JPH03122169A - Manufacture of n1-substituted nitro-p-phenylenediamine and intermediate product - Google Patents

Abstract

PURPOSE: To obtain the subject high-purity amine by reacting acetylaminonitroaniline with a chloroformic acid alkyl ester to form a carbamate followed by a basic treatment and deacetylation with a strong acid.

CONSTITUTION: (A) 4-acetylamino-2-nitroaniline is reacted with an approximately equimolar amount of a chloroformic acid alkyl ester of formula I wherein X represents H or CH₃ and Y represents Cl or CH₂Cl to obtain a carbamate of formula II. Then, this carbamate is subjected to a basic treatment to be converted to a compound of formula III wherein A represents H or CH₃ and B represents OH or CH₂OH, which is deacetylated with a strong acid to obtain the intended phenylenediamine of formula IV wherein R represent 2- hydroxyethyl, 3-hydroxypropyl or 2-hydroxypropyl.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a method for producing Nl-[converted nitro p-phenylenedi7mine and an intermediate product thereof.

[Prior Art 1 Nitro dyes are important in hair dyeing. These dyes, which are used both in direct dyeing and in oxidative dyeing, must produce the desired color in sufficient concentration during dyeing. The resulting color should have good light and acid resistance and should not have a tendency to discoloration of the original hue under the conditions of use. Furthermore, there should be no toxicological and dermatological concerns.

These requirements are not necessarily harmonized. This becomes particularly clear in the field of so-called red direct dyes. For nitro-p-phenylenediamine, the state of the art is -
There are compounds which are almost completely satisfactory from a technical standpoint in terms of their use, and which are toxicologically controversial in other respects.

Direct dyes that satisfy these requirements are compounds represented by the general formula (3).

[Means for Accomplishing the Invention] The objects of the present invention are: a) completely satisfactory in terms of staining; b)
The object of the present invention is to provide a technologically advanced method for producing a compound known as a red direct dye which is free from toxicological concerns and C) is characterized by high purity.

General Group I: Compounds represented by the formula [wherein R is 2-hydroxyethyl group, 3-hydroxypropyl group or 2-hydroxypropyl group] are known as dyes (UK Patent No. 1
No. 206491).

Various methods have been described for producing these compounds. For example, it has been reported that compounds represented by the general group 2, in which R represents a 2-hydroxyethyl group or a 3-hydroxypropyl group, can be obtained by partial reduction of the corresponding dinitro compound (UK Patent No. 95574).
No. 3, U.S. Pat. No. 3,168,442). in this way,
Generally two isomers are formed. Even when one isomer predominates, separation is difficult and tedious. moreover,
Depending on the reducing agent and reduction conditions, partially or completely reduced triamino products are also often produced, making the separation of the desired compound even more expensive.

Laser (E, S, Lazer), Underts 7
(J.

S, Anderson), Kizhiev (J, E,
Kijek) and Brown (K, C, Brown
) [“Synthetic Communicati
ons, Vol. 12(9)l, pp. 691-694 (1982) 1. ■-(2hydroxyethyl)amino-2-nitro-4-aminopenzole was prepared by partial reduction of the corresponding dinitro compound. The method for manufacturing is described.

However, the yield is only between 45% and 55% and the product contains starting materials as well as isomeric compounds as impurities.

Furthermore, a general group ■ in which R represents what is stated in claim 1;
It is also known to prepare compounds of the formula by reacting 2-nitro-4-aminofluoropenzole with the corresponding amino alcohol [UK Patent No. 1,206,491].
No., A.

T. Peters, “J. appl. Che.
m, Biotechnol.

1976, Vol. 26, pp. 131-134 1゜However, the compound represented by general formula I prepared in this way,
Does not have high purity. 2-nitro-4- by this method
The reaction of the amine fluoropenzole with ethanolamine produces, in addition to 2-[(4-7mino-2-nitrophenyl)amino1ethanol, by-products that are clearly visible in the thin layer chromatogram. The content of dye in the product thus obtained is only 82% compared to the purified compound (content determination spectrophotometrically; see also Comparative Example 1). The products obtained by reaction with 2-nitro-4-aminofluoropenzole 3 and l-aminopropanol 2 likewise contain the abovementioned by-products.

By the way, claims 1 to 3 are capable of producing a compound represented by the general group (3) in which R represents a 2-hydroxyethyl group, a 3-hydroquinglovir group, or a 2-hydroxypropyl group with high yield and high purity. We found a method using this method.

Next, details of the method according to the invention will be described.

The reaction of 4-acetylamino-2-nitroaniline with chloroformic acid alkyl ester is carried out in mimicry of the known selective hydroxyalkylation of amines with chloroformic acid chloroalkyl ester, followed by base treatment of the chloroalkyl carbamate [ Otto. ” J.P.
rak. Chem. .

"2, Volume 44, Page 15 (1890): R. Ad
ams and J. B. Segur, “J. Am.
Chem.

Soc, Vol. 45, p. 785 (1923)]. For the production of the compound represented by 1, 4-acetylamino-2-nitroaniline is initially introduced into an inert solvent (e.g. dioxane, monoethylene glycol dimethyl ether, chlorbenzole, doluol methyl ethyl ketone). , at a temperature between room temperature and the reflux temperature, in particular between 70°C and the reflux temperature, -drinking temperature: Cl2-Coo-CH(X)-CH2-Y [wherein X=
Hy-CQ; X-CH3, Y=CQ and X=HY-
The chloroformic acid alkyl ester represented by 1 representing CH2C12 is metered in an equimolar amount or in a small excess. Optionally, the solvent can also be combined with water. Acid binders include alkali metal hydroxides, bicarbonates, carbonates, alkaline earth metal oxides, hydroxides, bicarbonates and carbonates, and tertiary organic amines. Approximately 2
The reaction is complete after ~8 hours. For work-up, water is added, the batch is stirred cold or the inorganic salts are filtered,
The solvent can be partially or completely distilled off.

Drinking cost ■: In order to produce a compound represented by [in the formula, A=H, B=OH; A-CH3, B=○H and A=H, B=CH20H] - drinking cost ■ The carbamates of the formula are treated with strong bases (hydroxides of alkali metals and alkaline earth metals), especially 10-50% strength soda or potassium solution. The carbamate represented by the formula ■,
Water or an organic solvent, such as (01-C4)-alcohol, water-miscible ether or a mixture thereof, is introduced and then, at room temperature, approximately 3 mol of a strong alkaline solution per mol of carbamate is metered in. It is equally possible to charge a strong alkaline solution, which can be diluted with the solvents mentioned, and to meter the carbamate therein in pure form or dissolved in one of the abovementioned organic solvents. Subsequent stirring is then carried out to ensure complete reaction, with optional heating possible up to reflux. Reaction time is about 2~1O
It's time. For work-up, the reaction solution with a pH value of about 12-14 is diluted with an organic or inorganic acid to a pH of about 7-10.
Neutralize to H value. Subsequently, water is added, optionally the solvent is distilled off, and the product is isolated. Deacetylation can be carried out by heating to 60-95°C after an hour. Thus, 9
A compound of the formula -Drinkage ■ (wherein R represents the above) having a content of 3 to 95% is obtained.

Similarly, the compound represented by Eintop I can be prepared by a one-pot reaction (Eintop) starting from the carbamate represented by - Eintop ■ without isolating the compound represented by - Eintop ■.
freaktion). In this case, the carbamate indicated by -drinking price ■ is charged to water and added to it at a temperature of about 30 to 85 °C with a strong base (alkali metal or alkaline earth metal hydroxide), especially 10 to 85 °C.
Dispense 50% strength soda solution or strength potash solution. After the reaction is completed, the pH value of the reaction solution is adjusted to about 7 using an organic or inorganic acid. Thereafter, further strong inorganic acids (e.g. hydrochloric acid, sulfuric acid) are added and deacetylation is carried out at a temperature of about 60-95°C. Subsequently, the pH value is adjusted to approximately 7 again with a base (hydrous soda solution, potassium solution, ammonia) and the product is isolated.

In the above method, a water-miscible solvent [(0
By adding about 25 to 30% by weight of [1-C3)-alcohol, monoethylene glycol dimethyl ether], the reaction time is significantly shortened, with the inorganic salt still being dissolved in the reaction solvent.

The carbamate indicated by the symbol ■ is an equimolar amount of the base (
hydroxides of alkali metals or alkaline earth metals), especially 10 to 50% by weight of a strong soda solution or a strong potassium solution.

It can be changed to an oxazolidone represented by the formula [wherein Z represents a hydrogen atom or a CH3 group, and n=1 or 2].

The carbamate indicated by the number 1 is introduced into water or an organic solvent such as (01-G4)-alcohol, water-miscible ether or mixtures thereof. To this, 30 to 8
At a temperature of 5°C, approximately 1 mol of strong alkaline solution is metered in per mol of carbamate. Subsequent stirring is then carried out to ensure complete reaction, with optional heating possible up to reflux. The reaction time is about 1 hour. Subsequently, a strong inorganic acid (for example hydrochloric acid, sulfuric acid) is added to the reaction solution and the mixture is stirred at a temperature of approximately 60 DEG to 95 DEG C. The post-stirring time is approximately 3 hours. After the reaction has ended, the pH value of the reaction solution is adjusted to approximately pH 7 with a base, the salts are optionally filtered off, the solvent is distilled off and the product is isolated.

Then, the compound represented by -drinking cost (■) is introduced into water or an organic solvent such as (01-C4)-alcohol, water-miscible ether or a mixture thereof. For this, 45~
At a temperature of 85° C., approximately 2 mol of strong alkaline solution is metered in per mol of starting material. pi (value of pH) of reaction solution
7-8, optionally filtering off the salts and evaporating the solvent, the product is isolated. The compounds of formula I thus obtained have a high degree of purity. No by-products are observed in the thin layer chromatogram. The content by spectrophotometry is about 97% The production method is clarified by the following example [Example 1 Method: A ■, β-thalolethyl-N-(4-acetylamino-
Preparation of 2-nitrophenyl) carbamate: 195 g of 4-acetylamino-2-nitroaniline (
1 mol) are initially introduced together with 50 g of carbonate into monoethylene glycol dimethyl ether 6501112 and 75 mff of water. The reaction mixture was heated to about 80°C for about 5 hours.

Beta-chloroethyl luformate 1509 is added such that the reaction mixture is under mild reflux. Stir further for 2 hours under reflux, then cool the batch to 65°C, add water and
The precipitated product is isolated, washed with water and dried in a vacuum dryer.

Yield: 271.5g (90% of theory) Melting point = 159
°C IR spectrum: See Figure 1 Il, Preparation of 2-[(4-acetylamino-2-nitrophenyl)amino]-ethanol 2. 90.5 g (0.3 mol) of the carbamate produced in step ① above was added to 450 g of water.
Heat to approximately 75 °C with m(+) and add 50% potash solution 1089 for 45 minutes.
After an hour of stirring, the pH value was subsequently adjusted to 7 with glacial acetic acid,
Cool the batch to io'c. The precipitated product is filtered off with suction, washed with water and dried.

Yield: 63.29 (88% of theory) Melting point = 170°C IR spectrum: See Figure 2 IIl, Preparation of 2-[(4-amino-2-nitrophenyl)aminocoethanol Produced in step ① above Product 489 (0.2 mol),
Add to 200 g of 25% sulfuric acid for 30 minutes at approximately 95°C. After stirring for 1 hour at approximately 95° C., the pH value is then adjusted to 8 with aqueous ammonia. The batch is then cooled to 100C within 3 hours and the precipitated product is filtered off with suction, washed with water and dried.

Yield: 33.5 g (85% of theory) Melting point = 123°C IR spectrum: See Figure 3 Content: 94% (Content measurement is by spectrophotometry on purified samples) Method: B 1, 2-[( 4-Amino-2-nitrophenyl)-aminocoethanol Production Method A, 90.5 g of carbamate produced by I (0,
3 mol) are heated to 75° C. with 325 mQ of water and 30 g of 50% strength potassium solution. A further 79 g of 50% strength potassium solution are added dropwise to this within 11/2 hours.

After stirring for 1 hour at 80° C., the pH value is adjusted to 7 with hydrochloric acid. Add 50 mQ of hydrochloric acid to the reaction mixture and heat under reflux for 2 hours. The pH value is adjusted again to 8 with ammonia and the batch is slowly cooled. The precipitated product is filtered with suction,
Wash with water and dry.

Yield: 50.8g (86% of theory) Melting point: 122°
C content: 93% (content measurement is by spectrophotometry on purified samples) Method: C 1,N-[(4-amino-2-nitro)7enyl]oxazolidone-2 production method A, I 90.5g of carbamate (0,
3 mol) of water and 325 tQ of water and 50% strength potassium solution 3
Heat to about 80°C with 4g. After stirring for a further 1 hour at the same temperature, the pH value is adjusted to 7 with hydrochloric acid. Add concentrated hydrochloric acid 45+IIQ to the reaction mixture and heat to reflux for 3 hours. Subsequently, the pH value is again adjusted to 7 with aqueous ammonia.

The batch is allowed to cool down slowly and the precipitated product is filtered off with suction, washed with water and dried in a vacuum dryer.

Yield: 61.5g (92% of theory) Melting point: 195~
196°C IR spectrum: see Figure 4 Il, 2-[(4-amino-2-nitrophenyl)
Aminocoethanol 44.59% of the oxazolidone produced with ① above was mixed with 17% of water.
51112 and heat the reaction mixture to 80°C. To this, within 50 minutes, 50% strength potassium solution 459
Add dropwise. After stirring for another hour at 80° C., the pH value is adjusted to 8 with glacial acetic acid. Within 1 hour, the batch is cooled to 10° C. and the precipitated product is filtered off with suction, washed with water and dried.

Yield: 32.7g (83% of theory) Melting point: 124°
C content = 97% (Content measurement is by spectrophotometry on purified samples) Example 2 Method: A ■, Production of γ-chloropropyl-N-(4-acetylamino-2-nitrophenyl)carbamate 4-acetylamino -2-Nitroaniline 97.5g
(0.5 mol) and calcium carbonate 26.59 in a monoethylene glycol dimethyl ether/water mixture (
9: γ-chloropropyl chloroformate in l) 83.5
9 and Example IA.

The reaction is carried out under the conditions described under ① and the work-up is carried out accordingly.

Yield: 153 g (97% of theory) Melting point: 2112°C IR spectrum: See Figure 5 n, Preparation of 3-[(4-acetylamino-2-nidophenyl)amine]propanol I γ- Produced in above ① Chlorpropyl-N (4-acetylamino-2-
nitrophenyl) carbamate 63g (0.2 mol)
and Example 1A, I1. 72 g of 50% strength potassium solution was mixed with 200 mQ of water and 5Q of ethanol under the conditions described in
React in mf2. After adjusting the pH, bring the batch to 15°C.
The product is filtered with suction, washed with water and dried.

Yield: 42 g (83% of theory) Melting point: 129°C rR spectrum: See Figure 6 Ill, Preparation of 3-[(4-amino-2-nitrophenyl)amine]propanol-1 Product produced in step ① above 50.5 g (0.2 mol) of the product are placed in 180 m+2 water and 50 m12 ethanol and heated to approx. 75°C. 40 mQ of concentrated hydrochloric acid was added to this mixture over a period of about 30 minutes, and the mixture was stirred at reflux temperature for 2 hours. Cool it down. The precipitated product is passed through a suction line, washed with water and dried.

Yield: 33.8g (80% of theory) Melting point: 102°
C IR spectrum: See FIG. 7 Method: B 1, Method for producing 3-[(4-amino-2-nitrophenyl)amino]propertool=1 A, 1. γ-Chlorpropyl-N-(4
-acetylamino-2-nitrophenyl)carbamate (31.5 g (0.1 mol)) in Example 1-B, 1. 36.5 g of a 50% strength aqueous potassium solution under the conditions described in 1. and subsequently with 16 m of concentrated hydrochloric acid (2) and worked up accordingly.

Yield: 18.4g (87% of theory) Melting point = 100°
C Method: Method A for producing C 1,N-[(4-amino-2-nitro)phenyl 1-tetrahydro-1,3-oxazin-2-one, 1. Carbamate 31゜5g (0
, 1 mol) and 11.2 g of a 50% aqueous potassium solution,
Example I in 100 mf2 of water and 1 SraQ of concentrated hydrochloric acid
The reaction is carried out under the conditions described in C.1, followed by deacetylation and post-treatment.

Yield: 19.5g (82% of theory) Melting point: 181'
C! IR spectrum: see Figure 8 I [,3-[(4-amino-3-nitrophenyl)amino]propanol-1 19 g (0.08 mol) of oxazine prepared in above I
in 80 mQ of water and 20 mQ of ethanol and heated to about 75°C. To this, 20 g of a 50% aqueous potassium solution was added dropwise over 45 minutes. After stirring for a further 1 hour at 75° C., the pH value is adjusted to 8 with glacial acetic acid. During 45 minutes, the batch was cooled to 10° C. and the precipitated product was filtered with suction.
Wash with water and dry.

Yield: 15.7g (92.7% of theory) Melting point: 10
2°C Example 3 ■, (2-chloro-1-methyl)ethyl-N(4-
Preparation of acetylamino-2-nitrophenyl) carbamate 19.5 g of 4-acetylamino-2-nitroaniline
(0.1 mol) and 5.29 calcium carbonate in 75 mf2 of monoethylene glycol dimethyl ether with 15.7 g of chloroformic acid-(2-chloro-1-methyl)ethyl ester, Example 1-A, 1. The reaction is carried out under the conditions described in , and worked up accordingly.

Yield: 26.8g (85% of theory) Melting point: 134~
135°C IR spectrum: See Figure 9 n, Preparation of 3-[(4-amino-2-nitro7enyl)aminocopropanol-2 15.8 g of the carbameh produced in above I (0.05
mol) in Example 1-B, 1. 50% under the conditions described in
17 g of aqueous potassium solution, followed by 8 g of concentrated hydrochloric acid.
React with mQ and work up accordingly.

Yield: 8.59 (80% of theory) Melting point: 153-154°C IR spectrum: See Figure 1O Comparative Example 1 2-[(4-amino-2-nitrophenyl)amino 1
Production of ethanol 4-fluoro-3-nitroaniline I 5.69, monoethanolamine 13.59 and sodium carbonate 5.3
g in 100 TRQ of water and the mixture is heated under reflux for 5 hours. The batch is then cooled to room temperature and the precipitated solid is filtered off with suction, washed with water and dried.

Yield: 14.4g (73% of theory) Melting point +l18°
C (theoretical value 121-123 °C) content: 82% (content measurement is by spectrophotometry on purified samples). An R7 value of .36 is clearly visible.

[Brief explanation of drawings]

The attached drawings show infrared absorption spectra of the following compounds according to Examples. Figure 1 is the IR spectrum of β-chloroethyl-N-(4-acetylamino-2-nitrophenyl)-rubamate; The figure shows the IR spectrum of 2-[(4-acetylamino-2-nitrophenyl)amino-1 ethanol, and Figure 3 shows the IR spectrum of 2-[(4-amino-2-nitrophenyl)amino]ethanol. , Figure 4 shows N-[(4-amino-2-nitro)phenyl 1
Figure 5 is the IR spectrum of oxazolidone-2, Figure 5 is the IR spectrum of γ-chloropropyl-N-(4-7cetylamino-2-nitrophenyl)carbamate, and Figure 6 is the IR spectrum of 3-[(4-acetylamino-2-nitrophenyl)carbamate. FIG. 7 is the IR spectrum of 3-[(4-amino-2-nitrophenyl)amino]propanol I, and FIG. 8 is the IR spectrum of N -[(4-amino-2-nitro)phenyl 1
-IR of tetrahydro-1,3-oxazin-2-one
Figure 9 shows the spectrum of (2-chloro-1-methyl)ethyl N-(4-
Figure 1 is an IR spectrum of 7cetylamino-2-nitrophenyl)carbamate, and Figure 1O shows the I
This is the R spectrum.

Claims (1)

[Claims] 1. General formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R represents a 2-hydroxyethyl group, 3-hydroxypropyl group, or 2-hydroxypropyl group] In the method for producing Ni-substituted nitro-p-phenylenediamine represented by a) 4-acetylamino-2-nitroaniline is added in the first step in an approximately equimolar amount to the general formula: Cl
-COO-CH(X)-CH_2-Y [where X=H, Y
=Cl; X=CH_3, Y=Cl and X=H, Y=C
H_2Cl] is reacted with a chloroformic acid alkyl ester to form a carbamate represented by the general formula II: ▲Mathematical formula, chemical formula, table, etc.▼(II) b) In the second step, this carbamate represented by general formula II is treated with a base to give general formula III: ▲Mathematical formulas, chemical formulas, tables, etc.▼(III) CH_3, B=OH and A=H, B=CH_2OH]; c) In the third step, these compounds represented by the general formula III are deacetylated with a strong inorganic acid to form the general formula I [
A method for producing N^1-substituted nitro-p-phenylenediamine, characterized in that R represents a 2-hydroxyethyl group, a 3-hydroxypropyl group, or a 2-hydroxypropyl group. 2. A carbamate represented by general formula II is first treated with a base and then treated with a strong inorganic acid in a one-pot method to convert it into a compound represented by general formula I [wherein R represents the above]; The method according to claim 1. 3. A method for producing a compound represented by the general formula I [wherein R represents the previously described compound], a) the general formula II described in claim 1 [wherein X and Y represent the previously described compound] ] is first treated with an equimolar amount of a base and then treated with a strong inorganic acid to form the general formula IV: ▲Mathematical formula, chemical formula, table, etc.▼(IV) or represents CH_3 group, n=1
or 2], and b) converting this oxazolidone into a compound represented by the general formula I [wherein R represents the same as defined above] by treating this oxazolidone with twice the molar amount of a base. A method for producing N^1-substituted nitro-p-phenylenediamine, characterized by: 4. General formula II: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) An intermediate product represented by [In the formula, X and Y represent the one described in claim 1]. 5. General formula III: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) An intermediate product represented by [In the formula, A and B represent those described in claim 1]. 6. General formula IV: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IV) An intermediate product represented by [In the formula, Z represents the one described in claim 3].