JPH04316549A - Diazo compound and its production - Google Patents

Abstract

PURPOSE:To provide a new 4-arylazo-3-aryl or beta, beta-disubstituted-alpha, beta-unsaturated alkenyl-phenol useful as an intermediate for substituted p-aminophenol delivative for agricultural chemicals, pharmaceuticals, degradable polymers and various recording materials. CONSTITUTION:The compound of formula (Ra and Rb are alkyl, aryl, alkoxy, aryloxy, substituted amino, etc.; Ra and Rb may together form a 5 to 12-membered ring; Rc is H, alkyl, aryl, halogen, alkenyl, etc.; R5 and R6 may together form a 5 to 6-membered ring; Rx and Ry are Ra to Rc, etc., sulfo, nitro, carboxy, etc.), e.g. 4-phenylazo-3-phenylphenol. The compound of formula can be produced by reacting a 3-aryl or beta, BETA-disubstituted-alpha, beta-unsaturated alkenyl-phenol with a diazonium salt.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to 4-arylazo 3-aryl or β, -disubstituted α,β-unsaturated alkenyl-phenols.

0002

BACKGROUND OF THE INVENTION 4-arylazophenols having an unsaturated double bond at the 3-position have never been studied other than the unusual reaction discovered by the present inventors. After careful consideration, we found that the reaction was completely different from the conventional one.
It was discovered that phenols with specific unsaturated double bonds provide stable azo compounds, and rearrangement to indole rings is suppressed.

0003

[Problem to be Solved by the Invention] The present inventors have discovered that 4-arylazo 3-aryl or β,β-disubstituted α,β
Unsaturated alkenyl-phenols are used in various applications such as agricultural chemicals, pharmaceuticals, degradable polymers, phenolic couplers for photography, color developers for pressure- and heat-sensitive recording materials, color formers, photoconductive agents, EL materials, and diazonium salts. The present invention was accomplished by paying attention to the fact that it is useful for recording material applications.

0004

[Means for Solving the Problem] The above object is solved by 4-arylazo 3-aryl or β,β-disubstituted α,β-unsaturated alkenyl-phenol and 3-aryl or β,
The problem was solved by developing a production method characterized by the action of a diazonium salt on a β-disubstituted α,β unsaturated alkenyl-phenol. The aryl group is a 5- to 6-membered ring which may contain a single or fused heteroatom, such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyridine ring, a benzothiazole ring, a furan ring, a thiophene ring, or any of these. Indicates an analog of These may have a plurality of various substituents described later. β,β-disubstituted α,β unsaturated alkenyl groups have two substituents of various types other than hydrogen atoms at the β position, such as alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, halogen atoms, and alkoxy groups. say something These may form a ring. for example,
Particularly preferred are rings containing unsaturated double bonds which may have 4- to 15-membered heteroatoms. The ring may have a nitrogen atom, a substituted amino group, an ether bond, a thioether bond, a carbonyl group, a thiocarbonyl group, or the like. Of course, the ring may form part of a fused aromatic ring. Furthermore, the phenol moiety, aryl moiety or unsaturated alkenyl moiety includes an alkyl group, an aryl group, an alkoxy group, an acyl group, an alkenyl group, an alkynyl group, a halogen atom, a substituted amino group, a sulfo group, a carboxyl group,
1 to 6 various substituents selected from hydroxy groups, etc.
It is also possible to have approximately one. Needless to say, the arylazo bond is important as a precursor for an amino group. 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, Ra and Rb are an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a substituted amino group,
It is selected from acyl groups, halogen atoms, alkenyl groups, alkynyl groups, oxy groups, carbamoyl groups, sulfamoyl groups, and substituted groups thereof. Ra and Rb are
They can also be bonded to each other to form a ring containing an unsaturated double bond which may have a 4- to 15-membered heteroatom. Preferred is a 5- to 12-membered ring. As mentioned earlier, it may form an aromatic ring. Furthermore, the ring may have various heteroatoms in the number of members. Rc 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 halogen atom, an alkenyl group, an alkynyl group, an oxy group, and the like. R5 and R6 can also have a 4- to 8-membered cyclic structure. Preferably, it is a 5- to 6-membered ring. R
x and Ry can be water-soluble groups such as the above-mentioned groups, sulfo group, nitro group, carboxyl group, phenylazo group, sulfophenylazo group, and salts thereof.

The compounds of the present invention are 3-aryl or β
, β-disubstituted α,β-unsaturated alkenyl-phenol can be smoothly synthesized by a method for producing a compound characterized by reacting a diazonium salt with a β-disubstituted α,β-unsaturated alkenyl-phenol. Diazonium salt is
It is derived from conventional aromatic amines according to conventional methods. Already familiar with writing as a unit operation. For example, S. Pata
i,The Chemistry of Diazon
ium and Diazo Groups. John
Wiley & Sons (1978). K. H. S
unders, Aromatic Diazo Co
mpounds. Raw materials, usage, mixing methods, reaction conditions, etc. are described in detail in Edward Arnold et al., and can be used as a reference. Specific examples of the compound of general formula (1) of the present invention are shown below.

4-Phenylazo-3-Phenylpheno-
4-p-methoxyphenylazo-3-phenylphenol, 4-phenylazo-3-tolylphenol, 4
-p-butoxyphenylazo-3-phenylphenol, 4-sulfophenylazo-3-naphthylphenol,
4-phenylazo-3-xylylphenol, 4-m-
Methoxyphenylazo-3-phenylphenol, 4-
Phenylazo-3-methylallylphenol, 4-phenylazo-3-β-methylcyclohexenylphenol, 4-sulfophenylazo-3β-methylcyclooctenylphenol, 4-p-methylphenylazo-3 ─o
-chlorophenylphenol, 4-dimethylphenylazo-3-phenylphenol,

4-phenylazo-3-phenyl-6-
Methoxyphenol, 4-phenylazo-2,3-dimethylallylphenol, 4-phenylazo-3-β-butylcyclohexenylphenol, 4-sulfophenylazo-3-β-methylcycloheptenylphenol Le, 4
-deuterophenylazo-3,6-diphenylphenol, 4-deuterophenylazo-3-phenylphenol, 4-sulfonaphthylazo-3-phenylphenol, 4-o-carboxyphenylazo- 3-β-methylcyclohexadienylphenol, 4-phenylazo-3-β-methylcyclohexenylphenol, 5,6
─Methylenedioxy─4-pentadeuterophenylazo─3-phenylphenol, 4-phenylazo─3─
α-phenyl-β-furylvinylphenol, 4-phenylazo-3-1-naphthylphenol, 4-phenylazo-3-furylphenol, 4-phenylazo-3-
2-pyridylphenol, 3-2,6-dimethyl-1-
Cyclohexenyl-4-phenylazophenol, 3-
2,7-dimethyl-1-cycloheptenyl-4-phenylazophenol, 3-2,8-dimethyl-1-cyclooctenyl-4-phenylazophenol, 3-cyclohexylidenemethyl-4-phenylazophenol, 3
─β-acetylcyclohexylidene ─4-phenylazophenol,

4-(2-phenylazo-5-hydroxyphenyl)3,5-dimethyl-1-acetyl-1,2,
5,6-tetrahydropyridine, 3-2-methyl-β-methyl-1-cyclooctenyl-4-phenylazophenol, 3-α-isopropyl-β,β'-dimethylvinyl-4-phenylazophenol, 3-α- Propyl-β,β'-dimethylvinyl-4-phenylazophenol, 3-α-phenyl-β,β'-dimethylvinyl-
These include 4-phenylazophenol. These compounds behave completely differently from the compounds previously proposed by the present inventors, and are stable even under conditions such as concentration and heating in acidic conditions. These compounds, as detailed in the Examples,
It provides a skeleton that is completely unexpected from conventional methods.

[0011]

【Example】

Example 1 Synthesis of 4-phenylazo-3-phenylphenol. m-phenylphenol was stirred with a benzenediazonium salt synthesized from equivalent amounts of aniline and sodium nitrite in an acetone-methanol mixed solvent at -30 degrees or lower using triethylamine as a base. 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 in which a diazonium salt was coupled to the p-position of the raw material phenol, and could be stably extracted. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent. The product was an orange semisolid. Its UV spectrum had an absorption maximum at 358 nm, and ε was 18,300.

Example 2 Synthesis of 4-phenylazo-3(2,6-dimethyl-1-cyclohexenyl)phenol. The reaction and purification were carried out in the same manner except that 3(2,6-dimethyl-1-cyclohexenyl)phenol was used. The product was an orange semisolid similar to that of Example 1. Its UV spectrum had an absorption maximum at 358 nm, and ε was 19,100.

Reference Example 1 Synthesis of 4-phenylazo-3-cyclohexylphenol. The reaction and purification were carried out in the same manner except that 3-cyclohexylphenol was used. The product was an orange semisolid similar to that of Example 1. Its UV spectrum had an absorption maximum at 357 nm, and ε was 22,200. The yield was about 85% in all cases.

Claims (1)

[Claims] Claim 1: 4-arylazo 3-aryl or β
, β-disubstituted α,β-unsaturated alkenyl-phenol.Claim 2: The 3-aryl or β-disubstituted α,β-unsaturated alkenyl-phenol according to claim 1, characterized in that a diazonium salt is reacted with the 3-aryl or β,β-disubstituted α,β-unsaturated alkenyl-phenol. Method for producing compounds