JPH0228147A - Production of lactam derivative - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful for synthetic intermediate of nylon in short reaction time, without necessity of neutralization, without corrosiveness of stainless vessel, in high purification and high yield by reacting aniline derivative and lactone derivative using specific acid catalyst. CONSTITUTION:An aniline derivative expressed by formula I (R<1>, R<2> is H, 1-8C alkyl, alkoxy, dialkylamino, alkylamino, arylamino or halogen) is reacted with a lactone derivative expressed by formula II (R<3> is H, 1-9C alkyl; n is 2-13), preferably using 0.5-3.0mol compound expressed by formula I to 1mol compound expressed by formula II at 50-300 deg.C, especially 100-250 deg.C using phosphoric acid and/or phosphate (e.g., phosphoric acid, polyphosphoric acid or sodium hydrogen phosphate) as acid catalyst to obtain a compound expressed by formula III. Besides, amount of use of the acid catalyst is preferably in a range of 0.001-1.0mol, especially 0.01-0.5mol to 1mol of compound expressed by formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to the reaction of the general formula [
The present invention relates to a method for producing a lactam derivative represented by formula [III] by reacting an aniline derivative represented by formula [I] with a lactone derivative represented by general formula [n].

[I] [II] (CH2)n CH-R" [I11] "-R20(1) (wherein, R1 and R2 are hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, alkoxy groups, dialkylamino group, alkylamino group, arylamino group and halogen, R3 is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms,
n represents an integer from 2 to 13. ) (Prior art and problems to be solved by the invention) Lactam derivatives are useful as intermediates in the synthesis of nylon.

Regarding the production method of lactam derivatives, N-phenyl-2-
Taking pyrrolidone as an example, conventional reaction of cyclopentanone and aniline [HlKunz-ek, G, 3arn
i kOW: Chem, 3er.

, 102.351 (1969)], ]4-bromo n
-Reaction of butyrylchloride and aniline [M.

S, Manhas, S, J, JenCJ: J, Orc.
], Chem, 32.1246 (1967)], ]
Reaction of T-butyrolact and aniline [W, L.

Meyer, W., P., Vanghan: J., O-rg.
, Chem, 22.1554 (1957)], ]T
-Reaction of butyrolactate and aniline hydrochloride [8,S,K
ukal enko, N, A, Gr-acheva
:Kh in, Geterots i-ni! ,5o
ed in, 7.773 (1971), Chem, A.
bstr, 76.250079 (1972)], and the purification method used is a distillation purification method or a recrystallization method.

By the way, industrially, high-boiling substances such as N-phenyl-2-pyrrolidone (N-phenyl-2-pyrrolidone boiling point (21mm
When carrying out distillation purification at temperatures (HL) = 195 to 200°C, it is recommended to use a stainless steel distillation pot, taking into account thermal conductivity, durability (pressure resistance), material cost of the still, etc. It is customary.

Among the above manufacturing methods and purification methods, when manufacturing industrially,
The reaction of aniline and γ-butyrolactone is judged to be superior in terms of yield, shortness of the reaction process, and operability, and the distillation purification method is judged to be superior in terms of simplicity as a purification method. .

However, the problem with the method for producing N-phenyl-2-pyrrolidone through the reaction of aniline and γ-butyrolactone is that in the noncatalytic reaction conducted by W, L, MeV-er et al., the reaction time was only 3 days. Very long and industrially undesirable. Also, the above S, S, Kuka le enk
Although the reaction time of the reaction between aniline hydrochloride and γ-butyrolactone conducted by et al. was shortened to 4 to 20 hours, hydrochloric acid corrodes stainless steel, so it is difficult to use a glass or glass-lined reaction vessel. The problem is that it is very complicated in terms of operability, as it must be reacted and neutralized, then transferred to a stainless steel distillation pot, and purified by distillation.

(Means for Solving the Problems) As a result of extensive research in order to overcome the above problems, the present inventors have discovered that aniline derivatives [I ] and the lactone derivative [II] is completed in a very short time, and the lactam derivative [111J] can be obtained very easily in high yield by subsequent purification by distillation under reduced pressure without any neutralization. In addition, the present inventors have discovered that stainless steel does not corrode at all when phosphoric acid and/or phosphate is used as an acid catalyst, leading to the completion of the present invention.

Since the production method of the present invention uses phosphoric acid and/or phosphate as an acid catalyst, the reaction time is shortened, the neutralization operation is omitted, and the stainless steel reaction pot is less corrosive than the above-mentioned conventional method. This is an economically advantageous and industrially viable method because the vacuum distillation purification after the completion of the reaction can be carried out in the same stainless steel reaction vessel, which simplifies the operation.

Embodiments of the present invention will be specifically described below.

The phosphoric acid and/or phosphate salt used as an acid catalyst in the production method of the present invention includes phosphoric acid, bonolinic acid, metaphosphoric acid, ammonium dihydrogen phosphate, ammonium hydrogen phosphate,
Triammonium phosphate, sodium dihydrogen phosphate, sodium phosphate, disodium hydrogen phosphate, trisodium phosphate, potassium dihydrogen phosphate, potassium phosphate,
Examples include dipotassium hydrogen phosphate, tripotassium phosphate, bis(dihydrogen phosphate) calcium, calcium phosphate, calcium hydrogen phosphate, dicalcium phosphate, tricalcium phosphate, sodium hydrogen phosphate, etc. It is not limited to these.

Aniline derivatives [I] used in the production method of the present invention include aniline, p-toluidine, m-toluidine, o-toluidine, mixed toluidine, 2,3-xylidine, 2,4-xylidine, 2,5-xylidine, 2 ,6-xylidine,
3,4-xylidine, 3,5-xylidine, mixed xylidine, p-ethylaniline, m-ethylaniline, 0-
Ethylaniline, pn-propylaniline, pn-
Butylaniline, pn-pentylaniline, pn-hexylaniline, pn-hebutylaniline, pn-
Octylaniline, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, N-methyl-p-phenylenediamine, N-cyclohexyl-p-phenylenediamine, N-phenyl-p −
Phenylenediamine, N-tolyl-p-phenylenediamine, 0-chloroaniline, m-chloroaniline, p-
Chloroaniline, 0-bromoaniline, m-promoaniline, p-bromoaniline, p-methoxyaniline, p
-ethoxyaniline, etc., but are not limited to these.

The lactone derivative [II] used in the production method of the present invention is γ
-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, T-hexalactone, γ
-Heptalactone, γ-nonalactone, δ-nonalactone, δ-decalactone, T-undecalactone, γ-dodecalactone, δ-dodecalactone, δ-tetradecalactone, 15-pentadecalactone, etc.
It is not limited to these.

The reaction of the production method of the present invention is preferably carried out in the presence of a solvent or in the absence of a solvent, while water produced during the reaction is distilled out of the system, or when the reaction is carried out in the presence of a solvent, the solvent used is Examples include, but are not limited to, benzene, toluene, xylene, mesitylene, ethylbenzene, propylbenzene, butylbenzene, diethylbenzene and the like.

The amount of phosphoric acid and/or phosphate used as the acid catalyst used in the production method of the present invention is from 0.001 mol to 1.0 mol, preferably 0.00 mol, per 1 mol of lactone derivative [■].
The amount ranges from 0.01 mol to 0.5 mol.

The amount of aniline derivative [I] used in the production method of the present invention is 0.5 mol to 1 mol of lactone derivative [■].
3.0 mol, preferably in the range 1.0 mol - 2i 0 mol.

When carrying out the reaction in the presence of a solvent used in the production method of the present invention, the amount of solvent used is 1 mole of lactone derivative [■].
0d~1100 (, preferably 50III1~500
rIIIl range.

The reaction temperature used in the production method of the present invention is 50'C to 300°C.
It can be carried out at a temperature range of 100°C to 100°C.
Temperature range is 250℃.

(Effects of the Invention) The production method of the present invention provides phosphoric acid and/or phosphorus r! as an acid catalyst in the reaction to obtain a lactam derivative [I[1] from an aniline derivative [I] and a lactone derivative [■]. By using i-salt, the reaction and distillation purification can be carried out in the same stainless steel reaction vessel, the reaction time can be shortened without corroding the reaction vessel, neutralization operation can be omitted, and high yield and high purity can be achieved. It was made possible to easily raise the lactam derivative [I11] by 1.

EXAMPLES Next, the effects of the present invention will be roughly explained in detail using Examples, taking a method for producing N-phenyl-2-pyrrolidone as an example.

(Example) [Examples 1 and 2, Comparative Examples 1 to 3] 86.07 [1°0 mol 1] of γ-butyrolactone, 139.9% of aniline was placed in a four-bottle flask equipped with a reflux condenser, stirring paddle, and thermometer. 5 [1.5 mol 1, stainless steel (sus
Approximately 1 g of a 0.1Rg test piece of 304) weighed accurately in units and a predetermined amount of catalyst were charged, and after heating and raising the temperature, the reaction was carried out at a predetermined temperature for a predetermined time while stirring and distilling the generated water out of the system. The reaction was terminated when a predetermined amount of water (18d) was distilled off.

At this point, take out the stainless steel test piece, remove any oily substances adhering to the surface with acetone without damaging the surface of the test piece, and let it melt to zero. I!
It was again precisely weighed to the unit of Itg, and the weight change rate was taken as the corrosion rate of the test piece.

Next, 100 d of an aqueous solution in which 100 d of xylene and a neutralizing amount of sodium carbonate were dissolved was added to the reaction system, and after heating and stirring at 60° C. for 30 minutes, the mixture was left to separate. Zara, water 100
The water washing operation of adding ml, heating and stirring at 60° C. for 30 minutes, and then standing to separate the liquids was repeated twice. After distilling off xylene from the obtained organic phase, the target product N-phenyl-2-pyrrolidone was distilled under reduced pressure with a boiling point of 190°C to 19°C.
It was obtained as a fraction of 2'C (20mmH9>). The results are shown in Table 1.

As can be seen from Table 1, sulfuric acid and hydrochloric acid used as acid catalysts accelerate the reaction, but stainless steel (sus-
304> test piece was significantly corroded (comparative example -
2, 3), the phosphoric acid and ammonium dihydrogen phosphate used as acid catalysts have the same or higher ability to promote the reaction than 5A acid and hydrochloric acid, and also
It is clearly seen that the test piece made of SUS304) was not corroded at all (Examples 1 and 2).

[Examples 3 and 4] The neutralization operation using 100 ml of xylene and 100 d of a neutralization equivalent sodium carbonate aqueous solution and the water washing operation using 100 ml of water in Examples 1 and 2 were omitted, and after the reaction was completed, Except for vacuum distillation in the same reaction vessel (flask),
The same operation as in Examples 1 and 2 was performed. In addition, the stainless steel (sus-304) test piece was taken out from the flask after being purified by vacuum distillation, and the weight change rate was measured using the same procedure as in Examples 1 and 2. The results are shown in Table 2. .

As can be seen from Table 2, even if the neutralization operation is omitted and vacuum distillation purification is performed after the reaction, stainless steel (sus-30
4) The target product, N-phenyl-2-pyrrolidone, was produced with high yield and high purity without corroding the test piece.
I know that I will ascend.

[Example-5, Comparative Examples-4 and 5] In Example-1 and Comparative Examples-1 and 2, 100r111 of xylene was added at the time of raw material preparation, the reaction was carried out under xylene reflux, and the reaction took 35 hours. The same operations as in Example 1 and Comparative Examples 1 and 2 were performed except that .

The results are shown in Table-3.

As can be seen from Table 3, sulfuric acid as an acid catalyst corrodes the test piece (SUS-304), while phosphoric acid as an acid catalyst reacts without corroding the test piece (SUS-304). It can be seen that the target product, N-phenyl-2-pyrrolidone, can be obtained in high yield and purity.

Claims (1)

[Claims] (1) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R^1 and R^2 are hydrogen atoms, alkyl groups with 1 to 8 carbon atoms, alkoxy groups, represents a dialkylamino group, an alkylamino group, an arylamino group, and a halogen) in the presence of an acid catalyst. , where R^3 is a hydrogen atom, carbon atoms 1 to 9
n represents an integer of 2 to 13. ) is reacted with a lactone derivative represented by the general formula [III
] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [III] A method for producing a lactam derivative characterized by using phosphoric acid and/or a phosphate salt as an acid catalyst.