JP2797539B2 - Production method of β-lactone derivative - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a novel process for producing β-lactone derivatives, in one step from α-methylene-β-propanol to alcohol.
This is a method for selectively producing a lactone derivative.

It is known that α-methylene-β-lactone itself has herbicidal activity and is useful as a synthetic intermediate of β-lactam derivatives useful as antibacterial agents.

(Prior Art) As a method for producing a lactone derivative, it is known that α-methylene-γ and δ-lactone derivatives can be obtained from an acetylenic alcohol and carbon monoxide using a Pd complex as a catalyst (JACS101, 4107 ( 1979), however, no α-methylene-β-lactone derivative can be obtained by a similar reaction to propargyl alcohol.

(Problems to be Solved by the Invention) In the present invention, when a triorganosilyl group and carbon monoxide are introduced into a terminal acetylene portion, a substituent can be selectively introduced into the α-position, so that an acetylenic alcohol is determined. It is intended to provide a novel production method capable of selectively obtaining an object.

(Means for Solving the Problems) The method of the present invention is represented by the following formula: (Wherein R ¹ and R ² each represent a hydrogen atom or a lower alkyl group, or R ¹ and R ² together with the carbon atom to which they are attached represent a 5- to 7-membered alicyclic ring) An alcohol, and carbon monoxide, in the presence of a tertiary amine and a rhodium catalyst, have the formula Wherein Z ¹ , Z ² and Z ³ each represent a lower alkyl group or a phenyl group. (Wherein, R ¹ , R ² , Z ¹ , Z ² and Z ³ are the same as those described above).

In the above formula, as the lower alkyl group, for example,
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl.

In order to carry out the method of the present invention, a rhodium catalyst is added to a solvent saturated with carbon monoxide in a carbon monoxide atmosphere at 50 to 0.001 mol%, preferably 5 to 0.01 mol%, based on a substrate. Is cooled and stored in a pressure-resistant container. Under cooling, this container contains propargyl alcohol of formula (I) and formula (II)
Of triorganosilane substantially equimolar amounts, and a tertiary amine 1.2 to 0.95 mol was added to the substrate, 5~60kgf / cm ² with carbon monoxide gas pressure, preferably 30~50kgf / cm ^2, the reaction The reaction is carried out with stirring while maintaining the temperature at 30 to 250 ° C, preferably 80 to 150 ° C. After the reaction vessel is returned to normal pressure and normal temperature, it is concentrated under reduced pressure, and the obtained oil is separated and purified by silica gel column chromatography by a conventional method, and further distilled to obtain a target product.

Examples of the tertiary amine which is a base include triethylamine, triisopropylamine, triisobutylamine, PDA (N, N, N ', N'-tetramethyl-1,3-propanediamine, DABCO (1,4-diazabicyclo [ 2,2,2] octane), DBU (1,8-diazabicyclo [5,4,0] undec-7-ene), DBN (1,5-diazabicyclo [4,3,0] non-5-ene) And 1,2,2,4,4-pentamethylpiperidine.

Rhodium catalysts include, for example, Rh ₄ (CO) ₁₂ , Rh ₂ Co _{2
(CO) 12, RhCo (CO} ) 8, Rh 6 (CO) 16, [RhCl (CO)
₂ ] ₂ , RhH (CO) (PPh ₃ ) ₃ , RhH (PPh ₃ ) ₄ , RhCl
(PPh ₃ ) ₃ , RhCl ₃ , [Rh (COD) (DIPHOS)] X and [Rh (NBD) (DIPHOS)] X. Where Ph
Is phenyl, COD is 1,5-cyclooctadiene, NBD
The 1.5-norbornadiene, X a is _{PF 6 · BF 4 · ClO 4} , D
IPHOS Is shown.

Solvents used in this reaction include aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as chloroform and dichloromethane; N, N
-Dimethylformamide; dimethyl sulfoxide; hexamethylphosphoric triamide; ethers such as tetrahydrofuran and diethyl ether.

The raw material propargyl alcohol (I) can be easily obtained by reacting various aldehydes or ketones (IV) with alkali metal acetylene (V).

(Example) Hereinafter, the method of the present invention will be described in detail with reference to examples.

Example 1. 3- [Dimethyl (t-butyl) silyl] methylene-4,4
-Dimethyloxetane-2-one Under a carbon monoxide atmosphere, 2 ml of benzene saturated with carbon monoxide and 0.004 g of Rh ₄ (CO) _{12 were} placed in a glass reaction vessel.
(0.0052 mmol) and cooled to −78 ° C., and the glass container was placed in a stainless steel pressure-resistant container. Further, at the same temperature, 2-methyl-3-butyn-2-ol (0.097 g (1.15 mmol), dimethyl (t-butyl) silane
0.124 g (1.06 mmol) and triethylamine 0.105 g (1.
After dissolving each solution in 1 ml of benzene, the pressure vessel was immediately filled with carbon monoxide, pressurized to 32 kg / cm ² , heated at 100 ° C. for 2 hours, stirred and reacted. Immediately after the reaction, the entire pressure-resistant container was cooled to room temperature, the pressure in the container was returned to normal pressure, the reaction mixture was transferred to an eggplant-shaped flask and concentrated under reduced pressure, and the obtained oily substance was subjected to silica gel column chromatography (developing solvent; After separation and purification by hexane / ethyl acetate = 20/1), Kugelrohr distillation was performed to obtain 0.207 g (yield 86%) of the desired product.

Examples 2 to 6 One equivalent of 2-methyl-3-butyn-2-ol was mixed with 1 mol% of Rh ₄ (CO) ₁₂ and triethylamine in the presence of one equivalent of triorganosilane. The reaction was performed at 30 to 50 kgf / cm ² at 100 ° C. in a carbon oxide atmosphere to obtain a corresponding target product. Table 1 shows the results.

Examples 7 to 9 1 equivalent of each of 2-methyl-3-butyn-2-ol and dimethyl (phenyl) silane was added to 1 mol% of Rh ₄ (CO) ₁₂ and 1 equivalent of various tertiary amines (0.1 equivalent of DBU). Under a carbon monoxide atmosphere at 30 to 50 kgf / cm ² at 100 ° C.
3- [dimethyl (phenyl) silyl] methylene-4,4-
Dimethyloxetan-2-one was obtained. The result is
It is shown in the table.

Examples 10 to 15 3-buten-2-ol per equivalent of various tertiary amines in the presence of 1 equivalent (0.1 equivalent of DBU) to triorganosilane under a carbon monoxide atmosphere at 30 to 50 kgf / cm ^{2. The} desired product reacting at 100 ° C was obtained. Table 3 shows the results.

Examples 16 to 19 1 equivalent of various triorganosilanes in various propargyl alcohols, in the presence of 1 mol% of Rh ₄ (CO) ₁₂ and 1 equivalent of various tertiary amines (0.1 equivalent of DBU) in a carbon monoxide atmosphere Under the following conditions, the reaction was carried out at 30 to 50 kgf / cm ² at 100 ° C. to obtain a corresponding target product. Table 4 shows the results.

The physical properties of the target product obtained by the above method are as shown in Table 5.

Claims (1)

(57) [Claims] (1) Expression (Wherein R ¹ and R ² each represent a hydrogen atom or a lower alkyl group, or R ¹ and R ² together with the carbon atom to which they are attached represent a 5- to 7-membered alicyclic ring) An alcohol, and carbon monoxide, in the presence of a tertiary amine and a rhodium catalyst, have the formula Wherein Z ¹ , Z ² and Z ³ each represent a lower alkyl group or a phenyl group. (Wherein, R ¹ , R ² , Z ¹ , Z ² and Z ³ are the same as those described above).