JPS6348249A - Diarylethane derivative and production thereof - Google Patents

Abstract

PURPOSE:To efficiently and readily obtain the titled compound containing a novel compound in a short time by simple purifying and separating operation without requiring a special apparatus, by reacting an specific aniline compound with another compound. CONSTITUTION:An aniline derivative expressed by formula I [R1 and R2 are H, (substituted) saturated and unsaturated alkyl, (substituted) cycloalkyl and aralkyl or (substituted) aryl or R1 and R2 together may form a heterocyclic ring; R3-R6 are H, halogen, (substituted) alkyl and hydroxyl or (substituted) amino] is reacted with a compound expressed by formula II [R is (substituted) benzene ring and naphthalene ring or (substituted) heterocyclic ring], as necessary, in the presence of a dehydration condensing agent, e.g. concentrated sulfuric acid, etc., in an inert solvent at 30-200 deg.C to afford the aimed compound, expressed by formula III and containing a novel compound expressed by formula IV (R7-R11 are same as R1 and R2 except formation of the heterocyclic ring, amino or acylamino). USE:A raw material for diarylethylene derivatives which are intermediates for pressure-sensitive recording paper, etc.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention relates to diarylethane derivatives and a new method for producing the same, and in particular to diarylethane derivatives, which are intermediates for dyes for pressure-sensitive recording paper and heat-sensitive recording paper. The general formula (
The present invention provides a diarylethane derivative represented by I[[) and a novel method for producing the same.

[In the formula, R represents a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted heterocycle, and R1+R1 are each a hydrogen atom, a substituted or unsubstituted saturated alkyl group, a substituted or Indicates an unsubstituted unsaturated alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group,
R8 and R2 may be bonded to each other or may form a heterocycle with an adjacent benzene ring. Also, R'! , R4
, Rs, and Rh each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted hydroxyl group, and a substituted or unsubstituted amino group. [Prior Art] Generally, as a method for producing diarylethane derivatives, a method is known in which a diarylethane derivative and acetaldehyde are heated using an acid catalyst. However, this method requires a long time for the reaction and the yield is not good. In addition, since acetaldehyde with a low boiling point is used, the manufacturing equipment is limited to a specific one, so it cannot be said that it is an industrially advantageous manufacturing method. Moreover, although symmetrical diarylethane derivatives can be synthesized, asymmetrical derivatives cannot be synthesized, and there is also the problem that the types of compounds are limited.

``Problems to be Solved by the Invention'' The present invention provides a production method that can efficiently obtain diarylethane derivatives without the above-mentioned defects, and in which purification and separation operations are extremely simple.

"Means for Solving the Problem" The present invention relates to a method represented by the general formula (II[), characterized in that an aniline derivative represented by the general formula [I] and a compound represented by the general formula (II) are reacted. This is a method for producing diarylethane derivatives.

CI ) (n) [wherein, R,
R+, Rz, Rs, R4, Rs, R6 are respectively
゛ indicates the above meaning. [Operation] The reaction in the method of the present invention is carried out in the absence of a solvent or in the presence of a solvent. In the case of a solvent-free reaction, there is no need to separate the solvent after the reaction is completed, which simplifies the process.

As the solvent, water, an organic solvent inert to the reaction, or a mixed solvent thereof is used. Examples of the organic solvent inert to the reaction include acetone, chloroform, tetrahydrofuran, dioxane, toluene, xylene, etc., but the organic solvent is not particularly limited to these as long as it is inert to the reaction.

6-Although the reaction can be carried out without a dehydration condensation agent, the reaction temperature can be lowered by using a dehydration condensation agent. Examples of dehydration condensation agents include inorganic acids such as hydrochloric acid, sulfuric acid, polyphosphoric acid, pyrophosphoric acid, and phosphoric acid; organic acids such as p-)luenesulfonic acid, formic acid, acetic acid, and propionic acid; tin chloride, zinc chloride, and aluminum chloride. , anhydrous metal chlorides such as iron chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus pentoxide, etc. are used, but hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, and propionic acid are preferably used because they can also serve as a solvent. It will be done. Note that the amount used is appropriately adjusted depending on the type of dehydration condensation agent used.

Examples of the compound represented by the general formula (1) include dimethylaniline, diethylaniline, dipropylaniline, dibutylaniline, dimethyl-m-toluidine, diethyl-m-)luidine, dimethyl-m-chloroaniline, diethyl-m- -chloroaniline, dimethyl-m-anisidine, diethyl-m-phenetidine, N-methyl,
N-benzylaniline, N-ethyl-N-4-chlorobenzylaniline, diphenylaniline, dibrobagylaniline, N-methyl-N-ethoxyethylaniline, N
-ethyl-N-ethoxyethylaniline, N-methyl-
N,-2,3-dimethoxypropylaniline, N-ethyl-N-2,3-dimethoxypropylaniline, N-ethyl-N-β-chloroethylaniline, N-ethyl-N
-β-chloroethyl-m-toluidine, N-ethyl-N
-β-cyanoethylaniline, N-ethyl-N-β-cyanoethyl-m-toluidine, N-methyldiphenylamine, 4-methoxy-N-methyldiphenylamine, N
-Phenylpyrrolidine, N-phenylmorpholine, N-
Phenylpiperidine, N-3-methylphenylpiperidine, N-3-methylphenylmorpholine, aniline, N
-Methylaniline, N-benzylaniline, N-benzyl-N-ethylaniline, N,N-dibenzylaniline, N-4-chlorobenzyl-N-allylaniline, N-
Allylaniline, N-allyl-N-phenylaniline,
N-β-chloroethyl-N-ethyl-2゜3-dimethylaniline, N-β-chloroethyl-N-benzyl-2-
Methyl-3-chloroaniline, N-ethoxyethyl-N
-ethyl-m-)luidine, N-2-dimethylaminoethyl-N-methylaniline, N-cyclohexyl-N-
Ethyl-〇-toluidine, N,N-dimethyl-3,5-
Dimethoxyaniline, N-3-methylphenylpyrrolidine, N-3-acetylaminophenylpyrrolidine, N-
2-chlorophenylpyrrolidine, N-3-methyl-5-
Chlorophenylpyrrolidine, N.

N-dimethyl-m-acetylaminoaniline, N-3-
Methoxybenzyl-N-propargylaniline, N-4-
Methylbenzyl-N-isopropylaniline, Julolidine, 1-methyl-1,2゜3.4-tetrahydroquinoline, 1.2,2.4-tetramethyl-1,2-dihydroquinoline, N-α-naphthyl-N - methylaniline,
N-ethyl-N-isopropyl-〇-bromoaniline,
Examples include N-p-methylphenyl-N-butylaniline.

-8 = On the other hand, examples of the compound represented by the general formula (IF) include 1-phenylethanol, 1-(4-methylphenyl)ethanol, 1-(4-methoxyphenyl)ethanol, 1-(4-ethoxyphenyl) ) ethanol, 1-
(2,4-dimethylphenyl)ethanol, 1-, (4
-chlorophenyl)ethanol, 1-(2-chloro-3
-methylphenyl)ethanol, 1-(2-methyl-4
-aminophenyl)ethanol, 1-(2-chloro-4
-aminophenyl)ethanol, 1-(4-acetylaminophenyl)ethanol, 1-(4-dimethylaminophenyl)ethanol, 1-(4-pyrrolidinophenyl)ethanol, 1-(2-methyl-4-dimethylamino phenyl)ethanol, 1-(3-chloro-4-pyrrolidinophenyl)ethanol, 1-(4-morpholinophenyl)ethanol, 1-(4-piperidinophenyl)ethanol, 1-(4-p-chloro- phenoxyphenyl)ethanol, ■-(4-phenoxyethylphenyl)ethanol, 1-(4-bromophenyl)ethanol, 1-(2,4,6-titrachlorophenyl)ethanol, 1-(4-hydroxyphenyl)ethanol ,1
-(4-cyclohexylphenyl)ethanol, 1-
(4-p-methylphenoxyphenyl)ethanol, 1
-(4-p-ethylbenzylphenyl)ethanol, 1
- (2-methyl-4-allylphenyl)ethanol,
1-(4-N-methyl-N-benzylaminophenyl)
Ethanol, 1-(4-N-allyl-N-tetrahydrofurfurylaminophenyl)ethanol, 1-(4-
N-p-tolyl-N-ethylaminophenyl)ethanol, 1-(4-N-methoxyethyl-N-ethylaminophenyl)ethanol, 1-(4-N-β-chloroethyl-N-methylaminophenyl)ethanol , 1-(
4-N-p-chlorophenoxyethyl-N-propargylaminophenyl)ethanol, 1-(4-N-2-butenyl-N-ethylaminophenyl)ethanol, 1-(
4-N-isopropyl-N-methylaminophenyl)ethanol, 1-(4-phenylphenyl)ethanol,
1(4N-dimethylaminoethyl-N-ethylaminophenyl)ethanol, 1-(3-ethyl-4-phenethylphenyl)ethanol, 1-(3-methyl-4-chlorobenzylphenyl)ethanol, 1-(2- Chloro
4-amino-5-methylphenyl)ethanol, ■-α
-naphthylethanol, 1-β-naphthylethanol,
1-(4-methyl-2-naphthyl)ethanol, 1-(
4-dimethylamino-1-naphthyl)ethanol, 1-
(4-(isoindolin-2-yl)'phenyl)ethanol, 1-(4-N-methyl-N-tetrahydrofurfurylaminophenyl)ethanol, and the like.

The usage amount of these compounds represented by the general formula (I[) is:
Usually about 0.5 to 2 mol, more preferably 0.8 to 1.0 mol per mol of the aniline derivative represented by general formula [I].
The amount is adjusted within the range of 5 mol, and the reaction is usually carried out at a temperature of 30 to 200°C, preferably 50 to 150°C. The diarylethane derivative after the reaction is completed is isolated by distillation, crystallization, extraction, etc. in accordance with conventional methods.

The diarylethane derivative obtained by the above reaction is represented by the general formula (I[[), and among them, the compound represented by the following general formula [IV] is a new compound, It is a particularly preferable compound as an intermediate in the synthesis.

[In the formula, Rh, Rz, R3', Rh, Rs, Rh each have the above-mentioned meanings, and R7, R, R9, R+. , R
+ Each represents a hydrogen atom, a substituted or unsubstituted saturated alkyl group, a substituted or unsubstituted unsaturated alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group. group, amino group, and acylamino group. ] Specific examples of the compound represented by the general formula (II[) include the following.

1.1-bis(4-dimethylaminophenyl)ethane,
1.1-bis(4-pyrrolidinophenyl)=12-ethane, 1.1-bis(4-diethylaminophenyl)
Ethane, 1.1-bis(4-N-ethyl-N-methoxyethylaminophenyl)ethane, 1°1-bis(4-dibenzylaminophenyl)ethane, 1,1. - screw (4
-p-methoxybenzylaminophenyl)ethane, 1.
1-bis(4-N-ethyl-N-allylaminophenyl)ethane, 1.1-bis(4-N-cyclohexyl-N
-ethylaminophenyl)ethane, 1,1-bis(4-
N-p-)I flu N-ethylaminophenyl)ethane, 1.1-bis(4-N-p-chlorophenyl-N-propargylaminophenyl)ethane, 1.1-bis(juloligno-9-yl) Ethane, 1,1-bis(4-N-
chloroethyl-N-propylaminophenyl)ethane,
1.1-bis(2-methyl-4-dimethylaminophenyl)ethane, 1.1-bis(3-chloro-4-piperidinophenyl)ethane, 1.1-bis(2,3-dimethyl-4 -diethylaminophenyl)ethane, 1.1-bis(2-methoxy-4-morpholinophenyl)ethane, 1
．． 1-bis(N-methyl-1,2,3゜4-tetrahydroquinolin-6-yl)ethane, 1-phenyl-1-(
4-dimethylaminophenyl)ethane, 1-phenyl-
1-(4-pyrrolidinophenyl)ethane, 1-(4-
methoxyphenyl)-1-(4-pyrrolidinophenyl)
Ethane, 1-(4-ethoxyphenyl)-1-(4-dimethylaminophenyl)ethane, 1-(4-ethoxyphenyl)-1-(2-methyl-4-diethylaminophenyl)ethane, 1-(4- methylphenyl)-1-(2
-acetylamino-4-pyrrolidinophenyl)ethane,
■-(4-dimethylaminophenyl)-1-(4-pyrrolidinophenyl)ethane, 1-(4-diethylaminophenyl)-1-(4-dimethylaminophenyl)ethane, 1-(4-N-acetylamino phenyl)-1-(
4-piperidinophenyl)ethane, 1-(2,3-dimethylamino)-1-(2-methyl-4-N-allyl-
N-methylaminophenyl)ethane, 1-(4-cyclohexylphenyl)-1-(2-chloro-4-diallylaminophenyl)ethane, 1-(4-phenoxy-5
-methylphenyl)-1-(3-methyl-4-di-p-
chlorobenzylaminophenyl)ethane, 1-(4-p
-methylphenoxyethylphenyl')-1-(2-ethoxy-4-dibutylaminophenyl)ethane, 1-(
4-N-phenyl-N-propargylaminophenyl)-
1-(2-acetylamino-4-morpholinophenyl)
Ethane, 1-(4-acetylaminophenyl)-1-(
4-pyrrolidinophenyl)ethane, 1-(4-acetylaminophenyl)-1-(4-dimethylaminophenyl)ethane, l-(3,4,5-trimethylphenyl")
-1-(2-methyl-4-N-β-chloroethyl-N-
ethylaminophenyl)ethane, 1-(1,2-dimethylindol-3-yl")-1-(4-dimethylaminophenyl)ethane, 1-(1-ethyl-2-methylindol-3-yl) - 1-(4-diethylaminophenyl)ethane, 1-(1゜2-dimethylindole-
3-yl)-1-(4-pyrrolidinophenyl)ethane, 1-(pyridin-4-yl)-1-(4-dimethylaminophenyl)ethane, 1-(tetrahydrofuran-2)
-yl)-1-(4-pyrrolidinophenyl)ethane, 1
-(1-ethylcarbazol-4-yl)-1-(4-
dimethylaminophenyl)ethane, 1-(pyrrole-2)
-yl)-1-(4-pyrrolidinophenyl)ethane, 1
-(naphthalen-1-yl)-1-(4-dimethylaminophenyl)ethane, 1-(naphthalen-1-yl)-
1-(4-diethylaminophenyl)ethane, 1-(naphthalen-1-yl)-1-(4-pyrrolidinophenyl)ethane, 1-(1-methoxynaphthalen-4-yl)-1-(4-diethylamino phenyl)ethane, 1-
(1-Ethoxynaphthalen-4-yl)-1-(4-pyrrolidinophenyl)ethane, 1-(1-aminonaphthalen-4-yl)-1-(4-dimethylaminophenyl)ethane, 1-(1 -aminonaphthalen-4-yl)
-1-(4-pyrrolidinophenyl)ethane, etc.

The above-mentioned diarylethane derivatives can be easily converted into the corresponding carbinol derivatives or further into diarylethylene derivatives by an oxidation reaction using an oxidizing agent such as lead peroxide, chloranil, bromine, potassium permanganate, or the like.

"Example" The present invention will be described in more detail with reference to Examples below, but it is of course not limited to these. In addition, % in an example shows weight %.

Example 1 l-(4-dimethylaminophenyl)ethanol 16.
14.7 g of N-phenylpyrrolidine was mixed with 200 ml of a chloroform solution containing 5 g of N-phenylpyrrolidine, and 2 mj of concentrated sulfuric acid was added. was added, and the reaction was carried out under reflux for 6 hours while removing generated water. After cooling, the reactant was dissolved in 100ml of 2% caustic soda aqueous solution.
, l! After washing with , the organic layer was concentrated under reduced pressure, and the precipitated crystals were collected by filtration. The precipitated crystals were recrystallized with ethanol and the melting point was 6.
1-(4-dimethylaminophenyl)-1 at 9-70°C
21.4 g of -(4-pyrrolidinophenyl)ethane was obtained.

-18~ Note that the 1-(4-dimethylaminophenyl)ethanol used was synthesized by the following reaction.

16.3 g of 4-dimethylaminoacetophenone was dissolved in 100 ml of isopropyl alcohol, then 4.0 g of sodium borohydride was added, and after reacting at 60°C for 1 hour, the reaction product was poured into water at 300 mA, and then dissolved in 200 mj2 of chloroform. The extract was used as it was in the reaction with the above aniline derivative. Other ethanol derivatives were synthesized in the same manner.

Example 2 19.1 g of l-(4-pyrrolidinophenyl)ethanol
Dissolve 16.1 g of N-3-methylphenylpyrrolidine in 300 mf of a chloroform solution containing
mA was added thereto, and the mixture was allowed to react under reflux for 2 hours while removing the produced water. After cooling, the reactant was heated to a 2% aqueous solution of caustic soda at 100 mA! After washing with , the organic layer was concentrated under reduced pressure, and the precipitated crystals were collected by filtration.

The precipitated crystals were recrystallized with ethanol, and the melting point was 88-90℃.
22.7 g of 1-(4-pyrrolidinophenyl)-1-(3-methyl-4-pyrrolidinophenyl)ethane was obtained.

Example 3 7.6 g of l-(4-methoxyphenyl)ethanol and N
- 7.35 g of phenylpyrrolidine in 100 m of toluene
7! Add 2 ml of concentrated sulfuric acid, and reflux for 6 hours.
The reaction was carried out while removing the produced water. After cooling, the reaction product was diluted with 10Q m of 2% aqueous sodium hydroxide solution.12. After washing with
21.9 g of 4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethane was obtained. The boiling point was 150-b.

Example 4 l-(4-dimethylaminophenyl)ethanol 8.2
Dissolve 5 g of dimethylaniline in 10 Qml of toluene solution containing 5 g of dimethylaniline, and add 1 m of concentrated sulfuric acid.
j2 was added, and the mixture was reacted under reflux for 6 hours while removing generated water. After cooling, the reaction mixture was diluted with 100ml of 2% aqueous sodium hydroxide solution. After washing with , the organic layer was concentrated under reduced pressure, and the precipitated crystals were collected by filtration. The precipitated crystals were recrystallized from methanol to obtain 10.7 g of 1,1-bis(4-dimethylaminophenyl)ethane having a melting point of 67-68°C.

Examples 5-15 Substituting N-phenylpyrrolidine as listed in Table 1
According to Example 1, except that the compound of general formula [I] and the compound of general formula (n) listed in Table '1 were used instead of 1-(4-dimethylaminophenyl)ethanol. A diarylethane derivative was obtained. The melting points or boiling points of the obtained compounds are also listed in Table 1.

``Effects'' As is clear from the examples, according to the method of the present invention, diarylethane derivatives can be produced in a short time without the need for special equipment, and asymmetric compounds can also be easily produced. This is what you get.

=20-

Claims (1)

[Claims] 1) Aniline derivatives represented by the general formula [I] ▲ Numerical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R_1 and R_2 are each a hydrogen atom, a substituted or unsubstituted saturated This represents an alkyl group, a substituted or unsubstituted unsaturated alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group, but do R_1 and R_2 bond to each other? A heterocycle may be formed together with adjacent benzene rings. Also,
R_3, R_4, R_5, R_6 are each a hydrogen atom,
It represents a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted hydroxyl group, or a substituted or unsubstituted amino group. ] Compound represented by the general formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [II] [In the formula, R is a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted naphthalene ring, or a substituted or unsubstituted naphthalene ring. Indicates a heterocycle. ] A method for producing a diarylethane derivative represented by general formula [III], which comprises reacting with. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [III] [In the formula, R, R_1, R_2, R_3, R_4, R_5
, R_6 each have the above meaning. ] (2) Diarylethane derivative represented by general formula [IV]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [IV] [In the formula, R_1 and R_2 are each a hydrogen atom, a substituted or unsubstituted saturated alkyl group, a substituted or unsubstituted unsaturated alkyl group, a substituted or unsubstituted cyclo Although it represents an alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group, R_1 and R_2 may be bonded to each other or may form a heterocycle with an adjacent benzene ring. Also,
R_3, R_4, R_5, R_6 are each a hydrogen atom,
Indicates a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted hydroxyl group, a substituted or unsubstituted amino group, R_7, R_8, R_9, R_1_0, R_1_
1 is a hydrogen atom, a substituted or unsubstituted saturated alkyl group, a substituted or unsubstituted unsaturated alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group , an amino group, and an acylamino group. ]