CN102816112B - Method for preparing pesticide nitenpyram - Google Patents
Method for preparing pesticide nitenpyram Download PDFInfo
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- CN102816112B CN102816112B CN201210341712.0A CN201210341712A CN102816112B CN 102816112 B CN102816112 B CN 102816112B CN 201210341712 A CN201210341712 A CN 201210341712A CN 102816112 B CN102816112 B CN 102816112B
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- 238000000034 method Methods 0.000 title abstract description 14
- 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 62
- 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
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 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 18
- 239000002808 molecular sieve Substances 0.000 claims description 18
- 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 18
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 15
- 238000006482 condensation reaction Methods 0.000 claims description 14
- XMZRJPITAOAPLJ-UHFFFAOYSA-N 1-chloro-2-nitroethane Chemical compound [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
- 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
- 238000006200 ethylation reaction Methods 0.000 claims description 10
- 238000002360 preparation method Methods 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000013517 stratification 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
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 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
- 239000010457 zeolite Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 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
- 239000012043 crude product Substances 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
- 238000000926 separation method 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
- 239000011734 sodium Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000003379 elimination reaction Methods 0.000 abstract description 4
- 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
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 238000005576 amination reaction Methods 0.000 abstract description 2
- 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
- -1 N-ethyl-2-chloro-5-pyridyl methyl Chemical group 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
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 231100000614 poison Toxicity 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
- 239000005864 Sulphur Substances 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007096 poisonous effect Effects 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
- NJWIMFZLESWFIM-UHFFFAOYSA-N 2-(chloromethyl)pyridine Chemical compound ClCC1=CC=CC=N1 NJWIMFZLESWFIM-UHFFFAOYSA-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- 239000002917 insecticide Substances 0.000 description 1
- 230000002045 lasting effect Effects 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
- 239000002574 poison 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
- 238000010189 synthetic method Methods 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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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 synthetic method of sterilant, especially a kind of preparation method of take the Ti304 that vinyl trichloride and 2-chlorine chloromethylpyridine be main raw material.
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, there is unique chemistry and biological property, cynapse acceptor to insect has nerve block effect, various aphids, aleyrodid, rice-leaf hopper and thrips etc. are shown to remarkable activity, have efficient, low toxicity, environmentally safe, high in absorption, without cross resistance, to crop without advantages such as poisoning, be widely used in the various crop insect on control paddy rice, fruit tree, vegetables and tealeaves.Particularly this product has final hit effect to small brown rice planthopper and brown paddy plant hopper, after medication, about 10 minutes, takes effect, and quick-acting is obvious, and the lasting period can reach 14 days, and effect is better than the similar drugs such as acetamiprid, Provado.This product is by Japanese Wu Tian company, to be succeeded in developing for 1989, and has obtained Patents, as: EP302389, GB228003, US5935981, US5849768, US5364989, US4028379, US4347250, US5175301 etc.Domestic more late to this product research report, since 2002, once delivered three pieces of papers, as 2002 Nian Wang parties are raw, on " agricultural chemicals " magazine, first delivered and be entitled as " synthetic route of Ti304 ", introduced the synthetic route of domestic and international Ti304.
The applicant is in order to develop this sterilant Ti304 product, and the technology of preparation method that once adopted document to record is carried out lab scale.1. take Nitromethane 99Min. and dithiocarbonic anhydride as raw material, first prepare 1,1-dimethyl sulphur-based-2-nitroethylene, then to be that raw material is synthetic with CCMP obtain the chloro-5-picolyl of intermediate N ethyl-2-amine and react.Encounter in test many problems: intermediate 1,1-dimethyl sulphur-based-2-nitroethylene complicated process of preparation, and poisonous and have rank smell, has technical process complexity, operates dangerous, contaminate environment, high in cost of production shortcoming; 2. adopt document record technology, with technical hydrochloric acid and preparation of nitric acid 1,1, the chloro-2-nitroethane of 1-tri-, then in the route reacting with the chloro-5-picolyl of N-ethyl-2-amine, nitrifying process excessive acid is too many, and spent acid is difficult, and environmental pollution is serious.In the preparation process of the chloro-5-picolyl of intermediate N ethyl-2-amine, used a large amount of solvents, and yield is not high, reclaims solvent treatment difficulty, cost is high, and environment is caused to larger pollution.
Summary of the invention
The object of this invention is to provide a kind of yield and purity high, 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) eliminate reaction, take vinyl trichloride as starting raw material, react with sodium hydroxide solution, at-15 ℃～100 ℃, eliminate reaction, obtain vinylidene chloride, its reaction equation:
(2) nitration reaction, described vinylidene chloride, under catalyst A 1 exists, carries out nitration reaction with hydrochloric acid and nitric acid, and reaction finishes by separation and purification, to obtain the chloro-2-nitroethane of 1,1,1-tri-, 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-ethylation reaction, with CCMP starting raw material, with water, make solvent, at-10～50 ℃, react under the effect of phase-transfer catalyst A2 with ethamine, reaction product is through precipitation, alkali cleaning, distillation obtains the described chloro-5-picolyl of intermediate N ethyl-2-amine, its reaction equation:
The neat A2 of described catalysis is one of following: 1. Tetramethylammonium hydroxide, 2. tetraethyl ammonium hydroxide, 3. trimethyl benzyl ammonium hydroxide, 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, the chloro-2-nitroethane of 1-tri-is in dichloromethane solvent, add acid binding agent, under phase-transfer catalyst A3 effect, at-10～50 ℃, reaction obtains the chloro-N-{ of condenses 1-(6-chloropyridine-3-) methyl }-N-ethyl-2-nitroethylene amine, its reaction equation:
Described catalyst A 3 is one of following: 1. Tetramethylammonium hydroxide, 2. tetraethyl ammonium hydroxide, 3. trimethyl benzyl ammonium hydroxide, 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, described methylamine glycosylation reaction and described condensation reaction are carried out in same reactor, after described condensation reaction completes, obtain the chloro-N-{ of condenses 1-(6-chloropyridine-3-) methyl }-N-ethyl-2-nitroethylene amine, subsequently at-10～50 ℃, drip aqueous methylamine solution, reaction product obtains Ti304 through extraction, precipitation, recrystallization, its reaction equation:
The present invention is in order to improve the reaction product 1,1 of nitration reaction, and the chloro-2-nitroethane of 1-tri-intermediate content and yield, further arrange synthetic technical scheme:
Described nitration reaction is carried out according to the following steps: in the enamel reaction still of 2000L, add described in technical hydrochloric acid described in 412.5Kg31%, 324Kg68% SAPO-211 molecular sieve catalyst A1 described in industrial concentrated acid and 7.5kg, under vigorous stirring, control temperature of reaction well, in 5～6 hours, evenly splash into described vinylidene chloride 315Kg; Drip and finish, continue insulation reaction 3 hours; Reaction finishes, and stratification, takes off a layer oil reservoir, with 300Kg water washing once, obtains 534Kg1, the chloro-2-nitroethane of 1,1-tri-, and content >=90%, more than yield >=85%.
The present invention is in order to make N-ethylation reaction can improve intermediate purity and yield, and purge process is nontoxic, reduces environmental pollution, and synthetic technical scheme is further arranged:
Described N-ethylation reaction carries out according to the following steps: in the enamel reaction still of 2000L, with water, make solvent, add the described ethylamine solution of 289.2Kg70%, the described Tetrabutyl amonium bromide catalyst A 2 of 5Kg, stir, regulate the temperature of reaction, slowly the described CCMP of 304.5Kg95.9% is added to reactor, control temperature well, finish, continue insulation reaction 1 hour; Reaction finishes, and the ethylamine solution that Distillation recovery is excessive, adds 30% sodium hydroxide solution 240Kg, and stratification, gets oil reservoir, obtains the chloro-5-picolyl of 318Kg N-ethyl-2-amine crude product, content >=95%; Underpressure distillation, gets 162～164 ℃ of cuts/-0.095Mpa, obtains light yellow liquid 285Kg, content >=99%.
The present invention compared with prior art has the following advantages:
The present invention be take vinyl trichloride as starting raw material, through eliminating reaction and catalytic nitration reaction, adopts catalytic nitration technology, has greatly improved content and the yield of reaction, directly synthesizes to obtain content and reach more than 90% 1,1, the chloro-2-nitroethane of 1-tri-; Adopt phase transfer catalytic technology, it is solvent that the water of take replaces used poisonous of Japanese Wu Tian company to have the acetonitrile of pollution, complete second amination reaction and the purifying procedure thereof of CCMP, obtain the chloro-5-picolyl of the N-ethyl-2-amine of high purity (99%); Excessive ethamine, by film-falling absorption tower, can repeat to apply mechanically, and has reduced environmental pollution.The yield of this step reaction is increased to 92% by 85% of bibliographical information.
The present invention is by 1,1, the chloro-2-nitroethane of 1-tri-mixes with the chloro-5-picolyl of N-ethyl-2-amine, with the methylene dichloride of low toxicity, replacing the height poison chloroform of bibliographical information is reaction medium, under mild conditions, carry out condensation and eliminate reaction, and directly carry out phase transition methylamine glycosylation reaction without separation in same reactor, then through extraction, precipitation, crystallization and obtain purity and reach more than 97% Ti304.Total recovery is high, and cost is low, and product purity is high, is beneficial to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the present embodiment Ti304 synthesis technique flow diagram.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
As shown in Figure 1, the present embodiment is undertaken by following synthesis route and step:
(1) eliminate reaction, its reaction equation is:,
Described elimination reaction is carried out according to the following steps: in the enamel reaction still of 2000L, add 450Kg1,1,2-trichloroethane, is heated to certain temperature, under vigorous stirring, drips equably 30% sodium hydroxide solution 450Kg, and time for adding is about 5 hours.Between the reaction period, product vinylidene chloride is overflowed from distillation capital, and column top temperature, at 32～40 ℃, enters receiving tank after condensing tube condensation.Drip and finish, continue insulation reaction until substantially do not have product to overflow.Slowly be warmed up to again certain temperature 70 C reaction 1～2 hour, till distillating without product.Obtain 315Kg (>=98%) colourless transparent liquid product vinylidene chloride.
Described elimination reaction is through 6 batches of pilot scales, and pilot-scale experiment is as follows:
| ? | The 1st batch | The 2nd batch | The 3rd batch | The 4th batch | The 5th batch | The 6th batch | Mean value |
| 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 |
As seen from the above table, the highest yield that vinylidene chloride is prepared in elimination reaction is 97.3%, and minimum is 96.7%, and average yield is 97.1%, and average content is 98.3%.
(2) nitration reaction, its reaction equation is:
Described nitration reaction is carried out according to the following steps: in the enamel reaction still of 2000L, add 412.5Kg31% technical hydrochloric acid, 324Kg68% industrial concentrated acid and 7.5kg SAP0211 molecular sieve catalyst A1, under vigorous stirring, control well reaction temperature, in 5～6 hours, evenly splash into the 315Kg vinylidene chloride of the first step gained, drip and finish, continue insulation reaction 3 hours.Reaction finishes, and stratification, takes off a layer oil reservoir, with 300Kg water washing once, obtains 534Kg1, chloro-2-nitroethane 0 content >=90% of 1,1-tri-.
In the nitration reaction of this step, the effect of described SAP0211 molecular 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. NH
4y zeolite, 4. ReY molecular sieve and 5. SSY molecular sieve also have similar characteristic, also can do the catalyst A 1 of this nitration reaction.
Described nitration reaction is through 6 batches of pilot scales, and pilot-scale experiment is as follows:
| ? | The 1st batch | The 2nd batch | The 3rd batch | The 4th batch | The 5th batch | The 6th batch | Mean value |
| 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 |
As seen from the above table, the highest yield that nitration reaction is prepared the chloro-2-nitroethane of 1,1,1-tri-is 85.9%, and minimum is 84.8%, and average yield is 85.4%, and average content is 90.5%.
(3) N-ethylation reaction, its reaction equation is:
Described N-ethylation reaction carries out according to the following steps: in the enamel reaction still of 2000L, with water, make solvent, the ethylamine solution and the 5Kg triethyl benzyl ammonia chloride catalyst A 2 that add 289.2Kg70%, the temperature that stirring and adjusting is reacted well, slowly the CCMP of 304.5Kg95.9% is added in reactor, finish, continue insulation reaction 1 hour, reaction finishes, the ethylamine solution that Distillation recovery is excessive.Add 30% sodium hydroxide solution 240Kg, stratification, gets 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 described N-ethylation reaction, the effect of described Tetrabutyl amonium bromide catalyst A 2 is to make reaction mass in homogeneous system.Following material: Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, 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.
Described N-ethylation reaction is through 6 batches of pilot scales, and pilot-scale experiment is as follows:
| ? | The 1st batch | The 2nd batch | The 3rd batch | The 4th batch | The 5th batch | The 6th batch | Mean value |
| 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 |
As seen from the above table, the highest yield that N-ethylation reaction is prepared N-(6-chloro-3-pyridylmethyl)-N-ethamine is 92.9%, and 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:
Described methylamine glycosylation reaction and described condensation reaction are carried out in same reactor.
Described 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 sodium carbonate acid binding agent, 480Kg dichloromethane solvent, control temperature of reaction well, add 1, the chloro-2-nitroethane of 1,1-tri-65.4Kg, subsequently, drip N-(6-chloro-3-pyridylmethyl)-N-ethamine 52Kg, within 2～3 hours, drip off.Drip and finish, drip the aqueous methylamine solution of 46.5Kg40%, within 2～3 hours, drip off.Drip and finish, at this temperature, continue insulated and stirred 1 hour.Then, temperature rising reflux reaction is 2 hours.Reaction finishes cooling stratification, and water layer 220Kg dichloromethane extraction merges organic layer.Reclaim methylene dichloride, first normal pressure, and then decompression, obtain crude product 83.1Kg, adds 100Kg methyl alcohol to carry out recrystallization, filters, and dries and obtain the former medicine of 72Kg Ti304, content > 97%.
In described condensation reaction and methylamine glycosylation reaction, the effect of described Tetrabutyl amonium bromide catalyst A 3 is to make reaction mass in homogeneous system.Following material: Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, 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 described condensation reaction and methylamine glycosylation reaction, the effect of described sodium carbonate 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 bicarbonate, sodium hydroxide and potassium hydroxide.
Described condensation reaction and methylamine glycosylation reaction are through 6 batches of pilot scales, and pilot-scale experiment is as follows:
| ? | The 1st batch | The 2nd batch | The 3rd batch | The 4th batch | The 5th batch | The 6th batch | Mean value |
| 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 |
As seen from the above table, the highest yield that condensation reaction and methylamine glycosylation reaction one kettle way are prepared Ti304 is 86.8%, and minimum is 84.1%, and average yield is 85.5%, and average content is 97.3%.
In CCMP, the synthetic total recovery of Ti304 is 79%.
Claims (2)
1. a preparation method for sterilant Ti304, is characterized in that it is undertaken by following synthesis route:
(1) eliminate reaction, take vinyl trichloride as starting raw material, react with sodium hydroxide solution, at-15 ℃～100 ℃, eliminate reaction, obtain vinylidene chloride, its reaction equation:
(2) nitration reaction, described vinylidene chloride, under catalyst A 1 exists, carries out nitration reaction with hydrochloric acid and nitric acid, and reaction finishes by separation and purification, to obtain the chloro-2-nitroethane of 1,1,1-tri-, 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-ethylation reaction, with CCMP starting raw material, with water, make solvent, at-10～50 ℃, react under the effect of phase-transfer catalyst A2 with ethamine, reaction product is through precipitation, alkali cleaning, distillation obtains the described chloro-5-picolyl of intermediate N ethyl-2-amine, its reaction equation:
Described catalyst A 2 is one of following: 1. Tetramethylammonium hydroxide, 2. tetraethyl ammonium hydroxide, 3. trimethyl benzyl ammonium hydroxide, 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, the chloro-2-nitroethane of 1-tri-is in dichloromethane solvent, add acid binding agent, under phase-transfer catalyst A3 effect, at-10～50 ℃, reaction obtains the chloro-N-{ of condenses 1-(6-chloropyridine-3-) methyl }-N-ethyl-2-nitroethylene amine, its reaction equation:
Described catalyst A 3 is one of following: 1. Tetramethylammonium hydroxide, 2. tetraethyl ammonium hydroxide, 3. trimethyl benzyl ammonium hydroxide, 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, described methylamine glycosylation reaction and described condensation reaction are carried out in same reactor, after described condensation reaction completes, obtain the chloro-N-{ of condenses 1-(6-chloropyridine-3-) methyl }-N-ethyl-2-nitroethylene amine, subsequently at-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 described nitration reaction carries out according to the following steps: in the enamel reaction still of 2000L, add described in technical hydrochloric acid described in 412.5Kg31%, 324Kg68% SAPO-211 molecular sieve catalyst A1 described in industrial concentrated acid and 7.5kg, under vigorous stirring, control temperature of reaction well, in 5～6 hours, evenly splash into described vinylidene chloride 315Kg; Drip and finish, continue insulation reaction 3 hours; Reaction finishes, and stratification, takes off a layer oil reservoir, with 300Kg water washing once, obtains 534Kg1, the chloro-2-nitroethane of 1,1-tri-, and content >=90%, more than yield >=85%;
Described N-ethylation reaction carries out according to the following steps: in the enamel reaction still of 2000L, with water, make solvent, add the described ethylamine solution of 289.2Kg70%, the described Tetrabutyl amonium bromide catalyst A 2 of 5Kg, stir, regulate the temperature of reaction, slowly the described CCMP of 304.5Kg95.9% is added to reactor, control temperature well, finish, continue insulation reaction 1 hour; Reaction finishes, and the ethylamine solution that Distillation recovery is excessive adds 30% sodium hydroxide solution 240Kg, and stratification, gets oil reservoir, obtains the chloro-5-picolyl of 318Kg N-ethyl-2-amine crude product, content >=95%; Underpressure distillation, gets 162～164 ℃ of cuts/-0.095Mpa, obtains light yellow liquid 285Kg, content >=99%.
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