JPS62185034A - Production of cyclohexanedione derivative with immobilized catalyst - Google Patents

Abstract

PURPOSE:To obtain a cyclohexanedione derivative useful as an intermediate for agricultural chemicals in high yield in a short reaction time, by heating a specific compound in an inert solvent using a specific immobilized catalyst having sufficient durability. CONSTITUTION:A compound expressed by formula I [R is lower alkyl; R1 is H, R or lower alkoxycarbonyl; R2 is H or R; R3 is R, lower alkoxycarbonyl, halogen, cyano, (substituted) phenyl, 2-furyl, 2-thienyl, pyridium, etc.] is heated in the presence of a catalyst in which an aminopyridine derivative or imidazole derivative is immobilized on an inert polymer, e.g. immobilized inert resin expressed by formula II (P is polymer support, e.g. polyethylene, etc.), etc., in an inert solvent, e.g. toluene, etc., preferably at 70-110 deg.C, preferably for 1-7hr to afford the aimed compound expressed by formula III. EFFECT:The catalyst can be readily recovered and reused with great industrial significance.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing cyclo-xanedione derivatives useful as agricultural chemical intermediates.

(Prior art) Pyridine derivatives and imidazole derivatives have been known as catalysts for acyl transfer reactions (Japanese Patent Publication No. 58-409
39) However, if these were used as catalysts in synthesis reactions, operations such as separating the catalyst and products and collecting and reusing the catalysts would be complicated, and the recovery rate of the expensive catalysts was low and unsatisfactory. .

(Problems to be Solved by the Invention) The object of the present invention is to provide a production method that allows a cyclohexanedione derivative to be obtained in high yield and that allows easy recovery and reuse of the catalyst.

(Means for Solving the Problems) The present inventors have solved the problem by formula (I) [wherein R is a lower alkyl group, R1 is hydrogen, a lower alkyl group or a lower alkoxy group, a carbonyl group, and a bird is hydrogen or a lower The alkyl group, R, is a lower alkyl group, a lower alkoxycarbonyl group, a herogen atom, a cyano group, a phenyl group that may have a substituent, a 2-furyl group, a 2-chenyl group,
A pyridium group, a thianyl group, or a group represented by the formula -xs (o), a melon (in the formula).

X is linear or branched alkylene, mass is lower alkyl%
Phenyl group or benzyl group which may have a substituent, 1
represents O, 1 or 2. ). ] As a result of various studies on the anneal group transfer reaction of the compound represented by
By reacting an aminopyridine derivative or an imidazole derivative on an insoluble polymer (= in the presence of an immobilized catalyst C:), the general formula ([[) (wherein R, RQs R, , ) t, The present invention was completed based on the discovery that the target compound represented by (has the same meaning as above) was obtained, and the fixed catalyst used was easy to recover and reuse, and had sufficient durability. .

That is, 1. the present invention provides a method for immobilizing a compound represented by the general formula (I) C0R (wherein R, RQs Rt, and Rs have the same meanings as above) on an insoluble polymer with an aminopyridine derivative or an imidazole derivative. C: When heated in an inert medium, the general formula (II) dust 1 (in the formula, 几, gourd, bird, and bird have the same meanings as above) is formed.
This is a method for producing a cyclohexanedione derivative represented by

In the present invention, the phenyl group which may have a substituent as R3, and the phenyl group that may have a substituent as R4 (: The substituents include a halogen atom, a lower alkyl group, an alcogine group, etc.).

The compound represented by the general formula (I) of the present invention includes 3
-butyryloxyV-5-[2-(ethylthio)propyl-2-cyclohexen-1-one, l-butyryloxyV-4-methoxycarbonyl-5,5-dimethyl-1-
Cyclohexen-3-one, 3-buteryloxv-5-
(thian-3-yl)-2-cyclohexen-1-one, 3-butyrylox-V-5-(2,4,6-drimethylphenyl)-2-cyclohexen-1-one, etc.
:is important.

As the aminopyridine derivative used in the present invention) t,
4-N-methylaminopyridine, 4-N-ethylaminopyridine, 4-N-propylaminopyridine, 4-N-
Examples of the imidazole derivative include imidazole, 4(5)-alkylimidazole (alkyl is methyl, ethyl, propyl, butyl@), penzimidazole, and the like.

Among these aminopyridine derivatives and imidazole derivatives used as catalysts in the present invention, C2 is particularly preferred! , 4-N-methylaminopyridine, and imidazole.

Immobilized catalysts of aminopyridine derivatives or imidazole derivatives on insoluble polymers can be used for macromolecular hemi-, rabid chemical, i/:I ns(
Fdakromol, Chem, 几apid Com
mun, ) 3537-542 (1982), dan 397-401 (1985). The degree of crosslinking of the insoluble polymer is preferably one containing 1 to 10 mol% of a crosslinkable polymer such as divinylbenzene.

In carrying out the present invention, a compound represented by the general formula (■) (sometimes referred to as a substrate) is dissolved in a suitable reaction solvent (2) and heated in the presence of an immobilized catalyst to undergo the Anru rearrangement. Perform a reaction.

The immobilized catalyst used has a ring substitution rate (shown as the ratio of substituted phenyl groups in the aminopyridine derivative or imidazole conductor to the total phenyl groups in the polystyrene support).
is 5 to 60 mol %, preferably 10 to 10 mol %. The introduction of an alkylene chain (where n is the methylene chain length) between the support polymer and the aminopyridine or imidazole catalyst group improves the activity (=preferably, in practice n is 1-20, preferably 1-16).

The amount of aminopyridine acid or imidazole group on the substrate base of the catalyst used is 1 to 30 mol %, preferably 5 to 25 mol %.

As the reaction solvent, general inert solvents such as toluene, benzene, quinolene, ethylene dichloride, carbon tetrachloride, chloroform, trichlene, tetrahydrofuran, and diochitin are used, but toluene is particularly preferred.The reaction temperature is 70-110°C. It is preferable that one reaction time is preferably 1 to 7 hours.

(Example) Below is a production example (on polymer (=immobilized catalyst)).

The present invention will be further explained by giving examples.

The present invention is not limited to these C units.

Preparation of catalysts with immobilized aminopyridine or imidazole on insoluble polymers.

Production example 1゜250ff of water! (Nizelatene 0.68F, diallyl dimepur ammonium chloride dioxide @1 yellow copolymer 7.5g, boric acid 2.6Ii, sodium nitrite 0
．． A solution containing 1 Ii was adjusted to pH 9.5 (====== adjusted to pH 9.5 with 25 wt % sulfur hydroxide and placed in a reaction vessel (:). 4-(N-methyl-
0.10 mol of N-1r-vinylbenzylamino)pyridine.

Styrene 0.39 mol, vinylbenzene 0. 1 mol of O and 6 mmol of 2,2-azoisobutyronitrile were added. The reaction vessel was blown with dinitrogen for (9) minutes, and a nitrogen atmosphere (2) was maintained during the reaction.

The mixture was stirred at 70°C for 40 hours. The insoluble polymer was isolated, washed successively with water, acetone, and methanol, and then vacuum-dried at 80°C. Support (polymer support)
t)] An insoluble resin was obtained.

Similar suspension copolymerization (0.10 mol of N-vinylbenzylimidazole synthesized from vinylbenzyl chloride and imidazole, 0.39 mol of styrene).

From 0.01 mol of divinylbenzene to polystyrene like formula (2) (-20 mol% of imidazole group containing %)
3 with 30 fnl of hechitin to remove mineral oil.
Washed twice. Then 50 fnl of DMF was added. In the stirred mixture (so mt under nitrogen atmosphere at room temperature)
57 mmol of 4-(N-methylamino) in DMF of
Pyridine was added dropwise. After the hydrogen evolution is completed, 1.4 mmol of tetrabutylammonium bromide and 19.9 mmol of tetrabutylammonium bromide are added.
j177) 7-Fromoheptylsterene, styrene.

The degree of crosslinking obtained by copolymerization of divinylbenzene is 2 mol,
A polymer containing a bromoheptyl group (Br bottle 2B, 5 mm 9 mol) was added to the mixture. The mixture was stirred and reacted at room temperature under nitrogen atmosphere for 15 hours at r='5 and 60°C for 72 hours. In a similar manner, instead of methylaminopyridine, imidazole was reacted to obtain a spacer type imidazole as shown in formula (4).

Example 1 3-Buteryloquine-5-(2-(ethylthio)propyl)-2-cyclohegysen-1-one 7.1# was dissolved in 10 ml of toluene, and immobilized with the polymer synthesized in Example 1. N-methyl-N-benzylaminopyridine 2
．． 42jl (containing 15 mol % aminopyridine groups based on the substrate) was added, and the reaction was carried out at 80°C for 5 hours. Analysis of the reaction mixture by gas chromatography revealed that
The yield of the target product 2-butyryl-5-[2-(ethelthio)propylcocyclohechitin-1,3-dione is 95.0
%Met.

Example 2゜ Spacer-type immobilized aminopyridine 2゜8 having a heptamethylene chain shown in Production Example 2 under the same conditions as Example 1
Using 6I (containing 15 mol-' aminopyridine groups based on the substrate), the reaction was carried out at 80°C for 2.5 hours. The yield of the target product according to gas chromatography analysis C2 was 97.
It was 0%.

Example 3 A spacer-type immobilized imidazole 2.71 (containing 6 mol % imidazole group based on the substrate) with a heptamethylene chain synthesized by the method shown in Production Example 2 under the same conditions as Example 1 was synthesized by the method shown in Production Example 2. The reaction was carried out at 110°C for 7 hours.

Gas chromatography analysis (the yield of the target product was 9
It was 5.0%.

Example 4゜1-butyryluoquine-4-methoxycarbonyl-5,5
-Dissolve 6.71 JP of dimethyl-1-cyclohexen-3-one in 10 frIJ of toluene, and add 1.61 JP of the polymer-immobilized aminopyridine (containing 10 mol% aminopyridine groups based on the substrate) shown in AT Preparation Example 1. In addition, 80℃
The reaction was carried out for 1.5 hours. The yield of the target product, 2-butyryl-4-methquinecarbonyl-5,5-dimethyl-chitin-1,3-dione, was 99.0%.

Example 5゜Under the same conditions as in Example 4, the spacer type aminopyridine toaII (
(containing 5 mol % aminopyridine groups based on the substrate) was added, and the mixture was reacted at 70°C for 2 hours. Yield of target product is 98.5
%Met.

Examples 6 to 20 Tables 1 and 2 show the results using those shown by formulas (5) and (6) as polymer-immobilized catalysts (=shows CH
, CHs In the table, n and m are methylene elongated (m is considered rl+1)
The degree of crosslinking is expressed as the content of divinylbenzene (mol%
), and the ring substitution rate refers to the total phenyl group C of polystyrene.
The ratio of aminopyridine-substituted phenyl groups to 2) is shown. The amount used is based on the substrate aminopyridine group it (
(mol%).

Example 21 Polymer-immobilized catalyst was recovered from the reaction system by filtration, washed with tetrahydrofuran, dried, and reused.

Table 3 shows the yield of the target product when the product was used repeatedly 5 times under the conditions of Example 1. (Reaction time: 5 hours) Table 3 Example 22 When the spacer type catalyst was repeatedly used under the conditions of Example 20 five times, the yield of the target product was as shown in Table 144. (
(Reaction time: 2.5 hours) Table 4 Example 23-Example 50 Table 5 shows the yield of the target product when the spacer type catalyst was used 5 times under condition F. (Reaction time 2 hours) Table 5 (Effects of the invention) In the production method of the present invention, the target compound can be obtained in high yield in a short reaction time, and the immobilized catalyst used can be easily recovered and reused. It has sufficient durability and is of great industrial significance.

Claims (1)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R is a lower alkyl group, R_1 is hydrogen, a lower alkyl group, or a lower alkoxycarbonyl group, and R_2 is hydrogen or a lower alkyl group. , R_3 is a lower alkyl group, a lower alkoxycarbonyl group, a halogen atom, a cyano group, a phenyl group which may have a substituent, a 2-furyl group, a 2-thienyl group, a pyridium group, a thianyl group, or a group of the formula -XS(O )＿
A group represented by lR_4 (wherein, X is a linear or branched alkylene, R_4 is a lower alkyl, a phenyl group that may have a substituent, or a benzyl group, and l represents 0, 1 or 2). represent. ] is heated in an inert solvent in the presence of a catalyst in which an aminopyridine derivative or an imidazole derivative is immobilized on an insoluble polymer. ▼(II) A method for producing a cyclohequinanedione derivative represented by the formula (wherein R, R_1, R_2, and R_3 have the same meanings as above).