CN1858055A - Method for synthesizing chlopyrifos in water medium - Google Patents
Method for synthesizing chlopyrifos in water medium Download PDFInfo
- Publication number
- CN1858055A CN1858055A CN 200610044199 CN200610044199A CN1858055A CN 1858055 A CN1858055 A CN 1858055A CN 200610044199 CN200610044199 CN 200610044199 CN 200610044199 A CN200610044199 A CN 200610044199A CN 1858055 A CN1858055 A CN 1858055A
- Authority
- CN
- China
- Prior art keywords
- sodium
- water
- ammonium halide
- chlorpyrifos
- trichloropyridine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- -1 3,5,6-trichloro pyridyl Chemical group 0.000 claims abstract description 44
- 239000005944 Chlorpyrifos Substances 0.000 claims abstract description 24
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011734 sodium Substances 0.000 claims abstract description 21
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003444 phase transfer catalyst Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 235000011181 potassium carbonates Nutrition 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 4
- 230000003750 conditioning effect Effects 0.000 claims description 4
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 230000001737 promoting effect Effects 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 241000282326 Felis catus Species 0.000 claims description 3
- 241000047703 Nonion Species 0.000 claims description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229950009789 cetomacrogol 1000 Drugs 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 3
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 claims description 2
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- HCWYXKWQOMTBKY-UHFFFAOYSA-N calcium;dodecyl benzenesulfonate Chemical group [Ca].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 HCWYXKWQOMTBKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 claims description 2
- 229960003511 macrogol Drugs 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- KMJJJTCKNZYTEY-UHFFFAOYSA-N chloro-diethoxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(Cl)(=S)OCC KMJJJTCKNZYTEY-UHFFFAOYSA-N 0.000 abstract 1
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 210000000481 breast Anatomy 0.000 description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009313 farming Methods 0.000 description 2
- 238000003822 preparative gas chromatography Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The method of synthesizing chlorpyrifos in water medium features that through adding water into reaction kettle, adding surfactant, 3,5,6-trichloro pyridyl -2-sodium alcoholate and O, O-diethyl thiophosphoryl chloride via stirring for emulsifying and dispersing in water, adding composite catalyst, adding pH regulator to regulate system pH value to 9-10, reaction at 25-65 deg.c, lowering temperature to crystallize, suction filtering, water washing and drying, chlorpyrifos is prepared. The present invention features using water as medium to form high dispersed reaction system, simple and reliable synthesis process, easy operation, high product yield and purify, low production cost and environment friendship.
Description
Technical field
The present invention relates to a kind ofly with 3,5,6-trichloropyridine-2-sodium alkoxide and O, O-o,o-diethylthiophosphoryl chloride are the method for main material production Chlorpyrifos 94.
Background technology
Chlorpyrifos 94, chemical name O, O-diethyl-O-(3,5, the 6-trichloro-2-pyridyl) thiophosphatephosphorothioate is the organophosphorus desinsection miticide of a kind of efficient, wide spectrum, middle low toxicity, is the regeneration product that the current pesticide structure of China is adjusted.
The method of synthetic Chlorpyrifos 94 mainly contains solvent pairs method and water method on the current industrial.Main raw material adopts 3,5,6-trichloropyridine-2-sodium alkoxide and O, O-o,o-diethylthiophosphoryl chloride.The solvent pairs method is to constitute the solvent pairs system with water and organic solvent (adopting ethylene dichloride) more, can effectively suppress O, the hydrolysis of O-o,o-diethylthiophosphoryl chloride, and yield can reach 95%.But this method can only make Chlorpyrifos 94 crude oil, also must steam organic solvent, and with methyl alcohol equal solvent recrystallization, just can obtain former powder.The organic solvent toxicity height, pollute big, operational hazards, loss is many, be unfavorable for environment protection and safety in production, and damage HUMAN HEALTH and increase production cost.Common water method is 3,5, and 6-trichloropyridine-2-sodium alkoxide adds in the entry, adds catalyzer, drips O simultaneously, and O-o,o-diethylthiophosphoryl chloride and acid binding agent, decrease temperature crystalline directly obtain the former powder of Chlorpyrifos 94.This method troublesome poeration, wayward reaction, yield is 92～95%, and is not ideal enough.
Summary of the invention
It is medium with water that technical problem to be solved by this invention provides a kind of, and disposable adding reaction raw materials makes the synthetic method of the former powder of Chlorpyrifos 94, and is simple to operate, yield and purity height.
The method of the present invention synthetic Chlorpyrifos 94 in water medium is characterized in that water is dropped in the reactor, stirs to add tensio-active agent, 3 down, 5,6-trichloropyridine-2-sodium alkoxide and O, is scattered in the water emulsification of O-o,o-diethylthiophosphoryl chloride, adds composite catalyst then, and the PH conditioning agent makes the system pH value reach 9～10, react completely decrease temperature crystalline, suction filtration washing in 25～65 ℃ then, drying makes the former medicine finished product of Chlorpyrifos 94.
Major technique characteristics of the present invention are: be the disposable adding reactant of medium with water and form the high dispersing system by means of the effect of tensio-active agent and react.
Tensio-active agent of the present invention is meant can be with 3,5, and 6-trichloropyridine-2-sodium alkoxide and O, is dispersed in the material in the water at the emulsification of O-o,o-diethylthiophosphoryl chloride.Main select following a few class materials: the material that can function as described above in (1) anion surfactant, preferred calcium dodecylbenzene sulphonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, dispersing agent NNO, dispersing agent CNF, diffusant FM, (structural formula is polyoxyethylenated alcohol sodium sulfate: RO (CH
2CH
2O)
nSO
3Na, R=C
12～15Alkyl, n=2,3), sulfated castor oil, petroleum sodium sulfonate, sodium dibutyl naphthalene sulfonate, the material that can function as described above in (2) cats product can be that (wherein alkyl is C for cetyltrimethylammonium chloride, octadecyl trimethyl ammonium chloride or alkyl dimethyl amine oxide
12-18), (3) material that can function as described above in the amphoterics, preferred Varion CDG-K, (4) material that can function as described above in the nonionogenic tenside, preferred polyoxyethylene octylphenol ether OP series, polyoxyethylene nonylphenol ether NP series, Tween-65, tween-80, polyethers P104, (structural formula is R-O (C to fatty alcohol-polyoxyethylene ether
2H
4O) nH, R=C
12～16Alkyl, n=2,3,7,9,10,15,20 ...), benzylphenol Soxylat A 25-7 (agricultural newborn BP, BC), styryl phenol polyethenoxy ether (agricultural emulsifier NO, agricultural newborn BS, No. 1601, farming breast, No. 1602, farming breast, No. 32, peaceful breast), (structural formula is aliphatic amine polyoxyethylene ether: R
1-NH (C
2H
4O)
nH or
R wherein
1=C
8～22Alkyl, R
2=C
16～18Alkyl, n=2～30, m+r=17～23) material that can function as described above in (5) polymeric surface active agent, preferred sodium lignosulfonate, calcium lignin sulphonate, carboxymethyl cellulose, (6) material that can function as described above in the special surface promoting agent, preferred water-soluble silicon oil SF-908, Perfluorocaprylic Acid, non-ion fluorin carbon surface active agent FSN-100.
The consumption of tensio-active agent is a reaction raw materials 3,5,6-trichloropyridine-2-sodium alkoxide and O, 0.1～5% of O-o,o-diethylthiophosphoryl chloride total mass.Composite mixture, the proportioning between each material is any.When tensio-active agent adopts the special surface promoting agent, the usage quantity that its consumption should be provided according to manufacturer's specification sheets.
Composite catalyst used in the present invention is meant the mixture of being made up of Trimethylamine 99 and phase-transfer catalyst.Phase-transfer catalyst wherein can be one or more the composite mixture in the following material: trioctylphosphine methyl ammonium halide, the benzyl trimethyl ammonium halide, the benzyl triethyl ammonium ammonium halide, benzyl tributyl ammonium halide, the dodecyl trimethyl-ammonium halide, dodecyl triethyl ammonium halide, the cetyl trimethyl ammonium halide, hexadecyl triethyl ammonium halide, the tetramethyl-ammonium halide, the tetraethyl-ammonium halide, tetrabutyl ammonium halide, the 4-Dimethylamino pyridine, Macrogol 200, poly(oxyethylene glycol) 400, Polyethylene Glycol-600, polyoxyethylene glycol 800, cetomacrogol 1000, hexaoxacyclooctadecane-6-6,15-crown ether-5 or dibenzo-18-crown-6 (DB18C6).Halogen in the above ammonium halide is chlorine, bromine or iodine.These composite catalysts also are catalyzer commonly used during Chlorpyrifos 94 produces.Trimethylamine 99 is in 30% the aqueous solution, and consumption is 3,5,1～10% of 6-trichloropyridine-2-sodium alkoxide quality, and phase-transfer catalyst is 3,5,0.1～7% of 6-trichloropyridine-2-sodium alkoxide quality.
Described PH conditioning agent is meant one or both mixtures formed with arbitrary proportion in yellow soda ash, salt of wormwood, sodium hydroxide or the potassium hydroxide, and wiring solution-forming uses.
Optimized process conditions of the present invention is:
3,5,6-trichloropyridine-2-sodium alkoxide and O, the mol ratio of O-o,o-diethylthiophosphoryl chloride is 1: 1.0～1.2;
30～300 rev/mins of mixing speed;
Temperature of reaction: 25～65 ℃;
PH value: 9～10;
Reaction times: 0.25～2 hour;
Solution of potassium carbonate mass concentration 10～30%;
Sodium carbonate solution mass concentration 10～20%;
Potassium hydroxide solution mass concentration 5～30%;
Sodium hydroxide solution mass concentration 5～30%;
WATER AS FLOW MEDIUM and 3,5, the mass ratio of 6-trichloropyridine-2-sodium alkoxide is 1: 0.1～0.35.
Advantage of the present invention:
The present invention with water is the method for the synthetic Chlorpyrifos 94 of medium, and is simple and reliable, is convenient to operation, and product yield and purity all are improved, and all can reach more than 98%.Production cost is low, and environment improves.
Embodiment
Further specify the present invention by the following examples, but do not limit the present invention.
Embodiment 1:
Stirring is being housed, in the 250ml four-hole bottle of thermometer, add 118.5g water, 1g paregal O-20,0.5g Sodium dodecylbenzene sulfonate, 0.25g the aqueous solution of Trimethylamine 99 30%, the 1g tri-n-octyl methyl ammonium chloride, 0.5g 4-Dimethylamino pyridine, 20.7g O, the O-o,o-diethylthiophosphoryl chloride, 22.0g 3,5,6-trichloropyridine-2-sodium alkoxide, regulate PH=9.7 with 30% solution of potassium carbonate and 20% sodium hydroxide solution, be warming up to 55 ℃ of reactions 1 hour, be cooled to 20 ℃ of crystallizations, suction filtration, washing, dry, obtain the Chlorpyrifos 94 white crystals, yield 98.1%, content 99.0% (vapor-phase chromatography).
Embodiment 2:
In the 2000L glassed steel reaction vessels, add 1100kg water, 4.5kg polyoxyethylene octylphenol ether OP-10,3.5kg sodium lauryl sulphate, 5kg Trimethylamine 99 30% aqueous solution, 0.5kg4-Dimethylamino pyridine, the 5kg poly(oxyethylene glycol) 400,207kgO, the O-o,o-diethylthiophosphoryl chloride, 220kg3,5,6-trichloropyridine-2-sodium alkoxide, regulate PH=9.5 with 20% solution of potassium carbonate and 10% potassium hydroxide solution, be warming up to 50 ℃ of reactions 1.5 hours, be cooled to 20 ℃ of crystallizations, the blowing suction filtration, washing, dry, obtain the Chlorpyrifos 94 white crystals, yield 98.0%, content 98.2% (vapor-phase chromatography).
Embodiment 3:
Use the solution of potassium carbonate among the embodiment 1 instead 20% sodium carbonate solution, all the other are constant.Yield 98.0%, content 98.0%.
Embodiment 4:
Use the poly(oxyethylene glycol) 400 among the embodiment 2 instead Polyethylene Glycol-600, all the other are constant.Yield 98.3%, content 98.0%.
Embodiment 5:
Use the 1g tri-n-octyl methyl ammonium chloride among the embodiment 1 instead the 0.5g benzyltriethylammoinium chloride, all the other are constant.Yield 98.1%, content 98.2%.
Embodiment 6:
Use the 4.5kg polyoxyethylene octylphenol ether OP-10 among the embodiment 2 instead the 16.5kg tween-80, water is 2200kg, adopts the 3000L reactor, and all the other are constant.Yield 98.0%, content 98.3%.
Embodiment 7:
Use the 1g tri-n-octyl methyl ammonium chloride among the embodiment 1 instead palmityl trimethyl ammonium chloride 1g, water is 79g.Yield 98.0%, content 98.2%.
Embodiment 8:
Use the 1g paregal O-20 among the embodiment 1,0.5g Sodium dodecylbenzene sulfonate instead the 2g dispersing agent NNO.Yield 98.3%, purity 98.1%.
Embodiment 9:
Use 5kg Trimethylamine 99 30% aqueous solution, 0.5kg4-Dimethylamino pyridine, 5kg poly(oxyethylene glycol) 400 among the embodiment 2 instead 20kg Trimethylamine 99 30% aqueous solution, 2kg18-crown ether-6,5kg cetomacrogol 1000, all the other are constant.Yield 98.1%, content 98.0%.
Embodiment 10:
Use 4.5kg polyoxyethylene octylphenol ether OP-10,3.5kg sodium lauryl sulphate among the embodiment 2 instead 3kg sodium lignosulfonate, 6kg carboxymethyl cellulose, all the other are constant.Yield 98.3%, content 98.1%.
Embodiment 11:
Use the 4.5kg polyoxyethylene octylphenol ether OP-10 among the embodiment 2 instead 0.1kg non-ion fluorin carbon surface active agent FSN-100, all the other are constant.Yield 98.3%, purity 98.1%.
Claims (8)
1, the method for synthetic Chlorpyrifos 94 in a kind of water medium is characterized in that water is dropped in the reactor, stirs to add tensio-active agent, 3 down, 5,6-trichloropyridine-2-sodium alkoxide and O, is scattered in the water emulsification of O-o,o-diethylthiophosphoryl chloride, adds composite catalyst then, and the PH conditioning agent makes the system pH value reach 9～10, react completely decrease temperature crystalline, suction filtration washing in 25～65 ℃ then, drying makes the former medicine finished product of Chlorpyrifos 94.
2, the method for synthetic Chlorpyrifos 94 in the water medium according to claim 1, the consumption that it is characterized in that described tensio-active agent is a reaction raw materials 3,5,6-trichloropyridine-2-sodium alkoxide and O, 0.1～5% of O-o,o-diethylthiophosphoryl chloride total mass.
3, the method for synthetic Chlorpyrifos 94 in the water medium according to claim 1 and 2 is characterized in that described tensio-active agent can be a kind of component or two kinds and the two or more component in anion surfactant, cats product, amphoterics, nonionogenic tenside, polymeric surface active agent or the special surface promoting agent.
4, the method of synthetic Chlorpyrifos 94 in the water medium according to claim 3, it is characterized in that described anion surfactant is selected from calcium dodecylbenzene sulphonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, dispersing agent NNO, dispersing agent CNF, diffusant FM, polyoxyethylenated alcohol sodium sulfate, sulfated castor oil, petroleum sodium sulfonate, sodium dibutyl naphthalene sulfonate, described cats product can be a cetyltrimethylammonium chloride, octadecyl trimethyl ammonium chloride or alkyl dimethyl amine oxide, described amphoterics is a Varion CDG-K, described nonionogenic tenside is a polyoxyethylene octylphenol ether OP series, polyoxyethylene nonylphenol ether NP series, Tween-65, tween-80, polyethers P104, fatty alcohol-polyoxyethylene ether, the benzylphenol Soxylat A 25-7, the styryl phenol polyethenoxy ether, aliphatic amine polyoxyethylene ether, described polymeric surface active agent is a sodium lignosulfonate, calcium lignin sulphonate, carboxymethyl cellulose, described special surface promoting agent is water-soluble silicon oil SF-908, Perfluorocaprylic Acid, non-ion fluorin carbon surface active agent FSN-100.
5, the method of synthetic Chlorpyrifos 94 in the water medium according to claim 1, it is characterized in that the mixture that described composite catalyst is made up of Trimethylamine 99 and phase-transfer catalyst, phase-transfer catalyst wherein can be one or more the composite mixture in the following material: trioctylphosphine methyl ammonium halide, the benzyl trimethyl ammonium halide, the benzyl triethyl ammonium ammonium halide, benzyl tributyl ammonium halide, the dodecyl trimethyl-ammonium halide, dodecyl triethyl ammonium halide, the cetyl trimethyl ammonium halide, hexadecyl triethyl ammonium halide, the tetramethyl-ammonium halide, the tetraethyl-ammonium halide, tetrabutyl ammonium halide, the 4-Dimethylamino pyridine, Macrogol 200, poly(oxyethylene glycol) 400, Polyethylene Glycol-600, polyoxyethylene glycol 800, cetomacrogol 1000, hexaoxacyclooctadecane-6-6,15-crown ether-5 or dibenzo-18-crown-6 (DB18C6), halogen in the described ammonium halide is a chlorine, bromine or iodine, Trimethylamine 99 is in 30% the aqueous solution, consumption is 3,5,1～10% of 6-trichloropyridine-2-sodium alkoxide quality, phase-transfer catalyst is 3,5,0.1～7% of 6-trichloropyridine-2-sodium alkoxide quality.
6, the method for synthetic Chlorpyrifos 94 in the water medium according to claim 1, it is characterized in that reaction raw materials 3,5,6-trichloropyridine-2-sodium alkoxide and O, the mol ratio of O-o,o-diethylthiophosphoryl chloride is 1: 1.0～1.2, WATER AS FLOW MEDIUM and 3,5, the mass ratio of 6-trichloropyridine-2-sodium alkoxide is 1: 0.1～0.35.
7, the method for synthetic Chlorpyrifos 94 in the water medium according to claim 1, the reaction deadline that it is characterized in that described reaction system is 0.25～2 hour.
8, the method for synthetic Chlorpyrifos 94 in the water medium according to claim 1, it is characterized in that described PH conditioning agent adopts one or both mixture solutions formed with arbitrary proportion in yellow soda ash, salt of wormwood, sodium hydroxide or the potassium hydroxide, the solution of potassium carbonate mass concentration is 10～30%, the sodium carbonate solution mass concentration is 10～20%, the potassium hydroxide solution mass concentration is 5～30%, and the sodium hydroxide solution mass concentration is 5～30%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532195A (en) * | 2011-12-23 | 2012-07-04 | 湖北犇星农化有限责任公司 | Method for synthesis of chlorpyrifos |
| CN102977140A (en) * | 2012-11-08 | 2013-03-20 | 安徽国星生物化学有限公司 | Multiple composite catalyst-induced chlorpyrifos preparation method |
| CN102977139A (en) * | 2012-11-08 | 2013-03-20 | 安徽国星生物化学有限公司 | Purification method of chlorpyrifos |
| CN102977138A (en) * | 2012-11-08 | 2013-03-20 | 安徽国星生物化学有限公司 | Method for preparing chlorpyrifos by clean technology |
| CN102993236A (en) * | 2012-06-05 | 2013-03-27 | 湖北仙隆化工股份有限公司 | Synthesizing method of active compound of chlorpyrifos |
| CN102993237A (en) * | 2012-12-12 | 2013-03-27 | 江苏琦衡农化科技有限公司 | Aqueous-phase synthesis method of chlorpyrifos by using trichloro-acetic chloride as initial material |
| CN107216351A (en) * | 2017-08-09 | 2017-09-29 | 重庆华歌生物化学有限公司 | Chlopyrifos and preparation method thereof |
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2006
- 2006-05-18 CN CNB2006100441993A patent/CN100420691C/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532195A (en) * | 2011-12-23 | 2012-07-04 | 湖北犇星农化有限责任公司 | Method for synthesis of chlorpyrifos |
| CN102532195B (en) * | 2011-12-23 | 2015-02-04 | 湖北犇星农化有限责任公司 | Method for synthesis of chlorpyrifos |
| CN102993236A (en) * | 2012-06-05 | 2013-03-27 | 湖北仙隆化工股份有限公司 | Synthesizing method of active compound of chlorpyrifos |
| CN102977140A (en) * | 2012-11-08 | 2013-03-20 | 安徽国星生物化学有限公司 | Multiple composite catalyst-induced chlorpyrifos preparation method |
| CN102977139A (en) * | 2012-11-08 | 2013-03-20 | 安徽国星生物化学有限公司 | Purification method of chlorpyrifos |
| CN102977138A (en) * | 2012-11-08 | 2013-03-20 | 安徽国星生物化学有限公司 | Method for preparing chlorpyrifos by clean technology |
| CN102993237A (en) * | 2012-12-12 | 2013-03-27 | 江苏琦衡农化科技有限公司 | Aqueous-phase synthesis method of chlorpyrifos by using trichloro-acetic chloride as initial material |
| CN107216351A (en) * | 2017-08-09 | 2017-09-29 | 重庆华歌生物化学有限公司 | Chlopyrifos and preparation method thereof |
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