CN113402549B - Preparation method of glyphosate raw medicine - Google Patents
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- CN113402549B CN113402549B CN202110795055.6A CN202110795055A CN113402549B CN 113402549 B CN113402549 B CN 113402549B CN 202110795055 A CN202110795055 A CN 202110795055A CN 113402549 B CN113402549 B CN 113402549B
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- 239000005562 Glyphosate Substances 0.000 title claims abstract description 32
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 32
- 239000003814 drug Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 42
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 28
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 26
- 239000010452 phosphate Substances 0.000 claims abstract description 26
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 18
- 230000007062 hydrolysis Effects 0.000 claims abstract description 16
- 239000004471 Glycine Substances 0.000 claims abstract description 13
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940050176 methyl chloride Drugs 0.000 claims abstract description 12
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 238000007259 addition reaction Methods 0.000 claims abstract description 7
- 238000006482 condensation reaction Methods 0.000 claims abstract description 7
- 239000000498 cooling water Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000011084 recovery Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 22
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 19
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 19
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 19
- 239000013067 intermediate product Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 10
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 10
- 229930195729 fatty acid Natural products 0.000 claims description 10
- 239000000194 fatty acid Substances 0.000 claims description 10
- 150000004665 fatty acids Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 206010024769 Local reaction Diseases 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 9
- 241000196324 Embryophyta Species 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- CRFICXGOVSUJNA-UHFFFAOYSA-N 2-aminoacetic acid;phosphorous acid Chemical compound OP(O)O.NCC(O)=O CRFICXGOVSUJNA-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- GEVWHIDSUOMVRI-UHFFFAOYSA-N anisatin Chemical compound CC1(O)C(OC(=O)C2O)CC22C(C)CC(O)C2(O)C21COC2=O GEVWHIDSUOMVRI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002420 orchard Substances 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000001243 protein synthesis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 230000014616 translation Effects 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The invention discloses a preparation method of glyphosate raw medicine, which belongs to the technical field of fine chemical product synthesis, and the synthesis process comprises the following steps: firstly, adding methanol, triethylamine, paraformaldehyde and glycine into a synthesis kettle for addition reaction; secondly, adding dimethyl phosphite, and carrying out condensation reaction at 50-60 ℃ for 1-1.5 h; transferring the glyphosate into a hydrolysis kettle after the reaction is finished, introducing cooling water into a jacket, dropwise adding hydrochloric acid, adding a phosphate amphoteric surfactant, and preserving heat for 1h at 50-60 ℃ to obtain a glyphosate raw material, condensing methyl chloride generated in the hydrolysis process, introducing the condensed liquid into a methyl chloride production device, and introducing the condensed liquid into a methylal recovery process; according to the invention, the phosphate amphoteric surfactant is added in the synthesis of glyphosate, so that the reaction is milder, the local reaction is prevented from being too fast to a certain extent, black materials are formed, side reactions are caused, and the yield and purity are further improved.
Description
Technical Field
The invention belongs to the technical field of synthesis of fine chemical products, and relates to a preparation method of glyphosate raw medicine.
Background
Glyphosate is a non-selective, residue-free, biocidal herbicide, very effective against many years of rooting weeds, widely used in rubber, mulberry, tea, orchards and sugarcane fields. Mainly inhibit enolpyruvylshikimin phosphate synthase in plants, thereby inhibiting the conversion of shikimin into phenylalanine, tyrosine and tryptophan, and interfering protein synthesis, leading to death of plants. Glyphosate is absorbed by the stems and leaves and then transmitted to all parts of plants, and can prevent and kill more than 40 families of plants such as monocotyledonous and dicotyledonous plants, annual and perennial plants, herbaceous plants, shrubs and the like. Glyphosate is quickly combined with metal ions such as iron, aluminum and the like to lose activity after being buried in soil. The hydrolysis process of glyphosate comprises the following steps: adding the metered methanol, triethylamine and paraformaldehyde into a synthesis kettle, and then adding the mixture into an glycine synthesis kettle for addition reaction; then slowly adding dimethyl phosphite, and carrying out condensation reaction at 50 ℃ for 1-1.5h; after the reaction is finished, transferring the mixture into a hydrolysis kettle, introducing cooling water into a jacket, dropwise adding hydrochloric acid, preserving heat for 1h at 50 ℃, condensing chloromethane generated in the hydrolysis process, removing the chloromethane production device, and recovering condensate, namely the noracetal; the process has low production efficiency and low product yield, and a large amount of wastewater is generated in the production process, so that the labor intensity is high.
According to the thermochemical theory, the hydrolysis reaction of the glyphosate is an endothermic reaction, the concentration of hydrochloric acid participating in the hydrolysis reaction is not too high, and black materials are easily produced due to the too high concentration of the hydrochloric acid; the acid concentration is increased, the reaction speed is increased by times, a great amount of heat is instantaneously released, the temperature and the pressure in the kettle rise too quickly, and the control is difficult.
Disclosure of Invention
The invention aims to provide a preparation method of glyphosate raw medicine, which solves the problem of too fast local reaction in the background technology.
The aim of the invention can be achieved by the following technical scheme:
A preparation method of glyphosate raw medicine comprises the following steps:
Step A1, adding methanol, triethylamine, paraformaldehyde and glycine into a synthesis kettle for addition reaction, then adding dimethyl phosphite, and carrying out condensation reaction at 50 ℃ for 1-1.5h to obtain an intermediate product;
And A2, after the reaction is finished, transferring the mixture into a hydrolysis kettle, introducing cooling water into a jacket, dropwise adding a hydrochloric acid solution with the mass fraction of 20% into an intermediate product, adding a phosphate amphoteric surfactant, preserving the heat for 1h at 50 ℃ to obtain a glyphosate raw material, condensing methyl chloride generated in the hydrolysis process, flowing into a methyl chloride production device, and allowing condensate to enter a methylal recovery process.
Further, the mass ratio of the methanol, the triethylamine, the paraformaldehyde, the glycine and the dimethyl phosphite in the step A1 is 1:4.3:4.1:4.9:2.2.
Further, the mass ratio of the intermediate product, the hydrochloric acid solution and the phosphate amphoteric surfactant in the step A2 is 1.2-1.5:100:9-11.
Wherein the phosphate amphoteric surfactant is prepared by the following steps:
Step S11, weighing a sodium dihydrogen phosphate aqueous solution with the mass fraction of 40-50% prepared in advance, adding the sodium dihydrogen phosphate aqueous solution into a three-neck flask, taking epoxy chloropropane, placing the epoxy chloropropane into a constant pressure dropping funnel, adopting mechanical stirring, heating an oil bath to 105-110 ℃, dropwise adding the epoxy chloropropane, controlling the dropwise adding to be completed within 1 hour, reacting for 4 hours, removing solvent water by rotary evaporation after the reaction is completed, dissolving a product by ethanol, removing excessive sodium dihydrogen phosphate, recrystallizing a crude product by ethyl acetate and ethanol for 3-4 times, and vacuum drying at 40 ℃ for 12 hours to obtain an intermediate 1;
The reaction process is as follows:
Step S12, adding fatty acid into a three-neck flask, introducing nitrogen, heating to 120-130 ℃, slowly dropwise adding N, N-dimethyl-1, 3-propanediamine by using a constant pressure dropping funnel, controlling the dropwise adding to be completed within half an hour, separating water generated by the reaction by using a water separator, continuing the reaction at 150 ℃ for 8 hours, performing reduced pressure distillation after the reaction is completed to obtain a light yellow crude product, recrystallizing with petroleum ether for 3-4 times, and performing vacuum drying at 40-50 ℃ for 4 hours to obtain an intermediate 2;
The reaction process is as follows:
Step S13, adding the intermediate 1, the intermediate 2 and an ethanol solution with the mass fraction of 25% into a three-neck flask, and reacting for 8 hours at the temperature of 85 ℃ to obtain the phosphate amphoteric surfactant.
The reaction process is as follows:
Further, in step S11, the molar ratio of sodium dihydrogen phosphate to epichlorohydrin is 1:1.2.
Further, in step S12, the molar ratio of N, N-dimethyl-1, 3-propanediamine to fatty acid is 1:1.15.
Further, in step S13, the mass ratio of intermediate 2, intermediate 1, and the ethanol solution is 1:1:15.4-20.2.
The invention has the beneficial effects that:
1) According to the invention, the phosphate amphoteric surfactant is added in the synthetic hydrolysis of the glyphosate, and after the phosphate amphoteric surfactant is added, a relatively uniform environment can be formed, so that the reaction is milder, and the occurrence of side reactions caused by too fast local reaction is prevented to a certain extent; in addition, the bubbles generated in the reaction process form a small reaction environment, so that the reaction efficiency is improved, and the yield and purity are further improved.
2) The structure of the phosphate amphoteric surfactant prepared by the invention contains a phosphoric acid structure, has good heat stability and good temperature resistance in the later use process, and the structure contains phosphate groups and has excellent alkali resistance.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of phosphate amphoteric surfactant:
Step S11, weighing a sodium dihydrogen phosphate aqueous solution with the mass fraction of 40% prepared in advance, adding the sodium dihydrogen phosphate aqueous solution into a three-neck flask, taking epoxy chloropropane, placing the epoxy chloropropane into a constant-pressure dropping funnel, adopting mechanical stirring, heating an oil bath to 105 ℃, dropwise adding the epoxy chloropropane, controlling the dropwise adding to be completed within 1h, reacting for 4h, after the reaction is finished, removing solvent water by rotary evaporation, dissolving a product by ethanol, removing excessive sodium dihydrogen phosphate, recrystallizing a crude product by ethyl acetate and ethanol for 3 times, and vacuum drying at 40 ℃ for 12h to obtain an intermediate 1, wherein the molar ratio of the sodium dihydrogen phosphate to the epoxy chloropropane is 1:1.2;
Step S12, adding fatty acid into a three-neck flask, introducing nitrogen, heating to 120 ℃, slowly dropwise adding N, N-dimethyl-1, 3-propanediamine by using a constant pressure dropping funnel, controlling the dropwise adding to be completed within half an hour, separating water generated by the reaction by using a water separator, continuing the reaction at 150 ℃ for 8 hours, distilling under reduced pressure to obtain a light yellow crude product after the reaction is completed, recrystallizing with petroleum ether for 3 times, and vacuum-drying at 40 ℃ for 4 hours to obtain an intermediate 2, wherein the molar ratio of N, N-dimethyl-1, 3-propanediamine to fatty acid is 1:1.15;
step S13, adding the intermediate 1, the intermediate 2 and an ethanol solution with the mass fraction of 25% into a three-neck flask, and reacting for 8 hours at the temperature of 85 ℃ to obtain the phosphate amphoteric surfactant, wherein the mass ratio of the intermediate 2 to the intermediate 1 to the ethanol solution is 1:1:15.4.
Example 2
Preparation of phosphate amphoteric surfactant:
Step S11, weighing a sodium dihydrogen phosphate aqueous solution with the mass fraction of 45% prepared in advance, adding the sodium dihydrogen phosphate aqueous solution into a three-neck flask, taking epoxy chloropropane, placing the epoxy chloropropane into a constant pressure dropping funnel, adopting mechanical stirring, heating an oil bath to 108 ℃, dropwise adding the epoxy chloropropane, controlling the dropwise adding to be completed within 1h, reacting for 4h, removing solvent water by rotary evaporation after the reaction is finished, dissolving a product by ethanol, removing excessive sodium dihydrogen phosphate, recrystallizing a crude product by ethyl acetate and ethanol for 3 times, and vacuum drying at 40 ℃ for 12h to obtain an intermediate 1, wherein the molar ratio of the sodium dihydrogen phosphate to the epoxy chloropropane is 1:1.2;
Step S12, adding fatty acid into a three-neck flask, introducing nitrogen, heating to 125 ℃, slowly dropwise adding N, N-dimethyl-1, 3-propanediamine by using a constant pressure dropping funnel, controlling the dropwise adding to be completed within half an hour, separating water generated by the reaction by using a water separator, continuing the reaction at 150 ℃ for 8 hours, distilling under reduced pressure to obtain a light yellow crude product after the reaction is completed, recrystallizing with petroleum ether for 3 times, and vacuum-drying at 45 ℃ for 4 hours to obtain an intermediate 2, wherein the molar ratio of N, N-dimethyl-1, 3-propanediamine to fatty acid is 1:1.15;
Step S13, adding the intermediate 1, the intermediate 2 and an ethanol solution with the mass fraction of 25% into a three-neck flask, and reacting for 8 hours at the temperature of 85 ℃ to obtain the phosphate amphoteric surfactant, wherein the mass ratio of the intermediate 2 to the intermediate 1 to the ethanol solution is 1:1:18.2.
Example 3
Preparation of phosphate amphoteric surfactant:
Step S11, weighing a sodium dihydrogen phosphate aqueous solution with the mass fraction of 50% prepared in advance, adding the sodium dihydrogen phosphate aqueous solution into a three-neck flask, taking epoxy chloropropane, placing the epoxy chloropropane into a constant pressure dropping funnel, adopting mechanical stirring, heating an oil bath to 110 ℃, dropwise adding the epoxy chloropropane, controlling the dropwise adding to be completed within 1h, reacting for 4h, removing solvent water by rotary evaporation after the reaction is finished, dissolving a product by ethanol, removing excessive sodium dihydrogen phosphate, recrystallizing a crude product by ethyl acetate and ethanol for 4 times, and vacuum drying at 40 ℃ for 12h to obtain an intermediate 1, wherein the molar ratio of the sodium dihydrogen phosphate to the epoxy chloropropane is 1:1.2;
step S12, adding fatty acid into a three-neck flask, introducing nitrogen, heating to 130 ℃, slowly dropwise adding N, N-dimethyl-1, 3-propanediamine by using a constant pressure dropping funnel, controlling the completion of dropwise adding within half an hour, separating water generated by the reaction by using a water separator, continuing the reaction at 150 ℃ for 8 hours, distilling under reduced pressure to obtain a light yellow crude product after the reaction is finished, recrystallizing for 4 times by using petroleum ether, and drying in vacuum for 4 hours at 50 ℃ to obtain an intermediate 2, wherein the molar ratio of N, N-dimethyl-1, 3-propanediamine to fatty acid is 1:1.15;
step S13, adding the intermediate 1, the intermediate 2 and an ethanol solution with the mass fraction of 25% into a three-neck flask, and reacting for 8 hours at the temperature of 85 ℃ to obtain the phosphate amphoteric surfactant, wherein the mass ratio of the intermediate 2 to the intermediate 1 to the ethanol solution is 1:1:20.2.
Example 4
A preparation method of glyphosate raw medicine comprises the following steps:
Step A1, adding methanol, triethylamine, paraformaldehyde and glycine into a synthesis kettle for addition reaction, then adding dimethyl phosphite, and performing condensation reaction at 50 ℃ for 1h to obtain an intermediate product, wherein the mass ratio of the methanol to the triethylamine to the paraformaldehyde to the glycine to the dimethyl phosphite is 1:4.3:4.1:4.9:2.2;
Step A2, after the reaction is finished, transferring the mixture into a hydrolysis kettle, introducing cooling water into a jacket, dropwise adding hydrochloric acid solution with the mass fraction of 20% into an intermediate product, adding the phosphate amphoteric surfactant prepared in the example 1, and preserving the temperature at 50 ℃ for 1h to obtain a glyphosate raw material, wherein methyl chloride generated in the hydrolysis process is condensed and then removed from a methyl chloride production device, condensate is removed from methylal, and the mass ratio of the intermediate product, the hydrochloric acid solution and the phosphate amphoteric surfactant is 1.2:100:9.
Example 5
A preparation method of glyphosate raw medicine comprises the following steps:
Step A1, adding methanol, triethylamine, paraformaldehyde and glycine into a synthesis kettle for addition reaction, then adding dimethyl phosphite, and performing condensation reaction at 50 ℃ for 1h to obtain an intermediate product, wherein the mass ratio of the methanol to the triethylamine to the paraformaldehyde to the glycine to the dimethyl phosphite is 1:4.3:4.1:4.9:2.2;
step A2, after the reaction is finished, transferring the mixture into a hydrolysis kettle, introducing cooling water into a jacket, dropwise adding hydrochloric acid solution with the mass fraction of 20% into an intermediate product, adding the phosphate amphoteric surfactant prepared in the example 2, and preserving the temperature at 50 ℃ for 1h to obtain a glyphosate raw material, wherein methyl chloride generated in the hydrolysis process is condensed and then removed from a methyl chloride production device, condensate is removed from methylal, and the mass ratio of the intermediate product, the hydrochloric acid solution and the phosphate amphoteric surfactant is 1.3:100:10.
Example 6
A preparation method of glyphosate raw medicine comprises the following steps:
Step A1, adding methanol, triethylamine, paraformaldehyde and glycine into a synthesis kettle for addition reaction, then adding dimethyl phosphite, and carrying out condensation reaction for 1.5 hours at 50 ℃ to obtain an intermediate product, wherein the mass ratio of the methanol to the triethylamine to the paraformaldehyde to the glycine to the dimethyl phosphite is 1:4.3:4.1:4.9:2.2;
Step A2, after the reaction is finished, transferring the mixture into a hydrolysis kettle, introducing cooling water into a jacket, dropwise adding hydrochloric acid solution with the mass fraction of 20% into an intermediate product, adding the phosphate amphoteric surfactant prepared in the example 3, and preserving the temperature at 50 ℃ for 1h to obtain a glyphosate raw material, wherein methyl chloride generated in the hydrolysis process is condensed and then removed from a methyl chloride production device, condensate is removed from methylal, and the mass ratio of the intermediate product, the hydrochloric acid solution and the phosphate amphoteric surfactant is 1.5:100:11.
Comparative example 1
75G glycine and 160g phosphorous acid are dissolved in 400g methanol and stirred at normal temperature for 60min for later use. Putting 246g of formaldehyde with the mass fraction of 36.5%, 98g of sulfuric acid with the mass fraction of 50% and 600g of methanol into a high-pressure reaction kettle, heating to 70-75 ℃ while stirring, slowly adding glycine-phosphorous acid solution, sealing the reaction kettle after the addition, slowly heating to 180 ℃, controlling the pressure to 10MPa for reaction for 10 hours, cooling after the heat preservation is finished, adding a small amount of liquid alkali, regulating the pH of the system to 1-1.5, and obtaining 138.1g of glyphosate raw medicine by mass solid precipitation.
The glyphosate crude drugs obtained in examples 4-6 and comparative example 1 were tested for yield and purity, and the test results are shown in Table 1:
TABLE 1
| Project | Example 4 | Example 5 | Example 6 | Comparative example 1 |
| Yield% | 93.21 | 93.91 | 92.86 | 78.8 |
| Purity% | 99.46 | 99.65 | 99.57 | 95.1 |
As can be seen from Table 1, the yields of the glyphosate raw materials prepared in examples 4-6 were 92.86-93.91% and the purity was 99% as compared to comparative example 1.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (6)
1. The preparation method of the glyphosate raw medicine is characterized by comprising the following preparation steps:
Step A1, adding methanol, triethylamine, paraformaldehyde and glycine into a synthesis kettle for addition reaction, then adding dimethyl phosphite, and carrying out condensation reaction at 50 ℃ for 1-1.5h to obtain an intermediate product;
Step A2, after the reaction is finished, transferring the mixture into a hydrolysis kettle, introducing cooling water into a jacket, dropwise adding a hydrochloric acid solution with the mass fraction of 20% into an intermediate product, adding a phosphate amphoteric surfactant, preserving the heat for 1h at 50 ℃ to obtain a glyphosate raw material, condensing methyl chloride generated in the hydrolysis process, flowing into a methyl chloride production device, and allowing condensate to enter a methylal recovery process;
Wherein the phosphate amphoteric surfactant is prepared by the following steps:
step S11, reacting sodium dihydrogen phosphate aqueous solution with epichlorohydrin at 105-110 ℃ for 4 hours, removing solvent water by rotary evaporation, dissolving the product with ethanol, and then recrystallizing and drying to obtain an intermediate 1;
Step S12, adding fatty acid into a three-neck flask, introducing nitrogen, heating to 120-130 ℃, adding N, N-dimethyl-1, 3-propanediamine, reacting for 8 hours at 150 ℃, carrying out reduced pressure distillation, recrystallizing for 3-4 times with petroleum ether, and drying to obtain an intermediate 2;
Step S13, adding the intermediate 1, the intermediate 2 and the ethanol solution into a three-neck flask, and reacting for 8 hours at the temperature of 85 ℃ to obtain the phosphate amphoteric surfactant.
2. The method for preparing glyphosate raw medicine according to claim 1, wherein the method comprises the following steps: the mass ratio of methanol, triethylamine, paraformaldehyde, glycine and dimethyl phosphite is 1:4.3:4.1:4.9:2.2.
3. The method for preparing glyphosate raw medicine according to claim 1, wherein the method comprises the following steps: the mass ratio of the intermediate product to the hydrochloric acid solution to the phosphate amphoteric surfactant is 1.2-1.5:100:9-11.
4. The method for preparing glyphosate raw medicine according to claim 1, wherein the method comprises the following steps: in the step S11, the mass fraction of the sodium dihydrogen phosphate aqueous solution is 40-50%, and the molar ratio of the sodium dihydrogen phosphate to the epichlorohydrin is 1:1.2.
5. The method for preparing glyphosate raw medicine according to claim 1, wherein the method comprises the following steps: in the step S12, the molar ratio of N, N-dimethyl-1, 3-propylene diamine to fatty acid is 1:1.15.
6. The method for preparing glyphosate raw medicine according to claim 1, wherein the method comprises the following steps: in the step S13, the mass ratio of the intermediate 2 to the intermediate 1 to the ethanol solution is 1:1:15.4-20.2.
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