JPH0269489A - Production of asymmetric triorganotin halide - Google Patents

Abstract

PURPOSE:To obtain the subject compound effective in protecting plants from mite damage in high yield and purity by reacting a monoorganotin trihalide with an organomagnesium halide in the form of an ether solution. CONSTITUTION:The objective compound of formula III can be produced by reacting 1mol of a monoorganotin trihalide of formula I (R is alkyl or phenyl; X is Cl or Br) with essentially 2mol of an organomagnesium halide of formula II (R* is cyclohexyl or neophyl) in the form of an ether solution optionally in the presence of an inert organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing asymmetric triorganotin halides.

Asymmetric triorganotin halides are themselves biologically active and can effectively protect plants from attack by mites.

[Conventional technology]

As a method for producing an asymmetric triorganotin halide, a method is known in which a phenyl group-containing asymmetric tetraorganotin halide is reacted with a halogen of 7p such as phenyl group-containing asymmetric tetraorganotin halide to cleave the phenyl group (JP-A-62-149689).

In general, for 1 mole of monoorganotin trihalide,
Attempts have been made to synthesize symmetrical or asymmetrical triokattin halides using two moles of the same or different organomagnesium halides.

[Problem that the invention seeks to solve]

However, the method disclosed in JP-A-62-149689 requires a five-step reaction starting from diorganotin cybaride as a raw material, resulting in a long process and a disadvantage in that the yield is reduced.

Furthermore, in the method in which 1 mole of monoorganotin trihalide is reacted with 2 moles of the same or different kind of organomagnesium halide, in either case, tetraorganotin is mainly produced, and the target triorganotin halide can be obtained in low yield. Only. For this reason, it has been considered that it is industrially extremely difficult to directly convert monoorganotin trihalides to asymmetric triorganotin halides.

[Means for solving problems]

As a result of intensive research, the present inventors discovered that asymmetric triorganotin halide can be directly produced with high yield and high purity when a specific heterogeneous organomagnesium halide is used. 1. They have arrived at the present invention. .

That is, one aspect of the present invention is in the presence or absence of an inert organic solvent.

General formula [I] 1 mole of monoorgano trihalide represented by CH3 R-Si CH2Sn [1] Reacting substantially 2 moles of organomagnesium halide represented by R*MgX ([D (in the formula, R* represents a cyclohexyl group or a neophyll group, and X has the same meaning as above) as an ether solution. This is a method for producing an asymmetric triorganotin halide represented by the general formula [111] % (wherein R, R* and X have the same meanings as above).

The monoorganotin trihalide represented by the above general formula [I] can generally be produced by subjecting 1 mole of tetraorganotin and 2 moles of stannic halide to a redistribution reaction.

Furthermore, as a result of a redistribution reaction between an asymmetric tetraorganotin having two silicon-containing organo groups and two organo groups (R*) and an equimolar amount of stannic halide, silicon-containing organotin is produced simultaneously with an asymmetric triorganotin halide. Trihalides can also be used.

In the present invention, the monoorganotin trihalide is used in the reaction without a solvent or dissolved in an inert organic solvent.

The use of inert organic solvents is preferred to moderate the reaction and promote homogeneous reaction by reducing viscosity. Although the amount used is not particularly limited, it is preferably 100 to 500% by weight based on the tri-monoorganotin trichloride.

Examples of inert organic solvents include benzene, toluene,
Examples include aromatic hydrocarbons such as xylene, aliphatic D group hydrocarbons such as n-hexane, n-hebutane, and cyclohexane, and ether compounds such as diethyl ether, tetrahydrofuran, and dioxane. Preferably, xylene,
It is toluene.

The ether solution of the organomagnesium halide represented by the above general formula (II) is obtained as a Grignard reagent by reacting an organohalide with magnesium in ether. The ether used in this reaction is 5
Ring-membered or 6-membered ethers, such as tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, 2-ethoxytetrahydrofuran, tetrahydrofurfuryl ethyl ether, N-methylmolphon, dioxane etc. are mentioned,
Aliphatic ethers such as diethyl ether, digtyl ether, diethylene glycol/L/dimethyl ether, ethylene glycol dibutyl ether, etc. can also be used. Since the organomagnesium halide in the present invention is preferably used in the form of a solution of a complex with an ether, the use of the above-mentioned cyclic ethers that easily form complexes is suitable for that purpose. The amount of ether to be used is at least 2 times the molar amount, preferably 3 to 6 times the molar amount of the organomagnesium halide.

In the present invention, the organomagnesium halide to be reacted must be substantially 2 moles per mole of monoorganotin trihalide represented by -maximum [■]. Therefore, for 1 normal monoorganotin tripalite, 200 to 200 organomagnesium halide
240 mol%, preferably +, 2200-210 mol%
It can be used in the reaction within the range of .

The reaction of the present invention is an exothermic reaction.

Either the ethereal solution of monoorganotin trihalide or organomagnesium halide must be added dropwise to the other. In order to carry out the reaction smoothly, it is preferable to drop an ether solution of organomagnesium halide.

The present invention is generally carried out as follows.

1 mol of monoorganotin trihalide was dissolved in an inert organic solvent with stirring in a nitrogen stream.

An ether solution containing substantially 2 moles of organomagnesium halide prepared in advance was heated to an internal temperature of 20 to 60°C.
The solution is maintained at a temperature of about 0.5 to 2 hours and added dropwise over a period of about 0.5 to 2 hours. After dripping,
Heat to a temperature at which the solvent gently refluxes (approximately 60 to 1
00°C) for 0.5 to 4 hours.

The reaction mixture is hydrolyzed in an acidic aqueous solution, the organic layer is separated, and the solvent is distilled off to obtain asymmetric triorganotin halide in high yield and purity. If the asymmetric triorganotin halide is a solid, it can be dissolved in an alcohol such as methanol or ethanol, or an aliphatic hydrocarbon such as n-hexane or n-heptane, or a mixed solvent thereof, and then recrystallized. On the other hand, if it is a liquid, it can be purified by column chromatography.

The asymmetric triorganotin halide obtained by the method of the present invention is typically 9, for example cyclohexyl/L
/()limethylsilylmethy/L/)tin chloride and bromide dicyclohexy)V (ethyldimethylsilylmethy/I
/) Tin chloride and bromide dicyclohexy/V (isopropyldimethylsilylmethy) V) Tin chloride and bromide dicyclohexy)
V (n-butyldimethylsilylmethy)V) tin chloride and bromide dicyclohexy) Bromide cineophyl (trimethylsilylmethy/L/) tin chloride and bromide cineophyl (ethyldimethylsilylmethy/l/) tin chloride and bromide cineophyl (isopropyldimethylsilylmethyl) tin chloride and bromide cineophyl IV (n -butyldimethylsilylmethy/
v) fJ.

Chloride and bromide cineophyl (n-octyldimethy!resilylmethy/I
/) tin chloride and bromide cineofyl (phenyldimethylsilylmethy/I/) tin chloride and bromide.

[Action and effect]

According to the method of the present invention, no asymmetric tetraorganotin is produced as a by-product. In a short process. Asymmetric triorganotin halides can be produced in high yield and purity.

The above-mentioned asymmetric triorganotin halide itself has biological activity. Plants can be effectively protected from invasion by mites.

〔Example〕

Next, the present invention will be explained with reference to Examples.
shall indicate weight %.

+1+ Manufacture of neofilmagnesium chloride lt-four reflux condenser equipped with a stirrer, a thermometer, one dropping funnel and a nitrogen introduction device, ml K,
? Kuneshi 17 Muchichi 24.3? (1.0 mo/l
/) Neophyll chloride 52 and tetrahydrofuran 57 were charged, then 0.51 of n-butyl bromide was added as a reaction initiator, and the reaction vessel was heated. The same temperature is 6
When the temperature reached 0 to 70℃, white smoke was generated and 1 reaction started.
Started stirring. Waiting for the temperature rise to subside, neophyl chloride 163.6r (0.97 mo/L/) and tetrahydrofuran 295? A mixed solution of (4.1 mo/l/) was added dropwise through the dropping funnel. The dropwise addition was carried out at a rate at which tetrahydrofuran was slowly refluxed due to the heat of one reaction without external heating.

It took about 1 hour. After completion of the dropwise addition, the reaction mixture was heated under reflux for 3 hours and then cooled to 20-30°C. The obtained neophyll magnesium chloride solution (Grinard reagent solution) was a dark brown transparent liquid, which was placed in a 3- to 4-hole flask equipped with a magnetic stirrer, a thermometer, a dropping funnel, and a reflux condenser with a nitrogen introduction device. Trimethylurylmethy/L'! )
Lichloride (boiling point 102-102.5℃/7mmH
g: np 1.5078) 148, 3 r (0
, 475 mo/I/) and xylene 600? Prepare
Stir:. The Grignard reagent solution obtained in step m above was added dropwise from the dropping funnel.
The reaction was maintained at 40°C and took about 1 hour. After finishing dropping 1
The reaction mixture was heated and reacted at a temperature of 80-90°C for 3 hours. The reaction mixture was then cooled to below 30°C,
10% hydrochloric acid water 300 yen! After adding F and stirring for 10 minutes,
The organic layer was separated using a separatory funnel and filtered. By distilling off xylene and tetrahydrofuran under reduced pressure, the melting point was 41-4.
Cineofil (trinotylsilylmethyl) with 3°C
Tin chloride)'238.0 was obtained in a yield of 960%. Purity by gas chromatography was 97.0%.

Furthermore, this substance was recrystallized with methanol and purified to produce chloride.

Example 3 Dicyclohexy/I/(trinotylsili/') trimethylsilylmethyl resi-dolichloride in Example 1-+21 148.39 (0,475
phenyldimethylsilylmethyl trichloride (boiling point 167-170℃/8 mlnHg) instead of phenyldimethylsilylmethyl (mol)
; n91.5645 ) 177.8y (0,+7
A neophyll magnesium chloride solution was prepared in exactly the same manner as in Example 1 except for using phenyldimethylsilylmeldimethylsilylmethy/
1/) Tin chloride 265. ? f was obtained in a yield of 95.5%. Purity by gas chromatography was 973%.

Furthermore, this substance is recrystallized with methanol and refined.
M Example 1-Total neophyll chloride in t+)!
168.6? (1.0 mol) in total amount of cyclohexyl chloride 118.6 F (1.0 mol/L/
) was prepared in exactly the same manner as in Example 1 except that a cyclohexylmagnesium chloride solution was prepared, and this was reacted with trimethylsilylmethy/L/tin trichloride. /L/('Trimethylsilylmethyl chloride 191,62 was obtained in a yield of 95.0%. The purity by gas chromatography was 960%.

Further, when this substance was recrystallized and purified with methanol, it had a melting point of 74°C. A gas chromatographic purity of 99.0% and a chlorine content of 8.8% (calculated value 8.7%) was obtained.

I got something like this.

The total amount of neophyll chloride in Example 1-++) was 168.6? The total amount of cyclohexyl chloride is 118.65' (1,0-E
:/L/) to the trimethylsilylmethifucroid in Example 1-(21) 148.31 (0.47
A 1-volume solution of cyclohexylmagnesium chloride was prepared in exactly the same manner as in Example 1, except that phenyldimethylsilylmethy/l/tin trichloride (177, 0.475 mol) was used in place of 5 mol), respectively. When reacted with phenyldimethylsilylmethyl trichloride and processed. Oily dicyclohexy/L/
(Phenyldimethylsilylmethy/v)! Chloride 22
1. 71 was obtained in a yield of 95.8%. Purity by gas chromatography was 96.4%.

When this substance was further purified by column chromatography (filling material Nisilica gel, developing solvent: n-hexane-acetic acid), the refractive index (n): 1.5593,
Gas chromatography purity 99.0% and chlorine content 7
．． 6% (calculated value: 75%) was obtained.

Comparison ff Example G-n-butyl (
Total amount of neophyll chloride in Example 1-il+ 168.6 r (
Total amount of n-butyl chloride 9
2. Example 1 was carried out in exactly the same manner as in Example 1, except that 59 (1,0 mol) was used. Prepare n-butylmagnesium chloride solution. This was reacted with trimethylsilylmethyltin trichloride and a treatment operation was performed to obtain a reaction concentration residue of 168. About 9y.

Results of composition analysis using column chromatography.

It was as follows.

Reaction product Composition ratio di-n-buty/v (trimethylsilylmethy/l/) 21
．． 0 (%) Tin chloride trimethylsilyl citryl Tin trichloride 4.6n
-Butyl(trimethylsilylmethy/L/)tin 29.7
Dichloride

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. in the presence or absence of an inert organic solvent ▼ (In the formula, R is an alkyl group or phenyl group, and X is a chlorine atom or a bromine atom. 1 mol of monoorganotin trihalide represented by An asymmetric triorgano expressed by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (wherein R, R^* and X have the same meanings as above), which is characterized by reacting substantially 2 moles as an ether solution Method for manufacturing tin halide.