JPH04235965A - 1-arylamino-5-hydroxyindole derivative - Google Patents

Abstract

PURPOSE:To obtain a 1-arylamino-2,3-alkylene-5-hydroxyindole useful as agricul tural chemicals, developers of pressure- and heat-sensitive recording materials, etc., for recording materials. CONSTITUTION:For example, a compound expressed by the formula (R0 is H or 1-12C alkyl; R2, R5 and R6 are H, alkyl, aryl, etc.; X is bivalent organic group required to form a 4- to 15 membered ring; Rx and Ry are sulfo, nitro, etc.) is used as agricultural chemicals, medicines, degradable polymers, photographic phenolic couplers, etc. The ring in the compound expressed by the formula is preferably the 4- to 15-membered ring, which may have a hetero-atom such as N, a substituted amino, ether bond or thioeter bond in the cyclic structure or may form part of an aromatic ring.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION The present invention relates to an indole having a hydroxyl group at the 5-position and substituted with an aryamino group at the 1-position, which is useful for use in agricultural chemicals, medicines, degradable polymers, and various recording materials.

0002

[Prior Art] 1-arylamino-2,3-alkylene-5-hydroxyindoles have never been studied.

0003

[Problems to be Solved by the Invention] The present inventors have discovered that this compound can be used in agricultural chemicals, medicines, degradable polymers, phenolic couplers for photography, color developers and color formers for pressure-sensitive and heat-sensitive recording materials, or diazonium salts. The present invention was developed by paying attention to the fact that the present invention is useful for various recording material applications.

0004

[Means for Solving the Problems] The above problems were solved by developing 1-arylamino-2,3-alkylene-5-hydroxyindoles. In the present invention, the size of the ring is preferably 4 to 15 members. The ring may have a nitrogen atom, a substituted amino group, an ether bond, or a heteroatom such as a thioether bond in the cyclic structure. The ring may form part of an aromatic ring. It may also contain one to six substituents of various types, such as an alkyl group, an alkoxy group, a halogen atom, an aryl group, an acyl group, an optionally substituted amino group, a carboxyl group, an oxo group, and a carboxyl group. . These may be substituted with an aliphatic cyclic moiety or an aromatic nuclear moiety. The compounds of the present invention can also be represented by the following general formula. General formula (1)

[0005]

[Chemical formula 1]

In the formula, R0 represents a hydrogen atom or an alkyl group having about 1 to 12 carbon atoms which may have a substituent. Examples of the substituent include the various substituents mentioned above, such as an alkoxy group, an aryl group, an acyl group, a substituted aminoalkyl group, and a hydroxy group. R2, R5
, R6 are selected from a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a substituted amino group, an acyl group, a halogen atom, and the like. R5 and R6,
R2 and ring A can also have a 4- to 8-membered cyclic structure. Preferably, it is a 5- to 6-membered ring. Ra
is selected from a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a substituted amino group, an acyl group, a carboxyl group, and the like. X represents a divalent organic group necessary to constitute a ring consisting of 4- to 15-membered nonmetallic atoms. Rx and Ry can be water-soluble groups such as the groups mentioned above, sulfo groups, nitro groups, carboxyl groups, and salts thereof. Here, when X represents -(CH2)n-, it is called as follows for convenience. When n is 2, 3, 4, 6, or 8, they are respectively called ethylene, trimethylene, tetramethylene, hexamethylene, and octamethylene. Specific examples of the compound of general formula (1) of the present invention are shown below.

7-Hydroxy-N-anilino 1, 2,
3,4-tetrahydrocyclopenta(b)indole (1-anilino 2,3-trimethylene-5-oxindole). 6-hydroxy-9-anilino 1, 2,
3,4-tetrahydrocarbazole, 6-hydroxy-9-anilino 1,2,3,4-tetrahydro 2-methylcarbazole (1-anilino 2,3-tetramethylene-5-oxindole) 6-hydroxy-9-anilino 1,2,3,4-tetrahydro 2-butylcarbazole, 6-hydroxy-9-anilino 1, 2,
3,4-tetrahydro-2-phenylcarbazole, 6
-Hydroxy-9-anilino1,2,3,4-tetrahydro2,2-5,5-tetramethylcarbazole,
6-Hydroxy-9-anilino 1,2,3,4-tetrahydro-2-oxocarbazole, 6-hydroxy-9-p-toluidino 1,2,3,4-tetrahydrocarbazole, 6-hydroxy-9-p-benzoylanilino 1,2,3,4 -Tetrahydrocarbazole, 6
-Hydroxy-9-p nitroanilino 1, 2, 3,
4-tetrahydro-2-oxocarbazole, 6-hydroxy-9-(2,6-dimethylanilino)-1,2,
3,4-tetrahydrocarbazole, 6-hydroxy-9-p-sulfoanilino 1,2,3,4-tetrahydrocarbazole, 6-hydroxy-9-o-sulfoanilino 1,2,3,4-tetrahydrocarbazole, 6
-Hydroxy-9-o-carboxyanilino 1, 2,
3,4-tetrahydrocarbazole,5-hydroxy-6,7,8,9,10,11-hexahydro-5-anilinocycloocta(b)indole Synthesized by a totally unexpected reaction route.

[0008]

EXAMPLES Example 1 Synthesis of 1-anilino-2,3-trimethylene-5-hydroxyindole. 1-m-hydroxyphenyl-1-cyclopentene was stirred with a benzenediazonium salt synthesized from equivalent amounts of aniline and sodium nitrite in an acetone-methanol mixed solvent at -30 degrees Celsius or lower. After stirring for 15 minutes at 0 degrees, the mixture was treated with ice-cooled dilute sulfuric acid. The solvent was removed under heating and reduced pressure according to a conventional method. Next, column chromatography was performed using a hexane-ethyl acetate mixed solvent as a developing solvent and silica gel as a carrier to separate the target product. The product was a compound that was thought to have been caused by coupling of the diazonium salt to the p-position of the raw material phenol and then rearrangement by the acid used. 7-Hydroxy-N-anilino 1,2,3,4-tetrahydrocyclopenta(b) indole (1-anilino 2,3-trimethylene-5-oxindole)
I got it. It was a slimy semi-solid with a slight orange tinge.

Example 2 Synthesis of 1-anilino 2,3-tetramethylene-5-hydroxyindole. 1-m-hydroxyphenyl-1
-The reaction was carried out in the same manner as in Example 1, except that cyclohexene was used. The target product was separated by column chromatography using silica gel as a carrier. The product was a compound that was thought to have been caused by coupling of the diazonium salt to the p-position of the raw material phenol and then rearrangement by the acid used. 6-Hydroxy-1,2,3,4-tetrahydro-9-anilinocarbazole (1-anilino2
, 3-tetramethylene-5-oxindole). Melting point: 170-172 degrees, yield: 58%.

Example 3 Synthesis of 1-anilino 2,3-pentamethylene-5-hydroxyindole. 1-m-hydroxyphenyl-1
The same post-treatment as in Example 1 was carried out using -cycloheptene. The target product was separated by column chromatography using a hexane-ethyl acetate mixed solvent as a developing solvent and silica gel as a carrier. The product was a compound that was thought to have been caused by coupling of the diazonium salt to the p-position of the raw material phenol and then rearrangement by the acid used. 1-anilino 2,3-pentamethylene-5-oxindole. Melting point 152-154 degrees, yield 4
7%.

Example 4 Synthesis of 1-anilino 2,3-hexamethylene-5-hydroxyindole. 1-m-hydroxyphenyl-1
-The reaction was carried out in the same manner as in Example 1 except that cyclooctene was used. The target product was separated by column chromatography using silica gel as a carrier. The product was a compound that was thought to have been caused by coupling of the diazonium salt to the p-position of the raw material phenol and then rearrangement by the acid used. 1-anilino 2,3-hexamethylene-5-oxindole. Melting point: 161-162 degrees, crude yield: 87%.

Example 5 Synthesis of 1-anilino 2,3-decamethylene-5-hydroxyindole. The reaction was carried out in the same manner as in Example 1 except that 1-m-hydroxyphenyl-1-cyclododecene was used. The target product was separated by column chromatography using silica gel as a carrier. The product was a compound that was thought to have been caused by coupling of the diazonium salt to the p-position of the raw material phenol and then rearrangement by the acid used. 1-anilino 2,3-decamethylene-5-oxindole. Melting point 166.5-167 degrees, yield 5
6.7%.

Example 6 Synthesis of 1-pentadeuteroanilino 2,3-tetramethylene-5-hydroxyindole. Example 2 except that pentadeuteroaniline (aniline-d5) was used.
The reaction was carried out in the same manner. The target product was separated by column chromatography using silica gel as a carrier. The product was a compound that was thought to have been caused by coupling of the diazonium salt to the p-position of the raw material phenol and then rearrangement by the acid used. 6-hydroxy 1, 2,
3,4-tetrahydro9-pentadeuteroanilinocarbazole (1-pentadeuteroanilino2,3
-tetramethylene-5-oxindole) Melting point: 170-172 degrees, yield: 66.3%. Reference Example 6 - Hydroxy-perhydrocarbazole 1-anilino 2,3-tetramethylene-5-oxindole was weighed. Using Raney Ni catalyst, hydrogen gas is
It was packed at kg/cm2. When the catalytic reduction reaction was carried out under pressure at a temperature of 40 degrees, 6-hydroxy-1,2,3,4-tetrahydrocarbazole and aniline were obtained in a ratio of exactly 1:1. Under severe pressure conditions of 70 kg/cm2 and temperature of 60 degrees, 6-hydroxyperhydrocarbazole was obtained in high yield. (The aromatic nucleus was completely hydrogenated.)

Claims (1)

[Claims] Claim 1: 1-arylamino-2,3-alkylene-5-hydroxyindole