JPH0559021A - Synthesis of 2-oxazolidinone compound - Google Patents

Abstract

PURPOSE:To profitably obtain a 2-oxazolidinone compound in an industrial scale under a mild condition in a good yield directly from a compound having an oxirane ring and a carbamic acid ester by the use of a specific catalyst. CONSTITUTION:When a compound of formula I (R is H, organic group) having an oxirane ring is reacted with a carbamic acid ester of formula II (R<1> is alcohol residue) to produce a 2-oxazolidinone compound of formula III, the reaction is performed in the presence of a catalyst comprising an aliphatic amine, aromatic amine, tertiary amine such as a nitrogen-containing heterocyclic ring compound such as N,N-dimethylbenzylamine, or tin compound such as di-n-butyl tin dilaurate, stannous chloride or tin octenoate preferably in an amount of 0.01-5.0wt.%, especially 0.1-3.0wt.%, based on the starting raw materials, respectively, preferably at 100-180 deg.C to obtain the objective compound in a yield higher at least 20% than those of known methods using tertiary amines as the catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND ART Several synthesis methods are known for 2-oxazolidinone compounds starting from an oxirane compound. For example, phenylglycidyl ether is used as a starting material, and 1-amino-3-phenoxy-2-propanol obtained by ring-opening the starting material with ammonia is diethyl carbonate (US Pat. No. 2,399,118) or phosgene (UK patent). No. 8894198) can be reacted to synthesize 5-phenoxymethyl-2-oxazolidinone. Instead of diethyl carbonate or phosgene, urea, isocyanate, ethyl chlorocarbonate, carbon disulfide and the like can be used. These are two-step methods.

As one of the one-step methods, a method of reacting tris (2,3-epoxypropyl) isocyanurate with phenols is described in French Patent No. 1487641 and JP-A No. 51-88963.

Further, a direct method of reacting urea with an oxirane compound is also known. Japan Chemical magazine 92, 184
2 (1972)

Japanese Patent Publication No. 39-9886 describes a one-step method of reacting a carbamic acid ester with phenylglycidyl ethers. This method uses either a lithium base, a tertiary amine or betaine as a catalyst.

The known methods typified above have drawbacks such as complicated process steps, use of expensive or difficult-to-obtain starting materials, use of toxic reagents, lack of versatility, and low yield of the desired product. Therefore, the object of the present invention is 2-
It is to provide a synthetic method capable of obtaining an oxazolidinone compound in a high yield.

[0006]

DISCLOSURE OF THE INVENTION The present invention is carried out in the presence of a tertiary amine and a tin compound as a catalyst when synthesizing a 2-oxazolidinone compound by reacting a compound having an oxirane ring with a carbamate. A method for synthesizing a 2-oxazolidinone compound is provided.

The use of a tertiary amine as a catalyst in the synthetic reaction of a 2-oxazolidinone compound by the reaction of an oxirane compound and a carbamate ester is
As described above, as described in JP-B-39-9886, the yield of the desired product by this method is 5-[(2-
In the case of methoxyphenoxy) methyl] -2-oxazolidinone, it is 50% or less. By using both a tertiary amine and a tin compound as a catalyst according to the present invention,
The yield of the desired product can be improved by at least 20%.

[0008]

[Detailed Discussion] The reaction between the oxirane compound and the carbamic acid ester can be represented by the following reaction formula.

[0009]

[Chemical 1]

In the formula, R is hydrogen or an organic group, and R '
Is an alcohol residue.

Examples of the oxirane compound represented by the formula I are ethylene oxide, styrene oxide, 1,2-epoxybutane, 1,2-epoxyoctane, epichlorohydrin, epibromohydrin, phenylglycidyl ether and 4-t. -Butylphenyl glycidyl ether,
n-butyl glycidyl ether, glycidyl methacrylate, glycidyl benzoate, glycidyl-4-t-
A monofunctional epoxy compound such as butyl benzoate,
Alternatively, 1,2,3,4-diepoxybutane, 1,
2,7,8-diepoxy octane, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether , Triglycidyl ether of trimethylolpropane, tetraglycidyl ether of pentaerythritol, hydroquinone diglycidyl ether, resorcin diglycidyl ether, diglycidyl phthalate, diglycidyl hexahydrophthalate, N, N-diglycidyl aniline, N, N, N ' , N'-tetraglycidyl-
m-xylenediamine or 1,3-bis (N, N-
Examples thereof include polyfunctional epoxy compounds such as diglycidylaminomethyl) cyclohexane. Also, an epoxy resin such as a bisphenol A type epoxy resin, a phenol novolac type epoxy resin, or a cresol novolac type epoxy resin can be used.

Further, as the carbamate represented by the formula II, methyl carbamate, ethyl carbamate, isopropyl carbamate, butyl carbamate,
Examples thereof include benzyl carbamate, phenyl carbamate, and 2-hydroxyethyl carbamate. However, methyl carbamate, ethyl carbamate, and 2-hydroxyethyl carbamate are preferable because they are easily available.

The amount of the carbamic acid ester used with respect to the epoxy compound is 0.8 to 1.2 in terms of molar ratio because the reaction is an equimolar reaction, and preferably approximately equimolar amount.

The order of addition in the reaction is not particularly limited, and a carbamic acid ester may be added to the epoxy compound or an epoxy compound may be added to the carbamic acid ester. Alternatively, they may be added all at once.

Examples of the tertiary amine used as a catalyst in the reaction include aliphatic amines, aromatic amines, nitrogen-containing heterocycles, N, N-dimethylbenzylamine, N,
N-dimethylaniline, triethylamine, N, N-dimethylcyclohexylamine, N, N, N ', N'-tetramethylethylenediamine, N-methylmorpholine,
1,4-diazabicyclo [2.2.2] octane, 1,
8-diazabicyclo [5.4.0] -7-undecene,
Pyridine, quinoline, imidazole and the like are used.

As the tin compound used in combination with the tertiary amine, di-n-butyltin dilaurate, stannous chloride, tin octenoate, dibutyltin oxide, dioctyltin oxide, 1,3-diacetoxytetrabutyl. Examples thereof include distannoxane, 1,3-dichlorotetrabutyl distannoxane, dibutyl dibutoxy tin, and the like.

In the present invention, both the tertiary amine and the tin compound are indispensable, and a sufficient yield cannot be obtained when only one of them is used. The amount of each catalyst added is preferably 0.01 to 5.0% by weight, and particularly preferably 0.1 to 3.0% by weight of the starting material.

The reaction temperature is preferably 100 ° C. to 180 ° C., and the reaction rate is very slow below 100 ° C.
If it is higher than 80 ° C, there is a risk of side reaction. The reaction time is 0.2-10 hours, preferably 0.5 hours to 5 hours.
It's time.

This reaction can be carried out in the coexistence of a solvent which does not participate in the reaction, but when considering industrial use,
It is not necessary to use a solvent or the like unless otherwise required.

The present invention can be said to be a highly industrially useful method because it can directly synthesize a 2-oxazolidinone compound from an oxirane compound under mild conditions in a good yield.

The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited thereto.

Example 1 8.9 g (0.10 mol) of ethyl carbamate was dissolved in 15.0 g (0.10 mol) of phenyl glycidyl ether to prepare 0.3 g of N, N-dimethylbenzylamine and di-lauric acid di-. While adding 0.3 g of n-butyltin and blowing out nitrogen gas to remove by-product ethanol, 1
After reacting at 30 ° C. for 2 hours and then cooled to room temperature, the entire system solidified. The product was recrystallized from chloroform to obtain 20.0 g (0.098 mol) of white crystals of 5-phenoxymethyl-2-oxazolidinone. (Yield 9
8%) Melting point 122-123 ° C (literature value 121-122 ° C) ¹ H-NMR (CDCl ₃ , δ); 3.61 (dd, 1)
H), 3.76 (t, 1H), 4.16 (d, 2H),
4.93 (m, 1H), 5.97 (bs, 1H), 7.
15-7.40 (m, 5H) ¹³ C-NMR (CDCl ₃ , δ); 42.8, 68.
1, 74.3, 114.7, 121.7, 129.6,
158.2, 159.8

Comparative Example 1 8.9 g (0.10 mol) of ethyl carbamate was dissolved in 15.0 g (0.10 mol) of phenylglycidyl ether, 0.3 g of N, N-dimethylbenzylamine was added, and nitrogen gas was added. Was blown in to remove the by-product ethanol and reacted at 160 ° C. for 2 hours. From liquid chromatography analysis of the reaction product, 5-phenoxymethyl-
The yield of 2-oxazolidinone was 37%.

Comparative Example 2 8.9 g (0.10 mol) of ethyl carbamate was dissolved in 15.0 g (0.10 mol) of phenylglycidyl ether, 0.3 g of di-n-butyltin dilaurate was added, and nitrogen gas was added. After reacting at 160 ° C. for 2 hours while blowing in, the reaction product was subjected to ¹ H-NMR measurement, but the formation of the desired product, 5-phenoxymethyl-2-oxazolidinone, was not observed.

Example 2 7.5 g (0.10 mol) of methyl carbamate was dissolved in 15.0 g (0.10 mol) of phenyl glycidyl ether to prepare 0.3 g of N, N-dimethylbenzylamine and dilauric acid di-. While adding 0.3 g of n-butyltin and blowing in nitrogen gas to remove by-product methanol,
When reacted at 130 ° C. for 2 hours and cooled to room temperature, the whole system solidified. Recrystallize the product from chloroform,
12.5 g (0.065 mol) of white crystals of 5-phenoxymethyl-2-oxazolidinone were obtained. (Yield 65
%) The melting point and NMR spectrum of the compound obtained were in agreement with those of Example 1.

Example 3 20.6 g of 4-t-butylphenyl glycidyl ether
(0.10 mol), 8.9 g of ethyl carbamate (0.
10 mol) and 0.2 g of N, N-dimethylbenzylamine and di-n-butyltin dilaurate 0.2
g was added, nitrogen gas was blown in, the by-product ethanol was removed, the mixture was reacted at 130 ° C. for 2 hours, cooled to room temperature, and allowed to stand, whereupon the entire system solidified. The product was recrystallized from chloroform to give white crystals of 5- (4-t-butylphenoxymethyl) -2-oxazolidinone (22.4 g).
(0.090 mol) was obtained. (Yield 90%) Melting point 92-93 ° C. (literature value 93 ° C.) ¹ H-NMR (DMSO, δ); 1.26 (s, 9)
H), 3.32 (t, 1H), 3.71 (t, 1H),
4.11 (d, 2H), 4.89 (m, 1H), 6.8
9 (d, 2H), 7.31 (d, 2H), 7.57 (b
s, 1H) ¹³ C-NMR (DMSO, δ); 31.2, 33.7,
41.6, 68.6, 73.6, 114.1, 126.
0, 143.2, 155.9, 158.6

Example 4 8.9 g (0.10 mol) of ethyl carbamate was dissolved in 13.0 g (0.10 mol) of n-butyl glycidyl ether to prepare 0.2 g of N, N-dimethylbenzylamine and dilauryl acid. While adding 0.2 g of di-n-butyltin and blowing nitrogen gas to remove by-product ethanol, 1
The reaction was carried out at 60 ° C for 2 hours. The obtained product was distilled under reduced pressure to give 5-n-butoxymethyl-2-oxazolidinone 1
6.2 g (0.094 mol) were obtained. (Yield 94%) Boiling point 203-205 ° C. (bath temperature) / 3 mmHg ¹ H-NMR (DMSO, δ); 0.71-1.00
(T, 3H), 1.10-1.62 (m, 4H), 3.
05-3.61 (m, 6H), 4.53-4.80
(M, 1H), 7.53 (bs, 1H) ¹³ C-NMR (CDCl ₃ , δ); 13.0, 18.
3,30.8, 41.7, 70.4, 70.6, 74.
6,159.3

Example 5 17.0 g of diglycidyl ether of bisphenol A
8.9 g of ethyl carbamate to (0.050 mol)
(0.10 mol) was dissolved, N, N-dimethylbenzylamine (0.2 g) and dilaurylate di-n-butyltin (0.2 g) were added, and nitrogen gas was blown thereinto to remove ethanol as a byproduct, and the temperature was 130 ° C. After reacting for 2 hours at room temperature, the reaction product was purified by silica gel column chromatography (developing solution; ethyl acetate) to give a colorless transparent viscous liquid 1.
9.2 g was obtained. This product has ¹ H-NMR and ¹³ C-N
As a result of MR measurement, it was identified as 2,2-bis [4- (2-oxooxazolidin-5-yl) methoxyphenyl] propane. (Yield 90%) ¹ H-NMR (DMSO, δ); 1.48 (s, 6)
H), 3.32 (t, 2H), 3.50 (t, 2H),
4.10 (d, 4H), 4.88 (m, 2H), 6.8
5 (d, 4H), 7.13 (d, 4H), 7.55 (b
s, 2H) ¹³ C-NMR (CDCl ₃ , δ); 30.9, 41.
7, 42.6, 68.2, 74.3, 114.1, 12
7.8, 143.9, 155.8, 159.9

Example 6 23.4 g of glycidyl-4-t-butylbenzoate
(0.10 mol), 8.9 g of ethyl carbamate (0.
10 mol) was dissolved and 1,8-diazabicyclo [5.
4.0] -7-Undecene (0.2 g) and dibutyltin oxide (0.2 g) were added, and the mixture was reacted at 140 ° C. for 2 hours while blowing nitrogen gas to remove by-produced ethanol.
The reaction product was purified by silica gel column chromatography (developing solution; ethyl acetate) to give a colorless transparent liquid 20.
5 g was obtained. This product has ¹ H-NMR and ¹³ C-NM
As a result of R measurement, it was confirmed to be 5- (4-t-butylbenzoyl) oxymethyl-2-oxazolidinone.
(Yield 74%) ¹ H-NMR (DMSO, δ); 1.35 (s, 9)
H), 3.48 (dd, 1H), 3.77 (t, 1)
H), 4.50 (d, 2H), 4.95 (m, 1H),
6.15 (bs, 1H), 7.45 (d, 2H), 7.
99 (d, 2H) ¹³ C-NMR (CDCl ₃ , δ); 31.1, 35.
1, 42.6, 64.6, 74.0, 125.5, 12
6.5, 129.7, 157.2, 159.7, 16
6.2

Example 7 14.4 g (0.10 mol) of glycidyl isobutyrate
Ethyl carbamate (8.9 g, 0.10 mol) was dissolved in the mixture, 1,8-diazabicyclo [5.4.0] -7-undecene (0.2 g) and dibutyltin oxide (0.2 g) were added, and nitrogen gas was blown thereinto. The reaction was performed at 140 ° C. for 2 hours while removing by-product ethanol. The reaction product was purified by silica gel column chromatography (developing solution; ethyl acetate) to obtain 12.7 g of white crystals. As a result of ¹ H-NMR and ¹³ C-NMR measurements,
It was confirmed to be isobutyroyloxymethyl-2-oxazolidinone. (Yield 68%) Melting point 51-52 ° C ¹ H-NMR (CDCl ₃ , δ); 1.20 (d, 6)
H), 2.62 (m, 1H), 3.42 (dd, 1)
H), 3.74 (dd, 1H), 4.28 (d, 2)
H), 4.88 (m, 1H), 6.70 (bs, 1H) ¹³ C-NMR (CDCl ₃ , δ); 17.8, 32.
9, 41.4, 63.3, 73.1, 158.8, 17
5.6

Example 8 8.91 g (0.10 mol) of ethyl carbamate was dissolved in 9.25 g (0.10 mol) of epichlorohydrin to prepare 1,8-diazabicyclo [5.4.0] -7. -Undecene 0.36g and dibutyltin oxide 0.36g
Was added, and nitrogen gas was blown in to remove ethanol as a byproduct, and the mixture was heated at 125 ° C. for 1 hour and further at 140 ° C. for 1 hour. The reaction product was purified by silica gel column chromatography (developing solution, ethyl acetate) to obtain 8.16 g of white crystals. This product has ¹ H-NMR and ¹³ C
As a result of NMR measurement, it was confirmed to be 5-chloromethyl-2-oxazolidinone. (Yield 60%) Melting point 86-88 ° C ¹ H-NMR (CDCl ₃ , δ); 3.42-3.88
(M, 4H), 4.75-5.05 (m, 1H), 6.
78 (bs, 1H) ¹³ C-NMR (CDCl ₃ , δ); 42.8, 46.
3,74.2,158.5

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ryuzo Mizuguchi 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd.

Claims (1)

[Claims] 1. When a compound having an oxirane ring is reacted with a carbamic acid ester to synthesize a 2-oxazolidinone compound, it is carried out in the presence of a tertiary amine and a tin compound as a catalyst. Synthesis of oxazolidinone compounds.