1H-pyrrolo-[1,2-b][1,2,4,]triazole...

Details 1H-pyrrolo-[1,2-b][1,2,4,]triazole... 1H-pyrrolo-[1,2-b][1,2,4,]triazole...

1998-01-07

2002-05-07

Morris, Patricia L. (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Four or more ring nitrogens in the bicyclo ring system

C540S603000, C544S058400, C544S366000, C546S199000, C548S262400

Reexamination Certificate

active

06384219

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a novel 1H-pyrrolo-[1,2-b][1,2,4]triazole compound useful as a synthetic intermediate of physiological active substances, including medicines, agricultural chemicals, and the like, as a photographic cyan coupler, as a dye for heat transfer dye-donative materials, and as a precursor of a filter dye for solid state television camera tubes and color liquid crystal televisions. The present invention also relates to a 1H-1,2,-triazole compound that is an intermediate for synthesizing the same efficiently.
Further, the present invention relates to a method for synthesizing cyclohexyl acetates useful, for example, as synthetic intermediates of dyes and as synthetic intermediates of dye-forming couplers, in the field of photographic chemistry.
BACKGROUND OF THE INVENTION
1H-pyrrolo-[1,2-b][1,2,4]triazole derivatives are described, with respect to their reactivities, generally, in Ukrainski Khimicheskii Zhurnal, Vol. 41, No. 2, pages 181 to 185 (1975), and in Khimiya Geterotsiklicheskikh Scedine nii, No. 2, pages 261 to 267 (1974), and their use as medicines and the like is described in U.S. Pat. Nos. 4,358,457 and 4,962,202. Further, the derivatives are described as photographic magenta couplers and magenta dyes in Nihon Shashin Gakkai Showa 60-Nendo Nenji Taikai Koen Yoshi-shu, JP-A-62-278552 (“JP-A” means unexamined published Japanese patent application), JP-A-62-279339, JP-A-1-288835, U.S. Pat. No. 4,910,127 and EP-A-491 197.
Furthermore, U.S. Pat. Nos. 5,256,526, 5,384,236, and 5,547,826 disclose that 1H-pyrrolo-[1,2-b][1,2,4]triazole derivatives can be made into compounds useful as photographic cyan couplers by introducing electron-attracting groups to the 6-position and the 7-position of the 1H-pyrrolo-[1,2-b][1,2,4]triazole derivatives. As methods for synthesizing 1H-pyrrolo-[1,2-b][1,2,4]triazole derivatives having electron-attracting groups at the 6-position and the 7-position, synthetic methods wherein 1H-1,2,-triazole derivatives are used as a starting material are described in JP-A-5-202,004 and JP-A-5-255333. In addition, JP-A-7-48376 and JP-A-8-109172 disclose compounds useful as photographic cyan couplers and methods for synthesizing them, and also their efficient synthetic methods.
On the other hand, many general esterification methods that use condensation of carboxylic acids with alcohols are known, and examples are described in detail in Jikken Kagaku-koza, Vol. 22 (Maruzen, 1992), pp. 43 to 83. Among these, for example, a method for synthesizing an ester by using an equilibrium reaction in the presence of an acid catalyst under dehydration conditions, or a method for synthesizing an ester by using a condensing agent, such as dicyclohexylcarbodiimide and ethyl azodicarboxylate, are often used. Furthermore, there is an acid chloride method for synthesizing an ester, wherein a carboxylic acid is converted by means of thionyl chloride, phosphorus trichloride, or oxalyl chloride, to an acid chloride, and the acid chloride is subjected to addition reaction of an alcohol, in the presence of a base.
The foregoing general esterification methods, however, could not be applied to the synthesis of ester compounds represented by the below-shown formula (IX) using carboxylic acids represented by the below-shown formula (VII) and cyclohexanols represented by the below-shown formula (VI), which are intended to be condensed in the present invention. Namely, the method that uses acid catalysts is accompanied by the problem that large amounts of cyclohexanols are used, and the method that uses condensing agents and the acid chloride method can hardly give the intended ester compounds, because, in the esterification of cyclohexanols, carboxylic acid components are preferentially decomposed. Only one method, using trifluoroacetic anhydride ((CF
3
CO)
2
O), described in Journal of Organic Chemistry, Vol. 30, page 927 (1965), has been applied, but the reagent is expensive and the treatment of the waste liquid is complicated, making the method difficult for use as an industrial process.
SUMMARY OF THE INVENTION
Therefore, a first object of the present invention is to provide a compound represented by the below-shown formula (I) useful as a photographic cyan coupler.
A second object of the present invention is to provide a synthetic intermediate(s) necessary for the synthesis of the compound represented by formula (I).
A third object of the present invention is to provide an industrial production method for obtaining cyclohexyl acetates represented by the below-shown formula (IX), in a good yield, by reacting cyclohexanols with carboxylic acids under mild reaction conditions.
Other and further objects, features, and advantages of the invention will appear more fully from the following description.
DETAILED DESCRIPTION OF THE INVENTION
The inventors of the present invention have studied intensively in various ways to develop 1H-pyrrolo-[1,2-b][1,2,4]triazole compounds useful as photographic cyan couplers. The inventors have found that compounds wherein specific substituents are introduced to the 2-position and the 5-position of the pyrrolotriazole skeleton show excellent properties as photographic couplers in view of the hue of the dye formed, the coupling activity, the stain during and after photographic processing, the storage stability of them as couplers, the fastness of their dyes, etc., leading to the completion of the present invention.
The above objects have been attained by providing the compounds represented by the following formulas and the production method.
(1) A 1H-pyrrolo-[1,2-b][1,2,4]triazole compound represented by formula (I):
wherein, in formula (I), R represents an alkyl group; R
1
, R
2
, R
3
, R
1
′, R
2
′, and R
3
′ each represent a hydrogen atom or an alkyl group; R
1
and R
2
, and R
1
′ and R
2
′, may bond together to form a ring, respectively; R
4
represents a hydrogen atom or an alkyl group, and X represents a heterocyclic group, a substituted amino group, or an aryl group.
(2) A 1H-1,2,-triazole compound represented by formula (II):
wherein, in formula (II), R represents an alkyl group; R
1
, R
2
, R
3
, R
1
′, R
2
′, and R
3
′ each represent a hydrogen atom or an alkyl group; R
1
and R
2
, and R
1
′ and R
2
′, may bond together to form a ring, respectively; R
4
represents a hydrogen atom or an alkyl group, and R
5
represents a hydrogen atom or an alkyl group.
(3) A 1H-1,2,4-triazole compound represented by formula (III):
wherein, in formula (III), R represents an alkyl group; R
1
, R
2
, R
3
, R
1
′, R
2
′, and R
3
′ each represent a hydrogen atom or an alkyl group; R
1
and R
2
, and R
1
′ and R
2
′, may bond together to form a ring, respectively; R
4
represents a hydrogen atom or an alkyl group, and W represents a halogen atom.
(4) A method for producing an ester compound represented by the following formula (IX), by reacting cyclohexanols represented by the following formula (VI) and carboxylic acids represented by the following formula (VII), using a carboxylic acid anhydride represented by the following formula (VIII):
wherein R
11
represents a hydrogen atom or an alkyl group; R
12
, R
13
, R
14
, R
12
′, R
13
′, and R
14
′, which are the same or different, each represent a hydrogen atom or an alkyl group, R
12
and R
13
, and R
12
′ and R
13
′, may bond together to a form ring, respectively; R
15
and R
16
, which are the same or different, each represent a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, with at least one of R
15
and R
16
being a hydrogen atom; R
17
represents an aliphatic group or an aryl group; R
18
and R
19
, which are the same or different, each represent a hydrogen atom, a halogen atom, an alkyl group, or an aryl group; R
18
and R
19
may bond together to form a ring; M represents a hydroge

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