CN1044232C

CN1044232C - Thioether organo-thiosulfate

Info

Publication number: CN1044232C
Application number: CN93115891A
Authority: CN
Inventors: 许培元; 王雅君
Original assignee: Shenyang Research Institute of Chemical Industry Co Ltd
Current assignee: Shenyang Research Institute of Chemical Industry Co Ltd
Priority date: 1993-11-05
Filing date: 1993-11-05
Publication date: 1999-07-21
Anticipated expiration: 2013-11-05
Also published as: CN1102408A

Abstract

The present invention relates to thioether organo-thiosulfate whose structural formula is disclosed in the expression (I), wherein R in the expression (I) is alkyl containing substituents, such as ethyl and n-butyl containing halogen, nitryl, ether groups, etc., alkyl which does not contain substituents, such as ethyl and n-butyl, aryl containing substituents, such as phenyl or benzyl containing halogen, nitryl and ether groups or aryl which does not contain substituents, such as phenyl, benzyl, etc. M<1> and <M2> are the same or different metal such as K, Na and Ca, or NH4, H, etc. The compound I in the title has strong killing functions on Tetranychidae, Aphidoidae, etc.

Description

Thioether organo-thiosulfate

Thioether organo-thiosulfate belongs to desinsection, mite-killing preparation as Insecticidal and acaricidal agent.

Title compound structural formula of the present invention is:

Bionic pesticide and medicine are the directions that people develop novel pesticide and medicine always.Once reported among the Phyto chemistry 19 1228 (1980) and contained stonewort toxin (chara toxim)-be 4-methylthio group-1 in the stonewort (chata globubaris) of occurring in nature, the 2-dithiane.

Structural formula:

(II) has desinsection, miticidal effect, but higher to vegeto-animal toxicity, and people have developed the substituent dithiane Insecticidal and acaricidal agent of a kind of serial alkane again subsequently.The spy opens clear 63-196578 and has reported

Desinsection, miticidal effect, it be by

With R ' SSO ₃Reaction generates Make (III) through ring-closure reaction again.

With R in the following formula is the above alkyl of C2, and R ' is an alkyl, and X is a halogen, and the process of preparation (III) is longer, and cost is higher.

The title compound that the present invention proposes Can be by R-S-CH ₂-CHX-CH ₂-X (V) or With 2M ¹M ²SSO ₃Reaction makes (I)

R is for containing substituent alkyl in (I) formula, as ethyl, the normal-butyl of halogen-containing, nitro, ether etc., and do not contain substituent alkyl such as ethyl, normal-butyl; Contain substituent aryl, as phenyl, the benzyl of halogen-containing, nitro, ether or do not contain substituent aryl such as phenyl, benzyl etc.

M ¹, M ²Be identical or different metal such as K, Na, Ca or NH ₄, H etc.

The title compound I is simpler than known compound III manufacturing processed, and cost is low, be a kind of desinsection, the higher sterilant of miticidal effect, it all has killing action to Tetranychidae (Tetrany-chidae), Aphidiadae (Aphdidae) and Dulicidae (culi-cidae) etc.

(IV) or (V) and M ²SSO ₃The solvent of reaction is water, alcohols such as methyl alcohol, ethanol etc.; Hydro carbons such as sherwood oil, kerosene, benzene, toluene etc.; Halohydrocarbon such as CCl ₄, CH ₂Cl ₂CHCl ₃, ethylene dichloride etc., ethers such as dioxane, tetrahydrofuran (THF) etc.; Ketone such as acetone, methylethylketone etc.; One or more mixed solvents such as ester class such as methyl-formiate, ethyl formate, ethyl acetate.Temperature of reaction is 20-150 ℃, and the reaction times is decided by temperature of reaction, be generally 0.5-5 hour, reaction reach lower the temperature behind the terminal point, crystallization, filtration.And methods such as reconcentration, recrystallization are purified.

Title compound (I) with make wettable powder, pulvis, aqua, emulsion and granule.

Example 1

2-ethylmercapto group-1, synthetic (compound N 0,1) of two (Sulfothiorine) propane of 3-

In 250 milliliters of four-hole bottles, add 52.5 gram methyl alcohol and 26.1 grams 1,3-two bromo-2-ethylmercapto group propane, 17.5 gram water and 50.1 gram Na ₂S ₂O ₃5H ₂O stirs and to be warming up to 69-70 ℃, and back flow reaction reaction 3.5 hours is sloughed methyl alcohol at 75-90 ℃, cooling, in 10 ℃ of following stirred crystallization 2 hours, filter, dry white solid 40.1 grams (fusing point 65-70 ℃), excellent stratographic analysis content 90%, yield 96.9%.

NMR(D ₂O) δppm1.27(3Ht),

2.73(2H,g)

3.45-3.58(4H,m),3.61(1H,m)

Example 2

2-thiophenyl-1, synthetic (the compound N O2) of two (Sulfothiorine) propane of 3-

In 250 milliliters of four-hole bottles, add 52.5 gram methyl alcohol and 31.0 grams 1,3-two bromo-2-thiophenyl propane, 17.5 gram water and 50.1 gram Na ₂S ₂O ₃5H ₂O stir to heat up, and 70 ℃ of following back flow reaction 3.5 hours are sloughed methyl alcohol in 70-90 ℃ then, and cooling in 10 ℃ of following stirred crystallization 2 hours, is filtered, the filter cake oven dry, 41 gram pale yellow powders, excellent stratographic analysis content 88.0%, yield 85.9%.

NMR(D ₂O、NaoD) δppm3.29(4H,m)，

3.71(1H,m),7.49(4H,m)。

Test example 1: to the effect of cotton spider mites (Tatranycus chin-nabarinus).

To become mite to move and connect on the dry vegetalbe beans sheet, and behind the base number, immerse in the reagent solution that has prepared, and take out the observation ward that places 20 ℃ of room temperatures about 5 seconds, the dead worm rate of periodic investigation the results are shown in Table 1.

Test example 2: to the effect of black bean aphid (Aphis Laburni).

With three days young aphid of growth, immerse in the lump in the reagent solution that has prepared together with the broad bean seedling of parasitism, insert observation ward after the taking-up about 5 seconds, the dead worm rate of periodic investigation.The results are shown in Table 1.

Test example 3: the effect that culex pipiens pollens three is made larva (Culex Pipie-ns).

Culex pipiens pollens three is made larva, insert in the quantitative accumulated water of dosing container, add the test solution that has prepared, make its concentration that becomes design, the limit edged stirs, and places observation ward then, and the periodic investigation mortality ratio the results are shown in Table 1.Table 1 compound is to different insects indoor biometrics result

(mortality ratio %)

Compound	Experimental concentration	Light color storehouse number			Cotton spider mites			Black bean aphid
Compound	Experimental concentration	Light color storehouse number			Cotton spider mites			Black bean aphid			NO	ppm	1 day	2 days	3 days	1 day	2 days	3 days	1 day	2 days	3 days
1	250 500	0 35	35 65	65 93	42	54	60	10	60	70	NO	ppm	1 day	2 days	3 days	1 day	2 days	3 days	1 day	2 days	3 days
1	250 500	0 35	35 65	65 93	42	54	60	10	60	70	2	125 250 500	70 93 100	95 98 100	95 98 100	5 40	20 60	35 72	30	60	65

Claims

1, thioether organo-thiosulfate, the structural formula of compound of the present invention is:

R contains or does not contain substituent aryl, M for containing or not containing substituent alkyl in the formula ¹, M ²For identical or different, be K, Na, Ca or NH ₄

2, thioether organo-thiosulfate according to claim 1 is characterized in that R is ethyl, normal-butyl or halogen-containing, nitro, the ethyl of ether, normal-butyl.

3, thioether organo-thiosulfate according to claim 1 is characterized in that R is phenyl, benzyl or halogen-containing, nitro, the phenyl of ether, benzyl.

4, the thioether organo-thiosulfate of claim 1 is as sterilant and miticide.