JPS63270646A - Production of aminotrifluoromethyltoluene - Google Patents

Abstract

PURPOSE:To obtain the titled substance useful as an intermediate for drugs and agricultural chemicals readily and in high yield, by hydrating the nitro group of dichlorotrifluoromethylnitrotoluene by a hydrogenating catalyst and dechlorinating dichlorotrifluoromethylnitrotoluene in the presence of an acid acceptor. CONSTITUTION:Dichlorotrifluoromethylnitrotoluene is added to a stainless steel autoclave, an acid acceptor (e.g. NaOH or trimethylamine) and a hydrogenating catalyst (preferably Pd supported on active carbon), water and optionally a solvent are added to the autoclave, the reaction system is heated while stirring and hydrogen is introduced to the reaction system until no hydrogen absorbed to give the titled substance. The concentration of the catalyst is preferably 1-5wt.% based on the raw material and the reaction condition is 80-120 deg.C and 6-10kg/cm<2>.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to the use of methylaminobenzotrifluoride (abbreviated as ATF T) as a raw material for medicines and agricultural chemicals, particularly as an intermediate raw material for herbicides and tranquilizers. It is related to the manufacturing method (lit).

[Prior art] As a method for producing methylaminobenzotrifluoride,
The following are known:

Be1g, BE 899927 (1984) However, the production method of (1) uses expensive 3-trifluoromethyl-benzyl alcohol as a starting material;
SF4 as a fluorinating agent in the manufacturing method of n) is difficult to obtain in large quantities, is expensive and highly toxic, and has problems such as being reacted at high temperature and high pressure. Furthermore, the method for producing (III) also had the problem of using expensive 3-trifluoromethyl-toluene as a starting material.

[Means for Solving the Problems] As a result of studying an advantageous method for producing methylaminobensitrifluoride, the present inventor discovered a new compound (dichlorotrifluoromethylnitrotoluene) that is extremely excellent as a raw material for its production, and developed this compound. The present invention was achieved by discovering that the desired ATFT can be easily obtained by reducing and dechlorinating. That is, the present invention deals with the hydrogenation of the nitro group of novel dichlorotrifluoromethylnitrotoluene (excluding 2-nitro-3,4-dichloro-trifluoromethyl-toluene) using a hydrogenation catalyst in the presence of an acid acceptor. and a method for producing aminotrifluoromethyltoluene, which is characterized by advancing a dechlorination reaction.

Dichlorotrifluoromethylnitrotoluene (DCTFNT), which is a raw material for this reaction, can be easily obtained by nitration of the corresponding dichlorotrifluoromethyltoluene (DCTPT). DCTPT can also be easily obtained by fluorinating dichlorotrichloromethyltoluene (DCTCT) with carbon tetrachloride in the presence of aluminum halide.

Examples of the aluminum halide include anhydrous aluminum chloride and anhydrous aluminum bromide, and the amount of aluminum halide used is 1 to 6 mol, preferably 1 to 3 mol, based on dichlorotoluene as the raw material. Aluminum halide forms a complex with DCTCT, so when aluminum halide is insufficient, a by-product called dichlorobis(dichloromethylphenyl)methane (hereinafter referred to as DCBM) is selectively produced. Furthermore, the selectivity of DCTCT does not increase even if aluminum halide is used in excess.

The reaction temperature of this reaction is 0 to 100°C, preferably 20 to 80°C.

In addition, it is preferable to use a solvent in this reaction, and examples of the solvent that can be used include methylene chloride, tetrachloroethane, and fluorocarbons, but 1,2-dichloroethane is a solvent that can significantly improve the selectivity of DCTCT. and is the most preferable. Although the reaction time cannot be absolutely defined, it is from 20 minutes to 4 hours. Water is added to the reaction product thus obtained to decompose the complex,
Obtain DCTCT.

The fluorination reaction of DCTCT involves placing DCTCT and more than the theoretical amount of hydrogen fluoride in a stainless steel autoclave.
The reaction is carried out at a temperature of 0 to 150°C, preferably room temperature to 100°C, and the reaction pressure is 3 to 20 kfI/cf1, preferably 8 to 10 kg/-. The amount of hydrogen fluoride is 3.2 to 12 times the mole of DCTCT, preferably 6 to 9 times the mole.Although the reaction time cannot be unconditionally specified, the reaction product of 3 to 6 hours is After washing with an alkaline aqueous solution, vacuum distillation is performed to remove the reaction solvent, unreacted carbon tetrachloride, and high-boiling reaction products (thereby removing highly pure dichlorotrifluoromethyltoluene (hereinafter referred to as DCTPT)). can be obtained easily.

The DCTPT thus obtained was reacted with fuming nitric acid in the presence of concentrated sulfuric acid to produce dichloronitrotrifluoromethyltoluene, which is the raw material compound of the present invention.
DCTFNT) is generated. 96-9 in this reaction
The amount of 8% concentrated sulfuric acid used is 3 to 6 times the mole of DCTPT, and the amount of 94% fuming nitric acid used is 1 to 2 times the mole of DCTPT, preferably 1.05 to 1.20 times the mole. be. Moreover, the reaction temperature of this reaction is preferably in the range of 30 to 120°C, more preferably 60 to 100°C.

Although the reaction time cannot be absolutely specified, it is 2 to 5 hours. In this reaction, the position where the nitro group is introduced is 2
, 6 position in 3-dichloro-4-trifluoromethyltoluene, 4 position in 2.3-dichloro-6-trifluoromethyltoluene, 5 position in 2.4-dichloro-5-trifluoromethyltoluene, In the case of 2,5-dichloro-4-trifluoromethyltoluene, it is selectively introduced at the 6-position. DCTFNT thus obtained
The hydrogenation of DCTFNT is generally carried out by first adding the DCTFNT into a stainless steel autoclave, adding the acid acceptor, hydrogenation catalyst, water and optionally a solvent, heating with stirring, and adding the reaction mixture under reaction pressure and reaction. This is carried out by passing hydrogen until no more hydrogen is absorbed at the temperature.

Hydrogenation can be carried out either in a neutral or basic medium. The acid acceptor used is not particularly limited, and alkali metal hydroxides, carbonates or acetates, alkaline earth metal hydroxides, oxides, carbonates or acetates are used, and specifically, water Examples include sodium oxide, sodium carbonate, potassium hydroxide, potassium carbonate, lithium carbonate, calcium oxide, and magnesium oxide. Also used are ammonia and amines, especially tertiary amines such as trimethylamine, triethylamine, pyridine and picoline. As a general rule, the amount of acid acceptor used is at least 2 mol per mol of ATFT to be produced. However, it is also possible to use excess amounts of tertiary amines as solvent.

In a particular embodiment of the invention, the acid acceptor, catalyst and optional solvent are first added to the hydrogenation reactor and DCTFNT is metered in. In this case, the hydrogenation can be carried out in a solvent that is inert towards the reactants. The inert solvent preferably includes alcohols having 1 to 6 carbon atoms, such as methanol, ethanol, isopropanol, n-
propatool, isobutanol, 2-butanol, ethylene glycol, etc., and ethers such as glycol methyl ether, glycol dimethyl ether,
Tetrahydrofuran, dioxane and anisole, etc.
Alternatively, hydrocarbons such as cyclohexane, methylcyclohexane, toluene and xylene, etc.
Acetic acid, water, etc. may also be used. Of course, these can also be used in the form of a mixture. Among these, the most preferred solvents are water and ethanol. The concentration of DCTFNT in the solvent can be varied over a wide range, but 15 wt% or more is generally recommended.

The hydrogenation catalyst used in the present invention is preferably a commonly used catalyst such as palladium, nickel, platinum, etc.
Particularly preferably, palladium-supported activated carbon is used. The concentration of this hydrogenation catalyst is 0.01 to DCTFNT.
10-t% is preferred, more preferably 1-5 wt%
It is. The reaction temperature and reaction pressure are each 80 to 120
℃, 6 to 10 Kg/cd.

DCTFNT used in the present invention 2.5-dichloro-4-trifluoromethyl-6-nitrotoluene and 2,3-
Dichloro-4-trifluoromethyl-6-nitrotoluene gives AT F T2-amino-4-trifluoromethyltoluene, 2,4-dichloro-3-nitro-5-trifluoromethyltoluene and 2.6 -Dichloro-3-trifluoromethyl-5-nitrotoluene yields 3-amino-5-trifluoromethyltoluene, and 2,3-dichloro-6-trifluoromethyltoluene yields 4-amino-2- Trifluoromethyltoluene is obtained.

The present invention will be explained in detail below using examples.

Reference example 1 Anhydrous aluminum chloride 27.0g (0,203 mol)
A mixed solution of 16.1 g (0.1 mol) of 2゜3-dichlorotoluene and 54 g (total 1.0 mol) of carbon tetrachloride was added under stirring to a mixed solution of 100.0 g of carbon tetrachloride and 100.0 g of carbon tetrachloride.
The mixture was added dropwise at 2° C. over 2 hours, and the mixture was stirred and reacted for an additional 2 hours.

After cooling, the reaction solution was poured into ice water 700-1111 and stirred at room temperature to remove aluminum chloride. The aqueous layer was extracted with carbon tetrachloride, and the collected organic layer was washed with an aqueous sodium hydroxide solution, dried over anhydrous calcium chloride, and the solvent was distilled off under reduced pressure to obtain 24.5 g of crude DCTCT. When this was analyzed by gas chromatography, 2,3-dichloro-4-trichloromethyltoluene (DCTCT) was found to be 42.8% (
Yield: 37.6%''), 2.3-dichloro-6-trichloromethyltoluene (DCTCT■): 27.1wt%
(yield 23.8%) and dichlorobis(2,3-dichloro-4-methylphenyl)methane and dichlorobis(2-methyl-3,4-dichlorophenyl)methane (D
CBM) was contained at 30.1% (yield: 3666%), and unreacted dichlorotoluene was not detected.

After adding 725.2 g of crude pcTc to 50 Ill of fi"% xane and removing undissolved substances, the phthalate was concentrated under reduced pressure and distilled under reduced pressure to obtain DCTCT+DCT with a purity of 99.2%.
CT■10.5g (0,0377mol, yield 37.7
%) was obtained. From this, using gas chromatography, DCTCT■ with a purity of 99.5% (boiling point 120-125℃
/3ma+Hg) and purity 99.0
% DCTCT (boiling point 109-115℃/3 mm
Hg) was separated into 0.12g. DCTCT-@ (7
) structure is mass spectrum (M+276), +(--
NMR spectrum (CDC-solvent, δ 2.80 3H
(CH,) S, 7.991)1 (5-H')
Confirmed by S, 7.38 18 (6-H)S).

The structure of DCTCT■ is mass spectrum (M”276)
, H-NMR spectrum (CDCI, solvent, δ 2.
47 3H(CHs)S, 7.22 18(4-
Confirmed by H)S, 7°90 1H(5-H'')S).

Reference example 2 Anhydrous aluminum chloride 108 g (0,812 mol)
, and 125 g (0,812 mol) of carbon tetrachloride, and 1
, 2-dichloroethane 205g under stirring,
A mixed solution of 65.4 g (0,406 mol) of 2゜3-dichlorotoluene and 78.0 g of 1゜2-dichloroethane was added dropwise at 50 to 52°C over 30 minutes, stirred for another 2 hours, and left to cool, then poured into ice water. Perform the same operation as in Reference Example 1 except for pouring the reaction solution into 1000+ sl, and
102g was obtained. When this was analyzed by gas chromatography, DCTCT■ was 51.5% (yield: 46.5%).
8%), DCTCT■ was 30.4 wt% (yield 27.6
%) and DCBM was 18.5%1t% (yield 27.6
%), and unreacted 2,3-dichlorotoluene was not detected.

Reference example 3 Anhydrous aluminum chloride 27.0g (0,203 mol)
A mixed solution of 16.1 g (0.1 mol) of 2゜4-dichlorotoluene (0.1 mol) and 54 g of carbon tetrachloride (total 1.0 mol) was added to a mixed solution of 50 to 50 g of carbon tetrachloride (1.0 mol in total) under stirring.
The mixture was added dropwise at 52°C for 2 hours, and the mixture was stirred and reacted for an additional 2 hours. After cooling, the reaction solution was poured into 700 tal of ice water and stirred at room temperature to remove aluminum chloride. The aqueous layer was extracted with carbon tetrachloride, and the collected organic layer was washed with an aqueous sodium hydroxide solution, dried over anhydrous calcium chloride, and the solvent was distilled off under reduced pressure to obtain 24.3 g of crude DCTCT. When this was analyzed by gas chromatography, 2,4-dichloro-5-trichloromethyltoluene was found to be 70.2 wt% (yield 61.3
%), DCBM was contained at 29.8 wt% (yield 35.9%), and unreacted dichlorotoluene was not detected.

3g of crude DCT C724 was added to 50m of 71-hexane.
In addition to 1, after removing undissolved substances, the oral material was concentrated under reduced pressure and distilled under reduced pressure to obtain DCTC713 with a purity of 98.7%.
8g (0,0496 mol, yield 49.6%) was obtained (
melting point 79.0-80.2℃), the structure is determined by mass spectrometry (
M+273), H-NMR spectrum (CDC1g
Solvent, 62.60 H(CI,) S, ? , 72
1H(6-H)S, 8°21 1H(3-H)).

Reference example 4 Anhydrous aluminum chloride 27.0g (0,203 mol)
and 31.5 g (0,205 mol) of carbon tetrachloride; 1.
In a mixed solution of 50.5 g of 2-dichloroethane, under stirring,
2゜4-dichlorotoluene 16.1g (0.1 mol)
The same operation as in Reference Example 3 was performed except that a mixed solution of 19.1 g of 1,2-dichloroethane and 1,2-dichloroethane was added dropwise.
c724.3g (purity 70.2%, yield 61.3%)
I got it. Unreacted 2,4-dichlorotoluene was not detected in this crude DCTCT, and DCBM was detected as a by-product.
only was detected.

Reference example 5 Anhydrous aluminum chloride 27.0g (0,203 mol)
A mixed solution of 16.1 g (0.1 mol) of 2°5-dichlorotoluene and 54 g (total 1.0 mol) of carbon tetrachloride was added under stirring into a mixed solution of ioo, o g of carbon tetrachloride.
The mixture was added dropwise at 52°C for 2 hours, and the mixture was stirred and reacted for an additional 2 hours. After cooling, the reaction solution was poured into 1000 ml of ice water and stirred at room temperature to remove aluminum chloride. The aqueous layer was extracted with carbon tetrachloride, the collected organic layer was dried over anhydrous calcium chloride, and the solvent was distilled off under reduced pressure to obtain 1 g of crude DCTC. When this was analyzed by gas chromatography, 2.5-dichloro-4-trichloromethyltoluene was found to be 72.1wt.
% (yield: 62.4%), DCBM was contained at 27.9 wt% (yield: 33.3%), and unreacted dichlorotoluene was not detected.

After adding 725.5 g of crude DCTC @ 50 ml of n-hexane and removing undissolved substances, the liquid was concentrated under reduced pressure and distilled under reduced pressure to obtain 711.5 g of DCTC with a purity of 99.2% (
0,0410 mol, yield 41.0%) was obtained (melting point 41.0%).
．． 6-42.5°C). The structure is mass spectrum CM+27
3), H-N? IR spectrum (CDC13 solvent,
δ 2.39 H(CHs) S, 7.40
1H (3-H) S, 8゜13 1H (6-H)
Confirmed by S).

Reference example 6 Anhydrous aluminum chloride 27.0g (0,203 mol)
and 31.5 g (0,205 mol) of carbon tetrachloride; 1.
In a mixed solution of 50.5 g of 2-dichloroethane, under stirring,
2゜5-dichlorotoluene 16.1g (0.1 mol)
The same operation as in Reference Example 5 was performed except that a mixed solution of 19.1 g of 1,2-cycloethane and 1,2-cycloethane was added dropwise.
CT25.2g (purity 78.8%, yield 71.3%)
I got it. Unreacted 2,5-dichlorotoluene was not detected in this crude DCTCT, and DCBM was a byproduct.
only was detected.

Reference example 7 Anhydrous aluminum chloride 27.0g (0,203 mol)
and 31.5 g (0,205 mol) of carbon tetrachloride and 1.2
- Into a mixed solution of 50.5 g of dichloroethane, 2.
6-dichlorotoluene (16.1 g<0.1 mol) and 1.
A mixed solution of 9.1 g of 2-dichloroethane was added to the
The mixture was added dropwise at 2° C. over 2 hours, and the mixture was stirred and reacted for an additional 2 hours.

After cooling, the reaction solution was poured into 1000 ctrl of ice water and stirred at room temperature to remove aluminum chloride. The aqueous layer was extracted with carbon tetrachloride, the collected organic layer was washed with an aqueous sodium hydroxide solution, dried over anhydrous calcium chloride, and the solvent was distilled off under reduced pressure to obtain crude DCTCT26. Obtained Og. When this was analyzed by gas chromatography, 2,6-dichloro-3-trichloromethyltoluene was found to be 88.4% (yield: 82.7%).
), DCBM was contained at 11.6-t% (yield 15.0%), and unreacted DCT was not detected.

Reference Example 8 102 g of the crude DCTCT obtained in Reference Example 2 and 109 g of hydrogen fluoride were placed in a 300+n 1 stainless steel autoclave and stirred while heating at a reaction temperature of 95 to 100°C, resulting in a reaction pressure of 8 kg/ca! Hydrogen chloride gas, a by-product of the reaction, was continuously extracted from the upper part of the reflux column using a primary pressure regulating valve.

After 3 hours, when no rise in reaction pressure was observed, it was judged that the fluorination was complete, and the reaction product was taken out of the autoclave, washed with an aqueous sodium hydroxide solution to remove unreacted hydrogen fluoride, and then distilled under reduced pressure. Purity 9
7.42 g of 8.3% 2°3-,' chloro-4-trifluoromethyltoluene (hereinafter referred to as DCTFT■)
(0,0319 mol, yield 16.6%, boiling point 115~
118℃/35mdg) with a purity of 99.2%.
-dichloro-6-trifluoromethyltoluene (hereinafter referred to as D
CTFT■) 7゜45g (0,0323 mol,
Yield 28.3%, boiling point 108-110℃/35*mH
g) was obtained. The structure of DCTFT■ is based on the mass spectrum (M
228”), H-NMR spectrum (CDCI
3 fusing, δ2.48 3) 1 (CH,) S,
? .

24 1H(6-H) S, 7.52 1)1(5-
H) S), F-N liver spectrum (CDCI, solvent,
61.5ppm 3F (CF.

) Confirmed using the S reference material CFCI,'').

Similarly, the structure of DCTFT■ has a mass spectrum (M"2
2B), H-NMR spectrum (CDCI, solvent,
δ2.583 H(C)Is) S, 7,48 2H
(4,5-H)S), F-NMR spectrum (CD
CIs solvent, 63.3 ppm3F (CF,')S
, was confirmed using the reference material CFCI3).

Reference Example 9 24.3 g of crude DCTCT obtained in Reference Example 3 and 10.0 g of hydrogen fluoride were placed in a 100 ml stainless steel autoclave and stirred while heating at a reaction temperature of 95 to 102°C, so that the reaction pressure was 8 kg/ad. Hydrogen chloride gas, a side reaction product, was continuously extracted from the upper part of the reflux column using a primary pressure regulating valve.

After 3 hours, when no rise in reaction pressure was observed, it was judged that the fluorination was complete, and the reaction product was taken out of the autoclave, washed with an aqueous sodium hydroxide solution to remove unreacted hydrogen fluoride, and then distilled under reduced pressure. Purity 9
12.3 g of 8.2% 2°4-dichloro-5-trifluoromethyltoluene (0,0527 mol, yield 86.
0%, boiling point 83-85°C/6 mm) Ig) was obtained. The structure is mass spectrum (M"228'), H-NMR
Spectrum (CDC1, solvent, δ2°363H (CHI
') S, 7.43 18(6-H) S
, ? , 50IH(3-H)S), F-NMR
Spectrum (CDCI, solvent, 62.8 ppm 3F
(CFs)S, reference material CFCII).

Reference Example 10 724.1 g of crude DCTC obtained in Reference Example 5 and 10.0 g of hydrogen fluoride were placed in a 1001111 stainless steel autoclave and stirred while heating at a reaction temperature of 95 to 102°C, resulting in a reaction pressure of 8 kg/-. Hydrogen chloride gas, a side reaction product, was continuously extracted from the upper part of the reflux column using a primary pressure regulating valve.

After 3 hours, when no rise in reaction pressure was observed, it was judged that the fluorination was complete, and the reaction product was taken out of the autoclave, washed with an aqueous sodium hydroxide solution to remove unreacted hydrogen fluoride, and then distilled under reduced pressure. Purity 9
11.3 g (0,0483 mol, yield 77.8%) of 2°5-cyclo4-trifluoromethyltoluene.
3%, boiling point 83-85°C/6wsIHg). The structure is shown in the mass spectrum (M”228), H-NMR spectrum (CDCI solvent, 62°3538 (CH
s)S, 7.32 11((3-H)S, 7.611H
(6-H)S), F-NMR spectrum (CDC
1m solvent, 63. lppm3F (CF, )S,
Confirmed using reference material CFCI, ).

Reference Example 11 26.0 g of the crude DCT CT obtained in Reference Example 7 and 10.0 g of hydrogen fluoride were charged into a 100 ml stainless steel autoclave, stirred while heating at a reaction temperature of 95 to 102°C, and a reaction pressure of 8 kg/-. Hydrogen chloride gas, a by-product of the reaction, was continuously extracted from the upper part of the reflux column using a primary pressure regulating valve. After 3 hours, when no rise in reaction pressure was observed, it was judged that the fluorination was complete, and the reaction product was taken out of the autoclave, washed with an aqueous sodium hydroxide solution to remove unreacted hydrogen fluoride, and then distilled under reduced pressure. By doing this, 16.6 g of 2,6-dichloro-3-trifluoromethyltoluene (0,0
527 mol, yield 87.8%, boiling point 83-10 mmHg) was obtained. The structure is mass spectrum (M228
), H-NMR spectrum (CDCIs solvent, δ2.
583H (CHj) S, 7.33 1H (5-H)
S, 7.4318 (4-H) S), F-N
MR spectrum (CDCl m solvent, 62.8 pp+m
3F (CFI) S, reference object 1tCFC1”
) was confirmed.

Reference Example 12 DCTFT obtained in Reference Example 8 7.42g (0°0
319 moles) and 16.3 g of 96% concentrated sulfuric acid (0,160
moles) and 2.60 g of 94% fuming nitric acid (0,038
8 mol) was placed in a glass round bottom flask and reacted under normal pressure with stirring at a reaction temperature of 80°C for 1 hour. After the reaction was completed, 30 g of 1,2-dichloroethane was added as a solvent and dissolved, and then separated into two layers. The organic layer was washed with sodium hydroxide solution to remove acid. 1,2-dichloroethane was removed by distillation from the organic layer using an evaporator, and the purity was 97.8.
%D CT F NT■8.28g (0,0296
mol, yield 92.7%). Next, recrystallization with n-hexane yielded 2.3-dichloro-4- with a purity of 99.2%.
Trifluoromethyl-6-nitrotoluene (D CT
FNT■) was obtained (melting point 44.5-45.7°C), the structure was mass spectrum (M+273), H-NMR spectrum (CDCIs solvent, δ2.173H(CHs
) S, 8.04 18(5-H) S), F-N
MR spectrum (CDCIs solvent, 63.8 ppm
3F (CFs) S.

Confirmed using reference material CFCI, ').

Reference Example 13 7.45 g of DCTFT obtained in Reference Example 8 (0°0
323 moles) and 16.5 g of 96% concentrated sulfuric acid (0,162
moles) and 2.60 g of 94% fuming nitric acid (0,038
8 mol) was placed in a glass round-bottomed flask, and stirred and reacted at a reaction temperature of 80° C. for 1 hour under normal pressure. After the reaction was completed, 30 g of 1,2-dichloroethane was added and dissolved as a solvent, and the organic layer separated into two layers was washed with a sodium hydroxide solution to remove the acid content. 1,2-dichloroethane was removed by distillation from the organic layer using an evaporator, and the purity was 98.9.
% of 2.3-dichloro-6-trifluoromethyl-4-
Nitrotoluene (DCTFNT■) 8.36g (0
,0302 mol, yield 93.4%) was obtained.
DCTFNT with purity of 99.1% by recrystallization with hexane
(1) was obtained (melting point: 25.5-27.0°C). The structure is shown in the mass spectrum (M273) and H-NMR spectrum (C
DCl, solvent 1. δ0.483H(CHs)s, 5
．． 87 1H(5-H)S), F-NMR spectrum (coct, solvent, 62.lppm 3F (Ch
)S.

Confirmed using reference material CFCI).

Reference Example 14 14.3 g of D CT P T obtained in Reference Example 9 (
0,0616 mol), 31.4 g of 96% concentrated sulfuric acid (0,
308 mol) and 4.95 g of 94% fuming nitric acid (0,
0738 mol) was placed in a glass round-bottomed flask, and stirred and reacted for 1 hour at a reaction temperature of 80°C under normal pressure. After the reaction was completed, 30 g of 1,2-dichloroethane was added as a solvent and dissolved, and the organic mixture was separated into two layers. The layer was washed with sodium hydroxide solution to remove acid content, dried over anhydrous calcium chloride, and then 1,2-dichloroethane was distilled off using an evaporator to obtain 2゜4-dichloro-3- with a purity of 97.8%.
Nitro-5-)lifluoromethyltoluene 16.2g
(0,0578 mol, yield 93.9%) was then recrystallized with n-hexane to obtain DCTF with a purity of 99.5%.
NT was obtained (melting point 58.1-58.8°C). The structure is mass spectrum (M”273), H-NMR spectrum (CDCI solvent, δ2.493H(CH)S
, 7.68 1H(6-H)S), P-NMR spectrum (CDCI solvent, 61,'3pp■3F
(CFs)S, reference material CFCI).

Reference example 15 0. D CT P T obtained in Reference Example 10 13.6
g, 96% concentrated sulfuric acid 29.4 g (0,289 mol)
and 4.64 g (0,0692 mol) of 94% fuming nitric acid were placed in a glass round-bottomed flask, and under normal pressure, the reaction temperature was 8.
After the reaction was completed with stirring at 0° C. for 1 hour, 30 g of 1,2-dichloroethane was added as a solvent and dissolved, and the organic layer separated into two layers was washed with a sodium hydroxide solution to remove the acid content. 1,2-
Dichloroethane was removed by distillation to obtain 2. with a purity of 98.2%.
5-cyclo-4-trifluoromethyl-6-nitrotoluene 15.4 g (0,0552 mol, yield 95.7
%) was obtained. Then recrystallized with n-hexane to a purity of 9.
9.2% DCTFNT was obtained (melting point 48.5-49.
4℃), III structure is a mass spectrum (M 273
) ,) I-NMR spectrum (CIICI, solvent, 6
2.413H (CI,) S, 7.85 18 (3-
H) S), F-NMR spectrum (CDCI, solvent, 63.2 ppm 3F (CF, )81 reference material C
FC1m).

Reference Example 16 16.6 g of DCTPT obtained in Reference Example 11 (0,0
715 moles), 36.5 g of 96% concentrated sulfuric acid (0,358
moles) and 5.75 g of 94% fuming nitric acid (0,085
8 mol) was placed in a glass round-bottomed flask and stirred and reacted for 1 hour at a reaction temperature of 80°C under normal pressure. After the reaction was complete, 50 g of the solvents 1 and 2-dichloroethane were added and dissolved, and a two-layer mixture was formed. The separated organic layer was washed with sodium hydroxide solution to remove acid. 1,2-dichloroethane was removed by distillation from the organic layer using an evaporator, and the purity was 97.5.
% of 2.6-dichloro-3-trifluoromethyl-5-
18.9 g (0,0674 mol, yield 94.2%) of nitrotoluene was obtained. Next, DCTFNT with a purity of 99.5% was obtained by recrystallization with n-hexane (melting point 40.7
~41.5℃), the structure is mass spectrum (M+273
), H-NMR spectrum (CDCI.

Solvent, 62.683H(CI,)S, 8.07
18 (3-1() S), F-N? IR spectrum (CDCI, solvent, 63.7 ppm 3F (CF,
) S, reference material CFCI, ) was confirmed.

Example 1 DC:TFNT■15. obtained in the same manner as in Reference Example 12 was placed in a 100 ml stainless steel autoclave equipped with a stirrer.
4 g (0,0552 mol), 10-t as acid acceptor
% sodium hydroxide aqueous solution (53.0g (0,13
After adding 0.77 g of 5% palladium on carbon as a hydrogenation catalyst and replacing the air inside the autoclave with hydrogen gas, the reaction temperature was 100°C and the reaction pressure was 10 kg.
The reaction was carried out for 4 hours while stirring at /ad. After the reaction was completed, 30 g of 1,2-dichloroethane was added and mixed with the reaction solution, which was passed through the mouth to remove palladium and carbon, and the two layers were separated. Only the organic layer obtained was dried over anhydrous calcium chloride. . 1,2-dichloroethane was removed from this organic layer by vacuum distillation, and 2-dichloroethane with a purity of 99.5% was removed.
-Amino-4-trifluoromethyltoluene 9°29g
(yield 95.7%).

Example 2 8.28 g (0,02
The reaction was carried out in the same manner as in Example 1 except that 28.4 g (0,0710 mol) of a 10-t% aqueous sodium hydroxide solution was used as the acid acceptor, and the purity was 99.2.
% of 2-amino-4-trifluoromethyltoluene 4.
91 g (yield 94.1%) was obtained.

Example 3 In a 500 ml stainless steel autoclave equipped with a stirrer, 91 g of DCTFNT (0
, 332 mol), 380 g (1.32 mol) of a 28.5% aqueous sodium acetate solution as an acid acceptor, 180 ml of ethanol as a solvent, and 5% as a hydrogenation catalyst.
After adding 4.5 g of palladium and carbon and replacing the air inside the autoclave with hydrogen gas, the reaction temperature was increased to 100°C.
The reaction was carried out for 4 hours with stirring at a reaction pressure of 10 kg/cIA. After the reaction is completed, 100 g of 1,2-dichloroethane and 10 wt% sodium hydroxide aqueous solution are added to the reaction solution.
00 g was added and mixed, the palladium and carbon were removed by passing through the mouth, and the organic layer was separated into two layers and only the obtained organic layer was dried with anhydrous calcium chloride. From this organic layer 1
．． 2-dichloroethane is removed by simple distillation,
57.2 g (yield: 97.3%) of 3-amino-5-trifluoromethyltoluene with a purity of 98.9% was obtained.

Example 4 Ethanol in Example 3 was not used, and 10 wt% sodium hydroxide aqueous solution 3 was used instead of sodium acetate aqueous solution.
The reaction was carried out in the same manner except that the aqueous sodium hydroxide solution was not added after the completion of the hydrogenation reaction, and 56.3 g of 3-amino-5-trifluoromethyltoluene with a purity of 99.2% was obtained. 96.2%).

Example 5 78.36 g of DCTFN obtained in the same manner as Reference Example 16 was placed in a 100 ml stainless steel autoclave equipped with a stirrer.
(0,0302 mol), 29 g (0,0725 mol) of 104% aqueous sodium hydroxide solution as acid acceptor,
5% palladium carbon 0°77g as hydrogenation catalyst
After replacing the air inside the autoclave with hydrogen gas, the reaction was carried out for 4 hours with stirring at a reaction temperature of 100° C. and a reaction pressure of 10 kg/c11.

After the reaction was completed, 30 g of 1,2-dichloroethane was added and mixed with the reaction solution, which was passed through the mouth to remove palladium and carbon, and the two layers were separated. Only the organic layer obtained was dried with anhydrous calcium chloride. .

From this organic layer, 1.2-dichloroethane was removed by distillation under reduced pressure, and 3-amino-5-
4.98 g of trifluoromethyltoluene (yield: 93.
3%).

Example 6 In a 100 nil stainless steel autoclave equipped with a stirrer, 8.36 g (0°0302 mol) of DCTFNT obtained in Reference Example 13, 29 g (0,0725 mol) of a 10% aqueous sodium hydroxide solution as an acid acceptor, and hydrogenation were added. Add 0.42g of 5% palladium carbon as a catalyst,
After replacing the air inside the autoclave with hydrogen gas, the reaction was carried out for 4 hours with stirring at a reaction temperature of 100° C. and a reaction pressure of 10 kg/cn. After the reaction is complete, add 1.2- to the reaction solution.
30 g of dichloroethane was added and mixed, and the mixture was passed through the mouth to remove palladium and carbon.The resulting mixture was separated into two layers, and only the organic layer obtained was dried over anhydrous calcium chloride. 1,2-dichloroethane was removed from this organic layer by distillation under reduced pressure, and 4.92 g of 4-amino-2-trifluoromethyltoluene with a purity of 99.1% (yield 92.2%
) was obtained.

[Effects of the Invention] In the present invention, an aminotrifluoromethyltoluene derivative useful as an intermediate for medicines and agricultural chemicals can be obtained easily and in good yield using the novel dichlorotrifluoromethyltoluene.

Claims (1)

[Claims] dichlorotrifluoromethylnitrotoluene (but 2
-Nitro-3,4-dichloro-6-trifluoromethyltoluene is excluded) in the presence of an acid acceptor using a hydrogenation catalyst to proceed with the hydrogenation and dechlorination reaction of the nitro group. Method for producing trifluoromethyltoluene.