JPH04312548A - Production of chain dimer of 1-propen-3-al - Google Patents

Abstract

PURPOSE:To easily obtain the subject compound useful as an intermediate for resin modifiers, pharmaceuticals and agricultural chemicals and various other organic compounds by dimerizing 1-propen-3-al using a catalyst consisting of a combination of a group 8 metal element and a tertiary phosphine. CONSTITUTION:A chain dimer of 1-propen-3-al (e.g. 3-hydroxy-4-formyl-1,4- pentadiene and 2-methylene-1,5-pentanedial) can be produced by dimerizing 1-propen-3-al in the presence of a catalyst consisting of a group 8 metal element (especially preferably ruthenium or its compound) and a tertiary phosphine (especially preferably triphenyl phosphine) in the form of an organic metal complex containing both compounds as constituent components [e.g. dihydrotetrakis(triphenylphosphine)ruthenium] or a mixture of both compounds mixed in the reaction system.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is applicable to resin modifiers, pharmaceuticals and
The present invention relates to a method for producing a chain dimer of 1-propen-3-al (acrolein), which is useful as an intermediate for various organic compounds including agricultural chemicals.

0002

[Prior Art] Conventionally, as a method for dimerizing olefins having electron-withdrawing substituents, a method in which a ruthenium compound is used as a catalyst and acrylonitrile is reacted (
JP-A-44-24585), a reaction method using an organic phosphorus compound as a catalyst (JP-A-55-9814)
No. 9), and a method of reacting acrylic esters with ruthenium or palladium compounds (US Pat. No. 3).
, No. 013,066), a method for reacting α,β-unsaturated ketones with rhodium compounds (I.P.K.
ozalev etal, Journal of Or
Ganometallic Chemistry,v
ol. 385, 175, (1990)) etc. are known.

Regarding the dimerization reaction of 1-propen-3-al, it is known that 2,3-dihydro-2-formylpyran can be obtained by reacting it at 185 to 195°C without a catalyst (particularly Publication No. 40-9264). Furthermore, it is known that the polymerization reaction proceeds by using a ruthenium compound as a catalyst (S.
Komiya et al. Bulletin of t
he Chemical Society of Ja
pan, vol. 48, 101 (1975)). However, this paper does not include any description regarding the dimer formation of 1-propen-3-al.

0004

SUMMARY OF THE INVENTION The object of the present invention is to produce a linear dimer of 1-propen-3-al.

[0005]

[Means for Solving the Problems] The present invention is characterized in that 1-propene-3-al is reacted in the presence of a catalyst consisting of a Group 8 metal and a tertiary phosphine. -A method for producing a chain dimer of R.

(Catalyst) The catalyst used in the present invention consists of a Group 8 metal element and a tertiary phosphine, and may be an organometallic complex containing both of these components, or an individual compound in the reaction system. A mixture may also be used.

[0007] The Group 8 metal is preferably one of iron, ruthenium, and osmium, and more preferably ruthenium.

Examples of Group 8 metal compounds include halides such as chlorides, inorganic acid salts such as nitrates and sulfates, organic acid salts such as acetates, and acetylacetonate salts. Further, these compounds may contain water of crystallization and the like.

The tertiary phosphine compound has a trivalent phosphorus atom, for example, a chain alkyl group such as methyl, ethyl, propyl, or butyl; a cyclic alkyl group such as cyclohexyl or cyclooctyl; or a cyclic alkyl group such as phenyl, tolyl, xylyl, etc. It is defined as a combination of three same or different functional groups selected from aryl groups and alkenyl groups such as allyl. A particularly preferred tertiary phosphine compound is triphenylphosphine.

Examples of organometallic complexes containing a Group 8 metal element and a tertiary phosphine compound include dihydrotetrakis(triphenylphosphine)ruthenium and hydridochlorotris(triphenylphosphine)ruthenium. can.

The composition ratio of the tertiary phosphine to the Group 8 metal element in the catalyst is from 1 to 10, preferably from 2 to 5, in terms of molar ratio. The amount of the metal element used is 0.00001 to 0.00001 in molar ratio to the raw material 1-propene-3-al.
1, preferably 0.0001 to 0.1.

(Solvent) The reaction of the present invention can be carried out without using a solvent, but if necessary, it can be carried out in a suitable solvent that does not react with 1-propen-3-al. can. These solvents include, for example, hydrocarbons such as hexane and toluene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, and dioxane; esters such as ethyl acetate, butyl acetate, and butyrolactone; alcohols such as methanol, ethanol, butanol, etc. Examples include halogenated hydrocarbons such as chloroform and methylene chloride.

The concentration of 1-propen-3-al in these solvents is 1% by weight or more, preferably 10% by weight.

(Reaction Conditions) Although the reaction proceeds satisfactorily even below room temperature, it is usually carried out under heating in order to further improve the reaction rate. The reaction temperature is 50-200°C, preferably 60-150°C.

The reaction time depends on the reaction temperature, but is usually 0.
．． The time is 1 to 20 hours, preferably 1 to 10 hours. The reaction is carried out in an oxygen-free atmosphere in order to prevent oxidative deterioration of the phosphines, and the atmosphere is replaced with an inert gas such as nitrogen or argon, hydrogen, or the like.

The reaction pressure varies depending on the reaction temperature, but is generally from 2 to 100 bar, preferably from 5 to 50 bar.

(Reaction product) The chain dimer of 1-propen-3-al obtained by the production method of the present invention is 3
-hydroxy-4-formyl-1,4-pentadiene and 2-methylene-1,5-pentanedial. At the same time, oligomers of trimers or higher and heavy substances are also produced.

3-hydroxy-4-formyl-1,4-
Although pentadiene and 2-methylene-1,5-pentanedial have three unsaturated groups in their molecules, they do not have self-condensing properties even when distilled, and can be isolated by gas chromatography or the like.

[0019]

According to the present invention, a chain dimer of 1-propene-3-al can be easily produced.

[0020]

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples. Example 1 A magnetic stirrer was placed in a stainless steel autoclave with an internal volume of 30 ml and the autoclave was sealed, and then the inside of the system was replaced with argon gas. On the other hand, RuH2 (Ph3P
)4 0.07 mmol, 1-propene-3-al 31.4 mmol and tetrahydrofuran 20 m
1 was added to make a homogeneous solution. This solution was charged into the above-mentioned autoclave using a syringe, and 3 bar of argon was injected into the autoclave. The reaction solution was heated on an oil bath while being stirred externally using a magnetic stirrer, and reacted at 100° C. for 2 hours.

The product obtained was isolated by gas chromatography and identified by NMR and IR spectra. In addition, quantitative analysis was performed by gas chromatography using an internal standard method, and the following conversion rate and selectivity were determined.

Conversion rate (%) = 100 x (Number of moles of raw material reacted/Number of moles of raw material charged) Selectivity (%) = 100 x (Number of moles of product x 2/Number of moles of raw material reacted)

As a result, the conversion rate was 49.9%, the selectivity for 3-hydroxy-4-formyl-1,4-pentadiene was 28.4%, and the selectivity for 2-methylene-1,5-pentanedial. was 4.5%. Also 2-formyl-2
, 3-dihydropyran was not detected.

Example 2 61.2 mmol of 1-propene-3-al, RuH
2 (Ph3 P)4 was used at 0.16 mmol, hydrogen was injected at 3 bar instead of argon, and the reaction time was 3 bar.
The reaction was carried out in the same manner as in Example 1 except for changing the time.

The obtained product was treated in the same manner as in Example 1,
Identification and quantitative analysis were performed to determine conversion rate and selectivity. As a result, the conversion rate was 42.0%, the selectivity of 3-hydroxy-4-formyl-1,4-pentadiene was 23.9%, and the
-Selectivity of methylene-1,5-pentanedial is 9.
It was 8%. Moreover, 2-formyl-2,3-dihydropyran was not detected.

Example 3 Except that 30.4 mmol of 1-propen-3-al was used, 0.08 mole of RuHCl(Ph3P)4 as a catalyst, and the reaction time was 3 hours. ,
The reaction was carried out in the same manner as in Example 1.

The obtained product was treated in the same manner as in Example 1,
Identification and quantitative analysis were performed to determine conversion rate and selectivity. As a result, the conversion rate was 26.0%, the selectivity of 3-hydroxy-4-formyl-1,4-pentadiene was 8.4%, and the 2-
The selectivity of methylene-1,5-pentanedial is 6.9
%Met. Moreover, the selectivity of 2-formyl-2,3-dihydropyran was 2.4%.

Claims (1)

[Claims] 1. A chain dimer of 1-propen-3-al, characterized in that 1-propen-3-al is reacted in the presence of a catalyst consisting of a Group 8 metal and a tertiary phosphine. manufacturing method.