CN102816112A - Method for preparing pesticide nitenpyram - Google Patents

Abstract

The invention relates to a method for synthesizing a pesticide, and in particular relates to a method for preparing a pesticide nitenpyram. The method for preparing the pesticide nitenpyram is characterized in that 1, 1, 1, 2-trichloroethane is taken as a starting material, and an intermediate of 1, 1, 1-trichloro-2-nitroethane is directly synthesized through elimination reaction and catalytical nitration reaction; 2, 2-chloro-5-nitrapyrin is taken as a staring material, water is taken as solvent, a phase-transfer catalysis technology is adopted, and an intermediate of N-ethyl-2-chloro-5-pyridyl methyl amine is obtained through N-alkylation reaction; and 3, the two intermediates are mixed together, dichloromethane with low toxicity is taken as the solvent, condensation and methyl amination reaction are carried out in a same reaction vessel, and the nitenpyram is produced through extracting, desolventizing and crystallizing. The method for preparing the pesticide nitenpyram has high product yield and purity and a short technological process. Compared with the prior art, the method has the advantages of high total yield, low cost, high product purity, less environmental pollution, benefits for industrial production and the like.

Description

A kind of preparation method of sterilant Ti304

Technical field

The present invention relates to the compound method of sterilant, especially a kind of is the preparation method of the Ti304 of main raw material with vinyl trichloride and 2-chlorine PMC.

Background technology

Ti304 is the nicotinic insecticide of new generation after Provado, and its molecular structural formula is:

It is the new variety of the high malicious organophosphorus pesticide of replacement of latest domestic popularization; Have unique chemical and biological property; Cynapse acceptor to insect has the nerve block effect; Various aphids, aleyrodid, rice-leaf hopper and thrips etc. are shown remarkable activity, have efficient, low toxicity, environmentally safe, high in absorption, no cross resistance, crop do not had advantage such as poisoning, be widely used in the various crop insect that prevents and treats on paddy rice, fruit tree, vegetables and the tealeaves.Particularly this product has the final hit effect to small brown rice planthopper and brown paddy plant hopper, takes effect about 10 minutes after the medication, and quick-acting is obvious, and the lasting period can reach 14 days, and effect is superior to similar drugs such as acetamiprid, Provado.This product is to be succeeded in developing by Japanese Wu Tian company in 1989, and has obtained related patent U.S. Patent No., as: EP302389, GB228003, US5935981, US5849768, US5364989, US4028379, US4347250, US5175301 etc.Domestic later to this product research report, once delivered three pieces of papers since 2002, be entitled as " synthetic route of Ti304 " like living on " agricultural chemicals " magazine, at first having delivered of king party in 2002, introduced the synthetic route of domestic and international Ti304.

The applicant once adopted the technology of preparation method of document record to carry out lab scale in order to develop this sterilant Ti304 product.1. be raw material with Nitromethane 99Min. and dithiocarbonic anhydride, preparation 1 earlier, 1-diformazan sulfenyl-2-nitroethylene is that the synthetic intermediate N ethyl-2-chloro-5-picolyl amine that obtains of raw material reacts with 2-chloro-5-PMC again.Run in test many problems: midbody 1,1-diformazan sulfenyl-2-nitroethylene complicated process of preparation, and poisonous and rank smell is arranged has shortcomings such as technical process complicacy, operation are dangerous, contaminate environment, cost height; 2. adopt document record technology, prepare 1,1 with technical hydrochloric acid and nitric acid, 1-three chloro-2-nitroethanes, in the route that reacts with N-ethyl-2-chloro-5-picolyl amine again, the nitrifying process excessive acid is too many, and spent acid is hard to manage, and environmental pollution is serious.In the preparation process of intermediate N ethyl-2-chloro-5-picolyl amine, used a large amount of solvents, and yield is not high, reclaims the solvent treatment difficulty, cost is high, and environment is caused bigger pollution.

Summary of the invention

It is high to the purpose of this invention is to provide a kind of yield and purity, the sterilant Ti304 preparation method that technical process is short.

In order to achieve the above object, the present invention adopts following technical solution: a kind of preparation method of sterilant Ti304 is characterized in that it is undertaken by following synthesis route:

(1) eliminating reaction, is starting raw material with the vinyl trichloride, with the sodium hydroxide solution reaction, under-15 ℃～100 ℃, eliminates reaction, obtains vinylidene chloride, its reaction equation:

(2) nitration reaction, described vinylidene chloride are carried out nitration reaction with hydrochloric acid and nitric acid in the presence of catalyst A 1, reaction finishes after separation and purification obtains 1,1,1-three chloro-2-nitroethanes, and its reaction equation:

Described catalyst A 1 is one of following: 1. ZSM25 molecular sieve, 2. β 2 zeolite molecular sieves, 3. SAPO211 molecular sieve, 4. NH ₄Y zeolite, 5. ReY molecular sieve, 6. SSY molecular sieve;

(3) N-alkylated reaction with 2-chloro-5-PMC starting raw material, is made solvent with water; Under-10～50 ℃; React under the effect of phase-transfer catalyst A2 with ethamine, reaction product is through precipitation, alkali cleaning; Distillation obtains described intermediate N ethyl-2-chloro-5-picolyl amine, its reaction equation:

Described catalyst A 2 is one of following: 1. TMAH, 2. tetraethyl ammonium hydroxide, 3. trimethyl benzyl volatile caustic, 4. triethyl benzyl ammonia chloride, 5. Tetrabutyl amonium bromide, 6. cetyl trimethylammonium bromide;

(4) condensation reaction, described N-ethyl-2-chloro-5-picolyl amine and described 1,1; 1-three chloro-2-nitroethanes are in dichloromethane solvent; Add acid binding agent, under phase-transfer catalyst A3 effect, under-10～50 ℃; Reaction obtain condenses 1-chloro-N-{ (methyl of 6-chloropyridine-3-) }-N-ethyl-2-nitroethylene amine, its reaction equation:

Described catalyst A 3 is one of following: 1. TMAH, 2. tetraethyl ammonium hydroxide, 3. trimethyl benzyl volatile caustic, 4. triethyl benzyl ammonia chloride, 5. Tetrabutyl amonium bromide, 6. cetyl trimethylammonium bromide;

Described acid binding agent is one of following: 1. Na ₂CO ₃, 2. K ₂CO ₃, 3. NaHCO ₃, 4. KHCO ₃, 5. NaOH, 6. KOH;

(5) methylamine glycosylation reaction; Said methylamine glycosylation reaction and described condensation reaction are carried out in same reactor, after said condensation reaction is accomplished, obtain condenses 1-chloro-N-{ (methyl of 6-chloropyridine-3-) }-N-ethyl-2-nitroethylene amine; Subsequently under-10～50 ℃; Drip aqueous methylamine solution, reaction product obtains Ti304 through extraction, precipitation, recrystallization, its reaction equation:

The reaction product 1,1 of the present invention in order to improve nitration reaction, 1-three chloro-2-nitroethane midbody content and yields further are provided with synthetic technical scheme:

Said nitration reaction is carried out according to the following steps: in the enamel reaction still of 2000L; Add the said technical hydrochloric acid of 412.5Kg31%, the said industrial concentrated acid of 324Kg68% and the said SAPO-211 sieve catalyst of 7.5kg A1; Under the vigorous stirring; Control temperature of reaction well, in 5～6 hours, evenly splash into said vinylidene chloride 315Kg; Drip and finish, continued insulation reaction 3 hours; Reaction finishes, and standing demix takes off a layer oil reservoir, with the 300Kg water washing once, obtains 534Kg 1,1,1-three chloro-2-nitroethanes, and content >=90%, yield >=more than 85%.

The present invention can improve midbody purity and yield in order to make the N-ethylation reaction, and purge process is nontoxic, reduces environmental pollution, and synthetic technical scheme further is provided with:

Said N-ethylation reaction carries out according to the following steps: in the enamel reaction still of 2000L, make solvent with water, add the said ethylamine solution of 289.2Kg 70%, the said Tetrabutyl amonium bromide catalyst A 2 of 5Kg; Open stirring; Regulate the temperature of reaction, slowly the said 2-chloro-5-PMC with 304.5Kg 95.9% adds reaction kettle, controls temperature well; Finish, continued insulation reaction 1 hour; Reaction finishes, and excessive ethylamine solution is reclaimed in distillation, adds 30% said sodium hydroxide solution 240Kg, and standing demix is got oil reservoir, obtains 318Kg N-ethyl-2-chloro-5-picolyl amine bullion, content >=95%; Underpressure distillation, get 162～164 ℃ of cuts/-0.095Mpa, obtain light yellow liquid 285Kg, content >=99%.

The present invention compared with prior art has the following advantages:

The present invention is starting raw material with the vinyl trichloride, through eliminating reaction and catalytic nitration reaction, adopts the catalytic nitration technology, has improved the content and the yield of reaction greatly, directly synthesizes to obtain content and reach 1,1 more than 90%, 1-three chloro-2-nitroethanes; Adopt phase transfer catalytic technology; Replacing used poisonous of Japanese Wu Tian company that the acetonitrile of pollution is arranged with water is solvent; Accomplish the ethamine reaction and the purifying procedure thereof of 2-chloro-5-PMC, obtain the N-ethyl-2-chloro-5-picolyl amine of high purity (99%); Excessive ethamine can repeat to apply mechanically through film-falling absorption tower, has reduced environmental pollution.The yield of this step reaction is increased to 92% by 85% of bibliographical information.

The present invention is with 1; 1; 1-three chloro-2-nitroethanes mix with N-ethyl-2-chloro-5-picolyl amine, use the methylene dichloride of low toxicity to replace the high malicious chloroform of bibliographical information to be reaction medium, under mild conditions, carry out condensation and eliminate reaction; And in same reactor, directly carry out phase transition methylamine glycosylation reaction without separating, obtain purity through extraction, precipitation, crystallization again and reach the Ti304 more than 97%.Total recovery is high, and cost is low, and product purity is high, is beneficial to suitability for industrialized production.

Description of drawings

Fig. 1 is a present embodiment Ti304 synthesis technique flow diagram.

Embodiment

Below in conjunction with accompanying drawing and embodiment the present invention is done further explain.

As shown in Figure 1, present embodiment is undertaken by following synthesis route and step:

(1) eliminate reaction, its reaction equation is:,

Said elimination reaction is carried out according to the following steps: in the enamel reaction still of 2000L, add 450Kg1, and 1, the 2-trichloroethane is heated to certain temperature, under vigorous stirring, drips 30% sodium hydroxide solution 450Kg equably, and the dropping time is about 5 hours.Between the reaction period, the product vinylidene chloride is overflowed from the distillation capital, and column top temperature gets into receiving tank at 32～40 ℃ through behind the condensing tube condensation.Drip and finish, continue insulation reaction up to there not being product to overflow basically.Slowly be warmed up to 70 ℃ of certain temperature reaction 1～2 hour again, till not having product and distillating.Obtain 315Kg (>=98%) colourless transparent liquid product vinylidene chloride.

Said elimination reaction is through 6 batches of pilot scales, and pilot-scale experiment is following:

	The 1st batch	The 2nd batch	The 3rd batch	The 4th batch	The 5th batch	The 6th batch	MV
								Output	315.3	317.5	314.8	318.1	315.8	316.5	316.3
Content	98.5	98.1	98.4	98.0	98.7	98.3	98.3
								Yield	96.9	97.2	96.7	97.3	97.3	97.1	97.1

Can be known that by last table the highest yield of eliminating the prepared in reaction vinylidene chloride is 97.3%, minimum is 96.7%, and average yield is 97.1%, and average content is 98.3%.

(2) nitration reaction, its reaction equation is:

Said nitration reaction is carried out according to the following steps: in the enamel reaction still of 2000L; Add 412.5Kg31% technical hydrochloric acid, 324Kg 68% industrial concentrated acid and 7.5kg SAPO211 sieve catalyst A1, under the vigorous stirring, control the temperature of reaction well; In 5～6 hours; Evenly splash into the 315Kg vinylidene chloride of the first step gained, drip and finish, continued insulation reaction 3 hours.Reaction finishes, and standing demix takes off a layer oil reservoir, with the 300Kg water washing once, obtains 534Kg 1,1,1-three chloro-2-nitroethanes, content >=90%.

In the nitration reaction of this step, the effect of said SAPO211 sieve catalyst A1 is the selectivity that improves molecular transposition, reduces by product.Following material: 1. ZSM25 molecular sieve, 2. β 2 zeolite molecular sieves, 3. N H4Y type molecular sieve, 4. the ReY molecular sieve and 5. the SSY molecular sieve similar characteristic is also arranged, also can do the catalyst A 1 of this nitration reaction.

Said nitration reaction is through 6 batches of pilot scales, and pilot-scale experiment is following:

	The 1st batch	The 2nd batch	The 3rd batch	The 4th batch	The 5th batch	The 6th batch	MV
								Output	356.3	358.1	357.5	356.9	357.1	357.8	357.3
Content	90.1	89.8	90.4	90.8	91.1	90.7	90.5
								Yield	84.8	84.9	85.3	85.6	85.9	85.7	85.4

Can know by last table, nitration reaction preparation 1,1, the highest yield of 1-three chloro-2-nitroethanes is 85.9%, and minimum is 84.8%, and average yield is 85.4%, and average content is 90.5%.

(3) N-alkylated reaction, its reaction equation is:

Said N-alkylated reaction carries out according to the following steps: in the enamel reaction still of 2000L, make solvent with water, add ethylamine solution and the 5Kg triethyl benzyl ammonia chloride catalyst A 2 of 289.2Kg 70%; The temperature that stirring and adjusting is reacted well; Slowly the 2-chloro-5-PMC with 304.5Kg 95.9% adds in the reaction kettle, finishes, and continues insulation reaction 1 hour; Reaction finishes, and excessive ethylamine solution is reclaimed in distillation.The sodium hydroxide solution 240Kg of adding 30%, standing demix is got oil reservoir, obtains 318Kg brown liquid product, content 94.5%.Through underpressure distillation, get 162～164 ℃ of cuts/-0.095Mpa, obtain light yellow liquid 285Kg, content >=99%.

In said N-alkylated reaction, the effect of said Tetrabutyl amonium bromide catalyst A 2 is that reaction mass is in the homogeneous system.Following material: TMAH, tetraethyl ammonium hydroxide, trimethyl benzyl volatile caustic, triethyl benzyl ammonia chloride and cetyl trimethylammonium bromide also have similar character, also can be used as the phase-transfer catalyst of this N-alkylated reaction.

Said N-alkylated reaction is through 6 batches of pilot scales, and pilot-scale experiment is following:

	The 1st batch	The 2nd batch	The 3rd batch	The 4th batch	The 5th batch	The 6th batch	MV
								Output	285.7	286.1	286.8	285.8	288.5	284.3	286.2
Content	99.5	99.3	99.1	99.3	99.0	99.1	99.2
								Yield	92.5	92.4	92.5	92.4	92.9	91.7	92.4

Can be known that by last table the highest yield that the N-ethylation reaction prepares N-(6-chloro-3-picolyl)-N-ethamine is 92.9%, minimum is 91.7%, and average yield is 92.4%, and average content is 99.2%.

(4) condensation reaction and methylamine glycosylation reaction, its reaction equation is respectively:

Said methylamine glycosylation reaction and described condensation reaction are carried out in same reactor.

Said condensation reaction and methylamine glycosylation reaction carry out according to the following steps: in the enamel reaction still of 1000L, add 5Kg Tetrabutyl amonium bromide catalyst A 3,64Kg yellow soda ash acid binding agent, 480Kg dichloromethane solvent, control temperature of reaction well; Add 1; 1,1-three chloro-2-nitroethane 65.4Kg, subsequently; Drip N-(6-chloro-3-picolyl)-N-ethamine 52Kg, dripped off in 2～3 hours.Drip and finish, drip the aqueous methylamine solution of 46.5Kg 40%, dripped off in 2～3 hours.Drip and finish, under this temperature, continued insulated and stirred 1 hour.Then, the temperature rising reflux reaction is 2 hours.Reaction finishes the cooling standing demix, and water layer is used the 220Kg dichloromethane extraction, merges organic layer.Reclaim methylene dichloride, first normal pressure, and then decompression obtain bullion 83.1Kg, add 100Kg methyl alcohol and carry out recrystallization, filter, and oven dry obtains the former medicine of 72Kg Ti304, content＞97%.

In said condensation reaction and methylamine glycosylation reaction, the effect of said Tetrabutyl amonium bromide catalyst A 3 is that reaction mass is in the homogeneous system.Following material: TMAH, tetraethyl ammonium hydroxide, trimethyl benzyl volatile caustic, triethyl benzyl ammonia chloride and cetyl trimethylammonium bromide also have similar character, can be used as the phase-transfer catalyst of this condensation reaction.

In said condensation reaction and methylamine glycosylation reaction, the effect of said yellow soda ash acid binding agent is the hydrogenchloride that neutralization reaction generates.Therefore, described acid binding agent can also be for one of following: salt of wormwood, saleratus, sodium hydrogencarbonate, sodium hydroxide and Pottasium Hydroxide.

Said condensation reaction and methylamine glycosylation reaction are through 6 batches of pilot scales, and pilot-scale experiment is following:

	The 1st batch	The 2nd batch	The 3rd batch	The 4th batch	The 5th batch	The 6th batch	MV
								Output	70.5	73.1	72.5	71.8	72.4	70.3	71.8
Content	97.5	97.0	97.1	97.3	97.2	97.8	97.3
								Yield	84.1	86.8	86.2	85.5	86.1	84.2	85.5

Can be known that by last table the highest yield that condensation reaction and methylamine glycosylation reaction one kettle way prepare Ti304 is 86.8%, minimum is 84.1%, and average yield is 85.5%, and average content is 97.3%.

In 2-chloro-5-PMC, the synthetic total recovery of Ti304 is 79%.

Claims (2)

1. the preparation method of a sterilant Ti304 is characterized in that it is undertaken by following synthesis route:

(1) eliminating reaction, is starting raw material with the vinyl trichloride, with the sodium hydroxide solution reaction, under-15 ℃～100 ℃, eliminates reaction, obtains vinylidene chloride, its reaction equation:

(2) nitration reaction, described vinylidene chloride are carried out nitration reaction with hydrochloric acid and nitric acid in the presence of catalyst A 1, reaction finishes after separation and purification obtains 1,1,1-three chloro-2-nitroethanes, and its reaction equation:

Described catalyst A 1 is one of following: 1. ZSM25 molecular sieve, 2. β 2 zeolite molecular sieves, 3. SAPO211 molecular sieve, 4. N H ₄Y zeolite, 5. ReY molecular sieve, 6. SSY molecular sieve;

(3) N-alkylated reaction with 2-chloro-5-PMC starting raw material, is made solvent with water; Under-10～50 ℃; React under the effect of phase-transfer catalyst A2 with ethamine, reaction product is through precipitation, alkali cleaning; Distillation obtains described intermediate N ethyl-2-chloro-5-picolyl amine, its reaction equation:

Described catalyst A 2 is one of following: 1. TMAH, 2. tetraethyl ammonium hydroxide, 3. trimethyl benzyl volatile caustic, 4. triethyl benzyl ammonia chloride, 5. Tetrabutyl amonium bromide, 6. cetyl trimethylammonium bromide;

(4) condensation reaction, described N-ethyl-2-chloro-5-picolyl amine and described 1,1; 1-three chloro-2-nitroethanes are in dichloromethane solvent; Add acid binding agent, under phase-transfer catalyst A3 effect, under-10～50 ℃; Reaction obtain condenses 1-chloro-N-{ (methyl of 6-chloropyridine-3-) }-N-ethyl-2-nitroethylene amine, its reaction equation:

Described catalyst A 3 is one of following: 1. TMAH, 2. tetraethyl ammonium hydroxide, 3. trimethyl benzyl volatile caustic, 4. triethyl benzyl ammonia chloride, 5. Tetrabutyl amonium bromide, 6. cetyl trimethylammonium bromide;

Described acid binding agent is one of following: 1. Na ₂CO ₃, 2. K ₂CO ₃, 3. NaHCO ₃, 4. KHCO ₃, 5. NaOH, 6. KOH;

(5) methylamine glycosylation reaction; Said methylamine glycosylation reaction and described condensation reaction are carried out in same reactor, after said condensation reaction is accomplished, obtain condenses 1-chloro-N-{ (methyl of 6-chloropyridine-3-) }-N-ethyl-2-nitroethylene amine; Subsequently under-10～50 ℃; Drip aqueous methylamine solution, reaction product obtains Ti304 through extraction, precipitation, recrystallization, its reaction equation:

2. the preparation method of a kind of sterilant Ti304 according to claim 1; It is characterized in that said nitration reaction carries out according to the following steps: in the enamel reaction still of 2000L; Add the said technical hydrochloric acid of 412.5Kg31%, the said industrial concentrated acid of 324Kg68% and the said SAPO-211 sieve catalyst of 7.5kg A1, under the vigorous stirring, control temperature of reaction well; In 5～6 hours, evenly splash into said vinylidene chloride 315Kg; Drip and finish, continued insulation reaction 3 hours; Reaction finishes, and standing demix takes off a layer oil reservoir, with the 300Kg water washing once, obtains 534Kg 1,1,1-three chloro-2-nitroethanes, and content >=90%, yield >=more than 85%;

Said N-ethylation reaction carries out according to the following steps: in the enamel reaction still of 2000L, make solvent with water, add the said ethylamine solution of 289.2Kg 70%, the said Tetrabutyl amonium bromide catalyst A 2 of 5Kg; Open stirring; Regulate the temperature of reaction, slowly the said 2-chloro-5-PMC with 304.5Kg 95.9% adds reaction kettle, controls temperature well; Finish, continued insulation reaction 1 hour; Reaction finishes, and excessive ethylamine solution is reclaimed in distillation, adds 30% said sodium hydroxide solution 240Kg, and standing demix is got oil reservoir, obtains 318Kg N-ethyl-2-chloro-5-picolyl amine bullion, content >=95%; Underpressure distillation, get 162～164 ℃ of cuts/-0.095Mpa, obtain light yellow liquid 285Kg, content >=99%.

Images