JPS6012375B2 - Production method of bisanyl dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing yellow to blue bisanyl disperse dyes from diaminomaleonitrile.

Monocondensation products of diaminomaleonitrile and various aldehydes are known in the art.

Journal of the Japanese Society of Agricultural Chemistry, 3ran 21, 167-72 (1962
) (Onoda) has the formula ~1CH=N-C(CN)=C(CN)-N of diaminomaleonitrile and aldehyde.
H2 where Ar is phenyl, p-dimethylaminophenyl or furfuryl.

discloses a yellow monocondensation product of

J. Am. Chem. S.M. , 80, 2691 (195
8) Ro is rbon and Va Zhuhan) discloses yellow monocondensation products in the above formula where ~ is p-hydroxyphenyl, p-nitrophenyl or cinnamyl. It was reported that an attempt to introduce an additional 1 mole of the same aldehyde was unsuccessful, and that an attempt to introduce 1 mole of a different aldehyde into the monoanil (Schiff base) resulted in loss of aldehyde residues in the original derivative. A substitution has occurred. Such substitutions are more likely to occur when the second aldehyde has a carbonyl carbon atom that is highly electron deficient, such as p-nitrobenzaldehyde > penzaldehyde > p-hydroxybenzaldehyde (order of decreasing ease of substitution). . J. Chem
．． S.M. , 1432 (1937) (Hinkeieta
l) in the above formula, ~ is phenyl, p-anisyl,
Yellow monocondensation products that are salicyl or m-bromosalicyl are disclosed. The usefulness of monoadducts of diami/monomaleonitrile and aldehydes as dyes for synthetic fibers, especially polyester fibers, is not described in any of the above-mentioned documents. US Patent 22006
89 is a method of combining diami/maleonitrile with 1,2-dicarbonyl compounds such as diacetyl, glyoxal, benzyl, orthobenzoquinone, acenaphthenequinone, thionaphthenequinone, phenanthrenequinone and aceanthrenequinone at about 100-300°C. solvent,
Heterocyclic pyrazinocyanine pigment dyes obtained by condensation in the presence of pyridine and metal salts are disclosed.

This dye is further described for its excellent wax fastness.
J,Chem,SoC. 911 (1937) (Li ship teadetal) describes various phthalocyanine pigments whose color changes from blue to green as the molecular weight increases, and these pigments have the formula where R is day, C melon or phenyl. , by treating 2,3-dicyanopyrazine with a copper salt.

The 2,3-dicyanopyrazine can be prepared by condensing diaminomaleonitrile with glyoxal, diacetyl and penzyl, respectively. New and better dyes are being sought for use in current and newly developed dye systems and nut dye systems, and for use in textiles, blended fibers and fabrics.

For example, the fabric may be subjected to a post-treatment (post-dying) step such as the application of a permanent press resin composition to impart particularly desirable properties to the dyed fabric.
Dyes that combine sharpness of shade and high dyeability with good applicability and waxiness are particularly useful in such systems. Brightly colored dyes are more attractive than dull colored dyes and offer greater flexibility in preparing dye products of mixed shades. Commercially available disperse dyes used in polyester and other synthetic and semi-synthetic fibers tend to exhibit rather dull colors. Bright disperse dyes now suffer from poor photofastness, high cost, or both. It is an object of the present invention to provide yellow to blue disperse dyes. Another object of the present invention is to provide dyes which exhibit outstanding color sharpness and high dye strength and which are generally opalescent, luminescent and considerably more vivid than known existing disperse dyes. Yet another object of the present invention is to provide disperse dyes for use in polyester and polyester-cellulose blend fibers that have acceptable light fastness and sublimation fastness properties. Yet another object of the invention is to provide economically attractive dyes derived from low cost starting materials. Yet another object is to provide various methods for producing such dyes. According to the invention, the formula ~, -CH=N-C(CN)=C(C
N)-N=CH-F2 [In the above formula, ~ and ~2 are each independently [1] a penzo (5- and 6-membered) polycyclic group having one nitrogen atom as a heteroatom , ■ A 5-membered double cyclic group having one oxygen atom or one sulfur atom as a heteroatom, or one sulfur atom and one nitrogen atom as a heteroatom (in this case, these Double cyclic group [11 and (2} are halogen, C,
It may have a substituent selected from -4 alkyl and (C, -4 alkyl)2N-.

)'31 (C,-4 alkyl)2N-1-naphthyl group optionally substituted with a hydroxyl group, and '
[4--NQ, halogen, -CN, C,-4 alkyl, C,-4 alkoxyto -OH, -NHCOC, -
A phenyl group optionally having a substituent selected from 4 alkyl and -NR, R2 (where [a} R is C, -4 alkyl or C, -4 alkylene-R3, and L[b) R2 is C. 4 alkyl, C,
4alkylene-R4 or -CH2CH(OCONHC
6 days 5) CH20C 6 days 5 and 'c) R3 is -CN
, -COOC,4 alkyl or -OCOC6day5 and [d-R4 is -CN, -COOC,4alkyl or -OCOC6day5.

) was selected from.

] A method for producing a bisanyl dye is provided.

Bisanyl dyes of the above formula exist in two isomeric forms, the cis configuration and the trans configuration.

Moreover, this dye is either symmetric (~, and A are the same) or asymmetric (Ar, and Ar
2 are different). This dye can be prepared by condensing diaminomaleonitrile with aldehydes, CHO, and CHO as described below.

The invention also relates to other processes for producing symmetrical and asymmetrical cis and trans anil dyes as defined above. Diaminomaleonitrile is US Patent No. 24994
41, HCN can also be produced in low yield by base-catalyzed tetramerization of HCN;
It is called an N-tetramer.

Tetramerization of HCN to diaminomaleonitrile also occurs in the presence of a catalytic amount of a basic catalyst and at least one cocatalyst diminosuccinonitrile or cyanogen, as shown in U.S. Pat. No. 3,629,318. . Non-pu. catalyst in a ton solvent, e.g. dimethyl sulfoxide,
Tetramerization of HCN at atmospheric pressure in the presence of sodium cyanide, for example, produces diaminomaleonitrile by an alternative route, as shown in U.S. Pat. No. 3,704,797, and such operations are also
972 King July 12th issue page 36 and EmopeanCh
It is described on page 20 of the March 2, 1973 issue of ``Emical News''. Furthermore, diaminomaleonitrile is tJ. ○rg. Chem-37 4133 (1972
) can be prepared from diminosuccinonitrile obtained in high yield by base-catalyzed addition of HCN to cyanogen. Diminosuccinonitrile is known for its HC
By reaction with N, it can be converted to diaminomaleonitrile using chemical reagents. Additionally, diaminomaleonitrile can be prepared by reacting diminosuccinonitrile with hydrogen in the presence of a family transition metal hydrogenation catalyst as shown in US Pat. No. 3,551,473. This yellow to blue asymmetric bis-anyl disperse dye can be prepared by condensation of 1 mole of diaminomaleonitrile with 1 mole of each different aryl aldehyde Ar, CHO and ~2CHO.

Symmetrical bisanyl dyes can be prepared by condensation of 1 mole of diaminomaleonitrile with 2 moles of a single aryl aldehyde. Substituted aljaldehydes, CHO and/or Ar2, useful in the production of bisanyl dyes
Examples of CHO are shown in Table 1.

Table 1 4-[N-N-pis(methyl)ami/]penzaldehyde 4-bromo-2,5-diisopropylbenzaldehyde 4-[N-N-bis-(n-propyl)ami/]-2
-Methylbenzaldehyde 6-formyl-N-(methyl)-2,2,4,7-tetramethyl-112,3,4-
Tetrahydroquinoline 5-bromothiophene-2-carboxaldehyde 4-[N-ethyl-N-(2-methoxycarbonylethyl)amino]-2-methylbenzaldehyde 4'-[N-(2-butoxycarbonylethyl)
1N-ethylamino]-2'-methylbenzaldehyde 4-ethylcarbonylamidebenzaldehyde N-methylindole-3-carpoxyaldehyde 4-thiomethoxybenzaldehyde 4-thione n-butoxybenzaldehyde 4-methoxynaphthaldehyde 4-phenylsulfonylbenzaldehyde 4-Methylsulfonylbenzaldehyde 4-Thio(2-hydroxyethoxy)penzaldehyde Penzaldehyde 4-(N-cyanoethyl-N-methylamino)penzaldehyde 4-Chlorobenzaldehyde 2,6-dichlorobenzaldehyde 2-Nitrobenzaldehyde 3-Nitrobenzaldehyde 4- Nitrobenzaldehyde 4-[N-N-bis(ethyl)amino]penzaldehyde 4-[N-N-bis(ethyl)amino]-2-hydroxybenzaldehyde 3-hydroxybenzaldehyde 2-hydroxybenzaldehyde 4-hydroxybenzaldehyde 4-[N- Cyanoethyl-N-ethylamino]12-methylbenzaldehyde 41 [N・N-bis(hydroxyethyl)amino]penzaldehyde 41
N・N-bis(propyl)ami/penzaldehyde 3
-00-4-hydroxy-5-methoxybenzaldehyde 4-chloro-3 nitrobenzaldehyde 5-chloro-2 nitrobenzaldehyde 3,4-dibenzyloxybenzaldehyde 3,5-dibromosalicylaldehyde 3,5-di-t-butyl-4 -Hydroxybenzaldehyde 4'-[2-(diethylamino)-ethoxy]
Penzaldehyde 2.5-dihydroxybenzaldehyde 3.4-dihydroxybenzaldehyde 213-dimethyl-4-methoxybenzaldehyde 2.
5-dimethyl-4-methoxybenzaldehyde 214-dimethylbenzaldehyde 2,5-dimethylbenzaldehyde 2-ethoxybenzaldehyde 4-ethoxybenzaldehyde 3-ethoxy 4-hydroxybenzaldehyde 4-cyanobenzaldehyde 4-acetoxybenzaldehyde 2-methoxybenzaldehyde 3-methoxybenzaldehyde Do 3 -penzyloxybenzaldehyde 4-benzyloxybenzaldehyde 4-biphenylcarboxaldehyde 5-bromo-2-methoxybenzaldehyde 2-bromobenzaldehyde 3-promobenzaldehyde 5-bromosalicylaldehyde 5-promovanillin [5-bromo-4-hydroxy-3
-Methoxybenzaldehyde] 5-bromo-3,4-dimethoxybenzaldehyde 6-bromo-3,4-dimethoxybenzaldehyde 2-(2-chloroethyl)penzaldehyde 2-chloro6-fluorobenzaldehyde 4-ethoxy-3-methoxybenzaldehyde 3-ethoxysalicil Aldehyde 3-fluoro-4-methoxybenzaldehyde 3-fluorobenzaldehyde 4-fluorobenzaldehyde 3-hydroxy-4-methoxybenzaldehyde 2-hydroxy-4-methoxybenzaldehyde 2-hydroxy-5-methoxybenzaldehyde 4-hydroxy-3
-methoxybenzaldehyde (vanillin) 2-hydroxy-1-naphthaldehyde 3-hydroxy-4 nitrobenzaldehyde 4-hydroxy-3 nitrobenzaldehyde 5-hydroxy-
2-Nitrobenzaldehyde 2,4,6-trimethylbenzaldehyde (mesitaldehyde) 2-methoxy 1
Naphthaldehyde 4-methoxy 1-naphthaldehyde 3-methyl-4-methoxybenzaldehyde 4-hydroxy-3-methoxy-5-nitrobenzaldehyde (5
Nitrovanillin) 3,4-dimethoxy-6-nitrobenzaldehyde 2-methylbenzaldehyde 3-methylbenzaldehyde 4-methylbenzaldehyde 2,4,6-triethoxybenzaldehyde 2,3,4
-trimethoxybenzaldehyde 3,415-trimethoxybenzaldehyde 214,6-trimethoxybenzaldehyde 3,4,5-trimethoxybenzaldehyde 5-furomothioquine-2-rupoxyaldehyde 2-furaldehyde 5-methoxyindole-3-carboxaldehyde 5
-Methyl-2-furaldehyde 5-methylindole-3-carboxaldehyde 6-Methyl-2-pyridinecarboxaldehyde N-methylpyrrole-2-carboxaldehyde 3-methyl-bisanthiophenecarboxaldehyde 5-methyl-2-thio Phencarboxaldehyde 2-Pyridinecarboxaldehyde 3-Pyridinecarboxaldehyde 4-Pyridinecarboxaldehyde Pyrrole-2-Carboxaldehyde 3,5-Dichlorobenzaldehyde 204-Dichlorobenzaldehyde 314-Dichlorobenzaldehyde 4-[N·N-bis(ethyl)amino] -2-methylbenzalte'hyde 2-chloro5-nitrobenzaldehyde 2-chloro6-nitrobenzaldehyde 2,4-
Dinito-benzaldehyde 206-Dinito-benzaldehyde 2-acetamido 4-[N・N-bis(ethyl)amino]penzaldehyde 2-acetamido 4-[N'N
-bis(ethyl)amino]-5-methoxybenzaldehyde 2-benzamide 4-[N・N-bis(ethyl)
Amide] penzaldehyde 3-cyanobesozaldehyde indole-3-carboxaldehyde thiophene-2-carboxaldehyde quinoline-2-carpoxyaldehyde 4'-[N-(2-acetoxy-3-phenoxypropyl)-N -ethylamino]-2-methylbenzaldehyde 4'-[N-(2-benzoyloxy-3-phenoxypropyl)-1N-ethylamino]-2'-methylbenzaldehyde 2,5-dimethoxybenzaldehyde 2,4-dimethoxy Benzaldehyde 3,4-dimethoxybenzaldehyde 2-fluorobenzaldehyde 305-dimethoxybenzaldehyde 2-trifluoromethylbenzaldehyde 4-[N-cyanoethyl-N-n-propylamino]penzaldehyde 4-[N'N-bis(isopropyl)amino]benzaldehyde 4- [N・N-pis(n-butyl)amino]penzaldehyde 4-[N・N-bis(n-butyl)
Amino]-2-methylbenzaldehyde 1-naphthaldehyde 2-naphthaldehyde 4-promobenzaldehyde 4-[N·N-bis(methyl)amino]naphthaldehyde 4-[N·N-bis(ethyl)amino]naphtho Aldehyde 4-[N-cyanoethyl-N-ethylami/]naphthaldihyde 4-[N-ethylami/]naphthaldehyde[N-ethyl-N-(2-phenylcarbamoyloxy-3-phenoxypropyl)amino-methylbenzaldehyde 4-] [N-benzoyloxyethyl-N-ethylamino]penzaldehyde 4-[N-penzoyloxyethyl-N-thia/ethylamino]penzaldehyde 4-[N-cyanoethyl-N-propionyloxyethylamino]penzaldehyde 4-methoxybenzaldehyde 3- Chlorobenzaldehyde 2-chlorobenzaldehyde 4-[N-cyanoethyl-N-ethylamino]penzaldehyde 2-chloro-4-[N·N-bis(ethyl)amino]penzaldehyde 2-chloro4-[NON-bis(methyl)amino] Penzaldehyde 4'1 [N・N
-bis(2-chloroethyl)amino]penzaldehyde 4'-[N'N-bis(2-azetoxyethyl)amino]penzaldehyde 4'-[N.N-bis(2-acetoxyethyl)amino]-2'-penzamidebenzaldehyde 4'-[N. N-bis(2-butyloxyethyl)amino]penzaldehyde 4'-[N・N-bis(
2-acetoxyethyl)amino]-2'-acetamidobenzaldehyde 4-[N-cyanoethyl-N-hydroxyethylamino]penzaldehyde 4-[N-cyanoethyl-1-phenethylamino]penzaldehyde 4'
1[N・N-bis(2-valerylethyl)ami/]penzaldehyde 4'-[N-cyanoethyl-N-(2-phenoxycarponylethyl)ami/]penzaldehyde 4'-[N-(2-acrylic oxyethyl)-1N-cyanoethyl-amino]penzaldehyde 4'-[N-(
2-Ptoxycarponylethylamine/]-2-chlorobenzaldehyde 4'-[N-(2-methoxycarbonylethyl)amino]naphthaldehyde 4'-[N-(2-butoxycarbonylethyl)amino]naphthaldehyde 4- [N・N-pis(ethyl)amino]-2-ureidobenz alde'hyde 4'-[N-benzyl-N-(3
-cyanopropyl)amino]-2-ureido-penzaldehyde 4'-{N-[2-(3-dimethylaminophenoxycarponyl)ethyl]-N-ethylami/}penzaldehyde 4'-{N-[2-(3・5-Dichlorophenoxycarbonyl)ethyl]amino}-penzaldehyde 2-acetamide-4'-{N-[2-(4-methoxyphenoxycarbonyl)ethyl]amino}-penzaldehyde 4'-{N-[ 2-(2-Methyl-4-methoxyphenoxycarbonyl)ethyl]-N-methylamino}penzaldehyde 4'-{N-[2-(2-chlorobenzoyloxy)ethyl]-N-methylamino}penzaldehyde 4' -{N-ethyl-N-[2-(4-nitrobenzoyloxy)ethyl]-ami/}penzaldehyde 4'-{N-[2-(4-acetamidobenzoyloxy)ethylamino}penzaldehyde 2'-acetamide 4'-{N-[2-(2-chloro4-nitrobenzoyloxy)ethyl)-N-ethylamino}penzaldehyde 4'-{N-[3-(4-bromobenzoyloxy)propyl]amino}penzaldehyde 4 -{N-[2-(2-Methyl-3-nitrobenzoyloxyethoxycarbonyl)ethyl)amino}penzaldehyde4'-{N-[2-(4-methoxybenzoyloxyethoxycarbonyl)propyl]amino}penzaldehyde 4'-{N-[2-(3-cyanobenzoyloxyethoxycarbonyl)ethyl]amino}penzaldehyde 4'-{N-[2-(2-methylbenzoyloxyethoxycarbonyl)ethyl]amino}penzaldehyde 2 -Chloro-4'-{N-[2-(propionyloxyethoxycarbonyl)ethyl]amino}penzaldehyde 4'-{N・N-bis[2-(butyryloxyethoxycarbonyl)ethyl)amino}penzaldehyde 4-{N-[2-(benzoyloxyethoxycarbonyl)ethyl]-N-methylamino}penzaldehyde 4
1 (N-cyanoethylamino) 1 3-n-butylbenzaldehyde 4 1 [NON-bis(ethyl)amino] 1 2
-(3-methoxypropionamide)penzaldehyde 2-acetamide 4-(N-cyanoethyl-N-ethylamino)penzaldehyde 2'-butylamide-4'
-[N-cyanoethyl-N-(2-methoxycarbonylethyl)amino]penzaldehyde 2-(3-chloropropionamide)-4'-[N-phenethyl-N-propylamide]penzaldehyde 2-acetamide-[N -(2-Methoxycarbonylethyl)amino]-6-methoxybenzalde'hyde 4'-[N.N-bis(ethyl)amino/]15'-methoxy-2'-(3
-methylbenzamide)penzaldehydemechloroacetamide-4'-[NqN-bis(ethyl)amino]
-6-methoxybenzaldehyde 2-(3-chlorobutyramide)-47-[NON-bis(cyaethyl)amino]-5-methoxybenzaldehyde 2-acetamide 4'-[NON-pis(2-acetoxyethoxycarbonylethyl)] Amino]-5'-methoxybenzaldehyde 4'-[N.N-bis(2-acetoxyethyl)amino]-di(2-chlorobenzamide)-5-methoxybenzaldehyde 2-acetamide 4'-[N-(
2-acetoxyethyl)-N-cyanoethylamino]-5-methoxybenzaldehyde 4'-[N-cyanoethyl-N-ethylamino]-5-methoxy2-(4nito-benzamide)penzalde Jhyde 4'-[N-(
2-methoxycarbonylethyl)-N-methylamino]
Penzaldehyde 4'-[NGN-bis(2-acetoxyethyl)amino]-2-methylsulfonamide benzaldehyde 4-[N-(2-acetoxyethyl)-N-
Cyanoethylamino]-2-phenylsulfonamidebenzaldehyde 4'-[N-N-bis(2-acetoxyethyl)amino]-5-methoxy-dimethylsulfonamidebenzaldehyde[N-ethyl-N-(2 −
succinimidoethyl)amino]-2'-methylbenzaldehyde 4'-[N-ethyl-N-(2-phthalimidoethyl)amino]-2-methylbenzaldehyde 4'
-[N-cyanoethyl-N-(2-succinimidoethyl)amino]-methylbenzaldehyde 4-[N-ethyl-N-(2-glutarimidoethyl)amino]-dimethylbenzaldehyde 6-formyl-N-(B-
phenylcarbamoyloxyethyl)-2・20407
-Tetramethyl-1.21304-Tetrahydroquinoline 6-formyl-N-cyanoethyl-212 x 407-
Tetramethyl-102,314-tetrahydroquinoline-6-formyl-N-(3-acetoxyethyl)-2o2
8417-tetramethyl-1120314-tetrahydroquinoline 6-formyl-N-(8-penzoyloxyethyl)-2,2,4,7-tetramethyl-1,2,3
・4-tetrahydroquinoline 4'-[N. N-bis (2
-cyanoethylethoxyethyl)amino]methylbenzaldehyde 2'-acetamide 4'-[N-(2-cyanoethylethoxyethyl)-N-ethylamino]penzalde Jhyde 4-[N-ethyl-N-(2-methylsulfonylethyl)amino] /] 2-Methylbenzaldehyde 4-[N-cyanoethyl-N-(2-phenylsulfonyl)amino]penzaldehyde 4'-[N-cyanoethyl-N-(2-methoxyethylamine/)penzaldehyde-[N-ethyl-N-] (2-propionoxyethyl)amino]-2'-methylbenzaldehyde indole-2-carboxaldehyde N-ethylindole-3-carboxaldehyde N-(2-acetoxyethyl)indole-3-carboxaldehyde thianaphthene-2-carpoxy Aldehyde thianaphthene-3-carboxaldehyde 4,5-dibromothiophene-2-carboxaldehyde 4-bromothiophene-2-carboxaldehydethiophene-3-carboxaldehyde 5-[N-N-bis(ethyl ) Ami/] Indoru 3
- Ruboxyaldehyde 51 [N. N-bis(ethyl)
Amino]thiophene-2-carboxaldehyde 5-[
N・N-bis(methyl)amino]-1,3,4-thiadiazole-2-carboxaldehyde 5-[N・N-bis(ethyl)amino]-1,4-thiazole-2-carboxaldehyde 4-bromofuran-2-carboxy Aldehyde Pyridine-N-Oxide 3-Carboxaldehyde The aldehydes described above are either commercially available or prepared using well-known prior art procedures, such as Vilsmeier, using dimethylformamide, phosphorous oxychloride and the appropriate substituted aryl compound. (Vilsme
ier) reaction.

Furthermore, aryl aldehyde has a sulfonic acid group (SQH)
When condensed with diaminomaleonitrile as described above, it produces an acid dye which is important for use on nylon. Same machine, basic group (one☆
(Alkyl) 3) can be added to produce enteric ionic dyes that are important for polyacrylonitrile, acid-modified polyester and polyamide fibers. Symmetrical dyes, i.e. bisanyl dyes in which ~ and ~2 in the above formula are the same, have 1
50 to 150 moles of diaminomaleonitrile and 2 moles of aryl aldehyde in an organic solvent in the presence of an acidic catalyst.
It can be prepared in one step by condensation at 0.00 and at the same time continuous removal of the water formed during the reaction by azeotropic distillation or by the action of a dehydrating agent, such as phosphorus pentoxide or dimicrohexylcarbodiimide. Preferred catalysts for this condensation are, for example, sulfuric acid, polyphosphoric acid and p-toluenesulfonic acid. Organic solvents such as acetonitrile, tetrahydrofuran, dimethylformamide, hexamethylphosphoramide, dimethylacetamide, tolueso, xylene, benzene and monochlorobenzene are equally useful. After cooling the reaction mixture to room temperature,
The precipitated pisanyl dye can be isolated by filtration. 2 moles of 4-[N.N-bis(ethyl)amino]penzaldehyde and 1 mole of diaminomaleonitrile are mixed in hexamethylphosphoramide containing sulfuric acid as catalyst in the presence of phosphorus pentoxide for 6 hours. Removal of the water of reaction by condensation over a period of time produces a bright poppy, luminous red cis-supis-anyl dye with the structure N.N'-{41 [N.N-pis(
ethyl)amino]penzylidene}diaminomaleonitrino is obtained.

The cis configuration with respect to the central carbon-to-carbon double bond is evidenced by the observed large polar moment (14.B) of this dye. This result is from J. Am. Chem. S
oc. ,? 7, 3491-3 (1955) (Webbe
A good correlation is reached with the large dipole moment of diaminomaleonitrile, as reported in tal). Depending on the rotation of the amino group, a very small dipole moment is predicted for the trans configuration. In general, the cis symmetric bisanyl dyes produced by the aforementioned method are
Upon recrystallization from dimethylformamide, acetonitrile or nitromethane, it isomerizes and/or partially hydrolyzes to produce a mixture of cis and trans symmetric bis-anyls and a yellow monoanyl. A one-step process useful for making symmetrical bisanyl dyes involves combining at least about 2 moles of aryl aldehyde and 1 mole of diaminomaleonitrile in glacial acetic acid at about the boiling temperature of the acid.
It consists of condensation for a certain period of time.

This method yields a thermodynamically more stable trans isomer with the structure. Small dipole moment of this product3. supports this structure. Generally reaction times of up to about 4 hours at 115-120'0 are suitable to obtain substantially the trans isomer. Upon cooling to room temperature, the trans-bisanyl crystallizes and can be isolated from the acid medium. This operation yields 60-7
At 5%, highly pure symmetrical trans-pisanyl is obtained.
A similar result is obtained by condensing 1 mole of monoanyl of diaminomaleonitrile with 1 mole of aryl aldehyde under conditions similar to those described above.

Asymmetric bisanyl dyes, i.e. bisanyl dyes prepared from diaminomaleonitrile and two different aldehydes, are produced by monocondensation of 1 mole of a primary aryl aldehyde and 1 mole of diaminomaleonitrile to form a yellow monoanyl enigma. This allows for step-by-step manufacturing.

The mo/condensation reaction is preferably carried out in an organic solvent such as tetrahydrofuran, acetonitrile or benzene at the boiling point of the solvent in the presence of an acid catalyst such as sulfuric acid for up to about 4 hours. The resulting yellow monoanyl (1 mole) is then treated with 2 moles of different arylaldehyde's in an organic solvent in the presence of a secondary or tertiary amine catalyst and simultaneously subjected to a condensation reaction, in which the resulting water is co-condensed. Remove by boiling distillation. Preferred amine catalysts are piveridine and triethylene diamine. Condensation does not occur in the absence of a catalyst. Examples of useful organic solvents are monochlorobenzene,
Acetonitrile, dimethylformamide, isopropanol, dichloroethane, toluene and benzene, with benzene being the most useful. As an example of stepwise condensation, diaminomaleonitrile (1 mol) is converted into 4-[N・N-
Bis(ethyl)amino]penzaldehyde (1 mol) and 60-65'0 in tetrahydrofuran in the presence of sulfuric acid.
condensation for 3 hours at a high yield, e.g.
90% of yellow monoanyl N-{4-[N·N-bis(ethyl)amino]penzylidene}diaminomaleonitrile is obtained. This intermediate monoanyl has inherent disadvantages in use for polyesters when compared to bisanyl. Also, the monoanyl generally does not exhibit the fluorescence and sharpness characteristic of bisanyl derivatives of diaminomaleonitrile. Subsequent condensation of the aforementioned monoanyl (1 mol) and 2 mol of 4-chlorobenzaldehyde in the presence of a catalytic amount of piveridine at 75-80 qo and continuous azeotropic distillation of water over a period of 6 hours yields a solvent. After removing , trans asymmetric bisanyl N-{4-[N·N-bis(ethyl)amino]penzylidene}-N'-(4-chlorobenzylidene)diami/maleonitrile with the structure was obtained in 40-50% yield. can get.

When the amount of basic catalyst is less than 0.50 mole per mole of monoanyl, the trans asymmetric dye is a cis asymmetric dye and both cis and trans symmetric adducts N.N'
-{41 [N. Contaminated with N-bis(ethyl)ami/]penzylidene}diaminomaleonitrile. The latter derivative is obtained by first reacting N-{4-[N·N-bis(ethyl)amino]penzylidene}-N-(4-chlorobenzylidene)diaminomaleonitrile with N-(4-chlorobenzylidene)diaminomaleonitrile and 4- Hydrolysis to diethylamide/penzaldehyde, then the latter aldehyde and the starting monoanyl N-{4-[N·N-bis(ethyl)
It is produced by reacting with [amino]penzylidene}diaminomaleonitrile. The resulting cis and trans ratios do not change with increasing reaction times, e.g. However, if this condensation is carried out with the addition of an amount of basic catalyst, for example 0.50 mole catalyst per mole of monoanyl, only trans-symmetric and trans-unsymmetric bisanyls are formed. Increasing the amount of arylaldehyde, for example greater than 2 moles per mole of monoanyl, or using other solvents does not substantially change the product. The main drawback of the above-described two-step process for producing unsymmetrical bisanyls of diaminomaleonitriles is that under the reaction conditions the product mixture contains both symmetric and asymmetric dyes.

Because of the diversity of products produced by this method, trans-asymmetric dyes are generally obtained in only moderate yields, and complex separation methods are usually necessary to effect a satisfactory separation of the product mixtures. An improved process according to the invention (the presently preferred process) for producing trans-asymmetric bisanyl adducts of diaminomaleonitrile (the presently preferred adduct) is schematically illustrated below.

This four-step synthesis method includes an initial step of condensing 1 mole of diaminomaleonitrile with a first aryl aldehyde to form a monoanyl adduct.In practice, any organic solvent may be used in this initial step. Ketones and aldehydes that can react with diaminomaleonitrile are excluded. There is no need for diaminomaleonitrile to be in solvent form. Solvents that can be used for this condensation reaction include totetrahydrofuran, ethyl ``celoryl'' dimethylformamide, ``methanol'' Useful temperature ranges are from 20 to 8000°C, but temperatures between 25 and 30°C are preferred and give the best yield and quality of product. Reaction times can be employed. Acid catalysts such as sulfuric acid, hydrochloric acid, p-toluenesulfonic acid and trifluoroacetic acid can be used. The monoanyl can be used or the reaction mixture containing it can be used in the next step. Reduction of monoanyl, for example with sodium borohydride, provides N-penzyldiaminomaleonitrile complex in high yield.

Reduction of the monoanyl adduct is an important feature of this improved process in that it eliminates the formation of undesirable mixtures (as in the two-step process described above) during the subsequent condensation with COH. It is. Preferably, an organic solvent is present in this reduction step. The organic solvents include tetrahydrofuran, methanol, ethanol and ethyl Cellosolve, with ethyl Cellosolve being particularly preferred. Addition of sodium borohydride causes an exothermic reaction, and the reaction temperature is preferably 10-35 oo
External cooling is required to maintain this range. At temperatures higher than 3500, the quality of the product obtained is poor.

Sodium borohydride can be added over a period of 20 to 4 minutes while maintaining the temperature below 35 qo. Other reducing agents such as lithium aluminum hydride and lithium borohydride can also be used. The amount of reducing agent should be at least 0.50 moles per mole of monoanyl to complete the reduction. The reduced monoadduct can be used in the next step of the reaction without further purification. This reduction proceeds best when at least some amount of alcohol solvent is present in the reaction mixture. Therefore, first condensation of diaminomaleonitrile with ~, CHO in tetrahydrofuran (THF) to form the monoanil as described above, then addition of methanol to the THF reactant and reduction of the monoanyl with sodium borohydride results in high yields. A mono-adduct is obtained which is reduced at a reduced rate. Furthermore, the initial condensation reaction was adjusted to the boiling point of tetrahydrofuran (65
~6 is o) or more, for example 25-30 instead of 80qo
℃ and by keeping the subsequent reduction temperature below 2500° C., it is possible to obtain the reduced monoadduct in very good yields, e.g. more than 90% of theory. The reduced monoadduct is 1
Condensation with moles of a second aryl aldehyde, Ar2CHO, yields a monoreduced bis-adduct.

This step can be carried out using the same solvent and acid catalyst used in the initial monocondensation step. However, best results are obtained using solvents such as methanol or ethanol. In such solvents, the monoreduced bis-adduct is highly insoluble and precipitates as it forms. Room temperature (ambient temperature) (25-30
℃) is preferred; at higher temperatures the product becomes considerably browner. In order to obtain red pisanyl dyes, it is often necessary to have a dialkylamino group on at least one of the aromatic rings.

Preferably, the appropriate dialkylaminobenzaldehyde is added as a secondary aryl aldehyde rather than as a primary aryl aldehyde. This is because monoanyls formed from such aldehydes cannot be clearly reduced with sodium borohydride in some cases. Oxidation of the mono-reduced bis-adduct in an organic solvent with an oxidizing agent in the last step of the four-step process can, in some cases, produce the colorless isomer 2.
The desired asymmetric bisanyl dyes containing 3-dicyanoimidazole are provided.

This oxidation proceeds readily in tetrahydrofuran, acetonitrile, benzene, ethyl "cellosolve" and acetone. However, large amounts of imidazole are usually formed in these solvents. Preferred solvents that give bisanyl dyes and generate little or no isomeric imidazole are dimethyl formaldehyde, dimethyl acetamide, dimethyl sulfoxide, hexamethylphosphoramide and N-methylpyrrolidone. Oxidation at room temperature (ambient temperature) (25-30 qo) is preferred over oxidation at elevated temperatures. Oxidizing agents that can be used are, for example, nickel dioxide, Mm02, P2,12, N02, dichlorodicyanoquinone and chloranil. Manganese monoxide is preferred as it gives the highest yield and highest purity product. In particular, a reaction using manganese dioxide in dimethyl formaldehyde at 25-3000 °C for about 4 hours gives a bisanyl dye with a yield of 80%, which dye does not contain any isomeric imidazole. The bisanyl dye can be conveniently isolated by adding tetrahydrofuran to the reaction mixture and filtering to remove insoluble manganese dioxide, then adding isopropanol to the filtrate and filtering the precipitated solid, washing with isopropanol. This precipitate is the desired bisanyl dye.
Alternatively, to remove the tetrahydrofuran from the above operation, the reactants (after oxidation) are poured into water and, after acidification, hydrogen peroxide or sulfur dioxide is added to it to dissolve the manganese dioxide.

The resulting mixture is then filtered and the crude dyestuff thus obtained is thoroughly washed with isopropanol. This latter variant is a much more economical method since it eliminates the use of expensive tetrahydrofuran solvents and the time-consuming removal of insoluble manganese salts. The configuration of the central carbon-to-carbon double bond of pisanyl prepared by the four-step process is revealed to be exclusively trans by dipole moment measurements.

This preferred four-step process therefore provides high yields, e.g. 70-80%, of asymmetric trans-bisanyl dyes that are not contaminated with cis or isomeric imidazoles.
gives a total yield of . The above-mentioned symmetric pisanyl dye also has the above-mentioned 4
Although it can be produced by a process method, this dye is
It is more advantageously produced with excellent yield by the process method.

Yet another example of a process that can be used here is a two-step process by which symmetrical or asymmetrical bisanyl dyes can be prepared, especially such dyes with a predominantly trans configuration.

This process involves heating diaminomaleonitrile in dimethylformamide under acidic conditions, preferably sulfuric acid, with one molar equivalent of a primary aryl aldehyde A, CHO, to form a monoanyl; in place of diaminomaleonitrile and repeat this procedure with 1 molar equivalent of primary aryl aldehyde A
The second aryl aldehyde A, which is different from HO or the first aryl aldehyde, also consists of repeated use of CHO to produce symmetric or asymmetric pisanyl dyes. The reaction time is very short (usually 10 to 3 whiskers) and the water formed during the condensation does not need to be removed to promote the formation of the desired product. Dimethyl formaldehyde is the preferred aprotic solvent, but other solvents such as dimethylacetamide, hexamethylphosphoramide, dimethyl sulfoxide and N-methylpyrrolidone are also useful. The condensation is carried out in a temperature range from 140° C. to the boiling point of the solvent. The preferred range is 140-150°C. Acid catalysts useful for creating acidic conditions other than sulfuric acid are, for example, hydrochloric acid, p-toluenesulfonic acid, and trifluoroacetic acid. Preferred symmetrical bisanyl dyes in the present invention are:
For example: Preferred asymmetric bisanyl dyes in the present invention are, for example, as follows.

The crude wet dye from any of the above processes is mixed in a colloid mill or sand mill with about 2.5 parts of the crude dye, e.g. 1 part of anchor on a 100% basis, a dispersant of lignin sulfonate and water. By doing so, it can be conveniently made into a form that can be used industrially.

Until a fine stable aqueous dispersion or paste is obtained, i.e. dye particles approximately 10 microns (average size)
Continue milling until . Both symmetrical and asymmetrical bisanyl dyes have high dyeability and generally produce very bright poppy, light yellow to blue dyeings with good sublimation fastness and moderate light fastness on polyester. give.

These dyes are particularly useful in dyeing and dyeing polyesters where bright colors are desired. Because of the inherent chemical flexibility of the manufacturing process disclosed herein, and because of the very high dyeing power and the wide range of shades that can be obtained, these bisanyl dyes can be produced very easily without loss of color value. Bisanyl dyes can be applied to polyester fibers alone or in combination with cellulose fibers by aqueous operations, preferably under pressure, or by aqueous dispersions of the dyes. It can be applied by padding the fiber and then dry heat (eg thermosol) fixing.

Such staining methods are widely used in the art. Bisanyl dyes are also useful for dyeing and dyeing polyester fibers and cellulosic fiber blends thereof, preferably using fabric foils that are subsequently subjected to a durable press treatment. The following experiments are representative of the aqueous and thermosol operations described above.

Experiment 1 Aqueous (pressure) dyeing procedure A commercially available polyester fabric was placed in an autoclave containing the following ingredients:

Aqueous dye paste containing the dye of Example 4 (15% active ingredient) 0.1 anionic sodium hydrocarbon sulfonate (10% solution)
1.0 nonionic long chain alcohol-ethylene oxide adduct (10% solution)
0.5 [Ethylenediaminetetraacetic acid sodium salt (1% solution)]
1.25' benzoic acid butyl carrier (1
0% solution) 1. Une'water
Vinegar acid solution until 75'
．． Adjust the contents of the autoclave to 5 to 26 hours for 1 hour.
Heated to 5°C.

The dyed fabric foil was then rinsed with water and dried. The polyester fabric foil was dyed a very vivid poppy, light red color. Experiment 2 Thermosol operation A padding bath containing the following components was prepared.

Aqueous dye paste containing the dye of Example 5 (15% active ingredient) 50 tres purified natural gum thickener 20 tres water
Until 1st. This puzzling grade is available on the market at 6
3/35 polyester/cotton cloth, drying cloth <weight (o
wf) and then dried (preferably infrared pre-drying followed by hot air drying or hot can drying) to remove water. A thermosol operation in which the polyester component was dyed with this disperse dye was completed by heating the dried pigment padding fabric for 9 hours at 21 degrees. The surface dye, which is not fixed to the polyester or cotton or both, is padded on the fabric at 27 to 30 degrees in an aqueous bath containing 50 minutes of sodium hydroxide and 40 hours of sodium bisulfite, then 3 minutes. Steaming in the sand. Next, rinse this cloth with 270ml of water.
Scorch for 5 minutes at 93° C. in water containing 1% ether alcohol sulfate detergent, rinse with 270° C. water, then dry. After drying and cleaning, the material was heated in a bath containing the following ingredients:
% (owf) pick-up (for permanent pressing). Yu/Z Dimethylol dihydroxyethylene urea crosslinking agent 200
．． 0P-octylphenoxy (C25○) 9~,.

Wetting agent 2.5 dispersed acrylic thermoplastic binder
22.5 Non-ionic, paraffin-free polyethylene emulsion (acts as fabric softener) 22.
5 Nonionic polymer emulsion (imparts luster, silky feel, and antistatic properties to fibers) 30.020
% Aqueous Zinc Nitrate Magnetizing Catalyst 36.0 This resin-impregnated material is air dried to remove water and then cured at 16°C for 12 minutes. The durable pressed polyester/cotton fabric is dyed in an attractive vibrant poppy, light scarlet shade. The following examples illustrate the preparation of the bisanyl dyes described above.

All parts are by weight unless otherwise specified. Example 1 Preparation of symmetrical bisanyl 2.16 parts of diaminomaleonitrile, 9.16 parts of 4
A mixture of mono[N·N-bis(thia/ethyl)amino]penzaldehyde, 0.2 parts of p-toluenesulfonic acid, 30 parts of dimethylacetamide (DMAC), and 15 parts of benzene is heated to 80-90°C. At the same time, benzene and water were distilled off.

After one hour of distillation, the remaining benzene was distilled off under a nitrogen atmosphere.

After cooling the DMA solution to -5°C, 42 parts of red bisanyl were collected by filtration, with a melting point of 218-2
It was 20pm. When performing thin layer chromatography on a glass plate coated with silica gel and using benzene-acetonitrile (4:1) as the molten liquid, Rf
A scarlet point was shown at 0.1. C3, string 6N
, calculated value for o: C, 68.6: day 5.0: N, 2
6.5%. Actual value: C, streak. 2: Sun, 5.4; N, 26
．． 5%. The Nujoormal infrared spectrum of this product showed no N-day absorption at peaks 2.8 to 3.1. Based on the above, the structure of this product was:
p1(NCH4C2)2N-C6day4-CH=N-C(
CN)=C(CN)-N=CH-C6 ratio-p-N(C2
4CN) 2. Pour the mother liquor from the above filtration into a large amount of ice-cold water, isolate the precipitated solid by filtration, wash with water and dry. 3. $guo red solid, melting point 185-186℃
was gotten. Thin layer chromatography shows the presence of small scarlet dots at Rf<0.1 and Rf=0
．． 6 shows the main yellow dots. This product has an absorption band of 515 for bisanyl (aMx=10-1) and an absorption band of 410 for monoanyl produced by hydrolysis of bisanyl during DMF treatment (aMx=87).・Yu-1・Skin-1) were shown. Calculated value for C3 rainbow 26N,o: C, 68.6
: day, 5.0; N, 265% actual value: C, 6.70; day, 57; A mixture consisting of was formed. Example 2 Preparation of symmetrical bisanyl 3.24 parts of diaminomaleonitrile, 10.6 parts of 4
A mixture of mono[N.N-bis(ethyl)amino]penzaldehyde and 5 parts of glacial acetic acid was stirred at 115-120°C for 4 hours.

After standing at 25 to 30 qo for one hour, collect the solids,
After washing twice with 25 parts of acetic acid and then 25 parts of isopropanol and drying, 5. $ parts (yield 60.8%)
The symmetrical pis-anyl dye produces blue metallic flakes.

It was obtained in the form of a melting point of 2 to 270 qo. This dye is 56
265 evening, evening-1, suppression-1 at 1m wavelength (input max)
The absorption (aMx) was shown. Based on the above, this dye had the following structure. p-(WC2)2N-C6 days-
CH=N-C(CN); C(CN)-N=CH-C6 is -p-N(C2day5)2 by initiating the reaction using a suitable monoanyl derivative instead of diaminomaleonitrile. , similar results were obtained. Example 3 Preparation of unsymmetrical bisanyl by a two-step process All 32 parts of diami/maleonitrile, 21 parts of 4-[N·N-bis(ethyl)amino]penzaldehyde, 3 parts of concentrated hydrochloric acid and 200 parts of tetrahydrofuran. (THF)
The mixture was heated at 65°C for 3 hours.

The tetrahydrofuran was partially evaporated and 100 parts of ethanol were added. The precipitated solid was removed by filtration and air dried to yield 227 parts of yellow monoanil (76%
yield) was obtained. A mixture of 14.1 parts of 4-chlorobenzaldehyde, 20 drops of piveridine and 500 parts of benzene was heated to 80-90 DEG C., during which the water formed during the reaction was distilled azeotropically.

Mo/anil (13.4 parts) was then added in portions over 6 hours and heating at 80-90°C continued for an additional 2 hours. The solvent was distilled off and the resulting solid residue was boiled with 20 parts of isopropanol. After filtration and drying, 9.2 parts (47% yield) of a red product, melting point 207-20%, were obtained. Thin layer chromatography showed that the major component was the non-contrastive dye, accompanied by a small amount of purple impurity. This dye showed an absorption (amax) of 177〆・ei-1・arc-1 at a wavelength of 528 hayama (^Mx). Calculated value for C224oN5CI: C, 67.8; day, 5.2: N, 18.0%
Actual value: C, spots. 6:N, 5.6:N, 17.9% Based on the above, this dye had the following structure.

p1CI-C6day4-CH:N1C(CN)=C(CN
)-N=CH-C6 ratio-p1N(C2)2{b'6.
7 parts of monoanyl of 'a' above, 7.05 parts of 4-chlorobenzaldehyde, 0.85 parts of piverizine and 2
A mixture of 5 parts benzene was heated to 80-90 DEG C., during which the water formed during the reaction was continuously azeotropically distilled.

Thin layer chromatography of this reaction mixture showed the presence of approximately equal amounts of trans symmetric and trans asymmetric bisanyl dyes, with only small amounts of cis bisanyl dye detectable. 'c} When the condensation was carried out similarly except in the presence of only one drop of piberidine, the major products after 1 hour at 80-90 am were cis symmetric and cis asymmetric bis-anyl dyes.

Only trace amounts of transbisanyl were present. Example 4 Preparation of unsymmetrical bisanyl by a 4-step process 21.6 parts of diaminomaleonitrile, 1. Gunbe's 4-
A mixture of promobenzaldehyde, 5 drops of concentrated sulfuric acid, and 25 grams of tetrahydrofuran was stirred at 25-30°C for 4 hours.

Methanol (10 ml) was added and 7.95 parts of sodium borohydride was added in small portions over 20 minutes while maintaining the temperature at 20-25° C. with external cooling with ice water.
After heating at 20-25C0 for 18 minutes, most of the solvent was removed by distillation.

The residual solution was poured into 150 g of ice-cold water, stirred for 1 hour, and the resulting solid was collected and air dried to give 53.5 parts (97% yield) of the reduced monoadduct.
This material is used in the next step of the continuous reaction without purification. 5. A slurry of this reduced monoadduct of Moribe, 38.8 parts of 4-[N·N-bis(ethyl)amino]penzaldehyde, 1.2 parts of concentrated sulfuric acid, and 1000 parts of ethanol was added. It was stirred for 4 hours at 25-3 pi○.

The reaction mixture was filtered and the collected solids were air dried to give 83 parts (99% yield) of the orange reduced bis-adduct. This product was sufficiently pure to be used in the next reaction without purification. A mixture of 82 parts of this reduced bis-adduct, 75 parts manganese dioxide and 50 parts dimethylformamide was stirred at 25-30°C for 4 hours.

Tetrahydrofuran (50 mm) was added and the resulting mixture was filtered through a medium porosity anti-stain glass funnel. The solid thus obtained was washed with 400 parts of tetrahydrofuran to dissolve the precipitated bisanyl dye and separate it from the permanent manganese dioxide. Concentrate the cooled tetrahydrofuran filtrate under reduced pressure to form a thick sludge.
Anchorage of isopropanol was added, the resulting slurry was filtered, and the collected solid was washed three times with 10 parts of isopropanol, resulting in 61.5 parts (75.6% yield) of the bisanyl dye being metallic. It was obtained as a green flake, which showed an absorption of 1$, 1, and 1 at a wavelength of 531 cm (max). Recrystallization of this product from benzene gives very dark needle-like crystals m. p. 205-20
6°C is obtained, which is am at ^Mx = 531 kites.
It shows ax=166 evening, evening-1, moth-1. Calculated value for C day 2bu 58r: C, 60.8: day, 4.7; N
, 16.1% actual value: C, 59.5: day, 4.8: N,
Thin layer chromatography of the 15.6% product showed only a single purple spot. Based on these, the structure of this dye was as follows. p-Br-C rainbow 4-CH
=N-CCN)=C(CN)-NkoCH-C6 days 4-
p-N(C2&)2 Example 5 Preparation of an unsymmetrical bisanyl dye by a four-step process A mixture of 10.8 parts of diaminomaleonitrile, 15.6 parts of 1-naphthaldehyde, 5 drops of concentrated sulfuric acid and 125 parts of tetrahydrofuran The mixture was stirred for 1 hour at 25-30°C.

Methanol (35 parts) was added and the solution was cooled to 150°C. Sodium borohydride (3.8 parts) was added in portions while maintaining the temperature at 15-20°C with external ice-water cooling. After cooling for 1 insect life, this solution was heated to 150 ml.
The mixture was added to ice-cold water at the mountain pass, stirred for 3 hours, and a solid (a pale yellow monoadduct reduced as a colored powder) was obtained by filtration.

A slurry of this reduced monoadduct, 18 parts of 4-[N-N-bis(ethyl)amino]penzaldehyde, 13 parts of concentrated sulfuric acid, and 20 parts of ethanol was stirred at 25-3 picoC for 1 hour. did.

The solids were separated by filtration to yield 35.4 parts of reduced bis-adduct as an orange powder. A mixture of the reduced bis-adduct, 35 parts manganese dioxide and 15 parts dimethylformamide was stirred at 25-30°C for 5 hours.

The solid was separated by filtration and washed four times with 40 portions of tetrahydrofuran to obtain a solution of the desired bisanil.
Tetrahydrofuran and dimethylformamide were distilled under reduced pressure, and the solid thus obtained was washed with isopropanol and dried to give 32.5 parts (80 parts) as a red powder.
% yield) is obtained, which has an absorption of 183 m, m-1, arc-1 at the wavelength (input Mx) of
amax). Calculated value for C day scale N5: C
, 77.0: Day, 5.7: N, 17.3% actual value C, 7
6.3:day, 5.6:N, 17.4% thin layer chromatography showed only a single purple dot. From the above, this dye had the following structure. Example 6 Preparation of Unsymmetrical Pisanil in 4 Steps Example 5 was substantially repeated except that other solvents were used in place of tetrahydrofuran in both the reduction and oxidation steps.

A slurry of 12.7 parts of Example 5 in ethyl ``Cellosolve'' was brought to a temperature of 25-3 by external cooling in ice water.
0.95 parts of sodium borohydride was added in portions while maintaining the temperature at 5°C.

The resulting solution was stirred for 30 minutes, poured into 50 parts of ice water, and stirred for an additional hour. The pale yellow colored precipitate was collected by filtration and air dried to yield 12.4 parts (10
A reduced monoadduct was obtained (yield 0%). This reduced monoadduct was prepared as 4-[N·N-bis(ethyl)amino] in ethanol as described in Example 5.
Condensation with penzaldehyde gave the reduced bis-adduct.

5. This reduced bis-adduct of the apex, 5. A mixture of anchor manganese dioxide and 35 parts of dimethylformamide was stirred at 25-30°C for 2 hours.

This solution was poured into 35 parts of ice-cold water and 9 parts of concentrated sulfuric acid were added. Hydrogen peroxide (6 parts of a 30% aqueous solution) was added little by little to dissolve the manganese dioxide. The resulting mixture was filtered and the crude dyestuff thus obtained was washed twice with 5 parts of isopropanol and dried to give 4.5 parts (
A bisanyl dye (yield of 89.4%) was obtained as a red solid, which exhibited an absorption (max) of 169 SO-11 SO-1 at a wavelength (max) of 540 SO. Thin layer chromatography showed only a single purple dot and the Rf was identical to that of the Example 5 dye. Example 7 Preparation of unsymmetrical bisanyl by a four-step process The dye of Example 4 was prepared as a reduced bis-adduct (9.6 parts).
and 10.6 parts of lead dioxide (0.04 mol) in 200 parts of acetonitrile at 50-55 qo for 9 hours.

The suspended lead sludge was filtered off and the solvent was evaporated. Thin layer chromatography showed that this residue was found in almost the same amount as in Example 4.
was shown to consist of an asymmetric pisanyl dye and a colorless isomeric imidazole. Heat this solid (80 to 90 qo
) The imidazole was removed by prolonged extraction with ethanol, and the extracted product was shown to consist of a single purple dot by thin layer chromatography. The analytical data obtained for this product was substantially identical to that described in Example 4. Example 8 Preparation of symmetrical bisanyl 9.4 parts of 4-[N·N-bis(ethyl)amino]penzaldehyde, 2.16 parts of diaminomaleonitrile,
A mixture of 4.0 parts of phosphorous pentoxide, 6 drops of concentrated sulfuric acid, and 7 parts of hexamethylphosphoramide was dissolved at 50 to 590
I stirred for hours.

After each 2 hour interval, an additional 1.0 part of phosphorous pentoxide was added. The reaction mixture was then poured into 80 parts of water containing 2 parts of aqueous ammonium hydroxide. After stirring for 1 hour, the precipitated solid was collected by filtration, washed with water, and dried to give 5.5 parts (65% yield).
bluish-red symmetrical bisanyl, melting point 140-1
420 was obtained.

Recrystallizing this product three times from isopropanol gives
An analytically pure sample was obtained, melting point 162-165o. This product has a strong absorption band (
105 days/evenings - 10 skins - 1) and an additional 400 skins (6 skins)
15〆・Yu-1・Aku-1) and 382 mountains (56zo・
It showed two weak absorption bands in Yu-11 Kite-1). Existence of low wavelength absorption band and large dipole moment 1
Based on the observed 4.7 Debye, this product was confirmed to have a cis configuration with respect to the central carbon-carbon double bond. Based on the above data, the structure is as follows. p-(QC2)2N-C Rainbow 41CH
=NC(CN)=C(CN)-N=CH-C6 mountain-p
-N (C2 day 5) 2 Example 9 Preparation of symmetrical bisanyl 10.8 parts of diaminomaleonitrile, 29. A mixture of indole-3-carboxaldehyde, 40 ml of tetrahydrofuran, and 1 ps of concentrated sulfuric acid was added to 650
I stirred it for one hour at 0.

Partially evaporate tetrahydrofuran, 10% of 1 anchor
Aqueous sodium carbonate solution was added. The precipitated solid was filtered off, washed with water, then with isopropanol and dried to give 20.3 parts (86% yield) of yellow monoanil, mp 227.5-229°C. 14.1 parts monoanyl; 12. A mixture of concentrated sulfuric acid, 11.6 parts of indole-3-carboxaldehyde, and 15 parts of dimethylformamide was added to about 145 to 15 parts of dimethylformamide.
Heated for 0 minutes and held at this temperature for 20 minutes.

The reaction mixture was then poured into 100 parts of water. The precipitated solid was collected by filtration, washed with water, then with isopropanol, and dried. The product was recrystallized three times from acetonitrile-chloroform to yield 6.85 parts (3
1.7% yield) of yellow symmetrical pisanil, Kudzu point 33
1 to 33 chi0 were obtained. This dye exhibited an absorption (amax) of 220 and 1 arc-1 at a wavelength (max) of 480 degrees. 22nd, calculated value for 4N6: C, 72.9: day, 3.9: N, 232% actual value: C
, 71.4:N, 4.3:N, 22.3% Based on the above data, the structure of this dye is:

Example 10 Preparation of unsymmetrical bisanyl 4.7 parts of indole-3-carpoxyaldehyde diaminomaleonitrile monoanyl, 3.54 parts of 4-[
N・N-pis(ethyl)ami/penzaldehyde, 4
．． A mixture of concentrated sulfuric acid and dimethylformamide was heated to 145-150°C for 2 minutes.

The reaction mixture was then poured into 100 g of water. The precipitated solid was filtered, washed with water and dried. Thin layer chromatography analysis showed the presence of two possible symmetrical bisanyl condensates and a third bright reddish-orange component. The latter substance is referred to as “Florisil” (FIori).
sil) column chromatography using chloroform as eluent. After two recrystallizations from acetonitrile, a small amount (0.1 part) of the pure asymmetric pisanyl condensate, mp 265 ~
2 total °C was obtained. Infrared analysis showed NH band in 3395-1 and CN absorption in 0-1 and 66-1. The visible absorption spectrum has an r of 522
Entering max and 239 so/evening-1/n-1 amax
showed that. Based on the above data, the structure of this dye is
It is as follows. Example 11 Preparation of symmetrical bisanyl 2.16 parts of diaminomaleonitrile, 3.5 parts of 4-[N·N-bis(ethyl)amino]penzaldehyde,
8. A mixture of concentrated sulfuric acid and dimethylformamide was stirred at 145 to 150 qo for 2G minutes.

The reaction mixture was then poured into 100 parts of water,
The precipitated solid was collected by filtration, washed with water and dried. When this product is purified by "Fluocyl" column chromatography using chloroform as the eluent,
0.47 parts bluish bisanil, mp 265-2
A speck was obtained. This is 26 at a wavelength of 561wr.
5〆・Yu-1・Arc-1 absorption (aMx) was shown. The nuclear magnetic resonance absorption (NMR) spectrum of this product was found to be identical to that of the dye of Example 8. However, the absence of absorption at low wavelengths, the very high melting point, and the observed dipole moment as low as 3.2 deby indicate that this product is actually the trans form of the dye of Example 8. Show that. Isomerization of the cis dye of Example 8 to the trans form of this example occurred easily by heating the former dye in benzene containing a small amount of iodine.

The product obtained was identical in melting point and spectral properties to the trans isomer. Examples 12-118 Symmetrical pisanyl dyes were prepared by a similar procedure to that described in Example 2 (Examples 12-19).

Asymmetric bisanyl dyes were prepared by a preferred four step process analogous to that described in Examples 4 and 5 (Examples 20-118). Data for the dyes produced are shown in Table D'. Except as specifically indicated below, substituents A, B, C, X, Y and Z listed in column 1 of this Table D correspond to substituents of the formula: However, Example 343982,
The groups shown in the Y column for 87, 88 and 95 correspond to the groups shown in the B column for 78-8389, 99 and 118 in the above formula.

Similarly, Examples 27, 31, 49 5-stop 52, 53
It corresponds to the entire group of 55 61, 62, 6mu 6fu 60 76. Table □ Table ○ (continued) Table □ (continued) Table □ (continued) Table □ (continued) Table □ (continued) Front opening (continued) Table U (continued) Table □ (continued) Table □ (continued) This specification A comprehensive list of disclosures is as follows.
11 Formula, ~, CH=NC(CN)=C(CN)-N=CH-
~2 where each of A[, and A[2 is (i)0
penzo (5- and 6-membered) heterocyclic groups containing ~4 methyl groups, and (iil phenyl, naphthyl, 5
membered posterior heterocyclic groups and 6 true heterocyclic groups, these groups include N02, halogen, CN, C, ~4 alkyl, C, ~4
Alkoxy, DCH2-phenyl, phenyl CF3
, OH, OC, ~4 alkylene-N, ~4 alkyl)
2, C2-4 alkylene-CI, NHCONQ, NH
COA, NHS02A, SR8, S02R8, NHR,
, NHCOC, -4alkylene-B and -NR,R2
0 to 3 substituents selected from 'a'
R, is C, ~4 alkyl or C2-4 alkylene-R3, and "'b} R2 is C, ~4 alkyl, C2-4
4 alkylene-R4, or AJ, or A[
When 2 is phenyl, C3 alkylene is attached to the phenyl position that is ortho to the position where nitrogen is attached, 'c} R3 is CN, halogen, OH, phenyl, C,
~4 alkoxy, OC, ~4 alkylene-CN, C02
A, OCOA, OCONHA or CO2C, ~4 alkylene-OCOA, {d) R4 is CN, halogen, OH, phenyl, OC, ~4 alkylene
-CN, CO2A, OCOA, CO2C, ~4 alkylene -OCOA, S02A, phthalimide, succinimide, glutarimide, OCOCH=CH2, CQ-C
H(OCOA)CH20A or CH2CH(OCON
HA) C ratio OA, [e'A is C, ~4 alkyl or R5, 'f' B is halogen, C, ~4 alkoxy or R5, (g) R5 is C, ~4 alkyl , C, ~4 alkoxy, halogen, N02, CN,
C, ~4 alkyl is phenyl containing 0 to 2 substituents selected from CON and NR6R7, each of R6 and R7 being independently selected from C, ~4 alkyl, and at least one of R6 and R7 One is C,
~4 alkyl, and (h) R8 is C, ~4 alkyl, C2, G~8 cycloalkyl, or R5
A bisanyl dye, independently selected from .

(2) The dye of [1] above, in which ~ and ~2 are the same.

The dye of {1' above, in which ~ and ~2 are different. {41
The dye according to [1] above, in which the cyano group is in the cis configuration with respect to the carbon-to-carbon double bond. '5} The dye of {1' above, in which the cyano group is in the trans configuration with respect to the carbon-to-carbon double bond.

■ Ar, and each of A is C6 day 4-p-N (
The dye of [2-] above, which is C2ACN)2.

'7} Each of Ar and AJ2 is p-N・N-
The above dye (■) is jethylaminophenyl. ■ The dyes of ■ above, each of which is A stop, and A[2.

[9] Ar and AJ2 are o-chlorop-N・N
- The dye of the above '2} which is dimethylaminophenyl.

0Q A[, and each of A[2 is The dye of [21] above.

QD Ar, and the dye of [2] above, wherein each of A[2 is 3-indolyl.

02 Ar, is p-chlorophenyl, and AJ
The dye of {31] above, wherein 2 is p-N-N-diethylaminophenyl.

03 Ar, is p-bromophenyl, and AJ
The above in which 2 is p-N-N-diethylaminophenyl {
3' dye.

04 A, is 1 naphthyl, and AJ2 is p
-The dye of the above '3} which is N.N-jethylaminophenyl.

09 The above-mentioned dyes, wherein Ar, is o.o-dichlorophenyl and Ar2 is p1N.N-diethylaminophenyl.

08 The dye of '3' above, wherein H, is 1-naphthyl, and A[2 is.

07) The dye according to the above [3}, wherein Ar, is o·o-dichlorophenyl, and AQ is o-methyl-p1N·N-dithylaminophenyl.

0 vice Ar, is 1 naphthyl, and AJ2 is o
-Methyl-p-N-N-diethylaminophenyl [31].

(2) The dye of [3-] above, wherein Ar, is 2-hydroxy-1-naphthyl, and A[2 is p1N.N-diethylaminophenyl.

(2) The dye of (2) above, wherein Ar, is 2-hydroxy-1-naphthyl, and A[2 is o-methyl-p-N.N-jethylaminophenyl.

The legs Ar, are 1-naphthyl, and AJ2 is o-
The above dye (2) is methyl-p-N-N-di-n-butylamino/phenyl. ■ Ar, is 5-promo-2-dithienyl, and At2 is o-methyl-p-N・N
-diethylaminophenyl {31].

■ Ar, is 5-bromo 2-thienyl, and A
[The above dye (2), wherein 2 is p-N·N-diethylaminophenyl. The dye of '31 above, wherein Ar is 5-bromo-2-thienyl and A is 2.

Side Ar, is m-nitrophenyl, and A stop 2
The above glue dye, wherein p-N.N-diethylaminophenyl.

28 Diaminomaleonitrile as an aromatic aldehyde ~
, is condensed with CHO to form monoanyl~,1CH=N-C(C
N)=C(CN)-NH2 is produced, 'B} The monoanyl from the process is reduced to ~,C=NH-C(CN)=
The product from {C} step 'B} is condensed with an aromatic aldehyde ~2CMO that is the same as or different from the aromatic aldehyde of the step leg to produce a monoanyl ~, C ratio. NH-C(CN)=C(CN)-N=CH
-A et al., and oxidize the monoanyl from ′■ step) to bisanininole~,1CH=N-C(C
N) iC(CN)-N═CH--2, wherein Ar and Ar2 are as defined in m above, the method for producing the bisanyl dye of '11 above.

Suppression Ar. and ~2 are the same, the method of (26) above.

(2) The method of (26) above, in which ~ and ~2 are different.

2. The method of (26) above, wherein the oxidizing agent used in the process plate is lead dioxide.

(2) The method of (26) above, wherein the reducing agent used in step {B}' is sodium borohydride.

60 The presence of organic solvents other than ketones or aldehydes that can react with diaminomaleonitrile reduces process failure.
0° C. for 4 to 17 hours, the process leg is carried out in the presence of an organic solvent at a temperature below 35q° with at least 0.50 mole of reducing agent per mole of monoanyl, and the process step is carried out in the presence of an organic solvent. The method of (26) above, which is carried out at ambient temperature in the presence of

■ The above (31) in which an acid catalyst is used in step B and 'C}, and the temperature in step 'B is 10 to 35°C.
the method of.

■ At the end of the process, the solvent is selected from tetrahydrofuran, ethyl cellosorbate dimethylformamide, methanol, ethanol and mixtures thereof;
The catalyst was selected from sulfuric acid, hydrochloric acid, p-toluenesulfonic acid and trifluoroacetic acid, and the temperature was 25-3 psi, and the solvent was selected from tetrahydrofuran, methanol, ethanol and ethyl "cellosolve" while the process was in progress. and the temperature is below 0, and the solvent in the process is selected from tetrahydrofuran, acetonitrile, benzene, ethyl chloride, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide and N-methylpyrrolidone, and The method of (32) above, wherein the temperature is 25 to 30°C.

(3) The method of (33) above, wherein the solvent used in the spindle B is methanol or ethanol.

133. Diaminomaleonitrile is treated under acidic conditions in the presence of 1 molar equivalent of aromatic aldehyde CHO and an organic solvent selected from the group consisting of dimethylformamide, dimethylacetamide, hexamethylphosphoramide, dimethylsulfoxide and N-methylpyrrolidone. to 140℃
to the boiling point of the solvent to form monoanyl, CH=N-C(CN)=C(CN)-NH2, and an equimolar amount of an aromatic aldehyde ArCH○, which is the same as or different from the aldehyde, and the presence of an organic solvent selected from the group consisting of dimethylformamide, dimethylacetamide, hexamethylphosphoramide, dimethylsulfoxide and N-methylpyrrolidone. Condensation under acidic conditions at temperatures from 14 pi to the boiling point of the solvent yields bisanyl~,1CH=N-C(CN)=C(C
N) The method for producing a bisanyl dye according to [1] above, which comprises steps of producing -N=CH-~2, and Ar and Ar2 are as defined in [11' above].

(2) The method of (35) above, in which acidic conditions are created using sulfuric acid, hydrochloric acid, p-toluenesulfonic acid or trifluoroacetic acid.

The acid is sulfuric acid, the temperature is 140 to 15 pm,
The method of (36) above, wherein the solvent is dimethylformamide and the reaction time is 10 to 30 minutes.

■Shikiyama, 1CH=N-C(CN)=C(CN)-N=C
H-~2 where A[, and each of AJ2 is (i)
penzo (5- and 6-membered) polycyclic groups containing 0 to 4 methyl groups, and (ii) phenyl groups, naphthyl groups, 5
membered double cyclic group and 6-membered double cyclic group, these groups are NQ, halogen, CN, C, ~4 alkyl, C, ~4 alkoxy, OCH2-phenyl, phenyl, CF3, O
H, OC, ~4 alkylene-N(C, ~4 alkyl)2
, C2-4 alkylene-CI, NHCON ratio, NHC
OA, NHS02A, SR8, S02R8, NHR,,
containing 0 to 3 substituents selected from NHCOC, -4alkylene-B and -NR,R2, where [a1
R, is C, ~4 alkyl or C2-4 alkylene-R
3, [b} R2 is C, ~''alkyl, C2-4
alkylene-R4, or A[, or AJ2
is phenyl, C3 alkylene is bonded to the phenyl position that is ortho to the position to which nitrogen is bonded, [c'R3 is CN, halogen, OH, phenyl, C, ~
4 alkoxy, OC, ~4 alkylene-CN, C02A
, OCOA, OCONHA or CO2C, ~4 alkylene-OCOA, [dl R4 is CN, halogen, OH, phenyl, ○C, ~4 alkylene
-CN, CO2A, OCOA, C02C, ~4 alkylene-OCOA, S02A, phthalimide, succinimide, glutarimide, OCOCH=CH2, C ratio -CH
(OCOA)CH20A or CH2CH(OCONH
A) C French〇A, {e'A is C, ~4 alkyl or R2, 'f'B is halogen, C, ~4 alkoxy or R5, (g) R5 is C, ~4 Alkyl, C, ~4 alkoxy, halogen, N02, CN, C,
~4 alkyl is phenyl containing 0 to 2 substituents selected from CON and NRp7, R6 and R
each of 7 is independently selected from C, ~4 alkyl, at least one of R6 and R7 is C, ~4 alkyl, and [h) R8 is C, ~4 alkyl,
C2, C5-6 cycloalkyl, or R5, independently selected from C2, C5-6 cycloalkyl, or R5, is used to prepare a bisanyl dye of
Condensation with HO to form monoanyl~, 1CH=N1C(CN)
＝C(CN)NH2 is produced, and the monoanyl from the step B' is reduced ~, C ratio NH-C(CN)=C(CN
) to produce 1N2 and ■ condense the product from step (B} with an aromatic aldehyde 2CHO that is the same as or different from the aromatic aldehyde in the process style to form a monoanyl 2C ratio N2;
H1C(CN); C(CN)-N=CH-Ar2 is formed and the monoanyl from ' is treated at ambient temperature with dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide and N - An improved process for producing said bisanyl substantially free of imidazole impurities, comprising the steps of oxidation with manganese dioxide in the presence of a solvent selected from the group consisting of methylpyrrolidone.

Glue In step ①, the solvent is dimethylformamide, the temperature is 25-30qo, and the reaction time is about 4
Method '1} above, which is time. (2) The above method (2) in which ~ and ~2 are the same.

The above method (■) in which AU Δ and ~2 are different. ■ The method of (2) above, wherein the reducing agent in the process leg is sodium borohydride. ■ In the presence of an organic solvent other than a ketone or aldehyde that can react with diaminomaleonitrile, the process is repeated 4 to 1 times at 20 to 8 and 0, and the process is changed to monoanil 1 at a temperature below 390 in the presence of an organic solvent.
the above (wherein step C- is carried out in the presence of an organic solvent)
39) method.

(2) The method of (43) above, wherein an acid catalyst is used in steps (1) and (2), and the temperature of the step leg is 10 to 35 degrees Celsius.

In the QS process and [q, the solvent is selected from tetrahydrofuran, ethyl cellosolve, dimethylformamide, methanol, ethanol and mixtures thereof, the acid catalyst is selected from sulfuric acid, hydrochloric acid, p-toluenesulfonic acid and trifluoroacetic acid, and the temperature is 25-30q
C and in the process program the solvent is selected from tetrahydrofuran, methanol, ethanol and ethyl "Cellosolve" and the temperature is below 25 °C (4
Method 4).

(2) The method of (45) above, wherein the solvent used in step [B'1] is methanol or ethanol.

Shoe ceremony~, 1CH: N-C(CN)=C(CN)-N=C
H-~2 where A, and A [2 are the same, and (i) a penzo (5- and 6-membered) double cyclic group containing 0 to 4 methyl groups and (ii) a phenyl group, Naphthyl group, 5-membered cyclocyclic group and 6-membered cyclocyclic group, these groups are N02, halogen, CN, C, ~4 alkyl, C
, ~4 alkoxy, OCH2-phenyl, phenyl, C
F3, OH, OC, ~4 alkylene-N(C, ~4 alkyl)2, C2-4 alkylene-CI, NHCON
ratio, NHCOA, NHS02A, SR8, S02R8,
NHR,, NHCOC, -4 alkylene-B and -NR, 0 to 3 substituents selected from R2, where (a) R, is C,~4 alkyl or C2-4 alkylene-R3; , [bl R2 is C, ~4 alkyl, C2-4 alkylene-R4, or A[, or A[2 is phenyl, C3 alkylene is the position of the phenyl that is ortho to the position to which the nitrogen is attached. 'c} R3 is CN, halogen, OH, phenyl, C,
~4 alkoxy, OC, ~4 alkylene-CN, C02
A, OCOA, OCONHA or CO2C, ~4 alkylene-OCOA, [dI R4 is CN, halogen, OH, phenyl, OC, ~4 alkylene - CN, CO2A, OCOA; SQA, phthalimide, succinimide, glutimide, OCOCH=CH2,,CH2
-CH(OCOA)CH20A or CH2CH(OC
ONHA) C ratio OA, 'e1 A is C, ~4 alkyl or R5, 'f' B is halogen, C, ~
4 alkoxy or R5, (g) R5 is C, ~
4 alkyl, C, ~4 alkoxy, halogen, N02,
CN, C, ~4 alkyl- phenyl containing 0 to 2 substituents selected from
6 and R7 are each independently selected from C, ~4 alkyl, and at least one of & and R7 is C, ~4 alkyl.
, ~4 alkyl, and {h) R8 is C, ~4
alkyl, C24CH, G~6 cycloalkyl, or R5 cycloalkyl, selected from: Diaminomaleonitrile and at least 2 molar equivalents of an aromatic aldehyde ~, CHO are mixed in glacial acetic acid. A method for producing the bisanyl dye in one step, which method comprises reacting in the presence of a bisanyl dye.

(2) The method of (46) above, wherein the reaction is carried out at 115 to 12 psi for about 2 hours and the molar ratio of aromatic aldehyde to diaminomaleonitrile is about 2:1.

Claims (1)

[Claims] 1 (A) Diaminomaleonitrile is condensed with aromatic aldehyde Ar_1CHO to form monoanyl Ar_1-CH
=NC(CN)=C(CN)-NH_2 is generated, (
B) Reducing the monoanyl from step (A) to Ar_1
(C) condensing the product from step (B) with an aromatic aldehyde Ar_2CHO that is the same as or different from the aromatic aldehyde of step (A) to form a monoanyl Ar_1CH_2NH-C(CN)=C(CN)-N=
and (D) oxidizing the monoanyl from step (C) to produce bisanyl Ar_1-CH=
A method for producing a bisanyl dye characterized by producing N-C(CN)=C(CN)-N=CH-Ar_2 [In the above formula, Ar_1 and Ar_2 each independently represent (1)
a benzo (5- and 6-membered) heterocyclic group having one nitrogen atom as a heteroatom; (2) having one oxygen atom or one sulfur atom as a heteroatom; or having one sulfur atom as a heteroatom; a 5-membered heterocyclic group having one nitrogen atom, in which these heterocyclic groups (1) and (2) are selected from halogen, C_1_-_4 alkyl and (C_1_-_4 alkyl)_2N- ) (3) (C_1_-_4 alkyl)_2N- or a 1-naphthyl group optionally substituted with a hydroxyl group, and (4) -NO_2, halogen, -CN, C_1_-_
4 alkyl, C_1_-_4 alkoxy, -OH, -N
HCOC_1_-_4 alkyl and -NR_1R_2
A phenyl group optionally having a substituent selected from (a) R_1 is C_1_-_4 alkyl or C_1
_-_4 alkylene-R_3, (b) R_2 is C_1_-_4 alkyl, C_1_-_4 alkylene-
R_4 or -CH_2CH(OCONHC_6H_5
) CH_2OC_6H_5 and (c) R_3 is -
CN, -COOC_1_-_4 alkyl or -OCO
C_6H_5, and (d) R_4 is -CN,
-COOC_1_-_4 alkyl or -OCOC_6
It is H_5. ). 2 Condensation of diaminomaleonitrile with 2 molar equivalents of the aromatic aldehyde Ar_3CHO in the presence of an acidic catalyst to form the symmetrical bisanyl Ar_3-CH=N-C(CN)=C(
CN)-N=CH-Ar_3 [In the above formula, Ar_3 is halogen, C_1_-_4 alkyl, C_1_-_4 alkoxy and -NR_5R_6 (R_5 and R_6 are each C_1_- _4 alkyl, C_1_-_4 alkylene-CN or C_1_-_4 alkylene-COO
It is a phenyl group which may have a substituent selected from the group consisting of (C_1_-_4 alkyl)]. 3 (1) Diaminomaleonitrile in the presence of an acidic catalyst with 1 molar equivalent of the first aromatic aldehyde Ar_7CH
condensation with O to form the monoanyl and then (2) the monoanyl from step (1) in the presence of an amine catalyst in an organic solvent with one molar equivalent of a second aromatic aldehyde Ar_8C.
Condensation is performed while removing HO and the condensation water produced to form asymmetric bisanyl Ar_7-CH=N-C(CN)=C(CN
)-N=CH-Ar_8 (wherein Ar_7 and A
r_8 is different, Ar_7 is a phenyl group optionally substituted with -N(C_1_-_4alkyl)_2, and Ar_8 is a phenyl group optionally substituted with halogen). 4 (1) Condensation of diaminomaleonitrile with 1 molar equivalent of aromatic aldehyde Ar_9CHO under acidic conditions in an organic solvent selected from the group consisting of dimethylformamide, dimethylacetamide, hexamethylphosphoramide, dimethylsulfoxide, and N-methylpyrrolidone. to monoanyl Ar_9-CH=NC(CN)=C(CN
)-NH_2 and then (2) the monoanil from step (1) under acidic conditions in an organic solvent selected from the group consisting of dimethylformamide, dimethylacetamide, hexamethylphosphoramide, dimethylsulfoxide and N-methylpyrrolidone. is condensed with 1 molar equivalent of aromatic aldehyde Ar_1CHO (which may be the same as aldehyde Ar_9CHO) to form bisanyl Ar_9-CH=N
-C(CN)=C(CN)-N-CH-Ar_1_0, in which Ar_9 and Ar_1_0 are the same or different, Ar_9 is an indolyl group, and Ar_1_0
is an indolyl group or a phenyl group optionally substituted with -N(C_1_-_4alkyl)_2).