JPS5827775B2 - How to promote a reaction - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention involves a base-catalyzed elimination reaction using an alkali metal hydroxide in a liquid phase heterogeneous system consisting of an aqueous phase and an organic phase, a substitution reaction of active hydrogen of an active hydrogen compound with an organic group, By having a specific polyoxyalkylene diether present in the reaction system when performing an organic ion reaction selected from the group consisting of the addition reaction of an active hydrogen compound to an unsaturated compound and the self- or heterogeneous condensation reaction of a carbonyl compound. The present invention relates to a method for effectively advancing the organic ion reaction.

Conventionally, when conducting an organic reaction, in order to simplify the separation of products after the reaction and/or to make reactants and catalysts that are difficult to dissolve in the organic liquid to work effectively, the aqueous phase and the organic phase are separated. It is well known to use a liquid-phase heterogeneous system.

In order to effectively advance a reaction between different phases consisting of an aqueous phase and an organic phase, it is necessary to devise ways to facilitate the interaction between the components present in the aqueous phase and the components present in the organic phase. Methods include methods using surfactants and phase transfer catalysts.
This is a method using IV).

Examples of applications of methods using surfactants include emulsion polymerization and ester hydrolysis reactions in the biochemical field.

The main purpose of using this surfactant is to increase the contact interface between the organic phase and the aqueous phase to facilitate the movement of organic substances to the aqueous phase or the movement of components in the aqueous phase to the organic phase. Except in limited cases such as reactions, they generally do not produce a sufficiently satisfactory reaction promoting effect.

In the method using a phase transfer catalyst, a metal compound is dissolved in an aqueous phase, an active anion from the metal compound is transported into an organic phase by the phase transfer catalyst, and an organic reactant and an active anion are combined in the organic phase. The main point is to advance the organic ion reaction between the two.

Quaternary ammonium salts and phosphonium salts having a suitable carbon chain have been conventionally used as phase transfer catalysts, but these are generally expensive and their production methods are complicated, making it difficult to achieve the desired phase transfer. Catalysts are not easy to obtain.

Furthermore, since these quaternary ammonium salts and phosphonium salts are thermally unstable, they are easily decomposed when separating each component from the reaction mixture, resulting in loss of these salts and side reactions caused by decomposition products. There is a risk that this may result in the occurrence of oxidation, a decrease in product purity, etc.

Furthermore, since quaternary ammonium salts and phosphonium salts are cationic compounds, there are limits to the range of reactions in which they can be used.

On the other hand, reaction examples using nonionic phase transfer catalysts are also already known.

i.e. crown ether
It has been demonstrated in several cases that macrocyclic polyethers named ) can be used as phase transfer catalysts.

However, compared to the quaternary ammonium salts and phosphonium salts mentioned above, crown ethers are more complicated to manufacture and purify and are extremely expensive, and from an industrial standpoint, it is difficult to manufacture and purify them, and from an industrial standpoint, it is preferable to use a specific crown ether suitable for each reaction system. Choosing ether is very difficult.

Over the past few years, the following polyoxyethylene derivatives (
octopus molecule)
Research has also begun on the catalytic ability of

These polyoxyethylene derivatives are compounds characterized by having two or more di- or triethylene glycol chains located very close to each other or attached to the same atom, and these are used as phase transfer catalysts. It has been reported that, in some cases, it exhibits catalytic activity comparable to that of crown ethers.

In these polyoxyethylene derivatives, adjacent di- or triethylene glycol silver amounts form a pseudo-cyclic structure through weak bonds (for example, hydrogen bonds), and the catalytic activity is expressed by trapping metal cations in the pseudo-cyclic structure. It is considered.

As is clear from their unique structure, these polyoxyethylene derivatives are not easy to manufacture and are extremely expensive.

In particular, the above compound @AC) is said to have a fairly high catalytic ability as a phase transfer catalyst, but it is similar to the nonionic surfactants used in the hydrolysis of esters in the biochemical field. Since one end of the ethylene chain is a hydroxyl group, it often reacts itself in the coexistence of an alkali metal compound, which limits its applicability.

The inventors of the present invention have conducted extensive research in order to solve the problems of the conventional method as described above and more advantageously perform organic ion reactions in a liquid phase heterogeneous system consisting of an aqueous phase and an organic phase. discovered that certain polyoxyalkylene diethers have extremely excellent catalytic ability (reaction promoting effect) despite their completely linear polyether structure,
This led to the present invention.

That is, according to the present invention, a base-catalyzed elimination reaction using an alkali metal hydroxide between different phases consisting of an aqueous phase and an organic phase,
When performing an organic ion reaction selected from the group consisting of t from the substitution reaction of active hydrogen of an active hydrogen compound with an organic group, the addition reaction of an active hydrogen compound to an unsaturated compound, and the self- or heterogeneous condensation reaction of a carbonyl compound, the reaction In the military general formula for the system, n is a number of 0 or more with an average of 6 to 30, and R1 and R2 are substituted or is an unsubstituted hydrocarbon group or trialkylsilyl group, and
The organic ion reaction is significantly accelerated by adding a polyoxyalkylene diether represented by the following formula: -CH2CH20- and 9 CH3 CH3CHO- may be optionally selected.

The polyoxyalkylene diether of general formula (I) used in the present invention has an average oxyalkylene unit of nn
) is 6 to 30 (preferably 7 to 15).

In the case of diethers having n-, tri-, and tetraethylene glycol chains with n of 5 or less, especially 4 or less, catalytic activity is not substantially exhibited, and when n exceeds 30, not only does the catalytic activity decrease, It is not practical because catalyst synthesis becomes difficult and solubility and other properties deteriorate.

Note that n represents the average number of units and is not necessarily an integer.

R1 and R2 in general formula (I) are necessarily limited to some extent by the above, since the desired organic ion reaction is carried out between the aqueous phase and the organic phase.
When the total number of carbon atoms (m) in 2 is n/2 or more, the organic ion reaction rate increases significantly.

When the reaction system apparently forms an emulsion depending on R1 and R2, n, the alkali metal hydroxide concentration in the aqueous phase, the reaction temperature, the organic reactant, the reaction product, the solvent, the quantitative ratio of the aqueous phase to the organic phase, etc. However, such appearance (state of the system) is essentially unrelated to the catalytic action of the polyoxyalkylene diether in the present invention.

However, industrially, when separating the reaction product after the reaction by a method known per se, it is desirable that the aqueous phase and the organic phase be easily separated into two layers, so the desirable relationship between □ and m is Although it varies depending on the type of reaction and reaction conditions, one rule of thumb holds true.

Considering this, the ease of industrial introduction of R1 and R2, the solubility of the synthesized polyoxyalkylene diether in the organic reaction medium, the physical properties (physical constants) such as melting point, boiling point, etc., n and m is n, /2 <m <
60, and particularly preferably satisfies the relationship n≦m×40.

Typical examples of R1 and R2 include methyl, ethyl, furoyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, tesyl, undecyl, dodecyl,
cetyl, stearyl, allyl, pentenyl, decenyl,
saturated or unsaturated aliphatic hydrocarbon groups such as oleyl,
Substituted phenyl groups such as cyclohexyl, methylcyclohexyl, ethylcyclohexyl natonoalicyclic hydrocarbon group, phenyl group, butylphenyl, nonylphenyl, tesylphenyl, undecylphenyl, dotesylphenyl,
Substituted benzyl groups such as benzyl, methyl-substituted benzyl, nonyl-substituted hensyl, and trialkylsilyl groups such as trimethylsilyl are mentioned.

However, R1 and R2 are the above-mentioned n from among these substituted or unsubstituted hydrocarbon groups and trialkylsilyl groups.
/2<m, preferably n/2<m<60, particularly preferably n2m<40.

The polyoxyalkylene diether represented by the general formula (I) used in the present invention is generally a combination of the corresponding alcohol or phenol and ethylene oxide or (
and) industrially produced by the polyaddition reaction of propylene oxide with the following general formula [wherein and y have the same meanings as in general formula (I), and R is in general formula (I) The same as R1 or R2] can be easily produced by etherifying or silyl etherifying a compound represented by
and n(-x+y), and the optimum polyoxyalkylene diether can be easily selected depending on the type of organic ion reaction.

Furthermore, when the polyoxyalkylene diether of the general formula (I) is used as a reaction accelerator (or catalyst) according to the present invention, the polyoxyalkylene diether is chemically and thermally extremely stable, so that it can be used over a wide range of conditions. Organic ionic reactions can be carried out under a wide range of conditions.

In addition, the polyoxyalkylene diether acts as a high boiling point solvent when each component is distilled off from the organic phase after the reaction.
An additional advantage also arises in that the distillation yield of all) can be increased.

When the method of the present invention is carried out industrially, general formula (1,)
The amount of polyoxyalkylene diether added is not particularly limited, but it is usually a so-called catalytic amount (catalytic amount).
In general organic ion reactions, the amount is about 0.001 to 1 mol per mole of organic reactant.
A range of 1.0 mol, particularly from about 0.01 to about 0.3 mol, is preferred.

In the method of the present invention, the use of an organic solvent that is chemically stable under the reaction conditions is often advantageous in terms of process engineering and economics.

The solvent that can be used should be appropriately selected depending on the type of reaction, but representative solvents that can be used over a relatively wide range include hexane, octane, cyclohexane, benzene, toluene natonohydrocarbons, dibutyl ether, and Examples include ethers such as I. lahydrofuran and anisole, and nitriles such as acetonitrile and benzonitrile.

Depending on the type of organic ion reaction, esters such as ethyl acetate, butyl acetate, methyl propionate, and phenyl acetate, and alcohols such as methyl alcohol, ethyl alcohol, flobyl alcohol, and methyl alcohol can also be used.

There is no particular restriction on the amount of these solvents used.

However, the ratio of the organic phase to the aqueous phase in the reaction system is generally in a volume ratio of 10:1 to 1:10, preferably 3:1 to 1:3.

In order to carry out the reaction in a non-emulsion state, to increase the reaction rate, or to facilitate phase separation after the reaction,
It is desirable to have a relatively high concentration of alkali metal hydroxide in the aqueous phase, and for this purpose there is nothing wrong with adding various harmless salts to the reaction system or to the mixture after the reaction. .

The reaction temperature should be selected appropriately depending on the individual reaction, but for example, it is industrially difficult to carry out the reaction at the boiling temperature of the solvent, organic reactant, reaction product, etc. from the viewpoint of removing the reaction heat. is also useful.

When carrying out the method of the present invention, the general method for treating the mixed liquid after the reaction is to separate the reaction mixed liquid into an aqueous layer and an organic layer, and to separate each component from the organic layer by distillation. .

The organic ion reactions to which the method of the present invention is applicable are explained below.

■Base-catalyzed elimination reaction Base-catalyzed elimination reaction is the intramolecular taxation of organic halogen compounds...
It is typified by the hydrogen chloride reaction.

Typical examples of these dehydrogenation reactions that are industrially useful are carbene reactions, ring-closing reactions, and ylide reactions.

The base acts catalytically on the deno-hydrogenation reaction itself, but is consumed by the reaction with the generated hydrogen halogenide.

Therefore, the base used is usually referred to as a dehydrohalogenating agent.

When the method of the present invention is applied to this type of elimination reaction, it is possible to use the alkali metal hydroxide as a base in the form of an industrially easily available aqueous solution. The value is extremely high.

When carrying out the reaction, the concentration of the alkali metal hydroxide in the aqueous phase is preferably about 20 to 70% by weight.

Carbenes are generated by α-dissociation of hydrogen halides from halogenated hydrocarbons and their derivatives.

Example * (X is halogen) The conventional industrial method for generating di-locarbenes is to subject the corresponding haloform to an α-separation reaction in a non-aqueous system in the presence of a strong base such as potassium t-butoxide. According to the method of the present invention, carbene can be generated under mild conditions using an inexpensive alkali metal hydroxide.

As is well known, the carbene reaction is applied to cyclopropane ring formation, ring expansion, addition reactions to c=s, 〉C-0, 〉C-N- bonds, etc., and it is also an industrially useful compound. It is one of the basic reactions for the synthesis of

The carbene reaction is usually carried out in the presence of an excess unsaturated compound to be added in the presence of a solvent.

When the method of the present invention is applied to a carbene reaction, the alkali metal hydroxide acts catalytically on the elimination reaction itself, but reacts with the eliminated hydrogen halide to produce the corresponding metal halide. Therefore, a stoichiometric amount is consumed based on the amount of carbene generated.

Carbenes are not generated, but addition reactions of α-haloesters, chloroacetonyl, etc. to carbonyl compounds as exemplified by the following formula (Dar
(referred to as the ZenS reaction).

(R is an alcohol residue, for example, an alkyl group) In a sense, the ylide reaction can be considered to be in the same category as the carbene reaction, and is one of the preferred reaction examples to which the method of the present invention can be applied.

L-riphenylphosphine, trialkylphosphine
When a base acts on a phosphine or an adduct of a phosphite and a halogenated hydrocarbon, such as l.
Ittig reaction).

Example (X is halogen) Similarly, an S-ylide obtained by reacting a base with a halogenated hydrocarbon and a sulfide such as dialkyl sulfide or dialkyl sulfide is added to a carbonyl compound and the corresponding It is known to produce epoxy compounds.

Example (X is halogen) These ylide production reactions have conventionally been generally carried out in an anhydrous organic solvent using an organometallic compound of an alkali or alkaline earth metal or Alcola-I as a catalyst.
According to the method of the present invention, an inexpensive aqueous solution of alkali metal hydroxide can be used as is as a reaction medium.

The dehydropalogenation reaction also includes the β-elimination reaction of hydrogen halogenide from halogenated hydrocarbons and their derivatives.

This reaction produces alkenes or alkynes.

Similar reactions include the production of alkenes or alkynes through the vicinal dihalogenation carbonization reaction and the β-synthetic dihalogenation reaction of hydrogen, and the method of the present invention can also be used for this reaction.

A ring-closing reaction by dehydrohalokenation is also an industrially useful reaction, and an example of this type of reaction is described in, for example, JP-A-51-32.
No. 543, No. 51 39647, No. 51-65734, No. 5■6573
This can be seen in the descriptions of various publications such as No. 5 and No. 51-59839.

The reason why the ring-closing reaction takes precedence over the β-dissociation at a practical yield is, for example, when a carbon with a halogen that should be eliminated in the starting organic halogen compound is set as the α-position carbon, hydrogen is attached to the β-position carbon. This is the case when the hydrogen attached to the r-position carbon is activated by an electron-withdrawing group.

Examples (X is C1 or Br, R is an alcohol residue, e.g. an alkyl group, Y and Z are hydrogen, halogen or hydrocarbon groups e.g. methyl, vinyl, etc.) Ring-closing reactions as described above are also applicable to the method of the invention. Accordingly, the process can proceed smoothly under mild conditions using an inexpensive aqueous solution of alkali metal hydroxide.

2. Substitution reaction of active hydrogen of active hydrogen compound with organic group Active hydrogen atom attached to carbon bonded to electron-withdrawing atomic group represented by carbonyl group, cyano group, alkoxycarbonyl group, etc. - (α-hydrogen) In the presence of a base, organic compounds containing active hydrogen (active hydrogen compounds) such as hydrogen atoms bonded to oxygen or sulfur in alcohols, carboxylic acids, thiols, etc., and hydrogen atoms bonded to nitrogen in amines, amides, etc. When reacting with an organic halide, the halogen atom in the organic halide can be replaced with a carbanion, alkoxide anion, thiol anion, >N anion, etc. generated from the above-mentioned active hydrogen compound.

There are countless examples of such base-catalyzed substitution reactions, and the reactions 1) to (Vi) below can be cited as representative examples.

However, in the above formulas (1) to (■0, R and R' are the same or different and represent a hydrogen atom or an organic group represented by an alkyl group, a cycloalkyl group, an asol group, an alkenyl group, an acyl group, a cyano group, etc.) where R'' is generally a hydrocarbon group, such as an alkyl group.

R'' is a primary or secondary hydrocarbon group and does not include substituted or unsubstituted phenyl groups and vinyl groups.

X is...a rogene atom, and from an industrial standpoint, a chlorine or bromine atom.

In the reactions of this section represented by (1) to (vi) above, the base is also required in a stoichiometric amount relative to the organic compound.

This point is exactly the same as in the case of each organic ion reaction described in the previous section 3, and if the method of the present invention is applied to these reactions, an inexpensive alkali metal hydroxide is used as a base to separate the aqueous phase and the organic phase. The reaction can proceed smoothly between different phases.

3 Addition reaction of active hydrogen compound to unsaturated compound Olefinic compound activated (polarized) by carbanion carbonyl group, alkoxycarbonyl group, nitro group, cyano group, etc. generated from active hydrogen compound in the presence of a base. Additions to are well known, with Michael addition being a representative example.

There are many reactions of this type, and they are generally carried out in an organic solvent solution using an alkali metal alcolade or an organometallic compound of an alkali or alkaline earth metal as a catalyst in an amount of several mol % or less based on the organic reactant. By applying the method of the present invention, cheaper alkali metal hydroxides can be used as base catalysts in the form of aqueous solutions.

Typical examples of such addition reactions catalyzed by a very small amount of base include the following reactions.

Examples (R is, for example, an alkyl group, and R' is, for example, a phenyl group) Some addition reactions proceed at a practical reaction rate only in the presence of a large amount of base; In the addition reaction, the advantages of the method of the present invention are noticeable.

Among the addition reactions of active hydrogen compounds to polarized unsaturated bonds that are contacted in the presence of a large amount of base, the addition reaction of acetylene compounds to carbonyl compounds (the following formula ).

Here, R and R' are usually an alkyl group, an allyl group,
A hydrocarbon group such as a substituted allyl group, and R' is usually a hydrogen atom or an alkyl group, an alkenyl group, an alkynyl group,
Hydrocarbon groups such as aryl groups and cycloalkyl groups.

These hydrocarbon groups may be mixed with different atoms () as appropriate to the extent that no harm is caused.
・Tero atom) or an atomic group containing this may be substituted.

4. Self- and heterogeneous condensation reactions of carbonyl compounds The reactions in the title are typified by aldol condensation (including self-condensation and cross-aldol condensation between different carbonyl compounds), Claisen condensation, and benzoin condensation.

In these condensation reactions, a catalyst and an alkali metal hydroxide such as sodium hydroxide or hydroxide are generally used.

For example, aldol condensation of acetaldehyde, aldol condensation of n-butyraldehyde, crossaldol condensation of formaldehyde and acetaldehyde, and aldol condensation of acetone have been carried out industrially, and in these cases, a very small amount of base catalyst is used. , and the reaction is carried out under relatively mild reaction conditions.

Although the advantages of the method of the present invention are not necessarily apparent in the condensation reactions of carbonyl compounds that are extremely susceptible to condensation, as in these examples, by applying the method of the present invention, side reactions such as the Cannizzaro reaction can be suppressed. Advantages include scales, ease of product separation, and smooth reaction using water-insoluble higher aldehydes as raw materials.

On the other hand, the advantage of applying the method of the present invention is noticeable in condensation reactions that have conventionally been carried out only in the presence of a large amount of base or under severe reaction conditions.

For example, as seen in the Examples, benzoin condensation of benzaldehyde proceeds extremely smoothly even at room temperature according to the method of the present invention.

Condensation reactions of esters and condensation reactions of esters and carbonyl compounds (Stobe reaction) are also suitable examples of reactions to which the method of the present invention is applied.

Hereinafter, the present invention will be explained with reference to Examples, but these only show a part of the present invention, and the present invention is not limited by these Examples.

In the examples, wt% means weight%. Example 1 Contents 100 with thermometer, stirrer and reflux condenser
60wt of thorium hydroxide in a ml four-eye flask
% aqueous solution 20ml, chloroform 10ml, styrene 2
0 mmol and rimole were added, and the mixture was reacted at 40° C. for 3 hours with vigorous stirring.

After the reaction, the organic layer was analyzed by gas chromatography, and it was found that the product was produced in a yield of 85% based on styrene containing 1.l-dichloro-2-phenylcycloprobanca.

Example 2 Into the same reactor as in Example 1, 60% of thorium hydroxide was added.
wt% aqueous solution 20 rnl, chloroform 10 ml, benzoic acid amide 20 mmol, and C1s H370 (
C2H40) 7 C4Hg no Mi') was added in moles, and the mixture was reacted at 40° C. for 5 hours with vigorous stirring.

After the reaction, the organic layer was analyzed by gas chromatography, and it was found that 16 mmol of benzonitrile had been produced.

Example 3 Into the same reactor as in Example 1, 60% of sodium hydroxide was added.
wt% aqueous solution 20rnl, chloroform 10ml. 7
-20 mmol of hydroxynorbornane and C8H1
70(C2H40)7C8H1□1.029 mol was added, and the mixture was reacted at 40° C. for 3 hours with vigorous stirring.

After the reaction, the organic layer was analyzed by gas chromatography, and it was found that 11 mmol of 7-norbornane chloride was produced.

Example 4 Into the same reactor as in Example 1, 50 w of potassium hydroxide was added.
20 ml of t% aqueous solution, 50 mmol of cyclohexanone, 52 mmol of monochloroethyl acetate, and 1.0 SIJ mol were added, and the mixture was reacted at 70° C. with stirring for 48 hours.

After the reaction, the organic layer was analyzed by gas chromatography, and the corresponding condensate was added to the same reaction apparatus as in Example 1.
50 wt% aqueous solution of sodium hydroxide 2 o ml 11 50 mmol of benzaldehyde, separately synthesized methyltriphenylphosphonium bromide (CHs Pph 3”J B r
50 mmol, 30 ml of methylene chloride and 7.5 mmol of C8H170 (C2H40) and 910 mmol of C4H were added, and the mixture was allowed to react under reflux for 20 hours with vigorous stirring.

After the reaction, the organic layer was analyzed by gas chromatography, and it was found that 34 mmol of styrene had been produced.

Example 6 Into the same reactor as in Example 1, 50% of sodium hydroxide was added.
wt% aqueous solution 20ml! , 30 ml of methylene chloride, 50 mmol of benzaldehyde, separately synthesized iodide!・
Limethylsulfinium + (CH3)3S(■-) 50 mmol, and Cl2H
2,0(C2H40)1oC1□H2520 mmol was added and reacted for 48 hours under reflux with vigorous stirring.

After the reaction, the organic layer was analyzed by gas chromatography, and it was found that 44 mmol of styrene oxide had been produced.

For comparison, when no polyoxyarselene diethers were added, no styrene oxide was produced in the reaction under the same conditions.

Example 7 Into the same reactor as in Example 1, 50% of sodium hydroxide was added.
20 ml of wt% aqueous solution, 30 ml of benzene, 50 mmol of n-octanal, separately synthesized allyldimethylsulfinium bromide + [(CH3)25(CH2CH-CH2)(Br-)]
Add 50 mm 50 mm and 1 J mol and stir at room temperature for 24 hours with vigorous stirring.
Allowed time to react.

After the reaction, the organic layer was analyzed by gas chromatography, and it was found that the corresponding epoxy compound, n-C7H15CH-
42 mmol of CH-CH-CH2,\1 was produced.

Example 8 Into the same reactor as in Example 1, 50 w of potassium hydroxide was added.
j% aqueous solution 20 ml, β-phenylethyl bromide 5
0 mmol and 6.5 mmol of C3H1□0(C2H40) and 10 mmol of C4H0 were added, and the mixture was reacted at 90° C. for 2 hours with stirring.

After the reaction, the organic layer was analyzed by gas chromatography, and it was found that 47 mmol of styrene had been produced.

For comparison, when the reaction was repeated under the same reaction conditions as above without adding any polyoxyalkylene diethers, only 1 mmol of styrene was produced.

Example 9 Into the same reactor as in Example 1, 60% of sodium hydroxide was added.
20 ml of wt% aqueous solution, 10 ml of benzene, 10 ml of ethyl 3.3-dimethyl-4.6.6-trichloro-5-hexenoate! J mole and C3H1□0 (C2H40)
20 mmol of 1oC8H1□ was added, and the mixture was reacted at 40° C. for 5 hours with vigorous stirring.

After the reaction, the organic layer was analyzed by gas chromatography, and it was found that ethyl 2,2-dimethyl-3(2',2'-dichlorovinyl)cyclopropanecarboxylate was 3.8 mi1,
1 mole was produced.

Example 10 In the same reactor as in Example 1, 50 w of potassium hydroxide was added.
t% aqueous solution 20ml, benzyl cyanide 50mmol,
52 mmol of ethyl bromide and 1.0 mmol of ethyl bromide were added thereto, and the mixture was reacted at 50° C. for 7 hours with vigorous stirring.

After the reaction, the organic layer was analyzed by gas chromatography, and it was found that 45 mmol of α-ethylbenzyl cyanide had been produced.

Example 11 In the same reactor as in Example 1, 60% of sodium hydroxide was added.
20 ml of wt% aqueous solution, 350 mmol of acetone, Prenylchlor 91F029 C8H170 (C2H4.0)? -5 C8H]
．． 72.0 mm/l/ was added, and the mixture was reacted at 60° C. for 10 hours with vigorous stirring.

After the reaction, the organic layer was analyzed by gas chromatography, and it was found that 30 mmol of methylhebutenone was produced.

Example 12 In the same reactor as in Example 1, 50% of sodium hydroxide was added.
20 ml of wt% aqueous solution, 300 mmol of ethyl alcohol, 70 mmol of n-octylfuromide, and C
l8H3□0(C2H40)1oH4H92, QmiIJ
mol was added and reacted for 10 hours under reflux and stirring.

After the reaction, the organic layer was analyzed by gas chromatography, and it was found that 55 mmol of n-octylethyl ether had been produced.

Example 13 Into the same reactor as in Example 1, 50% of sodium hydroxide was added.
wt% aqueous solution 10ml, benzene 20ml, indole 2
0 mmol, 30 mmol of methyl iodide, and 1,0,-limol were added and heated under stirring at 40'C for 15 min.
Allowed time to react.

After the reaction, the organic layer was analyzed by gas chromatography, and it was found that 17 mmol of N-methylindole had been produced.

Example 14 In the same reactor as in Example 1, 12 of sodium hydroxide was added.
wt% aqueous solution 25Tnl, methylene chloride 40ml, n
-40 mmol of butanethiol, and Cl2H250
(C2H40)6.5C,-Hol. 0 mmol was added, and the mixture was reacted at 30° C. for 1 hour with vigorous stirring.

37 mmol of bis-(n-butylthio)methane was obtained.

Example 15 To the same reaction apparatus as in Example 1, 16 ml of a 50 wt% aqueous solution of IJium (hydroxide), 4 ml of acetone, 4-0 mmol of phenylacetylene, and 10 ml of benzene were added, and the mixture was heated under reflux while stirring vigorously. The mixture was allowed to react for 3 hours.

After the reaction, the organic layer was analyzed by gas chromatography, and it was found that 34 mmol of -phenyl-3-methyl-1-butyH3 nor-3-ol, phc3C,-(, -0H1) was present.

Example 16 In a reactor similar to Example 1, 60w of potassium hydroxide was added.
t% aqueous solution 20ml1. Acetone 10ml and C3H
Add 2.0 mmol of 1□0(C2H40)8C8H1□ and add 113 mmol of acetylene gas while stirring vigorously.
The reaction was carried out under reflux for 3 hours while blowing at a rate of /hr.

After the reaction, the organic layer was analyzed by gas chromatography, and it was found that 145 mmol of 3-methyl was produced.

Example 17 In the same reactor as in Example 1, 50% of thorium hydroxide was added.
20 ml of wt% aqueous solution, 50 mmol of prenyl chloride and C3H1□0 (C2H40) e, , s
Add 1,0 mmol of C8H and heat to 50'C under stirring.
The reaction was carried out for 5 hours.

After the reaction, the reaction mixture was extracted with diethyl ether, and the ether layer was analyzed by gas chromatography, and it was found that 1 mmol of dibrenyl ether was present.

Example 18 In the same reactor as in Example 1, 50 wt of hydroxylated cormorant was added.
5 ml of % aqueous solution, 80 mmol of benzaldehyde, and 1.1 mol of chloride were added, and the mixture was reacted at room temperature for 2 hours with vigorous stirring.

24 mmol of benzoin was produced.

Example 19 In the same reaction apparatus as in Example 1, 65 wt of potassium hydroxide was added.
% aqueous solution 20m, l, ethyl acetate 60mmol,
and Cl2H250(C2H40)8C4H91,0
1.1 mol of Mi was added thereto, and the mixture was reacted at 80° C. for 8 hours with stirring.

After the reaction, the organic layer was analyzed by gas chromatography, and it was found that 18 mmol of ethyl acetoacetate was produced.

Claims (1)

[Claims] 1 Base-catalyzed elimination reaction using an alkali metal hydroxide between different phases consisting of an aqueous phase and an organic phase, substitution reaction of active hydrogen of an active hydrogen compound with an organic group, activity on unsaturated compounds When carrying out an organic ion reaction selected from the group consisting of an addition reaction of hydrogen compounds and a self- or heterogeneous condensation reaction of carbonyl compounds, the general formula [wherein and y are the sum of both (x+y) is n] n is a number of 0 or more with an average of 6 to 30, and R1 and R2 have a total carbon number of n
/ 2 or more substituted or unsubstituted hydrocarbon groups or trialgylsilyl groups, and X -CH2C
H20- and y number of CH3 direct CH2CHO- may be optionally used.