CN1094396A

CN1094396A - N, N-dimethyl amido-1, the production technique of 3-dithio sodium sulfate base propane and analogue thereof

Info

Publication number: CN1094396A
Application number: CN 93110667
Authority: CN
Inventors: 江依国; 袁美和; 何志武; 周尧鑫
Original assignee: NO 9763 FACTORY PLA
Current assignee: NO 9763 FACTORY PLA
Priority date: 1993-04-11
Filing date: 1993-04-11
Publication date: 1994-11-02
Anticipated expiration: 2013-04-11
Also published as: CN1037964C

Abstract

N, N-dimethyl amido-1, the production technique of 3-dithio sodium sulfate base propane and analogue thereof, products obtained therefrom adds the reaction of unsaturated hydro carbons or reductibility compound to remove excessive chlorine after the acid chlorination, or organic solvent is heated up in a steamer in intensification after sour chlorination, deviate from excessive chlorine simultaneously, the anhydrous N of gained after amination, N-dimethyl allylamine hydrochloride is in organic solvent, anhydrous condition down and the addition reaction of liquid bromine adds sulfonation after the water sepn, advantage is in yield that can improve product and purity, yield can reach more than 93%, eliminates side reaction, reduces the corrodibility to production unit, reduce the consumption of alkali greatly, be suitable for nereistoxin insecticides production.

Description

N, N-dimethyl amido-1, the production technique of 3-dithio sodium sulfate base propane and analogue thereof

The present invention relates to a kind of NN-dimethyl amido-1, the production technique of 3-dithio sodium sulfate base propane and analogue thereof belongs to the production method of acyclic compound class.

Disosultap NN-dimethyl amido-1,3-dithio sodium sulfate base propane is a kind of of nereistoxin agricultural chemicals, its production technique is updated, at present, amination stage yield in its technology in three classes can reach more than 95%, and sour chlorination stage yield also can reach more than 95%, and effective body yield of its sulfonation stage has only about 80%, thereby the starting point of further improving the disosultap production technique should be to improve the yield in sulfonation stage, and the sulfonation reaction formula is as follows:

But because in the sour chlorination process of previous stage, the excessive 5-10% of chlorine meeting, though carry out dechlorination by backflow in the existing technology, but because the solubleness of chlorine in organic solvent such as ethylene dichloride is bigger, dechlorination still can not be clean, thereby after sour chlorination reaction, during the muriate that is dissolved in water (I), have following reaction to take place:

So the acidity in the muriate (I) is generally about 2%, in reaction process (1), just have following side reaction to take place like this:

Reaction product (III) is significantly reduced the yield of muriate (I), therefore under the optimum process condition that existing disosultap is produced, promptly adopt the method for No. 85102989, Chinese patent to carry out amination, by publication number is that method among CN1033378A, the CN1052111A is carried out acidifying and chlorination, and sulfonation stage yield also can only reach about 80%.

Purpose of the present invention just provides a kind of elimination ClO ^-The production technique of the disadvantageous effect of bringing, with the elimination side reaction, thus the yield and the purity of raising product (III).

The objective of the invention is to be achieved 1, the product of gained after the sour chlorination is added unsaturated hydro carbons or the reaction of reductibility compound removing excessive chlorine, sulfonation then by following proposal.2, intensification distillates organic solvent after the sour chlorination, deviates from excessive chlorine simultaneously, then sulfonation.3, carry out addition reaction with liquid bromine (replacement chlorine) at the anhydrous NN-dimethyl allylamine hydrochloride of gained after the amination in organic solvent, under the anhydrous condition, gains directly carry out sulfonation after adding water sepn.

The invention has the advantages that the yield and the purity that can improve product, yield can reach more than 93%, eliminate side reaction, reduction is to the corrodibility of production unit, treating processes is simple, and processing ease also greatly reduces the consumption of alkali, present method is not only for producing disosultap, and provides a good condition for the production of whole nereistoxin insecticides.

Concrete operations of the present invention are as follows:

1, with NN-dimethyl allylamine hydrochloride in organic solvent, anhydrous condition feeds dry chlorine gas down to chlorination fully, it is chlorination stage, the organic solvent that adopts is the halohydrocarbon that contains C1-10, ethers, sulfone and sulfoxide class, amides etc., after finishing aforesaid operations, add an amount of unsaturated hydro carbons or the reaction of reductibility compound to remove excessive chlorine, unsaturated hydro carbons is aliphatics unsaturated olefin and alkynes, aromatic series unsaturated olefin and alkynes, alkene is ethene, propylene, divinyl, pentadiene, turps, tetrahydrobenzene, vinylbenzene etc., alkynes is acetylene, monovinylacetylene, propine etc., reductibility compound are alcohols, amine, amides, phenols, the polycarboxylic acid class, SO ₂, H ₂S, Na ₂SO ₃, KI, Na ₂S, SnCl ₂, FeCl ₂Deng, the temperature when adding above-mentioned material is 10-100 ℃, carries out sulfonation after adding water sepn.

2, NN-dimethyl allylamine hydrochloride is fed dry chlorine gas to complete chlorination under the anhydrous condition in organic solvent, intensification is carried out sulfonation after distilling out organic solvent, distillation condition is temperature 40-160 ℃, and normal pressure or decompression are selected it according to the character of organic solvent.Can all distillate organic solvent, also can keep on a small quantity not distillating.

3, with anhydrous NN-dimethyl allylamine hydrochloride in organic solvent, in 20-100 ℃ of temperature range, add bromine reaction under the anhydrous condition after, add water sepn and carry out sulfonation.

The present invention also is suitable for the production process of other nereistoxin insecticides such as benzene sulphur desinsection fat etc.

Embodiment is as follows:

Embodiment 1:

In the 500ml reactor, add NN-dimethyl allylamine hydrochloride aqueous solution 60g, heat up vacuum hydro-extraction, reach till 135 ℃ to temperature, be incubated 20 minutes, add 1 then, 2-ethylene dichloride 130g makes material dissolution, feeds chlorine at 30 °-60 ℃, to using 0.1NKMnO ₄Colour-fast in solution is checked one minute is terminal point, then add an amount of turps, temperature is controlled at 40-50 ℃, be terminal point to no longer becoming orchid with the check of KI starch solution, add water 35ml, standing demix gets NN-dimethyl-2,3-dichloro-propyl-amine hydrochloride aqueous solution 78.3g, content is that 49.8%(is equivalent to 0.203mol).The NaOH aqueous solution neutralization that in this aqueous solution, adds 5ml30%.Add 108g sodium thiosulfate (content 99%) again in another 500ml reactor, rising temperature for dissolving adds above-mentioned corrective at 50-60 ℃, is warming up to 80 ℃, is incubated 4 hours, gets the 302.6g product, and content is that 22.34%(is equivalent to 0.1902mol), yield 93.7%.

Embodiment 2:

In the 500ml reactor, add NN-dimethyl allylamine hydrochloride aqueous solution 60g, heat up vacuum hydro-extraction, reach till 135 ℃ to temperature, be incubated 20 minutes, add 1 then, 2-ethylene dichloride 130g makes material dissolution, feeds chlorine at 30 °-60 ℃, to using 0.1NKMnO ₄Colour-fast in solution is checked one minute is terminal point, then add an amount of acetylene, temperature is controlled at 40-50 ℃, be terminal point to no longer becoming orchid with the check of KI starch solution, add water 35ml, standing demix gets NN-dimethyl-2,3-dichloro-propyl-amine hydrochloride aqueous solution 78.3g, content is that 49.8%(is equivalent to 0.203mol).The NaOH aqueous solution neutralization that in this aqueous solution, adds 5ml30%.Add 108g sodium thiosulfate (content 99%) again in another 500ml reactor, rising temperature for dissolving adds above-mentioned corrective at 50-60 ℃, is warming up to 80 ℃, is incubated 4 hours, gets the 302.6g product, and content is that 22.34%(is equivalent to 0.1902mol), yield 93.7%.

Embodiment 3:

In the 500ml reactor, add NN-dimethyl allylamine hydrochloride aqueous solution 60g, heat up vacuum hydro-extraction, reach till 135 ℃ to temperature, be incubated 20 minutes, add 1 then, 2-ethylene dichloride 130g makes material dissolution, feeds chlorine at 30 °-60 ℃, to using 0.1NKMnO ₄Colour-fast in solution is checked one minute is terminal point, then adds an amount of H ₂S, temperature is controlled at 40-50 ℃, is terminal point to no longer becoming orchid with the check of KI starch solution, adds water 35ml, and standing demix gets NN-dimethyl-2,3-dichloro-propyl-amine hydrochloride aqueous solution 78.3g, content is that 49.8%(is equivalent to 0.203mol).The NaOH aqueous solution neutralization that in this aqueous solution, adds 5ml30%.Add 108g sodium thiosulfate (content 99%) again in another 500ml reactor, rising temperature for dissolving adds above-mentioned corrective at 50-60 ℃, is warming up to 80 ℃, is incubated 4 hours, gets the 302.6g product, and content is that 22.34%(is equivalent to 0.1902mol), yield 93.7%.

Embodiment 4:

Add 50mlNN-dimethyl allylamine hydrochloride, intensification, vacuum hydro-extraction in the 500ml reactor, to 130 ℃, insulation dehydration 25 minutes adds the 130g ethylene dichloride while hot.Between 30-60 ℃, feed dry chlorine gas to terminal, add an amount of turps, make the excessive chlorine total overall reaction, add water 35ml, after the standing separation, NN-dimethyl-2,3-dichloro-propyl-amine hydrochloride solution 73.7g content 50.37%(are equivalent to 0.1928mol), in this aqueous solution, add the NaOH aqueous solution neutralization of 6ml30%, stand-by.

Add the 81g sodium benzenethiosulfonate in another 500ml reactor, (content is greater than 98%) adds water 25ml, rising temperature for dissolving, and controlled temperature adds above-mentioned corrective between 50-60 ℃, be warming up to 70 ℃, and insulation reaction 4 hours gets benzene sulphur desinsection

303.3g content is 25.84%, (being equivalent to 0.1818ml), yield 94.3%.

Embodiment 5: add NN-dimethyl allylamine hydrochloride aqueous solution 60g in the 500ml reactor, heat up vacuum hydro-extraction, till when temperature reaches 130 ℃, be incubated 15 minutes, add 1 while hot then, 2-ethylene dichloride 125g makes material dissolution, feeds chlorine down at 30-60 ℃, to using 0.1NKMnO ₄Colour-fast in dissolving is checked one minute is terminal point.Ethylene dichloride is reclaimed in the distillation that then heats up, just excessive chlorine is all deviate from simultaneously, add entry 35ml then, make 76.6gNN-dimethyl-2, the 3-dichloro-propyl-amine hydrochloride aqueous solution, content 50.23%(is equivalent to 0.20mol) in this muriate, add in the NaOH aqueous solution of 5ml30% and stand-by, neutral temperature is 20-30 ℃, adds 106.5g sodium thiosulfate (content 99%) again in another 500ml reactor, and heating up makes it dissolving, add neutral muriate in 60-70 ℃, be warming up to 80 ℃, be incubated 4 hours, get the 279.4g product, content is that 23.66%(is equivalent to 0.186mol), yield is 93.0%.

Embodiment 6:

In the 500ml reactor, add anhydrous NN-dimethyl allylamine hydrochloride 30g, rising temperature for dissolving, add 130g1, the 2-ethylene dichloride adds the liquid bromine down at 30-60 ℃, to 1, the reddish-brown of bromine is no longer taken off and is terminal point in the 2-ethylene dichloride, add water 50ml, standing demix gets 114.6gNN-dimethyl-2, the 3-dibromo propylamin hydrochloride aqueous solution, content is that 60.3%(is equivalent to 0.2455mol), in this aqueous solution, add the NaOH aqueous solution neutralization of 6ml30%, in another 500ml reactor, add 130.5g sodium thiosulfate (content is 99%) again, be warming up to 80 ℃, be incubated 3 hours, get the 350.8g product, content is that 23.55%(is equivalent to 0.2325mol), yield is 94.7%.

Claims

1, a kind of N, the production technique of N-dimethyl amido-1,3-dithio sodium sulfate base propane and analogue thereof, this technology comprises that N.N-dimethyl allylamine hydrochloride is in organic solvent, anhydrous condition feeds dry chlorine gas down to complete chlorination, it is characterized in that finishing and add an amount of unsaturated hydro carbons or the reaction of reductibility compound behind the aforesaid operations, carry out sulfonation after adding water sepn to remove excessive chlorine.

2, production technique according to claim 1, it is characterized in that unsaturated hydro carbons is aliphatics unsaturated olefin and alkynes, aromatic series unsaturated olefin and alkynes, alkene is ethene, propylene, divinyl, pentadiene, turps, tetrahydrobenzene, vinylbenzene etc., the alkynes class is acetylene, monovinylacetylene, propine etc., reductibility compound are alcohols, amine, amides, phenols, polycarboxylic acid class, SO ₂, H ₂S, Na ₂SO ₃, KI, Na ₂S, SnCl ₂, FeCl ₂Deng, adding above-mentioned material temperature is 10-100 ℃.

3, NN-dimethyl amido-1, the production technique of 3-dithio sodium sulfate base propane and analogue thereof, this technology comprises NN-dimethyl allylamine hydrochloride is fed dry chlorine gas to chlorination fully in organic solvent, under the anhydrous condition, intensification is carried out sulfonation after distilling out organic solvent, distillation condition is temperature 40-160 ℃, normal pressure or decompression.

4, NN-dimethyl amido-1, the production technique of 3-dithio sodium sulfate base propane and analogue thereof, this technology comprise when temperature is 20 °-100 ℃ in organic solvent, under the anhydrous condition with NN-dimethyl allylamine hydrochloride, normal pressure, after the bromine addition reaction, add sulfonation after the water sepn.

5, production technique according to claim 4 is characterized in that described and the optimal temperature bromine addition reaction is 35-80 ℃.