ , Co 2+ or Cu 2+ , m is a number from 1 to, 6, L a and L 2 are each 
independently of the other a ligand of formula 





WO 03/007296 



PCT/EP02/07434 



- 75 - 



Ri6, Ri7> R187 Ri9, R20 and R 2 i are each independently of the others hydrogen, 
halogen, cyano, R 24 , N0 2 , NR 24 R 25 , NHC0-R 24 , NHC00R 24 , S0 2 -R 24 , S0 2 NH 2 , 
S0 2 NHR 24) S0 2 NR 24 R 25 , S0 3 ~ or S0 3 H, preferably hydrogen, chlorine, S0 2 NH 2 
or S0 2 NHR 24 , and R 22 and R 23 are each independently of the others CN, 
CONH 2 , C0NHR 24 , C0NR 24 R 25 , C00R 24 or COR 24) wherein R 24 and R 25 are each 
independently of the other C r C 12 alkyl, Ci-Ci 2 alkoxy-C2-Ci 2 alkyl, C 7 -Ci 2 aralkyl 
or C 5 -Ci 2 aryl, preferably C r C 4 alkyl, each unsubstituted or substituted by 
hydroxy, halogen, sulfato, CrC 6 alkoxy, C r C 6 alkylthio, Ci-C 6 alkylamino or by 
di-C r C 6 alkylamino, or R 24 and R 25 together are C 4 -C 10 heterocycloalkyl; it also 
being possible for R 16 and R17, R 18 and R 19l and/or R 20 and R 21 to be bonded 
together in pairs in such a manner that a 5- or 6-membered ring is formed. 

7. A recording medium according to claim 1, 2, 3, 4 or 5, wherein Y n+ is 
[NH 2 R 38 R39] + , R38 being hydrogen or C r C 12 alkyl and R 39 being C r C 24 alkyl or 
C 7 -C 24 aralkyl, and R 38 and R 39 together having from 8 to 25 carbon atoms. 

8. A recording medium according to claim 1, 2, 3, 4 or 5, wherein m and n are 
each the number 1, p is a number from 1 to 2Vz, and q is a number from 0 to 
IV2, the sum of positive charges in formula (I) or (II) being equal to the sum of 
negative charges. 

9. A recording medium according to claim 1, 2, 3, 4 or 5, wherein the dye of 
formula (I) has an absorption maximum at from 540 to 640 nm in ethanolic 
solution and a refractive index of from 2.0 to 3.0 in the range of from 600 to 
700 nm in the solid. 

10. A recording medium according to claim 1, 2, 3, 4 or 5, wherein the 
substrate has a transparency of at least 90% and a thickness of from 0.01 to 
10 mm, preferably from 0.1 to 5 mm. 

11. A recording medium according to claim 1, 2, 3, 4 or 5, wherein the reflect- 
ing layer consists of aluminium, silver, copper, gold or an alloy thereof and has 
a reflectivity of at least 45% and thickness of from 10 to 150 nm. 

12. A recording medium according to claim 1, 2, 3, 4 or 5, wherein the 
recording layer is located between the transparent substrate and the reflecting 
layer and has a thickness of from 10 to 1000 nm, preferably from 30 to 



WO 03/007296 



- 76 - 



PCT/EP02/07434 



300 nm, especially from 60 to 120 nm.. 

13. A recording medium according to claim 1, 2, 3, 4 or 5, the uppermost 
layer of which is provided with an additional protective layer having a thickness 
of from 0.1 to 1000 jam, preferably from 0.1 to 50 jum, especially from 0.5 to 
15 jam, to which there may be applied a second substrate layer that is prefer- 
ably from 0.1 to 5 mm thick and consists of the same material as the support 
substrate. 

14. A recording medium according to claim 1, 2, 3, 4 or 5, which has a 
reflectivity of at least 15%. 

15. A recording medium according to claim 1, 2, 3, 4 or 5, wherein between 
the recording layer and the reflecting layer and/or between the recording layer 
and the substrate there is additionally arranged at least one interference layer 
consisting of a dielectric material. 

16. A method for the optical recording, storage and playback of information, 
wherein a recording medium according to any one of claims 1 to 15 is used. 

17. A method according to claim 16, wherein the recording and the playback 
take place in a wavelength range of from 600 to 700 nm. 

18. A process for the production of an optical recording medium, wherein a 
solution of a compound of formula (I) according to any one of claims 1 to 15 in 
an, organic solvent is applied to a substrate having pits. 

19. A process according to claim 18, wherein the application is carried out by 
means of spin-coating. 

20. A compound of formula (I) according to claim 1, provided it is not known at 
the priority date of this Application. 

21. Use of a compound of formula (I) according to claim 20 in the production 
of an optical recording medium. 

22. A process for the preparation of a compound of formula (I) according to 
claim 1, wherein a compound of structure 



WO 03/007296 PCT/EP02/07434 

- 77 - 




is oxidised in the presence of a C r Ci 8 carboxy]ic acid. 

23. A process according to claim 22, wherein (meta)periodate is used as 
oxidising agent. 



24. Use of a compound of formula (I) prepared according to claim 22 in the 
production of an optical recording medium. 



INTERNATIONAL SEARCH REPORT 



ational Application No 

PCT/EP 02/07434 



A. CLASSIFICATION OF SUBJECT MATTER , , 

IPC 7 G11B7/24 C07C251/20 C07D231/38 C09B11/02 C09D11/18 
C09B11/18 C09B11/28 

According to International Patent Classification (IPC) or to both national c}ass\fication and IPC 



B. FIELDS SEARCHED 



Minimum documentation searched (classification system followed by classification symbols) 

IPC 7 G11B C07C C07D C09B C09D 



Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched 



Electronic data base consulted during the international search {name of data base and, where practical, search terms used) 

WPI Data, PAJ, EPO-Internal 



C. DOCUMENTS CONSIDERED TO BE RELEVANT 



Category e 



Citation of document, with indication, where appropriate, of the relevant passages 



Relevant to claim No. 



A 



US 5 301 145 A (A INOUE) 

5 April 1994 (1994-04-05) 
column 5, line 48; claim 1 
column 2, line 45 

EP 0 295 145 A (CANON) 

14 December 1988 (1988-12-14) 

page 7, line 15 - line 16; claims 1,12 

page 7, line 38 

page 8, line 38 

page 8, line 42 

PATENT ABSTRACTS OF JAPAN 

vol. 1998, no. 01, 

30 January 1998 (1998-01-30) 

6 JP 09 226250 A (HITACHI), 

2 September 1997 (1997-09-02) 
abstract 

-/» 



HI 



Further documents are listed in the continuation of box C. 



[X j Patent family members are listed in annex. 



° Special categories of cited documents : 

"A" document defining the general state of the art which Is not 

considered to be of particular relevance 
"E" earlier document but published on or after the international 

filing date 

'L' document which may throw doubts on priority claim(s) or 
which is cited to establish the publication date of another 
citation or other special reason (as specified) 

"O" document referring to an oral disclosure, use, exhibition or 
other means 

■P" document published prior to the international filing date but 
later than the priority date claimed 



"T later document published after the international filing date 
or priority date and not in conflict with the application but 
cited to understand the principle or theory underlying the 
invention 

"X" document of particular relevance; the claimed invention 
cannot be considered novel or cannot be considered to 
involve an inventive step when the document is taken alone 

■Y" document of particular relevance; the claimed invention 

cannot be considered to involve an inventive step when the 
document Is combined with one or more other such docu- 
ments, such combination being obvious to a person skilled 
in the art. 

■&* document member of the same patent family 



Date of the actual completion of the international search 



1 November 2002 



Date of mailing of the international search report 



21/11/2002 



Name and mailing address of the ISA 

European Patent Office, P.B. 5818 Patentlaan 2 
NL-2280 HV Rijswijk 
Tel. (+31-70) 340-2040, Tx. 31 651 epo nl, 
Fax: (+31-70)340-3016 



Authorized oWicer 



Vanhecke, H 



Form PCT/IS/V210 (second sheet) (July 1992) 



IMEERNATIONAL SEARCH REPORT 



ational Application No 

PCT/EP 02/07434 



C.(Continuation) DOCUMENTS CONSIDERED TO BE RELEVANT 



Category ° Citation of document, with indication .where appropriate, of the relevant passages 



Relevant to claim No. 



US 5 851 621 A (H WOLLEB) 
22 December 1998 (1998-12-22) 
cited in the application 
claims 1-23 

US 3 781 711 A (K DREXHAGE) 

25 December 1973 (1973-12-25) 

cited in the application 

column 6, line 1 - line 10; claims 1,3,7 

DE 199 19 119 A (DREXHAGE) 
2 November 2000 (2000-11-02) 
cited 1n the application 
claims 1-19 



20 



20 



Form PCT/JSA/210 (continuation of second sheet) (July 1992) 



INTERNATIONAL SEARCH REPORT 



international application No. 
PCT/EP 02/07434 



Box I Observations where certain claims were found unsearchable (Continuation of item 1 of first sheet) 

This international Search Report has not been established in respect of certain claims under Article 17(2)(a) for the following reasons: 
1. | j Claims Nos.: 

because they relate to subject matter not required to be searched by this Authority, namely: 



1. Pn Claims Nos.: 20,22,23 

because they relate to parts of the International Application that do not comply with the prescribed requirements to such 
an extent that no meaningful International Search can be carried out, specifically: 

see FURTHER INFORMATION sheet PCT/ISA/210 



3. | I Claims Nos.: 

because they are dependent claims and are not drafted in accordance with the second and third sentences of Rule 6.4(a). 

Box II Observations where unity of invention is lacking (Continuation of item 2 of first sheet) 

This international Searching Authority found multiple inventions in this international application, as follows: 



1 . I I As all required additional search fees were timely paid by the applicant, this International Search Report covers all 
I 1 searchable claims. 

2. j As at! searchable claims could be searched without effort justifying an additional fee, this Authority did not Invite payment 

of any additional fee. 



3. I I As only some of the required additional search fees v/ere timely paid by the applicant, this International Search Report 
' 1 covers only those claims for which fees were paid, specifically claims Nos.: 



4. | No required additional search fees were timely paid by the applicant. Consequently, this International Search Report is 

restricted to the invention first mentioned in the claims; it is covered by claims Mos.: 



Remark on Protest | j The additional search fees were accompanied by the applicant's protest. 

1" | No protest accompanied the payment of additional search fees. 



Form PCT/lSA/210 (continuation of first sheet (1)) (July 1998) 



International Application No. PCT/EP 02 /)7434 

FURTHER INFORMATION CONTINUED FROM PCT/ISA/ 210 



Continuation of Box 1.2 
Claims Nos. : 20,22,23 



Present claims 20,22 and 23 relate to an extremely large number of 
possible compounds and methods. In fact, the claims contain so many 
options that a lack of clarity (and/or conciseness) within the meaning 
of Article 6 PCT arises to such an extent as to render a meaningful 
search of the claims impossible. Consequently, the search has been 
carried out for those parts of the application which do appear to be 
clear namely: those compounds comprising a metal complexing anion as 
recited in the examples 



IWffERN ATIONAL SEARCH REPORT 

Information on patent family members 



ational Application No 

PCT/EP 02/07434 



Patent document 
cited in search report 



Publication 
date 



Patent family 
member(s) 



Publication 
date 



us 


5301145 


A 


05- 


-04- 


-1994 


JP 


1019532 


A 


23-01-1989 


EP 


295145 


A 


14- 


-12- 


•1988 


OP 


1091340 


A 


11-04-1989 














JP 


2712030 


B2 


10-02-1998 














JP 


1093395 


A 


12-04-1989 














JP 


2524504 


B2 


14-08-1996 














DE 


3855186 


Dl 


15-05-1996 














DE 


3855186 


T2 


05-09-1996 














EP 


0295145 


A2 


14-12-1988 














US 


4946261 


A 


07-08-1990 



JP 09226250 A 02-09-1997 NONE 



US 


5851621 A 


22- 


•12- 


■1998 


CA 


2204209 


Al 


03-11-1997 












EP 


0805441 


Al 


05-11-1997 












JP 


10097732 


A 


14-04-1998 


us 


3781711 A 


25- 


•12- 


■1973 


DE 


2351142 


Al 


02-05-1974 












FR 


2202920 


Al 


10-05-1974 












JP 


49074895 


A 


19-07-1974 


DE 


19919119 A 


02- 


11- 


■2000 


DE 


19919119 


Al 


02-11-2000 












AU 


4297100 


A 


10-11-2000 












WO 


0064986 


Al 


02-11-2000 












EP 


1173519 


Al 


23-01-2002 



Form PCT/13A/210 (patent family annex) (July 1992)