CN102816112A - Method for preparing pesticide nitenpyram - Google Patents
Method for preparing pesticide nitenpyram Download PDFInfo
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- CN102816112A CN102816112A CN2012103417120A CN201210341712A CN102816112A CN 102816112 A CN102816112 A CN 102816112A CN 2012103417120 A CN2012103417120 A CN 2012103417120A CN 201210341712 A CN201210341712 A CN 201210341712A CN 102816112 A CN102816112 A CN 102816112A
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- 238000000034 method Methods 0.000 title abstract description 15
- CFRPSFYHXJZSBI-DHZHZOJOSA-N (E)-nitenpyram Chemical compound [O-][N+](=O)/C=C(\NC)N(CC)CC1=CC=C(Cl)N=C1 CFRPSFYHXJZSBI-DHZHZOJOSA-N 0.000 title abstract 5
- 229940079888 nitenpyram Drugs 0.000 title abstract 5
- 239000000575 pesticide Substances 0.000 title abstract 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 31
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006396 nitration reaction Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 N-ethyl-2-chloro-5-pyridyl methyl Chemical group 0.000 claims abstract description 7
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 19
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 16
- 239000002808 molecular sieve Substances 0.000 claims description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 15
- 238000006482 condensation reaction Methods 0.000 claims description 14
- XMZRJPITAOAPLJ-UHFFFAOYSA-N 1-chloro-2-nitroethane Chemical class [O-][N+](=O)CCCl XMZRJPITAOAPLJ-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 238000006206 glycosylation reaction Methods 0.000 claims description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 9
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 9
- 210000003298 dental enamel Anatomy 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- LQOBMKYCRQDMTN-UHFFFAOYSA-N 3-(2-ethylphenyl)pentan-3-amine;hydrochloride Chemical compound Cl.CCC1=CC=CC=C1C(N)(CC)CC LQOBMKYCRQDMTN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 239000003518 caustics Substances 0.000 claims description 6
- 239000003444 phase transfer catalyst Substances 0.000 claims description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000006200 ethylation reaction Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 238000003379 elimination reaction Methods 0.000 abstract description 3
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract 3
- SBFICQFUERLNDG-UHFFFAOYSA-N 1,1,1-trichloro-2-nitroethane Chemical compound [O-][N+](=O)CC(Cl)(Cl)Cl SBFICQFUERLNDG-UHFFFAOYSA-N 0.000 abstract 1
- 238000007126 N-alkylation reaction Methods 0.000 abstract 1
- 238000005576 amination reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000003408 phase transfer catalysis Methods 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000011020 pilot scale process Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241001498622 Cixius wagneri Species 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- WCXDHFDTOYPNIE-RIYZIHGNSA-N (E)-acetamiprid Chemical compound N#C/N=C(\C)N(C)CC1=CC=C(Cl)N=C1 WCXDHFDTOYPNIE-RIYZIHGNSA-N 0.000 description 1
- 239000005875 Acetamiprid Substances 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- 241000209094 Oryza Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 241000194622 Tagosodes orizicolus Species 0.000 description 1
- 241001414989 Thysanoptera Species 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 235000021329 brown rice Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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
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%.
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