DE2651683A1 - DYE WITH A PYRIMIDE DINER - Google Patents

Description

Dye with a pyrrimidine core

The invention relates to a dye with a pyrimidine core for photographic light-sensitive material. She concerns in particular one derived from 6-oxo-1,6-dihydropyrimidine Dye used as a sensitizing dye for a sil-. Overhalide-containing photographic emulsion or as a dye, which can be incorporated into a light-absorbing layer and bleached, is used.

A photographic emulsion layer or other hydrophilic colloidal layer in silver halide-containing photographic Photosensitive material is often colored with a dye or pigment to generate light in a specific wavelength

709821/1002

TELEPHONE (OHB)

TELEX O8-90S8O

TELEQRAMS MONAPTH TELECOPER

absorb area.

If necessary, the spectral composition of the incident Light on the photographic emulsion layer generally, a colored layer is provided which is further from the support than the photographic emulsion layer. This colored layer is called the filter layer. When multiple photographic emulsion layers are applied, the filter layer can lie in between.

Halation is caused by light coming through it is scattered through a photographic emulsion layer and then on the surface of the photographic material opposite the emulsion layer or on the intermediate layer between the emulsion layer and reflecting support which is again incident on the emulsion layer. To prevent halation, a colored layer, called an antihalation layer, is placed between the emulsion layer and the support or on attached to the side of the support opposite the emulsion layer. When two or more photographic emulsion layers are present, an antihalation layer can be provided between two of these emulsion layers. The photographic Emulsion layer itself is often colored to improve image sharpness by being scattered within the emulsion layer Light absorbed (such light scattering is generally called irradiation (diffusion or diffusion atria).

In these hydrophilic colloid layers to be colored, generally incorporated a water-soluble dye. Such a dye is said to have the following properties:

709821/1002

1. The dye must be suitable for its intended use Possess spectral absorption;

The dye should be photographic and chemically inert. This means that the dye does not have the photographic properties of the silver halide photographic emulsion layer is intended to adversely affect, such as lowering the sensitivity, latent images to disappear bring or cause veil.

3 · The dye must be used during photographic processing Bleachable or leachable into a developer solution or water used for washing, so that no unwanted staining on the developed photographic photosensitive material remains.

Numerous attempts have been made by professionals to To develop dyes with these properties mentioned. Examples of such developed dyes are oxonol dyes with a pyrazolone core (GB-PS 506 385), oxonol dyes with a barbituric acid core (US Pat. No. 3,247,127), other oxonol dyes US Pat. Nos. 2,533,472, 3,379,533 and US Pat. No. 1,278,621, hemioxonol dyes (US Pat. No. 584,609), styryl dyes according to US Pat 2,298,733 merocyanine dyes disclosed in U.S. Patents 2,493,747 and Cyanine dyes disclosed in U.S. Patent 2,843,486.

Many dyes used during photographic processing Can be bleached by being in the developer-processing solution given sulfite (or bisulfite) or through this

709821/1002

Compounds bleached under alkaline conditions, e.g. as described in GB-PS 506 385.

Dyes for coloring photographic layers with a barbituric acid core are in the FB-PSs 1 290 430, 1 378 648, 1 401 591, 1 419 703 and 1 599 873. These dyes are inert towards photo graphi see emulsions and are easily bleached during photographic processing; however, they have flaws, such as low solubility and difficulty in introducing the required light absorption Amount of dyes in the photographic layer.

The purpose of the invention is a dye with a pyrimidine core, which has high solubility and for coloring photographs Layers is useful.

Another purpose of the invention is a dye for coloring photographic layers, the high solubility in an organic Has solvent and is water soluble.

These purposes and objects are accomplished by a dye containing a best derived from any given by the general formula (IV) again given connection comes from:

OR ²

H_C C = O

C-N

■ ^{| l 1} I 0 R ^x

(IV)

709821/1002

in which R ^{1 is} an aliphatic hydrocarbon, aromatic

2 is a hydrocarbon, aralkyl or acyl group and E is an aliphatic group Mean a hydrocarbon group or an aralkyl group.

The invention relates in particular to a dye having a pyrimidine core with one of the general formulas (I) to (III):

OR ²

I I

/ - - \ F ■ ⁿ n

O = CC = CH- (L = LMj ₁ -C _x C = O

\ - C CN

I -i Il

ΈΓ O

HO

(D

' _R 5

O = C C = (L-LM,

NC I ₁ II

R ¹ ο

■ Cn)

OR

N = C Γ "- ^W - / \ '''O = CC = (L-LM _n = C- (CH = CH) -N-R'

I ₁ "W-

R ^x 0

(III)

709821/1002

in which E is an aliphatic hydrocarbon, aromatic hydrocarbon, aralkyl or acyl group,

p
E is an aliphatic hydrocarbon or an aralkyl group, Br and E, which can be the same or different, an aliphatic hydrocarbon, aromatic hydrocarbon

5 6
or aralkyl group, Br and E, which can be the same or different, are each hydrogen, halogen, an aliphatic hydrocarbon group, an alkoxy or acylamino group, E 'an aliphatic hydrocarbon, aromatic hydrocarbon or an aralkyl group; V is the grouping of non-metal atoms required to form a 5- or 6-membered heterocyclic ring; L and L ¹ , which may be the same or different, each represent an optionally substituted methine group; 1 is 0, 1 or 2 and m, η and ρ each represent 0 or 1.

Examples of aliphatic hydrocarbon groups in the meaning of E of the general formula I, II »III and IV described above are alkyl groups having 1 to 8 carbon atoms (e.g. a methyl, ethyl, isopropyl, η-butyl, tert-butyl or n-hexyl group), a substituted alkyl group with 1 to 12 carbon atoms, by one or more of the following substituents: halogen, alkoxy, alkoxycarbonyl, aryloxy, cyano and sulfo group (e.g. chloromethyl, B-chloroethyl, "^ -chloropropyl, Ethoxycarbony! Methyl, ß-lthoxyäthylJOC-phenoxyethyl, 2-methyl-1- (chloromethyl) propyl, ß-cyanoethyl or ß-sulfoethyl); one Hydrocarbyl group of 5 to 8 carbon atoms inclusive a 5- or 6-membered carbon ring (e.g. a cyclopentyl, Cyclohexyl or cyclohexylmethyl group) j and an alkenyl group with 2 to 4 carbon atoms (e.g. yinyl or allyl) can be substituted.

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Examples of the aromatic hydrocarbon represented by E. group are a monocyclic or bicyclic, optionally substituted aryl group (such as phenyl, Uaphthyl, substituted phenyl and substituted naphthyl groups, where one or more of the following groups serve as substituents: halogen, nitro, alkyl, alkoxy, alkoxycarbonyl and sulfo group (e.g. p-tolyl, 4-chlorobphenyl, 4-- Nitrophenyl, 4-methoxyphenyl, 3-methoxyphenyl, 4-ithoxycarbonylphenyl, 4-dimethylaminophenyl, 4-sulfophenyl and 2,5-disulfonyphenyl)).

An example of the aralkyl group represented by E. is an alkyl group with a benzene ring and 7 to 10 carbon, atoms (e.g. benzyl and phenethyl). The aryl radical of the aralkyl group can be unsubstituted or with one or more the following substituents: alkyl group with 1 to 3 carbon atoms, halogen, sulfo and carboxy group.

1
Examples of the acyl group represented by E are an acyl group, e.g. a carboxylic acid or a sulfonic acid acyl group with up to 8 carbon atoms in the alkyl radical, ie an alkyl sulfonyl group with up to 8 carbon atoms (e.g. methanesulfonyl and butanesulfonyl), a monocyclic arylsulfonyl group (e.g. benzoelsulfonyl , p-toluenesulfonyl), an alkylcarbonyl group with »2 to 8 carbon atoms (eg acetyl» propionyl etc.), or a monocyclic arylcarbonyl group (eg a benzoyl group and a p-methylbenzoyl group).

Examples of aliphatic hydrocarbon groups represented by E. are an alkyl group with 1 to 6 carbon atoms (e.g. methyl, ethyl, n-propyl, isopropyl, η-butyl and isobutyl),

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85

a substituted alkyl group having one or more of the following substituents: halogen, sulfo group and alkoxy group is substituted and 2 to 4 carbon atoms in the alkyl radical possesses (e.g. ß-chloroethyl, ß-sulfoethyl, ß-alkoxyethyl with an alkyl radical with 1 to 3 carbon atoms (e.g. ß-methoxyethyl)).

An example of the aromatic hydrocarbon represented by E. group is an aralkyl group with 7 to 9 carbon atoms (e.g. benzyl or phenethyl).

• ζ μ

Examples of aliphatic hydrocarbon groups represented by Br and E are an unsubstituted alkyl group having 1 to 6 carbon atoms (eg methyl, ethyl, isopropyl, n-butyl, n-hexyl); a substituted alkyl group with 1 to 6 carbon atoms in the alkyl radical which is substituted with one or more of the following substituents: halogen, cyano, hydroxy, sulf o, alkoxy group with 1 to 3 carbon atoms, acyloxy group with 2 to 4 carbon atoms, alkoxycarbonyl group with 2 to 5 carbon atoms, alkyl sulfonyloxy group with 1 to 4 carbon atoms, alkylcarbonylamino group with 2 to 4 carbon atoms or an alkyl sulfonylamino group with 1 to 3 carbon atoms (e.g. ß-chloroethyl, ß-bromoethyl, - ß-cyanoethyl, ß-sulf Ethyl, / -Sulfoppropyl, T-sulfobutyl, ß-hydroxyethyl, ß, ^ -dihydroxypropyl, ß-methoxyethyl, ß, ^ dimethoxypropyl, ß- (ß'-cyanoethyl) -oxyethyl , ß-acetoxyethyl, ß-C ^ -acetylacetoxy) -ethyl, ß - $? enoxyacetyl) -ethyl, ß-methoxycarbonylethyl, ß-ethoxycarbonylmethyl, ß-ethoxycarbonylethyl, ß-methylsulfonyloxyethyl, ß-methylsulfonyloxyethyl, ß-ethyl ethyl ethyl, ^ - (&. c e tylamino) -propyl, ß- (methyl sulfonylamino ) ethyl, ß- ^ ethyl sulfonylamino) ethyl); and a cycloalkyl group having 5 to 6 carbon atoms (eg, cyclohexyl).

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- * r-Ά

Ή / and E can each denote an aralkyl group with 7 to 10 carbon atoms (for example benzyl or phenethyl) in which the aryl radical is unsubstituted or substituted, for example by a sulfo group.

An example of E ^ and E meaning an aromatic Hydrocarbon group is a monocyclic aryl group containing 6 to 10 carbon atoms (e.g. phenyl and p-tolyl).

Suitable examples for Ή? and E are halo gen ^ z. B. chlorine or <C bromine, an aliphatic ^ hydrocarbon group, such as an alkyl group with 1 to 6 carbon atoms (e.g. methyl or ethyl), an alkoxy group with 1 to 6 carbon atoms (e.g. methoxy, itoxy, butoxy), an acylamino group (e.g. an acylamino group with 2 to 6 carbon atoms (eg acetylamino, propionylamino) and a substituted acylamino group with 2 to 4 carbon atoms (eg chloroacetylamino and methoxyacetylamino)).

Examples of R ^f in the meaning of aliphatic hydrocarbon groups are an unsubstituted alkyl group with 1 to carbon atoms (for example methyl, ethyl, n-propyl, η-butyl and n-hexyl) and a substituted alkyl group with 1 to 8 carbon atoms, which with one or several of the following. Substituents can be substituted: Hydroxy, alkoxy-y substituted alkoxy group (eg alkoxyalkoxy group, SuIfοalkoxygruppe, SuIfoalkoxyalkoxygruppe etc.), COOH, SO ₅ H, PO ₅ H, CONH ₂ , COKHB, CONER ¹ , SO ₂ NH ₂ , SO ₂ NHESO ₂ NEE ¹ , where E and E ¹ denote an alkyl group with 1 to 5 carbon atoms or a monocyclic aryl group (e.g. carboethoxymethyl, 2-methoxycarbonylethyl, 2-5thoxy-. Carbonylethyl, β-carboxyethyl, β-sulfoethyl, X-sulfopropyl, and J-sulfobutyl). . .

709821/1002

η

Examples for Ή. ⁽ The meaning of aromatic hydrocarbon groups are monocyclic or bicyclic aryl groups with 6 to 10 carbon atoms (for example phenyl and 4-methylphenyl), preferably a monocyclic aryl group.

W is that to form a 5- or 6-membered heterocyclic Rings (itfie thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, Kaphthoxazole, selenazole, benzoselenazole, naphthoselenazole, Thiazoline, 2-quinoline, 4-quinoline, 1-isoquinoline, 3-isoquinoline, 3i3-dialkylindolenine, pyridine, etc.) required Kichtmetallatomgruppe.

Examples of heterocyclic hinge completed by W. are 5- or 6-membered heterocyclic hinge with an or several sulfur, selenium, oxygen or nitrogen atoms as a hetero atom, the heterocyclic ring being substituted can be with one or more substituents, such as an alkyl group with 1 to 4 carbon atoms, phenyl group, halogen, such as chlorine or bromine, alkoxy group with 1 to 4 carbon atoms, Alkylenedioxy group with 1 to 3 carbon atoms, hydroxyl group or alkoxycarbonyl groups with 2 to 5 carbon atoms, e.g. thiazo rings such as thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-pkenylthiazole, 4,5-dimethylthiazole, 4-, 5-diphenylthiazole and 4- (2-thienyl) thiazole; Benzthiazole rings such as benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-clilorobenzothiazor, 4-methylbenzthiazole, 5 "methylbenzthaizole, 6-methylbenzthiazole, 5-bromobenzothiazole, 6-bromobenzothiazole , 4-phenylbenzothiazole, 5-pienylbenzthiazole, 4-methoxybenzthiazole, 5-methoxybenzthiazole, 6-methoxybenzthiazole, 5-indobenzothiazole, 6-indobenzothiazole, 4-lthoxybenzthiazole, 5-itoxybenzthiazole, Tetrahydrobenzthiazole, 5,6-dimethoxybenzthiazole, 5,6-methylenedioxybenzthiazole, 5-hydroxybenzthiazole and

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6-hydroxybenzothiazole; Naphthotniazole rings such as OCrHaphthotbia-ζοΙ, .β-naphthothiazole, 5-methoxy-ß-naphthothiazole, 5- & fckoxyß-naphthothiazole, 8-methoxy ^ -naphthothiazole and 7-methoxy-cC-naphthothiazole; Thionaphtheno-7 ¹ , 6 ', 4-, 5-tniazole rings, such as, for example, 4- ^L -metnoxythionaphtheno-7', 6 ', 4,5>-thiazole; Oxazole rings such as 4-metnyloxazole, 5-metnyloxazole, ^ -phenyloxazole, ^, 5-dipiienyloxazole, 4-ltliyloxazole, 4,5-dinietliyloxazole and 5- ^ iienyloxazole, benzoxazole, benzoxazole, 5-benzoxazole-Hazol, 5-Cblorbenzoxazole, - ^ lienylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4-, 6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5--2thoxybenzoxazole, 5-clilorobenzoxazole, 6-methoxybenzoxazole, 5-2ydroxybenzoxazole and 6-hydroxybenzoxazole; NapiLth oxazole rings, such as (^ .- naphthoxazole and β-kaphthoxazole; selenazole rings such as -4-methylselenazole and 4-phenylselenazole; benzselenazole rings, such as benzselenazole, 5-cnlorobenzelenazole, 5-methoxybenzelene, 5-methoxybenzelene-azole and tetrahylenetylenazole; e.g. oC-ISraphthoselenazole and ß-iraphthoselenazole; thiazoline rings such as thiazoline and 4-methyltmazoline; 2-CMnbline rings such as'2-quinoline, 3-methyl-2-quinoline, 5-methyl-2-quinoliji, 7-methyl-2- quinoline, S-methyl ^ -cninoline, 6-ch.loro-2-quinoline, 8-chloro-2-quinoline, 6-methoxy-2-cninoline, 6-ithoxy-2-quinoline, 6-hydroxy-2-cninoline and 8-hydroxy-2-quinoline; 4- quinoline rings such as 4-quinoline, 6-methoxy-4-quinoline, 7-methyl-4-cninoline and 8-methyl-4-cninoline; 3 »3-dialkylindolenine rings such as 3i3 -Diiaethylindolenine, 3j3j5-trimethylindolenine and 3 »3 _? 7-"trimethylindolenine; lyridine ™ rings such as 2-pyridine, 4-py2? Idine and 5-methyl-2-pyridine; benzimidazole rings such as benzimidazoles 1-butyl-4-raethylbenz imidazole, "1-ethyl-A · -phenylbenzimidazole and 4-, 5-dichlorobenzinidazole; and hapnthoimidazole rings include, for example, Ί-methyl-X-naphthoimidazole and ß- ^ aphthoimidazole and 5-methoxy-ß-naplitlioimidazole.

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L and L ¹ , which can be the same or different, can represent an unsubstituted methine group or a methine group substituted with a Gy, ^, - alkyl group »

The compounds of the general formulas I to III also include their alkali metal salts, i.e. those compounds in which the HO substituent is replaced by an MO substituent in which II is an alkali atom such as sodium or potassium became.

The method of making the by the above-described The compound given general formula IV is described in Japanese patent application 1344-68 / 74-.

H ₀ CC = O

C-N

. HI ₁

0 YC

(IV)

OR

C-N

HC

C H O

C-OH

- N (V)

The compounds of the general formula IV can be represented by the tautomer of the general formula V. The one described above Compound of the general formula IV can be obtained in high yield by reacting an isocyanate of the general formula VI

709821/1002

- 4-r-

ε ¹ - ν = σ

in which E has the meaning described above, with a Acrylic acid derivative of the general formula YII:

, ft /

G = CH-COY

in which H has the meaning described above, in the presence a base (1) or in the absence of a base (2) to form an intermediate as an addition product with the following Formula VIII:

R-NHCNH 'II

O R ² C-

C = CH-COY

(viii).

709821/1002

12th
in which E and E have the meanings given above and Y is a hydroxy, alkoxy, aryloxy, amino, alkylamino or dialkylamino group and addition of a basic condensing agent followed by inclusion. Examples of basic condensation agents which are used after the intermediate product has been formed are preferably alcoholates, such as, for example, sodium methoxide or sodium ethoxide.

The dye according to the invention is, as described below, generally prepared by reacting a compound of the general formula IV with such an intermediate. These conditions are explained in more detail in the general preparation method given below.

Oxonol dyes represented by the general formula I can be obtained by condensing a suitable compound of the general formula IV with diethoxymethyl acetate, ethyl orthoformate, H ", K-diphenylformamidine hydrochloride (whereby monomethine oxonols are obtained), trimethoxypropane, tetramethoxypropane, malonaldehyde dianil hydrochloride (whereby trimethine oxonols are obtained) -Anilino-5-phenylimino-1,3-pentadiene hydrochloride (whereby pentamethine oxonols are obtained) in a suitable inert solvent and preferably in the presence of a basic condensing agent. The condensation reaction is carried out by heating the reaction mixture, preferably to a temperature between tree temperature (approx 20 to 30 ⁰ C) and reflux temperature carried out.

Styryl dyes represented by the general formula II can be prepared by condensing a suitable one by the general Formula IV represented compound with p-dimethylaminobenzaldehyde, p- (N-ethyl-M-ß-sulfoethyl) -aminobenzaldehyde, p- (IT-ethyl-H-

821/1002

sr

β-chloroethylaminobenzaldehyde, 2-methyl-4-dimethylaminobenzaldehyde or p-dimethylamino tin amaldehyde ir », a suitable one Solvent and preferably in the presence of a basic one Condensation agent are produced. This condensation reaction is carried out by heating the reaction mixture, preferably to a temperature between room temperature (20 'to 30 C) and Reflux temperature carried out.

Merocyanine dyes represented by the general formula III can be prepared by condensing a suitable compound represented by the general formula IY and a compound represented by the general formula IX in a suitable inert solvent and preferably in the presence of a basic condensing agent. This condensation reaction is by heating the mixture Reakti ons, preferably ⁽⁰ to 30 C for about 20) and reflux temperature, carried out at a temperature between room temperature.

₇ :!

r ⁷ -n4ch-ch) -cz

in this formula, R ', V and ρ have the meanings given above; X means a group such as ityl (this becomes a obtained simple merocyanine), ß-acetoanilidovinyl or thioacetonylidene (Merocarbocyanine is obtained from this), 4-methoxybutadienyl or 4-anilinovinyl-1,3-butadienyl (where a Merodicarbocyanine dye obtained); X ~ is an acid anion like Chloride, bromide, methyl sulfate, ethyl sulfate, p-toluene sulfate or Perchlorate.

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Any of the known basic condensing agents can be used, e.g. a trialkylamine (e.g. triethylamine, tri-n-propylamine, triisopropylamine _; or tri-n-butylamine), Ν, Ν-dialkylaniline (e.g. F, IT ~ dimethylaniline or N, N-diethylaniline), N-alkylpiperidine (e.g. N-methylpiperidine or N-Sthylpiperidin),

Preferred inert solvents are methanol, ethanol, propanol, Cyclohexane, pyridine, rf-butylolactone. and anhydrous acetic acid.

The dye according to the invention with a pyridine nucleus can be used in photographic light-sensitive material can be incorporated. It is particularly useful as a dye for coloring a filter layer, an antihalation layer and an emulsion layer useful. It is also used as a spectral sensitizing dye for a silver halide emulsion.

Typical dyes and their syntheses are given below. Of course, the invention is not restricted to these particularly preferred exemplary embodiments. Unless otherwise given, in the examples all parts, percentages, ratios, etc. are given in terms of weight.

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C. S ° x ^c ; C. = N - N = \ C. / \ C = / HO C = O O = C J CH-C / \ Q - N W. \ / 0 CH ₃ CH-

OC C. 2 ^H 5 OC π KO 2 ^H 5 N = \ ß = N / C. \ O = C / = CH - C \ Q / N - V - N / O \ C ₂ H C ₂ H ₅

N = C

OC ₀ Hj- / 25

OC ₀ Hc · \ 2

.C = N

O = C N

C = CH - C C = O

- N

O HO

70982

N
O = C

N =

N CH ₀

N O = C

N - ^C 2 ^H 5

/ ^OC 2 ^H 5 ° \ ^C 2 ^H 5

C C = N

C = CH - C C = O

C C-N

W /

0 HO

OC ₂ H ₅ C. OC
\ C = CH-CH = CH-C 0 W. 2 ^H 5 \ C. / C. = N C. . KO ⁷ \ C = O / - N
CH-,

OC ₀ H _n

\ 2

= C

C = N

C = CH-CH = CH-C C = O / \ /

C. C-N

0 KO C ₀ H _n

OC ₂ H ₅

OC ₂ H ₅

C = CH-CH = CH-C

C \

W /

0 HO C = O

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OCH ₀ CH ₀ CJl / 22 \

/ = ^c x ■ ■ / ^C

O = C C = CH-CH = CH-C

N-C C

= N

C = O

• HO

N \

OCH, OCH-

/ 3 \

^c x F \

C = CH-CH = CH-C C = O

C C-N

HO

OC,

O = C C = CH-CH = CH-CH = CH-C

N-C. C.

HO C = O

C ₂ H ₅ O

O = C

N =

OCH ₃

NC ₂ H ₅

C = CH-CH = CH-CH = CH-C

HIGH OCH ₃ ρ - _N

2 ^H 5 I.

21/1002

O = C OCH ₂ CH ₂ CS. • OCH ₂ W. HO CH ₂ CJl \ f = C - * \ N = N - C = CH-CH = CH-CH = CH-C. C = O / / ifil C. N

NO = C

- C

OC ₂ H ₅

-cujr \

CH-

= C

OC ₀ H ₁ - / 25

- C

= CH

OC ₂ H ₅

N =

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OCH ₃ = C

O = C "C = CH

r- \ CH ₃ 0

-N

O = C
\

C = CH - //

/ ^N -1

CHo (-CH ₂ CH ₂ SO ₃ Na

N = C O = C C = CH-CH = CH - //

CH-

O = C
\

CH-

OC ₅ H ₁ - / 25

C = CH-CH =

.CH-

-CH.

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N = _{/ O} C ₂ H ₅ 0 / ° N 1 r / ° \ / I. I. O = C C = CH-CHK C. \ / \ N - C. / 2 ^H 5 CH ₃

O = C

h — ητΐ ι

p-CE-l

CH ₃ 0

(CH ₂ ) SO ₃ Na

N = OC ₅ He
J ^{2 5} / \ / ^ r; nN O = C C = CH-CH = K \ / \ Λ 'J N - C N ^ \ ^^ / ^ I CH ₃ ⁰ CH
C ₂ H ₅

- Ö ⁷

"Λ y

O = C C = CH-CH = ^

N - C "N '

/ W ι

^CH 3 ° (CH ₂ I ₃ SO ₃ Na

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N /

O = C

N = C /

(CH ₂ I ₃ SO ₃ Na

OCH ₂ CH ₂ SO ₃ H,

O = C • NC CH ₃ ^N 0

C ₂ H ₅

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3 »

example 1 Synthesis of the dye (2)

5 _? 5 S 4-lthoxy-1-ethyl-2-hydro3q7-6-oxo-1,6-dihydrop3rrimidiii and 14.8 g of o-ethyl format were suspended in 30 ml of acetic acid, 20 ml of triethylamine were added and the mixture was heated and heated for 3 min long refluxed. After cooling, the solution was washed twice with 200 ml of diethyl ether, and then 20 ml of methanol was added to the oily residue to prepare a solution. 20 ml of methanol in which 2.9 g of anhydrous potassium acetate had been dissolved were added with stirring, crystals immediately separating out. The methanol solution was concentrated under reduced pressure, and the crystals thus produced were filtered off and taken out. The crystals were washed with an acetone-methanol mixture (volume ratio 2: 1) to give 2.9 g of dye (2); F 248 to ⁰

Dye (2) is easily soluble in water, methanol or ethanol; the maximum absorption is at a wavelength of 447 nm in water and 449 nm in methanol.

Example 2 Synthesis of the dye (4)

7 g of 4-ethoxy-2-hydroxy-1-phenyl-6-oxo-1,6-dihydropyriraidine and 14.8 g of o-ethyl format were suspended in 30 ml of vinegar and then heated and refluxed for 3 minutes. After the To the mixture at 70 ° C., 12 ml of triethylamine were added and the mixture was heated and refluxed for 1 minute.

The reaction mixture was cooled to room temperature and washed twice with 200 ml of diethyl ether by decanting; then

709821/1002

ST

the oily residue was crystallized. The crystals were washed with diethyl ether and acetone (1: 1 parts of the tree) gevraschen and dried to give 6.1 g of Dye (4) having a melting point of ^173-0

Dye (4) was readily soluble in water, methanol, or ethanol. The maximum absorption for the dye solution was at a wavelength of 445 nm in water and 447 nm in methanol.

Example 5 Synthesis of the dye (6)

13.8 g of 4-oxy-6-oxo-2-hydroxy-1-methyl-1,6-dihydropyrimidine and 9 g of malonaldehyde dianil were in a mixture of 100 ml Acetic anhydride and 10 ml of glacial acetic acid suspended, heated and refluxed for 30 minutes. The suspended crystals dissolved and the crystals of the dye separated. After cooling in water, the crystals were filtered off and separated, washed with acetone and dissolved in a mixture of 200 ml of methanol and 12 ml of triethylamine. 30 ml of a methanolic egg Solution of 8 g of anhydrous potassium acetate was added; thus the potassium salt of dye 6 was formed.

9i3 "g red powdery crystals were obtained with a melting point of 266 ⁰ C.

Dye (6) was easily dissolved in water and methanol; the maximum absorption of the dye in water was one Wavelength of 513 nm.

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Example 4 Siynthesis of the dye (7)

5.5 g of 4-ithoxy-6-oxo-1-ethyl-2-hydroxy-1,6-dihydropyriinidiri and 16.4 g of 1,1,3,3-tetraethyoxypropane became acetic acid added and heated to a homogeneous solution for 10 min. After cooling the mixture to tree temperature with water were 5 g of triethylamine were added; then -15 was miscarriage Boiled reflux and the solvent filtered off with suction under reduced pressure. The concentrated oily residue was washed with diethyl ether washed and added to 20 ml of methanol to form a solution. To the solution obtained were 20 ml of methanol, in which 3g of anhydrous potassium acetate was dissolved, was added. The separated red dye was treated with an acetone-methanol mixture (1: 1 YoI) and gave 4 g of powder from F = 264 to 267 ° C

The dye was easily soluble in water, methanol and ethanol and the maximum absorption was at a wavelength of 507 µm in water and 5 ^ 1 nm. in methanol.

example Synthesis of the dye (11)

5.5 g of 4-thoxy-1-ethyl-2-hydroxy-6-oxo-1,6-dihydropyrimidine and 4.3 g of glutaconaldehyde dianil chloride were dissolved in a mixture of 40 ml of acetic acid, 10 ml of methanol and 20 ml of triethylamine warmed ^{to 50 to 60 °} C. on a steam bath for 5 h. After cooling, the solution was washed twice with 100 ml of diethyl ether by decantation. 100 ml of diethyl ether were added to the oily residue and the crystals were separated off

709821/1002

chilled in a refrigerator. There were 2.4 g of needle-shaped Crystals of the dye (11) were obtained. F = 215 ° C

The dye was readily soluble in water, methanol and ethanol. The maximum absorption of the dye solution was a wavelength of 614 nm in water and 616 nm in methanol.

Example 6 Synthesis of the dye (14)

3> 7 g of 4-3thoxy-6-oxo-1-ethyl-2-hydroxy-i, 6 ~ dihydropyrimidine and 3 S ρ-Ν, ΪΓ-dimethylaminobenzaldehyde were suspended in a mixture of 50 ml of methanol and 2 g of triethylamine. Then 5 ml of glacial acetic acid was added and the solution was refluxed on a steam bath for 2 hours. The solvent was removed from the reaction solution under reduced pressure. Ethyl acetate was added to the obtained residue for crystallization. 3.8 g of the dye (14) were obtained as a powder. F = 243 to 248 ⁰ C.. .

The wavelength for the maximum absorption of the methanolic Solution was 487 nm. ■

Example 7 Smthesis of the dye

4.6 g of 4-ethoxy-6-oxo-2-hydroxy-1-phenyl-1,6-dihydropyrimidine and 3 »3 g of 2-methyl-4-F, lJ-dimethylaminobenzaldehyde were in dissolved in a mixture of 50 ml of methanol and 3 g of triethylamine.

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- 2S--

10 ml of glacial acetic acid were then added and the mixture was then refluxed for 3 hours. The reaction mixture was concentrated with removal of the solvent under reduced pressure in the α to the concentrated residue for crystallization of acetonitrile.

2.7 g of the dye (15) were obtained as a powder with a melting point 230 to 231 ° C.

The dye was light in water, methanol and ethanol soluble. The wavelength for the maximum absorption in the methanolic solution was 498 nm.

Example 8 Synthesis of the dye (20)

10 g of anhydro-2- (2-anilinovinyl) -3- (3-sulfopropyl) -benzoxazolium hydroxide were suspended in 30 ml of anhydrous acetic acid and the mixture was heated for 5 minutes until a homogeneous solution was obtained. 4.75 g of 4-lthoxy-2-hydroxy-1-methyl-6-0X0-1,6-dihydropyrimidine and 100 ml of ^ f-butyrolactone were then added and the mixture was then heated for 5 minutes. Furthermore, 10 ml of S-triethylamine were added and the mixture was heated directly for 20 minutes. The undissolved substances were filtered off. After cooling, 100 ml of acetone were added and then, with stirring, 50 ml of an acetone solution of 8 g of sodium iodide * - the precipitated crystals were filtered, separated off, washed with acetone and dried. 9 »2 g of the dye (20) with a melting point of 291 to 294 ^° C. were obtained. The dye was readily soluble in water, methanol and ethanol. The wavelength for the maximum absorption of the methanolic dye solution

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was 44-4- run.

Example 9 Synthesis of the dye (21)

5 g of 2- / 2 ^ (N-acetyl-li - piien7l) -aininovinyI7-3-ethylbenzo2cazolium iodide and 2 g of 4-ithoxy ^ -hydroxj-i-methyl-e-oxo-lje-dihydropyrimidine were suspended in 50 ml of ^ -butyrolactone and that Mixture. Heated to a homogeneous solution for -10 min. It 2.3 ml of triethylamine were added and the mixture. 20 min heated for a long time and left to cool. The precipitated crystals were washed with acetone and dried. 1.33 g of dye (21) with a temperature of 263 to 265 ° C. were obtained.

The dye was readily soluble in water, ethanol and methanol and the wavelength for maximum absorption in methanolic solution was 444 nm.

Example 10 Synthesis of the dye (22)

10 g of anhydro-2- (2-anilinovinyl) -3- (3-sulfopropyl) -5-phenylbenzoxazolium hydroxide were suspended in 30 ml of anhydrous acetic acid and the mixture refluxed on an oil bath for 7 minutes cooked. There were 4.1 g of 4-ethoxy-2-hydroxy-1-methyl-6-oxo-1,6-dihydropyrimidine and 100 ml of 'j-butyrolactone added and that Mixture refluxed for 16 minutes. Then 15 ml of triethylamine were added and a further 15 minutes under reflux cooked. After cooling, 700 ml of diethyl ether were added and mixed. The supernatant liquid was decanted

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and the residue dissolved in 50 ml of added acetone. 100 ml of acetone, in which 3 S sodium iodide was dissolved, were added under stretchers, whereupon a precipitate immediately formed formed. The precipitate was filtered, removed and suspended in 300 ml of acetone; this was followed by 15 min refluxed on a steam bath.

There were 7 »1 g of the dye (22) with a melting point of about 300 ° C. The dye easily dissolved in water, methanol and ethanol. The wavelength for the maximum The absorption of the aqueous dye solution was 429 and 44-6 mn.

Example 11 Synthesis of the dye (23)

10 g of 2- (2-anilinovinyl) -3-ethyl-5-phenylbenzoxazolium p-toluenesulfonate were dissolved in 30 ml of anhydrous acetic acid and refluxed with heating for 7 minutes. There were 3.3 g ^ -Thoxy ^ -hydroxy-i-methyl-e-oxo-i, 6-dihydropyrimidine and 100 ml of "J ^ -Bu tyrolact on added and the mixture for 10 min refluxed until a homogeneous solution was obtained. Furthermore, 10 ml of triethylamine were added and for 10 minutes refluxed. After cooling, 500 ml of diethyl ether were added mixed. The supernatant liquid was decanted off and the residue crystallized. The failed dye was filtered off and separated, washed and dried. 6 g of dye (23) with a melting point of 279 to 280 ° C. were obtained.

The dye was readily soluble in water, methanol and ethanol;

982

the wavelength of the maximum absorption of the methanolic Solution was 4-51 nm.

Example 12

Synthesis of the dye (24 x) .

3.5 g of inh7dro-2- (2-anilinovinyl) -3- (3-sulfopropy ^ -benzthiazolium hydroxide were suspended in 50 ml of glacial acetic acid and that Mixture refluxed on an oil bath for 10 minutes. There were 2 g of 4-ithoxy ^ -hydroxy-i-methyl-G-oxo-1,6-dihydropyrimidine and 80 ml of ^ -butyrolactone added and for 10 minutes on Boiled reflux. Then 20 ml of triethylamine were added and refluxed for a further 10 min, the solution was with Chilled water and mixed with 500 ml of diethyl ether. The supernatant liquid was decanted off and 4-0 ml were added to the residue Acetone added, whereupon a homogeneous solution was obtained. 50 ml Acetone in which 1.8 g of sodium iodide was dissolved was added with stirring added, whereupon the dye precipitated. The dye was suspended in 200 ml of acetone; it was placed on a steam bath refluxed and washed. 2.5 g of the dye (24) with a melting point of over 300 ° C. were obtained. The dye easily dissolved in water, methanol and ethanol. The wavelength for the maximum absorption of the methanolic Solution was 4-83 nm.

example S; mthesis of dye (26)

8 g of anhydro-2- (2-anilinovinyl) -1-ethyl-3- (5-sulfopropyl) -5,6-

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dichlorobenzimidazolium hydroxide were made in a mixture 30 ml acetic anhydride, 20 ml glacial acetic acid and 50 ml ^ -butyrolactone suspended, then 3.5 g of ^ -ethoxy ^ -hydroxy-i-methyl-6-oxo-1,6-dihydropyrimidine added and the mixture refluxed on the oil bath for 2 minutes. After adding 15 ml of triethylamine and further refluxing for 15 min Cooled the solution and added 500 ml of diethyl ether with mixing. The supernatant liquid was decanted off and 30 ml of methanol was added to the residue, after which a homogeneous solution was obtained received. There were 10 ml of methanol in which 3 »5 g of sodium iodide was dissolved, after which the dye was added as the sodium salt failed.

5 »3 of the dye (26) with a melting point were obtained from above 300 C. The dye was light in water and methanol soluble. The wavelength for the maximum absorption of the methanolic solution was 4-72 nm.

A particular example of the use of the invention Dye in a photographic photosensitive material is given below.

Comparative example

Conventionally, silver halide grains are made by the single jet method manufactured, physically ripened, desalted and chemically ripened, after which a silver iodobromide emulsion is obtained (Iodide content: 8.5 mol%). The average diameter the silver halide grains in the emulsion were 0.7 microns. In 1 kg of emulsion there were 2.5 mol of silver halide. 1 kg emul

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sion was placed in a container and melted at a constant temperature bath at 50 ⁰ C. A methanolic solution of the dye (21) according to the invention was added in the amount shown in Table 1 and mixed at 4-0 ° C. with stirring. 10 ml of a 1% by weight aqueous solution of ^ -hydroxy-e-methyl-i ^^ a ^ -Tetrazaindene, 10 ml of a 1% by weight aqueous solution of 1-hydroxy-^, 5 dichlorotriazine, sodium salt and 10 ml of a 1% strength by weight aqueous solution of sodium dodecylbenzenesulfonate were added with stirring. The emulsion thus prepared was coated in a shaft shape on a gelulose tetra acetate film to a dry thickness of 5 microns, dried to give a sample of the photosensitive material. The film sample was cut into strips. Each strip was through an optical wedge to a sensitometer with a light source having a color temperature of 5400 ⁰ K (and with a yellow filter (SC-50, manufactured by Fuji Photo Film Co., Ltd.) and a blue filter Wratten 4-7B manufactured by Eastman Kodak Co., Ltd.) was exposed.

.Anschließend was developed in sequence at 20 ⁰ C for 7 min using a developing solution of the composition indicated below, stopped and fixed gexvaschen with water to a strip with the desired receive monochrome images. The density was measured using a p-type densitometer (manufactured by Fuji Photo Film Co., Ltd.); the values for yellow sensitivity (Sy), Eot sensitivity (StJ, blue sensitivity (Sg) and haze were obtained in this way.

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The sensitivity was determined based on the point the characteristic curve where the density is 0.20 above the Veil fraud.

Composition of the developer solution

Water 700 ml

H-methyl-p-aminophenol sulfate 2 g

Sodium sulfite (anhydrous) 100 g " ^s .

Hydroquinone '5 S

Borax (pentahydrate) 1.5 g

Water on .11

The results obtained are given as relative values in Table 1. '

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Table 1

Try dye and amount Sy Sg veil

⁵ ((i

g y g

~ ⁵ Mo-η (relative (relative noi;))

Mo-η noi;

((Value) value)

100 00 0.04

Dye (21) 16 I30 96 0.04

"32 1 ^ -2 96 0.04

"48 148 90 0.04

The sensitivity (Sy) is the relative sensitivity, with Sy of the original emulsion being taken as 100.

From the results in Table 1 it is clear that the emulsion with the colors according to the invention compared to the original emulsion of "Experiment No. 1 a pronounced spectral sensitization shows. . .

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Claims (1)

2651o83 Claims SS Sä SSSS SS SSSSSS w SS SSSS SS SSSS SSSSSSSSSSSSSS ^- SSSSSSSSsS 1. Dye with a pyrimidine core of the general formulas (I), (II) or (III) OR ' N-C R ^x O OR ² O = CC = (LL ¹ N-C R ^X O 0R ^£ C = N C C C = O C - N 6th 1 W —— Ί OR * N = C O = C C = (L-L ') = C- (CH = CH) -N-R' \ / η Ρ NC R- ¹ O (D (ID (III) 709821/1002 ORIGINAL! MSPSCTED in which R is an aliphatic hydrocarbon, aromatic 2 hydrocarbon, aralkyl or acyl group; R is an aliphatic hydrocarbon or aralkyl group; Br and R, which may be the same or different, each represent an aliphatic hydrocarbon, aromatic hydrocarbon or aralkyl group; R and R, which can be the same or different, are each hydrogen, halogen, an aliphatic hydrocarbon substance, an alkoxy or an acylamino group; R is an aliphatic hydrocarbon, aromatic hydrocarbon, or aralkyl group; W a grouping of spruce metal atoms necessary to complete a 5- or 6-membered heterocyclic ring; L and L ¹ each represent a methine group; 1 0, 1 or 2; and m, η and ρ each represent 0 or 1. 2. dye according to claim 1, characterized in that that E is an optionally substituted alkyl group having 1 to 8 carbon atoms, an alkenyl group, monocyclic ^ or bicyclic aryl group, aralkyl group with 7 to 10 carbon atoms, an aliphatic carboxylic acid acyl group, an aromatic carboxylic acid acyl group, an aliphatic sulfonic acid acyl group or an aromatic sulfonic acid acyl group. 5- dye according to claim 1 and / or 2, characterized in that - indicates that E is an optionally substituted one Denotes an alkyl group having 1 to 6 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. 4. dye according to at least one of claims 1 to 3, characterized in that 'S? and R, respectively 709821/1002 an optionally substituted alkyl group with 1 to 6 carbon atoms, an optionally substituted aralkyl group having 7 to 10 carbon atoms or an optionally substituted aryl group with 6 to 10 carbon atoms. 5. Dye according to one of claims 1 to 4-, characterized in that ΈΡ and E each denote hydrogen, halogen, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms or an optionally substituted acylamino group with 2 to 6 carbon atoms . 6. Dyestuff according to one of claims 1 to 5, characterized in that g e- mark ei chnet that R 'is an optionally substituted one Denotes an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. 7 · Dye according to one of Claims 1 to 6, characterized in that it is marked chnet that W to form a thiazole, benzothiazole, oxazole, benzoxazole, haphthoxazole, selenazole, '' Benzoselenazole Naphthoselenazole, thiazoline, 2-quinoline, 4-quinoline, 1-isoquinoline, 3-isoquinoline, 3 * 3'-dialkylindolenine or pyridine ring means atomic group required. 8. Dye according to one of claims 1 to 7 »characterized in that L and L ¹ each have an unsubstituted 709821/1002 265-683 tuted or with an alkyl group with 1 to 4 · carbon atoms mean substituted methyl group. 9 · Dye according to one of claims 1 to 8, characterized in that - ρ
indicates that E represents an unsubstituted alkyl group, a halogen-substituted alkyl group, a sulfo-substituted alkyl group or an aralkyl group. 10. Dye according to any one of claims 1 to 9 * marked that E is an unsubstituted Means alkyl group or unsubstituted aryl group. 11. Dyestuff according to one of claims 1 to 10, characterized in that Br and E each represent an optionally substituted alkyl group. 12. Dye according to one of claims 1 to 11, characterized in that B. is hydrogen. 13. Dye according to one of Claims 1 to 12, characterized in that R is hydrogen and E is hydrogen or an alkyl group. 14-. Dyestuff according to one of Claims 1 to 13 , characterized. η indicates that E ^{r is} a possibly means substituted alkyl group. 709821/1002 15 · Dyestuff according to one of the. Claims 1 to 14 ·, characterized in that W is used to form a
Thiazole, benzothiazole, oxazole, benzoxazole, naphthoxazole, benzoselenazole, thiazoline, 2-quinoline, 4-quinoline or pyridine ring means the atom grouping necessary. 16. Dye according to one of claims 1 to 15j characterized in that H is an unsubstituted one Means alkyl group. 17 · Dye according to any one of claims 1 to 16 * 7th
characterized in that E 'is an unsubstituted one Denotes an alkyl group or a sulfoalkyl group. 18. Dye according to one of claims 1 to 17 »thereby π
marked that E ^{r is} an unsubstituted one Means alkyl group. 19. Dye according to one of claims 1 to 18, characterized characterized in that L and L 'each represent an unsubstituted methine group. 20. Dye according to claim 1, characterized by one of the following general formulas: 709821/1002 N
O = C • OC ₂ H ₅ . OC ₂ H ₅ = 6 , C = N C = CH - ^N o = o - C C-N CH- HO CH- OC ₂ H ₅ 0C ₀ Hc γ d O O = C • C = CH C ₂ H ₅ O - C W / ^c KO ) = 0 C ₂ H ₅ N = OC ₂ H ₅ O _n C ₂ H ₅ C .C = N O = C = CH - C _x C = O - C HO OC ₂ H 2 "5 = C CH - 709821/1002 , A ° v ^C 2 ^H 5 N = C C = N / \ / \ O = C C = CH-CH = CH-C C = O - C CN CH ₃ 0 KO CH ₃ r \ n τι ηπ τι OC ₂ H ₅ OC ₂ H ₅ / ^Ν = ^C N F '\ O = C C = CH-CH = CH-C C = O N - C _v CN C ₂ H ₅ O KO C ₂ H ₅ O = C
\ OC ₂ H ₅ C = CH-CH = CH-CH = CH-C N-C \ 2 C = O HO ^C 2 ^H 5 N = C OCH- / 3rd OCH \ C C ₂ H ₅ O HO C ₂ H ₅ O = CC = CH - // ^X ) -N CH. 709821/1002 O = C N - OC
/ 0 2 ^H 5. / CH N = s, - // \\ -N ° C = CH - // \) "^ CH- / V- / 3 C. } ■ CH ₃ OC ₂ H ₅ f ⁼ O = C N / CH ^c \ C = CH C W N = C OCH-, / 3 CH ₂ CH ₃ CH ₂ CH ₃ -CH- U V-cnJ / Vn " ³ N-C / ^ CH- CH ₂ CH ₂ Cl N = C 0 / = C VcH - // '' Vn " ³ Z / ^ CH ₂ CH ₂ SO ₃ Na CH ₃ 0 O = C N = C CH- NC /
CH ₃ C = CH-CH = CH - // Λ-Ν \ - / ^ CH 709821/1002 OC ₀ H ₁ - / 25 O = C = C = CH-CH = CH ₃ \> / 25. N - O _x O = C C = CH-CH Λ-V / W CH-> 0 N
O = C N
/ ■ = CH-CH -C CH ₃ 0 "N- (CH ₂ KSO ₃ Na C ₂ H ₅ (CHg) ₃ SO ₃ Na / 2 "5 O = C C = CH-CH = K \H 709 821/1002 OC ^ H O = C N = OC ₀ H ₁ -
d ⁵ \ _N ^ 5 / \ / (CH ₂ I Τ O = C
N - C = CH-CH = <\
C. /
CH ₃ \ > 3 ^S °: ^ CH • Ss,
cn .N / A 709821/1002