JPS5948664B2 - Catalyst for organic ion reactions - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a catalyst for organic ion reactions, and more particularly, a catalyst having the general formula -CH2-CH in CH2(OA)nQ suitable for use in promoting organic ion reactions in the presence of an alkali metal compound. (In the formula, the nuclear substitution is at the para or meta position, and A has 2 to 2 carbon atoms.
4 alkylene group, n is a number from 3 to 25, Q represents an -ORI group or -NR2R3 group, R1 is a hydrogen atom or a substituted or unsubstituted hydrocarbon group, R2 is a substituted or unsubstituted hydrocarbon group, R3 represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a +A'O)mQ'group;
' is an alkylene group having 2 to 4 carbon atoms, m is a number of 1 or more, Q
'represents a hydrogen atom or a lower alkyl group).

It has been known that in organic ion reactions using alkali metal compounds as reactants or catalysts, the reaction is significantly accelerated by adding and dissolving macrocyclic polyethers in the reaction system.

Furthermore, the present inventors have previously discovered that acyclic polyalkylene glycols having about 6 or more oxyalkylene units, their mono- or diethers, etc. exhibit similar effects. Regarding the catalytic ability of high molecular weight polyethylene oxide, there was also a presentation by Yamazaki et al. (September 1970, The Society of Polymer Science and Technology). However, macrocyclic polyethers are extremely expensive due to the complexity of their synthesis method, making them unsuitable as industrial catalysts, and dissolving high molecular weight polyethers in the reaction system increases the viscosity of the reaction system. This is not preferable in terms of reaction operation. Furthermore, even if any of the above-mentioned polyether compounds is used, since they are used after being dissolved in the reaction system, it cannot be said that separation of the reaction product and the catalyst is extremely easy. As a result of intensive research aimed at improving the above points, the present inventors discovered that an insoluble polymer containing the unit represented by the above general formula 1 in its molecular chain has excellent catalytic ability, and has led to the present invention. Ivy.

If the catalyst of the present invention is used, it is possible to achieve the same or higher catalytic effect with easier reaction operations than when using various polyether compounds used in the above-mentioned dissolved state as a catalyst, and after the reaction Catalyst separation can be omitted or made very easy.

In the above general formula 1, the alkylene group A is preferably -CH2CHl. The value of n needs to be 3 or more and 25 or less, preferably in the range of about 5 to about 15, from the viewpoint of ease of polymer production, mechanical properties and catalytic ability. When n is less than 3, the catalytic ability is extremely poor or not fully expressed, and n
If it is too large, exceeding 25, it will not be easy to produce such a polymer, and the mechanical properties of the polymer will deteriorate, as well as its catalytic ability. Q in general formula 1 represents a -0R1 group or a -NR2R3 group, preferably a -0R' group. Here, R1 is a hydrogen atom or a substituted or unsubstituted hydrocarbon group, preferably a hydrogen atom or a hydrocarbon group having about 20 or less carbon atoms, such as methyl, ethyl, propyl, butyl, amyl, 2-ethylhexyl, octyl, decyl, stearyl. , hexenyl, oleyl, methylphenyl, nonylphenyl, benzyl, etc., and particularly preferably a lower alkyl group having 1 to about 5 carbon atoms. R2 is a substituted or unsubstituted hydrocarbon group, preferably having about 20 carbon atoms
Examples of such hydrocarbon groups include the same groups as mentioned above for R1, and particularly preferred are lower alkyl groups having 1 to about 5 carbon atoms. R3 represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a +A'O)MQ' group, and R3
is a hydrocarbon group, the hydrocarbon group is R1
Although the same range of groups as mentioned above should generally be considered, the total number of carbon atoms of R2 and R3 (when R3 is a hydrocarbon group) in the same molecule is less than or equal to about 20, particularly less than or equal to about 10. Preferably A'' represents an alkylene group in the same range as A, particularly preferably -
One CH2CH2 group. The value of m is n-1-m is 2
A range of no more than 5 is suitable, and Q' is a hydrogen atom or a lower alkyl group such as methyl, ethyl, propyl, butyl, amyl and the like. Both n and m are generally understood as average values, and are expressed as such average values. The insoluble polymer containing the unit represented by the above general formula 1 constituting the catalyst of the present invention can be produced, for example, by the following method.

The first method is to use a copolymer of styrene and a crosslinked monomer typified by divinylbenzene, or a copolymer of styrene and a crosslinked monomer with another copolymerizable monomer (preferably a monomer with good alkali resistance, such as acrylonitrile, After chloromethylating a copolymer with vinylpyridine, butadiene, isoprene, etc. using a conventional method,
In the presence of a base (preferably sodium hydroxide or/and potassium hydroxide), the general formula H(0A)NQ (wherein A
sn and Q have the same meanings as in General Formula 1). The second method is to copolymerize mono- or meta-chloromethylstyrene with a crosslinked monomer, or copolymerize para- or meta-chloromethylstyrene with a crosslinked monomer and another copolymerizable monomer (preferably with good alkali resistance). (such as styrene, acrylonitrile, vinylpyridine, butadiene, isoprene, etc.), and the resulting copolymer is copolymerized with a polyoxyalkylene compound represented by the general formula H(0A)NQ above in the presence of a base. This is a method of causing a reaction.

The polymerization can be carried out by various polymerization methods known as vinyl monomer polymerization methods. The third method is
Para- or meta-chloromethylstyrene is reacted with the polyoxyalkylene compound represented by the above general formula H(0A)NQ in the presence of a base, and the resulting styrene derivative is converted into a crosslinked monomer or This is a method of copolymerizing with a crosslinking monomer and other copolymerizable monomers (for example, styrene, acrylonitrile, vinylpyridine, methacrylonitrile, butadiene, isoprene, etc.).

In any of the above methods, the manufacturing conditions ( monomer composition, etc.).

Approximately 10 to 50 mol% of units represented by general formula I, approximately 85 to 25 mol% of styrene units, and approximately 5 to 50 mol% of divinylbenzene units.
An insoluble vinyl polymer comprising 25 mol % and 0 % to about 10 mol % of other copolymerized components is a particularly suitable polymer as the catalyst of the present invention from the viewpoint of catalytic ability and mechanical properties. The insoluble polymer containing units represented by the general formula I can be formed into any shape such as granules, films, sheets, fibers, etc. by a method known per se and used as a catalyst. For example, suspension polymerization or precipitation polymerization in a suitable liquid medium is used to obtain granules, and casting in the presence or absence of a plasticizer is used to obtain film or sheet materials. Polymerization method is applied. The above-mentioned insoluble polymer can also be used in the form of a mixture with other polymers for the purpose of improving the mechanical properties of the catalyst. The catalyst of the present invention can be widely used to promote organic ion reactions in which an alkali metal compound (particularly a sodium compound or a potassium compound) is used as a reactant or catalyst. As types of reactions, the following may be mentioned:

Ha substitution reaction The substitution reaction mentioned here is represented by the following formula.

RXfMY→RYfMX RX is an organic halogen compound in which a halogen atom (especially Cl or Br) is bonded to a primary or secondary carbon, such as methylbromide, ethylbromide, butyl chloride,
Examples of octylbromide include 2-ethylhexyl chloride, decyl chloride, allyl chloride, prenyl chloride, geranyl chloride, benzyl chloride, stearyl bromide, 1,4-dichlorobutane, and isopropyl bromide.

M is an alkali metal, particularly sodium or potassium, and Y is a halogen atom, a cyano group, a hydroxyl group, an organic carboxylic acid residue, an alkoxy group, a phenoxy group, a thiocyanate group, or the like. Representative examples of MY include sodium iodide, potassium fluoride, potassium cyanide, sodium cyanide, sodium hydroxide, sodium acetate, potassium propionate, sodium benzoate, sodium methylate, potassium t-butoxide, sodium phenoxide, Examples include potassium thiocyanate. This substitution reaction can be carried out in an organic solvent solution by vigorously stirring the suspension of the catalyst of the present invention and the alkali metal compound MY.

In this case, the organic solvents generally include hydrocarbons such as benzene, toluene, xylene, cyclohexane, and heptane, ethers such as dibutyl ether, tetrahydrofuran, diglyme, triglyme, and dioxane, and nitriles such as acetonitrile, propionitrile, and benzonitrile. , substituted benzenes substituted with substituents that do not interfere with the reaction such as chlorobenzene, dichlorobenzene, nitrobenzene, methanol, ethanol, n-
Alcohols such as butanol and t-butanol, amides such as dimethylformamide, acetamide, hexamethylphosphoramide, etc. can be used, and when the alkali metal compound MY is other than an alkali metal hydroxide, methyl acetate, acetic acid Esters such as ethyl, butyl acetate, and methyl benzoate can also be used as solvents. After the reaction, the unreacted alkali metal compound MY, the produced alkali metal halide MX and the catalyst are removed by filtration or centrifugation, and the oral fluid is treated by a method known per se, for example by distillation, to produce products and raw materials. The RXl solvent and the like can be separated and recovered. On the other hand, MY,
The mixture of MX and catalyst is washed with water and, if necessary, with an organic solvent to remove MY and MX, and then dried to recover a catalyst that can be reused. The above substitution reaction is
When the alkali metal compound MY is water-soluble, the MY
The process also preferably proceeds between different phases consisting of an aqueous solution phase containing organic halide RX, an organic solution phase containing organic halide RX, and the catalyst of the present invention. The most important factor in the substitution reaction between different phases is the concentration of the alkali metal compound MY in the aqueous solution, and the concentration is at least 40% by weight? Practical reaction rates can be obtained in the above cases. Suitable solvents used in the organic solution phase include water-insoluble organic solvents such as benzene, toluene, xylene, chlorobenzene, dibutyl ether, butyl acetate (butyl acetate can be used when MY is other than metal hydroxide), and the like. be. In both the substitution reaction in an organic solvent solution and the substitution reaction between different phases, there are no special restrictions on reaction conditions such as reaction temperature, reaction pressure, and organic halide concentration, and in general organic ion reactions. Conditions similar to can be used. In addition, in this substitution reaction, contact efficiency (in other words, reaction rate)
From this point of view, the catalyst of the present invention is preferably used in the form of granules, films, or sheet pieces. ′)
Base-catalyzed elimination reactions Base-catalyzed elimination reactions are typified by intramolecular dehydrohalogenation reactions of organic halides.

Among these dehydrohalogenation reactions, typical industrially useful ones are carbene reaction, ring-closing reaction, and ylide reaction. These reactions can proceed in an organic solvent solution or in a different phase consisting of an aqueous solution phase and an organic solvent solution phase, as described in the section of the substitution reaction above, and the present invention can be carried out in either of these cases. are preferably applied. The types of organic solvents that can be used are generally the same as in the case of the substitution reaction. As a base, sodium hydroxide, potassium hydroxide,
Sodium alcoholade, potassium alcoholade, sodium phenolade, potassium phenolade, etc. can be used, and sodium hydroxide and/or potassium hydroxide are preferably used in reactions between different phases. In a reaction between different phases, the concentration of sodium hydroxide and/or potassium hydroxide in the aqueous phase is 40% by weight? It is preferable to have it present at an initial concentration above. The catalyst of the invention is preferably used in the form of granules or sheet or film pieces. Substitution reaction of active hydrogen of O active hydrogen compound with organic group carbonyl group, cyano group,
Active hydrogen atoms (α-hydrogen) attached to carbons bonded to electron-withdrawing atomic groups such as alkoxycarbonyl groups, hydrogen atoms bonded to oxygen or sulfur in alcohols, carboxylic acids, thiols, etc., and amines When an organic compound (active hydrogen compound) containing active hydrogen, such as a hydrogen atom bonded to nitrogen in amides, etc., is reacted with an organic halide in the presence of a base, the halogen atom in the organic halide is converted into the active hydrogen. Although substitution can be made with carbanions, alkoxide anions, thiol anions\N-anions, etc. generated from compounds, the catalyst of the present invention can also be preferably applied to these organic ion reactions.

When performing these organic ion reactions using the catalyst of the present invention, inexpensive bases such as sodium hydroxide, potassium hydroxide, sodium alcoholade, potassium alcoholade, and sodium phenoxide can be used. The industrial value of the catalyst of the present invention is great. In these reactions as well, the catalyst of the present invention is preferably used in the form of granules, sheets, or film pieces. 4
) Self- and heterogeneous condensation reactions of carbonyl compounds Condensation reactions of carbonyl compounds are represented by aldol condensation (self-condensation and cross-aldol condensation), Claisen condensation, and benzoin condensation, and the catalyst of the present invention can also be used in these condensation reactions. Used effectively.

These condensation reactions are catalyzed by a base, but by using the catalyst of the present invention in combination, the base (especially an alkali metal compound) is significantly activated, making it possible to reduce the amount of base used. The selectivity of the reaction is improved. EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited by these Examples.

Example 1 (Catalyst production example) Styrene and divinylbenzene were suspension polymerized in the presence of benzoyl peroxide by a conventional method to obtain a granular styrene-divinylbenzene copolymer (divinylbenzene 5 mol %) with an average particle size of 0.3 mwL. ) was synthesized, and this was chloromethylated using chloromethyl ether using a conventional method (Cl content in the resin was 17% by weight; chloromethylation mainly occurred at the rose position, but chloromethylation at the meta position also occurred). mixed).

The above chloromethylated resin 109, acetonitrile 50%, micronized potassium hydroxide 129 and CH3
O(C2H4O)7H (average molecular weight 370) 101 ml containing 200 m equipped with thermometer, stirrer and reflux condenser
The mixture was charged into a Mitsuro flask (No. 1) and reacted at 70° C. for 24 hours with stirring under a nitrogen atmosphere. The reaction mixture was passed through the mouth, and the resulting resin was thoroughly washed with water, dilute aqueous hydrochloric acid, distilled water, and acetone in this order, and air-dried.11.
5y granular resin (catalyst of the present invention) was obtained. When this resin was measured by elemental analysis and infrared absorption spectrum, it was found that Cl was not contained at all in the resin and that a new absorption based on the C-O-C bond was present at 1100CfrL-1. was confirmed. A part of the resin was weighed and treated with concentrated hydrochloric acid to remove the
C2H4)70CH3 group is liberated, and the liberated CH3O
As a result of measuring the amount of (C2H4O)7HC7) by the barium phosphotungstate method, it was found that the resin before the hydrochloric acid treatment contained 0.65 meq. (0C2H4) per 1θ of the resin, TOCH Todoroki. It turned out that they were connected. Example 2 (Catalyst production example) Contents 200 equipped with thermometer, stirring device and reflux condenser
259 chloromethylstyrene (meta, bulk mixture) rectified into a three-bottle flask, 30 ml of chlorobenzene
) 35 ml of a 60% sodium hydroxide aqueous solution and 509 ml of C4H9O (C2H4O), 0H were charged, and the mixture was reacted at 35° C. for 6 hours with vigorous stirring under a nitrogen stream.

After the reaction, the reaction mixture was separated and the chlorobenzene layer was mixed with water and
After thoroughly washing with a dilute aqueous hydrochloric acid solution and distilled water in this order, chlorobenzene and unreacted chloromethylstyrene were distilled off under reduced pressure to obtain 499 pale yellow viscous liquid. When this viscous liquid was measured by elemental analysis, infrared absorption spectrum, NMR spectrum, and gel permeation chromatography (GPC), it was found to be a substance represented by the following formula.

A homogeneous solution was prepared by thoroughly mixing this styrene derivative 169, styrene 109, a mixture of divinylbenzene and ethylstyrene (divinylbenzene 40 mol%) 4θ, dibutyl phthalate 99, and benzoyl peroxide 6Tnf7 under a nitrogen atmosphere. A portion of this solution was placed in a cast polymerization vessel made by combining two glass plates (distance between the two glass plates: 1 m2K) and kept at 80°C for 2 days. The obtained sheet-shaped resin is vertically 1CTIL and horizontally 1C!
After cutting the RL into small pieces, the plasticizer dibutyl phthalate was extracted and removed using ethanol, and the pieces were thoroughly washed with ethanol and air-dried to obtain sheet-like resin pieces (the catalyst of the present invention). This resin is 0.84me per 1f1
q. -O(C2H4O)10C4H, was bonded. Example 3 (Catalyst use example) Catalyst consisting of the particulate polymer obtained in Example 1: 2.59%, n-octyl bromide: 3.89%
, chlorobenzene 10ml and 60wt? 15 ml of potassium iodide aqueous solution was charged into a 100 ml Mituro flask equipped with a thermometer, a stirrer, and a reflux condenser.
The mixture was stirred vigorously at 80° C. for 3 hours under a nitrogen atmosphere.

After the reaction, a part of the organic layer was taken and analyzed by gas chromatography, and the amount of n-octyl iodide was 3.959.
It was found that the product was produced (82.5% yield based on the added n-octyl bromide). After the reaction, the catalyst was separated, washed with water, and used again as a catalyst for the above reaction. catalyst(
(resin) was recycled five times. The reaction result in the 5th reaction (reaction time 3 hours) was 80.3 in terms of yield of n-octyl iodide based on the charged n-octyl bromide.
It was %.

For comparison, instead of the above catalyst 2.59, a resin immediately after chloromethylation of the same styrene-divinylbenzene copolymer as in Example 1 (CH3O(C2H4O)7H
Using 2.5 f1 of (resin before reacting with), the reaction was carried out for 5 hours under the same reaction conditions as above, but no n-octyl iodide was produced. Example 4 (Catalyst Usage Example) In the same reaction apparatus as in Example 3, 2.59 ml of the granular resin catalyst produced in Example 1, 10 ml of toluene, 39 ml of 11,4-dichlorobutane, and 1 ml of a 60% by weight aqueous potassium cyanide solution were added.
0ml was charged and stirred vigorously at 100°C for 5 hours.

After the reaction, the toluene layer was analyzed by gas chromatography, and it was found that 2.49% of 1,4-dicyanobutane was produced in this reaction (94% yield based on the added 1,4-dichlorobutane). Example 5 (Catalyst Usage Example) 2.5 f of the granular resin catalyst produced in Example 1 was placed in the same reactor as in Example 3! , 15 ml of acetonitrile, 30 mmol of 2-ethylhexyl chloride and 1 ml of potassium acetate.
59 was charged, and the mixture was vigorously stirred at 80°C for 10 hours.

After the reaction, a portion of the reaction mixture was collected using Rigas Chroma. Analysis using a tograph revealed that 2-ethylhexyl acetate was produced in a yield of 86% based on the starting 2-ethylhexyl chloride. Example 6 (Example of catalyst use) In the same reaction apparatus as in Example 3, 2.59% of the catalyst made of the sheet-like resin produced in Example 2, 20 mmol of chloroform 10a1 styrene, and 60% by weight of sodium hydroxide were placed. Add aqueous solution 20a and stir at 40°C.
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 16 mmol of 1,1-dichloro-2-phenylcyclopropane had been produced. Example 7 (Catalyst Usage Example) In the same reaction apparatus as Example 3, 2.59% of the granular resin catalyst, 4.69% of benzyl cyanide, 119% of n-butyl bromide, and 60% by weight were produced in the same manner as in Example 1. A sodium hydroxide aqueous solution 109 was charged, and the mixture was reacted at 80° C. for 3 hours with stirring under nitrogen.

After the reaction, a part of the organic layer was taken and analyzed by gas chromatography, and it was found that phenylbutylacetonitrile was 6.
41 (93% yield based on added benzyl cyanide)
It was generating. Example 8 (Catalyst Usage Example) In the same reactor as Example 3, granular resin catalyst 59, which was produced in the same manner as in Example 1, acetone 20ml, brenyl chloride 7.59 and 60% by weight? Sodium hydroxide aqueous solution 2
0 ml was charged and reacted at 60° C. for 10 hours with vigorous stirring.

After the reaction, the acetone layer was measured using gas chromatography, and it was found that 2.89 methylheptenone was produced.
Example 9 (Catalyst Usage Example) Sheet-shaped resin catalyst pieces 3f11 benzaldehyde 100 produced using the recipe of Example 2 in the same reaction apparatus as Example 3
mmol, chlorobenzene 10d1 and 50wt? 10 d of potassium cyanide aqueous solution was charged, and the mixture was reacted at 40° C. for 3 hours with vigorous stirring.

37 mmol of benzoin was produced. Example 10-1
6 (Catalyst production and usage example) A styrene-divinylbenzene copolymer was chloromethylated in the same manner as in Example 1, and then reacted with various polyoxyalkylene compounds H(0A)NQ shown in Table 1 below. Therefore, a granular polymer containing a styrene derivative unit represented by the general formula I having the corresponding -CH, (0A)NQ group as a nuclear substituent (the nuclear substitution is mainly at the para position, but also at the meta position) These resin catalysts were prepared by combining 2.5
An exchange reaction between n-octyl bromide and potassium iodide was carried out under the same conditions as in Example 3 using 1 (80'
C, 3 hours).

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, nuclear substitution is at para or meta position, A is carbon number 2 to
4 alkylene group, n is a number from 3 to 25, Q is -OR^1
group or -NR^2R^3 group, R^1 is a hydrogen atom or a substituted or unsubstituted hydrocarbon group, R^2 is a substituted or unsubstituted hydrocarbon group, R^3 is a hydrogen atom, a substituted or Represents an unsubstituted hydrocarbon group or ■A'O)mQ' group, A' is an alkylene group having 2 to 4 carbon atoms, and m is 1
A catalyst for organic ion reactions comprising an insoluble polymer containing a unit represented by the above number (Q' represents a hydrogen atom or a lower alkyl group).