JPS6352938B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a liquid phase heterogeneous system consisting of an aqueous phase and an organic phase, and is suitable for promoting a heterogeneous organic reaction in the presence of an alkali metal compound. or (However, R is an alkyl group having 10 to 18 carbon atoms, R ₁ and R ₂ are lower alkyl groups having 1 to 4 carbon atoms, R ₃ is a lower alkyl group having 1 to 3 carbon atoms, or a benzyl group,
(X represents a halogen atom) The present invention relates to a liquid-phase heterogeneous reaction catalyst comprising a quaternary ammonium salt represented by: Phase transfer catalysts, typified by quaternary ammonium salts, quaternary phosphionium salts, macrocyclic polyethers, etc., have traditionally been used to promote heterogeneous organic reactions in the presence of alkali metal compounds in a liquid phase heterogeneous system. Catalyst) is known to be used. The mechanism of action of phase transfer catalysts between different phases between the aqueous phase and the organic phase is that the catalysts represented by these quaternary salts exchange counter anions and move back and forth between the aqueous phase and the organic phase, thereby performing the catalytic action. It is understood to indicate.
However, although conventional phase transfer catalysts exhibit high catalytic activity in carbene-generating reactions, they have a low promoting effect in carbonian-generating reactions. Because it is thermally unstable, there is a risk of salt decomposition loss or side reactions occurring due to decomposition products during the reaction process or the purification process to extract the product from the reaction solution, depending on the type of reaction and reaction conditions. There were constraints on technological choices. As a result of various studies on heterogeneous organic reactions in the presence of alkali metal compounds in a liquid-phase heterogeneous system from an industrial and practical standpoint, the present inventors have developed a reaction catalyst that has wide applicability and a high reaction promoting effect. We have arrived at the heading Invention. That is, the gist of the present invention is that the general formula or (However, R is an alkyl group having 10 to 18 carbon atoms, R ₁ and R ₂ are lower alkyl groups having 1 to 4 carbon atoms, R ₃ is a lower alkyl group having 1 to 3 carbon atoms, or a penzyl group,
(X represents a halogen atom) A liquid phase heterogeneous reaction catalyst consisting of a quaternary ammonium salt represented by: By using the catalyst of the present invention, in a liquid phase heterogeneous system consisting of an aqueous phase and an organic phase, an alkali metal compound is used as a reactant, and the reaction is effectively promoted between the reaction substrate or reactant in the organic phase. I can do it. The quaternary ammonium salt that is the catalyst of the present invention has a long-chain β-hydroxyalkyl group and a lower β-hydroxyalkyl group.
- Compared to quaternary ammonium salts having a hydroxyalkyl group, such as a β-hydroxyethyl group, or quaternary ammonium salts having a long chain and lower alkyl group without a hydroxyl group at the β position, its catalytic activity is Since there are large differences and generally high thermal and chemical stability, the range of application is expanded by itself, and its usefulness is obvious. By the way, according to the literature by Nozaki et al. (Kagaku to Kogyo Vol. 28, No. 9, pp. 639-641), high selectivity is disclosed in the carbene generation reaction using β-hydroxyethylammonium salt, but the yield is low. It is actually inferior to other types of quaternary ammonium salts. This is also supported by experiments conducted by the present inventors, and a simple β
-Hydroxyethylammonium salt gave an unsatisfactory yield (see Comparative Example 2). In the above general formula [][′], the hydrocarbon group R is an alkyl group having 10 to 18 carbon atoms, such as decyl, undecyl, dodecyl, tetradecyl,
Groups such as pentadecyl, hexadecyl, octadecyl, etc. are particularly preferred, and decyl, undecyl,
It is a dodecyl group. The hydrocarbon groups R ₁ and R ₂ are lower alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl and the like. The hydrocarbon group R ₃ is a lower alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, propyl, etc.
Or a benzyl group. Examples of the halogen atom X include fluorine, chlorine, bromine, and iodine, with chlorine and bromine being particularly preferred. In order to effectively utilize the quaternary ammonium salt of the present invention, the amount of catalyst added is usually about 0.001 to 0.5 mol, preferably about 0.01 to 0.5 mol, per 1 mol of reaction substrate or reactant in the organic phase. A range of 0.2 mol is appropriate, and the ratio of the aqueous phase to the organic phase is approximately 10:1 by volume.
The ratio may be selected in the range of 1 to 1:10, preferably about 3:1 to 1:3. Operating conditions such as reaction temperature should be appropriately selected depending on the type of reaction, reaction substrate or reactant, reaction product, solvent, etc. Furthermore, when a reaction is carried out using the catalyst of the present invention, the reaction mixture is usually treated by separating the reaction mixture into an aqueous phase and an organic phase, and separating each component from the organic phase by distillation. method is adopted. The aqueous phase as referred to in the present invention is composed of an amount of water necessary and sufficient to dissolve the alkali metal compound, and an alkali metal compound concentration that promotes the heterogeneous organic reaction and facilitates layer separation after the reaction. Here, as the alkali metal compound, the alkali metal is particularly sodium and potassium, and the anionic constituent units include a halogen atom, a cyano group, a hydroxyl group, a cyanate group, a thiocyanate group, an organic carboxylic acid residue, etc. I can do it. The organic phase referred to in the present invention is composed mainly of reaction substrates or reactants consumed in the heterogeneous organic reaction, but organic solvents such as hexane, benzene, toluene, etc. that are harmless to the reaction may be used. There is no problem. Heterogeneous organic reactions to which the catalyst of the present invention can be applied are those in which phase transfer catalysts have traditionally been used.
Although there are a large number of reactions, the typical ones include (1) carbene generation reaction, (2) ion pair extraction reaction, (3) nucleophilic substitution reaction, and
(4) An example is the oxidation reaction of purplebenzene. Specifically, (1) a typical example of a carbene generation reaction is to add a quaternary ammonium salt to a two-phase system of chloroform and an aqueous sodium hydroxide solution to generate dichlorocarbene, which undergoes an addition reaction to the olefin moiety. Examples include insertion reactions into the C--H moiety, and reactions of carbenes with primary amines, alcohols, aldehydes, and Schiff bases. (2)
The ion pair extraction reaction is a name coined by Brandstro¨n et al., in which an ion pair of an organic compound with an active proton and a quaternary ammonium salt is extracted and isolated, and then reacted with an electrophilic reagent.A typical example is C There is a reaction between (carbonion) and alkylating agent, but other
Ion pair reactions with anions such as O, N and S are also well included in this category. (3) Nucleophilic substitution reaction is a so-called anion exchange reaction in which an alkali metal compound in the aqueous phase acts as a nucleophile and undergoes a substitution reaction with a reactant in the organic phase. Examples are given below to clarify the specific content and effects of the present invention, but the embodiments are not intended to limit the scope of the present invention. Example 1 (Carbene generation reaction) Styrene C ₆ H ₅ CH= was placed in a 100 ml eggplant flask equipped with a reflux condenser and a stirrer.
CH ₂ 10.4 g (0.1 mol), chloroform CHCl ₃ 11.9
g (0.1 mol) and 20 ml (0.35 mol) of 50% NaOH aqueous solution
(equivalent amount) and add catalyst to this. (Mixture of R having 10 to 12 carbon atoms) 0.72 g (0.0017 mol) was added and immersed in a 40° C. hot water bath for 4 hours while stirring. After the reaction was completed, the organic phase was collected and analyzed by gas chromatography. 1,1-dichloro-2-phenyl cyclopropane

[Formula] 15.86g (0.0848mol) was produced (yield 84.8%). Examples 2 to 4 and Comparative Examples 1 to 4 (Carbene generation reaction) The same procedure as in Example 1 was carried out except that the quaternary ammonium salt shown in Table 1 was added as a catalyst in the amount shown in Table 1. In addition, Comparative Example 1 was made without a catalyst. The results are shown in Table-1. Example 5 (Ion pair extraction reaction) In the same reaction apparatus as in Example 1, 11.7 g (0.10 mol) of phenylacetonitrile C ₆ H ₅ CH ₂ CN and 10.9 g (0.10 mol) of ethyl bromide C ₂ H ₅ Br were added. , NaOH4.00g
(0.10 equivalent) and 20ml of pure water, add catalyst (Mixture of R having 10 to 12 carbon atoms) 0.40g (0.001 mol)
was added and immersed in a 70°C hot water bath for 5 hours while stirring. Except for the above, the same treatment as in Example 1 was carried out, and ethylphenylacetonitrile was

It was confirmed that 9.09 g (0.0627 mol) of [Formula] was produced (yield: 62.7%). Comparative Examples 5 to 6 (Ion pair extraction reaction) The same procedure as in Example 5 was carried out except that the quaternary ammonium salt shown in Table 1 was added as a catalyst in the amount shown in Table 1. The results are shown in Table-1. Example 6 (Nucleophilic substitution reaction) In the same reaction apparatus as in Example 1, 9.65 g (0.05 mol) of n-octyl bromide n-C ₈ H _{17 Br} ,
Prepare 2.08 g (0.052 equivalent) of NaOH and 5 ml of pure water, add catalyst (R has 10 to 12 carbon atoms) 0.21 g (0.0005 mol) was added and stirred, and immersed in an oil bath at about 110 to 120° C. for 30 hours under reflux. Except for the above, the process was carried out in the same manner as in Example 1, and it was confirmed that 2.55 g (0.0198 mol) of n-octyl alcohol C ₈ H _{17 OH} was produced. (Yield 39.6%). Comparative Example 7 (Nucleophilic Substitution Reaction) The same procedure as in Example 6 was carried out except that the quaternary ammonium salt shown in Table 1 was added as a catalyst in the amount shown in Table 1. The results are shown in Table-1.

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Claims (1)

[Claims] 1. General formula or (However, R is an alkyl group having 10 to 18 carbon atoms, R ₁ and R ₂ are lower alkyl groups having 1 to 4 carbon atoms, R ₃ is a lower alkyl group having 1 to 3 carbon atoms, or a benzyl group,
A liquid phase heterogeneous reaction catalyst consisting of a quaternary ammonium salt represented by (X represents a halogen atom).