CN114685334B - Preparation method of prosulfocarb - Google Patents
Preparation method of prosulfocarb Download PDFInfo
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- CN114685334B CN114685334B CN202011597167.2A CN202011597167A CN114685334B CN 114685334 B CN114685334 B CN 114685334B CN 202011597167 A CN202011597167 A CN 202011597167A CN 114685334 B CN114685334 B CN 114685334B
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- propylamine
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- NQLVQOSNDJXLKG-UHFFFAOYSA-N prosulfocarb Chemical compound CCCN(CCC)C(=O)SCC1=CC=CC=C1 NQLVQOSNDJXLKG-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000005603 Prosulfocarb Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims abstract description 56
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- -1 benzyl halide Chemical class 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000012074 organic phase Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 38
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 25
- 229940073608 benzyl chloride Drugs 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- LRDIEHDJWYRVPT-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC(O)=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 LRDIEHDJWYRVPT-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 5
- NCPDPTXSMJDCIH-UHFFFAOYSA-N dipropylcarbamothioic s-acid Chemical compound CCCN(C(S)=O)CCC NCPDPTXSMJDCIH-UHFFFAOYSA-N 0.000 claims description 5
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- XJTQJERLRPWUGL-UHFFFAOYSA-N iodomethylbenzene Chemical compound ICC1=CC=CC=C1 XJTQJERLRPWUGL-UHFFFAOYSA-N 0.000 claims description 2
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 abstract description 36
- 239000012535 impurity Substances 0.000 abstract description 16
- 239000007788 liquid Substances 0.000 abstract description 13
- 238000010438 heat treatment Methods 0.000 abstract description 9
- 238000009423 ventilation Methods 0.000 abstract description 9
- 238000005406 washing Methods 0.000 abstract description 9
- 230000035484 reaction time Effects 0.000 abstract description 5
- 239000010815 organic waste Substances 0.000 abstract description 4
- 238000004321 preservation Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 239000012043 crude product Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 11
- 238000010813 internal standard method Methods 0.000 description 10
- 238000004821 distillation Methods 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 239000002024 ethyl acetate extract Substances 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 4
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000003810 ethyl acetate extraction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UJXIOVIFPTXDHU-UHFFFAOYSA-N 2-phenylethanethioyl chloride Chemical compound ClC(=S)CC1=CC=CC=C1 UJXIOVIFPTXDHU-UHFFFAOYSA-N 0.000 description 1
- 241001290610 Abildgaardia Species 0.000 description 1
- 235000003826 Artemisia Nutrition 0.000 description 1
- 235000003261 Artemisia vulgaris Nutrition 0.000 description 1
- 240000006891 Artemisia vulgaris Species 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical group NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 241000234653 Cyperus Species 0.000 description 1
- 241000234272 Dioscoreaceae Species 0.000 description 1
- 244000058871 Echinochloa crus-galli Species 0.000 description 1
- 244000025670 Eleusine indica Species 0.000 description 1
- 235000014716 Eleusine indica Nutrition 0.000 description 1
- 241001290564 Fimbristylis Species 0.000 description 1
- 235000014820 Galium aparine Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 1
- 241001236817 Paecilomyces <Clavicipitaceae> Species 0.000 description 1
- 241001268782 Paspalum dilatatum Species 0.000 description 1
- 241000205407 Polygonum Species 0.000 description 1
- 240000009132 Sagittaria sagittifolia Species 0.000 description 1
- 235000010086 Setaria viridis var. viridis Nutrition 0.000 description 1
- 241001330502 Stephania Species 0.000 description 1
- 240000001085 Trapa natans Species 0.000 description 1
- 235000014364 Trapa natans Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000009052 artemisia Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DXHPZXWIPWDXHJ-UHFFFAOYSA-N carbon monosulfide Chemical compound [S+]#[C-] DXHPZXWIPWDXHJ-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 244000230342 green foxtail Species 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PUADMGQHCWUWEM-UHFFFAOYSA-N n-benzylcarbamoyl chloride Chemical compound ClC(=O)NCC1=CC=CC=C1 PUADMGQHCWUWEM-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/02—Monothiocarbamic acids; Derivatives thereof
- C07C333/04—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to hydrogen atoms or to acyclic carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of prosulfocarb, which comprises the following steps: introducing carbon oxysulfide into di-n-propylamine solution, adding benzyl halide after ventilation is finished, carrying out heat preservation reaction after the addition is finished, adding water into the system after the reaction is finished, heating, acidifying, stirring, standing, separating liquid, washing an organic phase twice, and distilling to obtain the prosulfocarb with the purity of more than 98%, the yield of more than 92% and the content of impurity dibenzyldisulfide of less than 0.04%. The preparation method of the invention does not use water or other organic solvents when carrying out the preparation reaction, has simple operation, safety and controllability, short reaction time, high preparation yield, high product purity and low content of impurity dibenzyl disulfide in the product; the unreacted raw material di-n-propylamine can be recycled, so that the organic waste liquid is less, and the treatment capacity and cost of three wastes are reduced.
Description
Technical Field
The invention belongs to the technical field of pesticide preparation, and particularly relates to a method for preparing prosulfocarb.
Background
Prosulfocarb (prosulfocarb), i.e., S-benzyl dipropyl thiocarbamate, is a thiocarbamate selective systemic conduction type soil treatment herbicide. The prosulfocarb is a carbamate herbicide, has an action mechanism of lipid synthesis inhibitor, can be used for weeding in rice transplanting fields and direct seeding fields, and can effectively prevent and remove grassy weeds, cyperaceous weeds and broadleaf weeds, such as grassy barnyard grass, stephania, marsupium, green bristlegrass, paspalum, goosegrass and the like; annual and perennial sedge such as Cyperus, water chestnut, fimbristylis and Florida, broadleaf weeds such as Polygonum syringae, sagittaria, paecilomyces, dioscoreaceae, iris and Artemisia, etc., has special effects on Japanese glossoides.
The methods for preparing prosulfocarb reported at present are mainly divided into two ways, one is to prepare prosulfocarb through amine and sulfur-containing intermediate. For example, US4740623 reports a four-step route for the synthesis of prosulfocarb starting from an amine, namely: 1) Firstly, preparing hydrogen sulfide by reacting concentrated hydrochloric acid with sodium hydrosulfide; 2) The generated hydrogen sulfide reacts with benzyl chloride in the same reactor to obtain benzyl mercaptan; 3) Followed by the reaction of phosgene with benzyl mercaptan to give benzylcarbamoyl chloride; 4) Finally, the benzylthio formyl chloride reacts with di-n-propylamine to prepare the prosulfocarb. The method has complex operation steps, and uses the raw materials such as highly toxic concentrated hydrochloric acid and phosgene which is easy to decompose and escape when preparing the sulfur-containing intermediate, the generated hydrogen sulfide gas is also highly toxic substance, and the benzyl mercaptan intermediate is easy to oxidize and deteriorate, so the preparation method has very high risk and a series of environmental protection and safety problems. Furthermore, the content of the impurity dibenzyldisulfide in the prosulfocarb prepared by the method is 0.3 percent.
Secondly, the prosulfocarb is prepared by using benzyl chloride and thiocarbamate, namely, a synthetic route using benzyl chloride as a raw material, and after amine and carbonyl sulfide are synthesized into thiocarbamate, the thiocarbamate is directly reacted with benzyl chloride to prepare the prosulfocarb.
For example, CN108997181a discloses a process for preparing prosulfocarb, which is to introduce carbonyl sulfide into a mixture of di-n-propylamine and water, and then to drop benzyl chloride to react, and then to process the mixture to obtain prosulfocarb. The method has long reaction time, only the benzyl chloride is dripped for 6 hours, and the method always keeps lower temperature and has high energy consumption. The mass ratio of water in the mixture of di-n-propylamine and water is about 10-15%, the inventor conducts experiments according to the method, and discovers that the content of the impurity dibenzyldisulfide is between 0.25-0.40% (the mass content is the same as the following) through detection of the prepared prosulfocarb, and the impurity is difficult to separate from prosulfocarb so as to be reduced to below 0.20%, so that the prosulfocarb produced according to the process method can not meet the approval requirement that the impurity content in prosulfocarb is registered and sold by the government is not more than 0.20%.
EP0697402A1 discloses a technical method for preparing prosulfocarb, which comprises the steps of introducing carbon oxysulfide into a mixture of di-n-propylamine and water, starting to dropwise add benzyl chloride when the carbon oxysulfide accounts for 30% -60% of the total amount, ending the carbon oxysulfide and benzyl chloride feeding simultaneously, starting to dropwise add alkali solution in the benzyl chloride dropwise process for neutralization reaction to generate HCl, and then processing to obtain prosulfocarb. The method has the advantages of numerous control points, complex operation, accurate and stable control difficulty in industrial production, and difficult stability of the product with good quality. The water accounts for about 42% of the total mass of the mixture of the di-n-propylamine and the water, and the process is applied to continuous industrial production and tends to generate a large amount of wastewater containing organic matters. The prosulfocarb prepared by the method has the dibenzyldisulfide content of about 0.80 percent through detection, so that the prosulfocarb produced by the process method can not meet the approval requirement that the impurity content in prosulfocarb is registered and sold by the government is not more than 0.20 percent.
In view of the above, developing a technique for preparing prosulfocarb with simple operation process, short reaction time, less wastewater, and less than 0.20% of dibenzyldisulfide impurity in prosulfocarb product is still needed in industry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing prosulfocarb, which can effectively solve the problems of complicated operation process, long reaction time, more wastewater and higher content of impurity dibenzyldisulfide in prosulfocarb in the prior art.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of prosulfocarb, which comprises the following steps:
1) Di-n-propylamine reacts with carbonyl sulfide to produce dipropylamiothioformic acid S-acid;
2) The dipropyl amino thiocarboxylic acid S-acid reacts with benzyl halide to obtain prosulfocarb;
the reaction formula is as follows:
the invention provides a preparation method of prosulfocarb, wherein water or an organic solvent is not added in the step 1).
The invention provides a preparation method of prosulfocarb, wherein the mol ratio of di-n-propylamine to carbonyl sulfide in the step 1) is (2.0-2.5): 1, such as 2.0:1, 2.2:1, 2.3:1 or 2.5:1, etc.;
Preferably, the molar ratio of di-n-propylamine to carbonyl sulfide in step 1) is (2.14-2.22): 1, e.g., 2.14:1, 2.15:1, 2.20:1, or 2.22:1, etc.
The invention provides a preparation method of prosulfocarb, wherein the temperature in the step 1) is controlled at 10-20 ℃, and carbon oxysulfide is introduced into a reactor to react with di-n-propylamine within 45min-1 h.
The invention provides a preparation method of prosulfocarb, wherein the purity of raw material carbonyl sulfide in the step 1) is equal to or more than 98% by mass, and the purity of raw material di-n-propylamine is equal to or more than 99% by mass;
Preferably, in the step 1), the purity of the raw material carbonyl sulfide is more than 98% by mass, the purity of the raw material di-n-propylamine is more than 99% by mass, and the mass content of water in the raw material di-n-propylamine is not more than 0.5%.
The invention provides a preparation method of prosulfocarb, wherein benzyl halide used in the step 2) is benzyl chloride, benzyl bromide or benzyl iodide;
Preferably, the benzyl halide used in step 2) is benzyl chloride.
The invention provides a preparation method of prosulfocarb, wherein the molar ratio of the using amount of benzyl halide in the step 2) to the carbon oxysulfide used in the step 1) is 1 (1-1.10), such as 1:1.0, 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, 1:1.08, 1:1.09 or 1:1.10, etc.;
Preferably, the molar ratio of the amount of benzyl halide used in step 2) to the carbon oxysulfide used in step 1) is 1 (1.02-1.10).
The invention provides a preparation method of prosulfocarb, wherein in the step 2), the temperature is controlled to be 25-30 ℃, benzyl halide is added into dipropyl amino thiocarboxylic acid S-acid generated in the step 1) within 40min-1h, and the reaction is finished after the continuous stirring for 3h at 25-30 ℃.
The invention provides a preparation method of prosulfocarb, which comprises the steps of adding water into the obtained mixture after the reaction in the step 2), acidifying at 45-50 ℃ until the pH value is 1-2, standing, separating liquid, washing the obtained organic phase twice at 65-75 ℃, and distilling under reduced pressure to obtain prosulfocarb.
The invention provides a preparation method of prosulfocarb, which comprises the following steps:
1) The temperature is controlled at 10-20 ℃, and carbon oxysulfide is introduced into a reactor to react with di-n-propylamine within 45min-1h to generate dipropylamiothioformic acid S-acid;
2) The temperature is controlled at 25-30 ℃, benzyl halide is added into the dipropyl amino thiocarboxylic acid S-acid generated in the step 1) within 40min-1h, the reaction is finished after the continuous stirring for 3h at 25-30 ℃, then water is added into the mixture, the mixture is acidified to pH value of 1-2 at 45-50 ℃, standing and liquid separation are carried out, and the obtained organic phase is washed twice at 65-75 ℃ and distilled under reduced pressure to obtain the prosulfocarb.
Step 2) judging method of reaction end point: ending the reaction when the mass percentage of the halogenated benzyl in the reaction liquid is lower than 1%; 1% herein means that the percentage of benzyl halide is calculated by area normalization during the liquid chromatography central control analysis. The acid used for acidification is hydrochloric acid, sulfuric acid, phosphoric acid, etc., preferably 20% -32% hydrochloric acid; the temperature of stirring and standing after acidification is 45-50 ℃. The temperature of the organic phase is controlled between 65 ℃ and 75 ℃ during the twice water washing. The organic phase obtained after the twice water washing distillation at the temperature of 115-118 ℃ and the pressure of-0.1 MPa is used for obtaining the prosulfocarb, the purity is more than 98 percent, the yield is more than 92 percent, and the content of the impurity dibenzyldisulfide is less than 0.04 percent.
According to the preparation method of prosulfocarb, ethyl acetate extract liquid obtained by each batch preparation is collected, reduced pressure distillation is carried out to remove ethyl acetate, prosulfocarb is recovered, the content of prosulfocarb recovered can reach 98.5% or more, and the content of dibenzyldisulfide in prosulfocarb recovered is less than 0.04% as measured by a gas chromatography.
According to the preparation method of prosulfocarb, water phases after ethyl acetate extraction are prepared in batches and combined, the pH value is regulated to be 12-13 by using sodium hydroxide solution, standing and layering are carried out, the separated upper layer is a di-n-propylamine crude product, the di-n-propylamine crude product is subjected to caustic soda flake drying and rectification to obtain di-n-propylamine, the water content is lower than 0.5% by a moisture meter, the content reaches 99% by a gas phase internal standard method, and the recovery rate is 95% -96%. The recovered di-n-propylamine can be further used for preparing prosulfocarb.
The inventor unexpectedly discovers through a large number of experiments that the di-n-propylamine and the carbonyl sulfide can smoothly react to generate the dipropylaminosthioformic acid S-acid by only increasing the di-n-propylamine to a proper amount without adding water or an organic solvent in the step 1); and the content of the impurity dibenzyldisulfide in the prosulfocarb obtained by the step 2) is lower than 0.035%, thereby completely meeting the approval requirement of the government that the content of the impurity in prosulfocarb is registered and sold by no more than 0.20%.
Compared with the prior art, the invention has the following beneficial effects:
1. According to the preparation method of prosulfocarb provided by the invention, the content of the impurity dibenzyldisulfide in the prosulfocarb is lower than 0.04%, and the approval requirement of the government on registration and sales of the impurity content in prosulfocarb is completely met; the preparation method has the advantages that the process operation is easy to control, the quality of the obtained product is stable, the yield is high, the purity of the obtained prosulfocarb is more than 98%, the yield is more than 92%, and the content of the impurity dibenzyldisulfide is less than 0.04%.
2. The preparation reaction does not use water or organic solvent, so that the production operation and material consumption are simplified, the whole process is simple to operate, safe and controllable, the preparation reaction time is short, and the product yield in unit time can be improved; this also allows step 1) to be carried out without waste water or organic waste, and these process improvements can ultimately reduce the cost of manufacture per product.
3. The di-n-propylamine which does not participate in the reaction can be recovered, and the recovered di-n-propylamine has high quality, can be recycled, and realizes the full utilization of raw materials, so that the amount of organic waste liquid generated by preparing prosulfocarb by adopting the preparation method is very small, and the treatment cost of the organic waste liquid is low.
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The purity and content of the present invention and the examples below are not particularly limited to mass content.
Drawings
FIG. 1 is a diagram showing the reaction scheme for preparing prosulfocarb according to the present invention.
Detailed Description
Example 1
In this example, prosulfocarb was prepared by the following method, specifically comprising the steps of:
A four-neck flask reaction device with an air duct, a bubbler, a stirring paddle and a thermometer and a tail gas absorbing device of sodium hydroxide solution are built, 99.76g (0.976 mol) (content 99%) of di-n-propylamine is weighed, cooled to 10 ℃, 26.97g (0.440 mol) (content 98%) of carbonyl sulfide is introduced, the ventilation time is 1h, the whole-course temperature is 10-20 ℃, after the ventilation is finished, the system is heated to 25 ℃, 54.98g (0.430 mol) (content 99%) of benzyl chloride is started to be dropwise added for 1h, the whole-course temperature is 25-30 ℃, after the dropwise addition is finished, the sample analysis is carried out after the heat preservation at 25-30 ℃ for 3h, the HPLC analysis benzyl chloride content is 0.5119%, the prosulfocarb content is 93.0803%, and the reaction is finished.
Adding 41.6g of water into the system, heating to 45 ℃, acidifying with 32% hydrochloric acid solution until the pH value is=1.62, stirring at the whole course temperature of 45-50 ℃ and the temperature of 47 ℃, standing, separating liquid, wherein an organic phase is a prosulfocarb crude product, washing the prosulfocarb crude product twice at 65-75 ℃, and carrying out reduced pressure distillation on the washed prosulfocarb crude product for 2h to obtain 102.81g of prosulfocarb, wherein the content of the prosulfocarb is 98.73% by a gas-phase internal standard method, and the yield is: 93.90% by gas chromatography to give a dibenzyldisulphide content of 0.025%. After the water phases separated for 3 times are combined, ethyl acetate is used for extraction, 68.52g of ethyl acetate extract is obtained, and the content of prosulfocarb is detected by a gas phase internal standard method: 4.31%, thus calculating the total yield of the prosulfocarb in the preparation reaction as follows: 96.63% (calculated as benzyl chloride).
Example 2
In this example, prosulfocarb was prepared by the following method, specifically comprising the steps of:
Setting up a four-neck flask reaction device with an air duct, a bubbler, a stirring paddle and a thermometer and a tail gas absorbing device of sodium hydroxide solution, weighing 101.09g (0.989 mol) (content 99%) of di-n-propylamine, cooling to 13 ℃, introducing 27.71g (0.452 mol) (content 98%) of carbonyl sulfide, introducing the carbon sulfide for 50min, heating the system to 25 ℃ after the whole-course ventilation is finished, starting to dropwise add 54.98g (0.430 mol) (content 99%) of benzyl chloride for 1h, heating the system to 25 ℃ after the whole-course ventilation is finished, preserving the temperature at 25-30 ℃ for 3h after the whole-course dropwise addition is finished, sampling and analyzing, wherein the content of benzyl chloride by HPLC analysis is 0.4263%, the content of prosulfocarb is 93.8094%, and the reaction is finished.
Adding 41.6g of water into the system, heating to 45 ℃, acidifying with 32% hydrochloric acid solution until the pH value is=1.46, stirring at the whole course temperature of 45-50 ℃ under the temperature of 46 ℃, standing, separating liquid, wherein an organic phase is a prosulfocarb crude product, washing the prosulfocarb crude product twice at 65-75 ℃, and carrying out reduced pressure distillation on the prosulfocarb crude product after washing for 2h to obtain 102.04g of prosulfocarb, wherein the content of the prosulfocarb is 98.85% by a gas-phase internal standard method, and the yield is: 93.31% and the dibenzyl disulfide content of 0.032% by gas chromatography. After 3 times of water phase combination of the liquid separation, ethyl acetate extraction is carried out, 69.35g of ethyl acetate extract is obtained, and the content of prosulfocarb is detected by a gas phase internal standard method: 5.36%, thus calculating the total yield of the prosulfocarb in the preparation reaction as follows: 96.75% (calculated as benzyl chloride).
Example 3
Setting up a four-neck flask reaction device with an air duct, a bubbler, a stirring paddle and a thermometer and a tail gas absorbing device of sodium hydroxide solution, weighing 103.23g (1.01 mol) (content 99%) of di-n-propylamine, cooling to 13 ℃, introducing 28.81g (0.47 mol) (content 98%) of carbonyl sulfide, introducing the ventilation time to 1h, heating the system to 25 ℃ after the ventilation is finished, starting to dropwise add 54.98g (0.430 mol) (content 99%) of benzyl chloride for 1h, sampling and analyzing after the dropwise adding is finished and preserving the heat for 3h at 25-30 ℃, and performing HPLC analysis to obtain 0.4039% of benzyl chloride content and 93.8831% of prosulfocarb content after the dropwise adding is finished.
Adding 41.6g of water into the system, heating to 45 ℃, acidifying with 32% hydrochloric acid solution until the pH value is=1.55, stirring at the whole course temperature of 45-50 ℃ and the temperature of 49 ℃, standing, separating liquid, wherein an organic phase is a prosulfocarb crude product, washing the prosulfocarb crude product twice at 65-75 ℃, and carrying out reduced pressure distillation on the washed prosulfocarb crude product for 2h to obtain 101.30g of prosulfocarb, wherein the content of the prosulfocarb is 98.79% by a gas-phase internal standard method, and the yield is: 92.58% and 0.030% dibenzyl disulfide content by gas chromatography. After the water phases separated for 3 times are combined, ethyl acetate is used for extraction, 70.03g of ethyl acetate extract is obtained, and the content of prosulfocarb is detected by a gas phase internal standard method: 6.55%, thus calculating the total yield of the prosulfocarb in the preparation reaction as follows: 96.82% (calculated as benzyl chloride).
Collecting ethyl acetate extract obtained by each batch, performing reduced pressure distillation to remove ethyl acetate, and recovering prosulfocarb, wherein the recovered prosulfocarb is as follows: the content can reach 98.5 percent and above, the total yield of the preparation of each batch is calculated to be more than 96 percent, and the content of dibenzyl disulfide measured by gas chromatography is less than 0.04 percent.
Mixing water phases after ethyl acetate extraction in each batch, regulating the pH value to be 12-13 by using a sodium hydroxide solution, standing for layering, separating an upper layer to obtain a di-n-propylamine crude product, drying the di-n-propylamine crude product by caustic soda flakes, rectifying to obtain di-n-propylamine, detecting by a moisture detector, wherein the water content is lower than 0.5%, detecting by a gas-phase internal standard method, the content reaches 99%, and the recovery rate is 95-96%. The recovered di-n-propylamine can be further used for preparing prosulfocarb.
Comparative example 1
In this comparative example, prosulfocarb was prepared by the following method, specifically comprising the steps of:
Setting up a four-neck flask reaction device with an air duct, a bubbler, a stirring paddle and a thermometer and a tail gas absorbing device of sodium hydroxide solution, weighing 101.09g (0.989 mol) (content 99%) of di-n-propylamine, stirring, cooling to 14 ℃, introducing 27.34g (0.446 mol) (content 98%) of carbon oxysulfide, introducing the mixture for 1h, heating the system to 25 ℃ after the whole process of ventilation, starting to dropwise add 54.98g (0.430 mol) (content 99%) of benzyl chloride for 1h, heating the system to 25-30 ℃ after the whole process of ventilation, preserving the temperature at 25-30 ℃ for 3h, sampling and analyzing, and performing HPLC analysis to obtain the benzyl chloride content of 0.7042%, the prosulfocarb content of 92.7981%, and ending the reaction.
After 26.6g of water is added into the system, the temperature is raised to 45 ℃, 32% hydrochloric acid solution is used for acidification until the pH value is=1.56, the whole process temperature is 45-50 ℃, the temperature is controlled to be 48 ℃, the mixture is stirred, the mixture is kept stand, the liquid is separated, the organic phase is the prosulfocarb crude product, the prosulfocarb crude product is washed twice at 65-75 ℃, the prosulfocarb crude product after washing is subjected to reduced pressure distillation for 2 hours, 102.08g of prosulfocarb is obtained, colorless liquid is obtained, the gas phase internal standard method detection content is 98.39 percent, and the yield is: 92.91%, gas chromatography: dibenzyldisulfide: 0.328%. After the water phases separated for 3 times are combined, ethyl acetate is used for extraction, 68.90g of ethyl acetate extract is obtained, and the content of prosulfocarb is detected by a gas phase internal standard method: 4.72%, total yield: 95.92% (calculated as benzyl chloride).
This example illustrates that the same synthesis procedure was used, but when the water content in the amine-water mixture reached about 13%, the dibenzyldisulfide impurity content was higher, far higher than that obtained by the preparation procedure with very low water content (less than 0.5%).
The applicant states that the present invention describes the preparation method of prosulfocarb of the present invention by the above examples, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (8)
1. The preparation method of prosulfocarb is characterized by comprising the following steps:
1) Di-n-propylamine reacts with carbonyl sulfide to produce dipropylamiothioformic acid S-acid;
2) The dipropyl amino thiocarboxylic acid S-acid reacts with benzyl halide to obtain prosulfocarb;
the reaction formula is as follows:
the step 1) is not added with water or organic solvent; the mol ratio of di-n-propylamine to carbonyl sulfide in the step 1) is (2.0-2.5) 1, the temperature is controlled at 10-20 ℃, and the carbonyl sulfide is introduced into a reactor for reacting with di-n-propylamine within 45min-1 h; the molar ratio of the amount of the halogenated benzyl in the step 2) to the carbon oxysulfide used in the step 1) is 1: (1-1.10), controlling the temperature at 25-30 ℃, adding benzyl halide into the dipropyl amino thioformic acid S-acid generated in the step 1) within 40min-1h, and continuing stirring at 25-30 ℃ for 3h to finish the reaction.
2. The method according to claim 1, wherein the molar ratio of di-n-propylamine to carbonyl sulfide in step 1) is (2.14-2.22): 1.
3. The process according to any one of claims 1 to 2, wherein the carbon oxysulfide content of the raw material in step 1) is 98% or more and the di-n-propylamine content of the raw material is 99% or more.
4. The process according to any one of claims 1 to 2, wherein the carbon oxysulfide content of the raw material in step 1) is more than 98%, the di-n-propylamine content of the raw material is more than 99%, and the water content of the raw material di-n-propylamine is not more than 0.5%.
5. The process according to any one of claims 1 to 2, wherein the benzyl halide used in step 2) is benzyl chloride, benzyl bromide or benzyl iodide.
6. The process according to claim 5, wherein the benzyl halide used in step 2) is benzyl chloride.
7. The process according to claim 1, wherein the molar ratio of the amount of benzyl halide used in step 2) to the carbon oxysulfide used in step 1) is 1: (1.02-1.10).
8. The preparation method of claim 1, wherein after the reaction of the step 2), water is added into the obtained mixture, the mixture is acidified to a pH of 1-2 at 45-50 ℃, the mixture is stood and separated, and the obtained organic phase is washed twice at 65-75 ℃ and distilled under reduced pressure to obtain the prosulfocarb.
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| CN108997181A (en) * | 2018-08-28 | 2018-12-14 | 陕西恒润化学工业有限公司 | A kind of prosulfocarb and its synthetic method |
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| EP0697402A1 (en) * | 1994-08-19 | 1996-02-21 | Monsanto Europe S.A./N.V. | Manufacturing process for the production of prosulfocarb |
| CN108997181A (en) * | 2018-08-28 | 2018-12-14 | 陕西恒润化学工业有限公司 | A kind of prosulfocarb and its synthetic method |
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