CN114181120A - Preparation method of p-toluenesulfonyl isocyanate - Google Patents
Preparation method of p-toluenesulfonyl isocyanate Download PDFInfo
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- CN114181120A CN114181120A CN202210131439.2A CN202210131439A CN114181120A CN 114181120 A CN114181120 A CN 114181120A CN 202210131439 A CN202210131439 A CN 202210131439A CN 114181120 A CN114181120 A CN 114181120A
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- chlorobenzene
- toluenesulfonyl isocyanate
- toluenesulfonamide
- dimethyl carbonate
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- VLJQDHDVZJXNQL-UHFFFAOYSA-N 4-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)N=C=O)C=C1 VLJQDHDVZJXNQL-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 p-toluenesulfonamide chlorobenzene Chemical compound 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims abstract description 7
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 6
- 238000007670 refining Methods 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims abstract description 3
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 claims description 17
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 31
- 239000000460 chlorine Substances 0.000 abstract description 31
- 229910052801 chlorine Inorganic materials 0.000 abstract description 31
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000004821 distillation Methods 0.000 abstract description 8
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000012824 chemical production Methods 0.000 abstract description 2
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 2
- 238000003756 stirring Methods 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PAJALBWYDSQWAV-UHFFFAOYSA-N 1-isocyanosulfonyl-4-methylbenzene Chemical compound CC1=CC=C(S(=O)(=O)[N+]#[C-])C=C1 PAJALBWYDSQWAV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- BOVGTQGAOIONJV-BETUJISGSA-N 1-[(3ar,6as)-3,3a,4,5,6,6a-hexahydro-1h-cyclopenta[c]pyrrol-2-yl]-3-(4-methylphenyl)sulfonylurea Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(=O)NN1C[C@H]2CCC[C@H]2C1 BOVGTQGAOIONJV-BETUJISGSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229940100389 Sulfonylurea Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003472 antidiabetic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229960000346 gliclazide Drugs 0.000 description 1
- WIGIZIANZCJQQY-RUCARUNLSA-N glimepiride Chemical compound O=C1C(CC)=C(C)CN1C(=O)NCCC1=CC=C(S(=O)(=O)NC(=O)N[C@@H]2CC[C@@H](C)CC2)C=C1 WIGIZIANZCJQQY-RUCARUNLSA-N 0.000 description 1
- 229960004346 glimepiride Drugs 0.000 description 1
- 229960001381 glipizide Drugs 0.000 description 1
- ZJJXGWJIGJFDTL-UHFFFAOYSA-N glipizide Chemical compound C1=NC(C)=CN=C1C(=O)NCCC1=CC=C(S(=O)(=O)NC(=O)NC2CCCCC2)C=C1 ZJJXGWJIGJFDTL-UHFFFAOYSA-N 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229940126904 hypoglycaemic agent Drugs 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- YROXIXLRRCOBKF-UHFFFAOYSA-N sulfonylurea Chemical class OC(=N)N=S(=O)=O YROXIXLRRCOBKF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 208000001072 type 2 diabetes mellitus Diseases 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of chemical production, and particularly relates to a preparation method of p-toluenesulfonyl isocyanate, which comprises the following steps: (1) chlorination reaction: adding dimethyl carbonate into a reaction kettle, and introducing chlorine; (2) esterification reaction: adding a p-toluenesulfonamide chlorobenzene solution into the reaction kettle, and refluxing at 90-110 ℃; (3) refining: and after the esterification reaction is finished, decompressing the reactant to recover chlorobenzene, and distilling the reactant after recovering the chlorobenzene in high vacuum to obtain the p-toluenesulfonyl isocyanate. The raw materials adopted by the invention do not contain phosgene, the safety is high, the synthesis requirement can be met without high-pressure reaction equipment, the reaction is carried out in an almost anhydrous environment, the p-toluenesulfonyl isocyanate is prevented from undergoing hydrolysis reaction, the product yield reaches more than 95 percent, the product purity can reach more than 98 percent by adopting a distillation method for refining; the reaction solvent has high recovery and utilization rate and almost no process wastewater.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a preparation method of p-toluenesulfonyl isocyanate.
Background
The p-toluenesulfonyl isocyanate is an important organic chemical intermediate, is mainly used as a medical intermediate, is used for synthesizing hypoglycemic agents such as glimepiride, gliclazide, glipizide and the like, and is used for treating type II diabetes. Can be used for synthesizing sulfonylurea herbicides in the field of pesticides.
At present, the domestic production process mostly adopts p-toluenesulfonamide and phosgene for preparation under the conditions of high pressure and high temperature, the adoption of the preparation method has high requirements on equipment, and has the existence of the highly toxic raw material phosgene, so the production safety is poor.
Disclosure of Invention
The invention aims to provide a safe preparation method of p-toluenesulfonyl isocyanate without high pressure and with high product yield and purity, so as to solve the problems in the background technology.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of p-toluenesulfonyl isocyanate comprises the following steps:
(1) chlorination reaction: adding dimethyl carbonate into a reaction kettle, and introducing chlorine gas to carry out chlorination reaction;
(2) esterification reaction: dissolving p-toluenesulfonamide in chlorobenzene to form a p-toluenesulfonamide chlorobenzene solution, adding the p-toluenesulfonamide chlorobenzene solution into the reaction kettle, and carrying out reflux reaction at 90-110 ℃ for 3-5 h;
(3) refining: and after the esterification reaction is finished, decompressing the reaction product to recover chlorobenzene, and distilling the reaction product after recovering the chlorobenzene in high vacuum to obtain the p-toluenesulfonyl isocyanate.
Chlorination reaction:
the dimethyl carbonate reacts with chlorine to produce solid phosgene.
Esterification reaction:
as an improvement, in the step (1), the molar ratio of the dimethyl carbonate to the chlorine gas is 1: 6 to 6.6.
As an improvement, in the step (1), the temperature of the introduced chlorine gas is 30-90 ℃.
As an improvement, in the step (2), the molar ratio of the p-toluenesulfonamide to the dimethyl carbonate is 1: 1 to 1.1.
In the step (3), the pressure for recovering the chlorobenzene under reduced pressure is-0.06 to-0.08 MPa, and the recovery temperature is 90 to 110 ℃.
As an improvement, in the step (3), the recovered chlorobenzene is recycled to the step (2)
As an improvement, in the step (3), the vacuum degree of the high vacuum distillation is less than or equal to-0.095 Mpa.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
according to the preparation method provided by the invention, the carbonyl dimethyl ester is used as a reaction raw material to replace virulent phosgene for synthesis reaction, the safety is high, the synthesis requirement can be met without high-pressure reaction equipment, and the production equipment is simple; the reaction is carried out in an almost anhydrous environment, the p-toluenesulfonyl isocyanate is prevented from undergoing a hydrolysis reaction, the product yield is high, and the product yield reaches more than 95%; the distillation method is adopted for refining, so that the product purity is high and can reach more than 98 percent; the reaction solvent has high recovery and utilization rate and almost no process wastewater.
Drawings
FIG. 1 is a process flow diagram provided by the present invention;
FIG. 2 is a gas chromatogram of a p-toluenesulfonyl isocyanate standard;
FIGS. 3 to 8 are gas chromatograms of samples of p-toluenesulfonyl isocyanate obtained in examples 1 to 6.
Detailed Description
The present invention will be further described with reference to the following detailed description and accompanying drawings.
Example 1
47.76g (content: 99%, 0.525 mol) of dimethyl carbonate is added into a 500ml four-product bottle, 228.14g (content: 99.9%, 3.21 mol, dimethyl carbonate: chlorine = 1: 6.11) of chlorine is introduced into the bottle with stirring, the chlorine is slowly introduced, the temperature is gradually increased along with the reaction, a water bath is added, the temperature is controlled to be 30 ℃, and the chlorine introduction time is about 8 hours.
86.04g of p-toluenesulfonamide (content: 99.5%, 0.5mol, p-toluenesulfonamide: dimethyl carbonate = 1: 1.05) and 86g of chlorobenzene were dissolved with stirring, and added to a constant pressure dropping funnel.
After the chlorine introducing reaction is finished, adding the p-toluenesulfonamide chlorobenzene solution into a four-mouth bottle, stirring and heating to above 90 ℃, controlling the temperature to be 90 ℃ for reaction for 4 hours, sampling and detecting that the raw materials are completely reacted, connecting a condensing tube and a receiving bottle, starting to recover the solvent chlorobenzene, and controlling the vacuum degree to be-0.06 Mpa and the recovery temperature to be 90 ℃.
After the solvent chlorobenzene is recovered, transferring the material into a distillation flask, vacuumizing to be below-0.095 Mpa by using a vacuum pump, and heating and distilling to obtain 96.55 g of p-toluenesulfonyl isocyanate, wherein the detection content is 99.29 percent, and the experimental yield is 97.05 percent.
Example 2
45.49g (content: 99%, 0.5 mol) of dimethyl carbonate is added into a 500ml four-product bottle, 234.53g (content: 99.9%, 3.3mol, dimethyl carbonate: chlorine = 1: 6.6) of chlorine is introduced into the bottle with stirring, the chlorine is slowly introduced, the temperature is gradually increased along with the reaction, a water bath is added, the temperature is controlled to be 40 ℃, and the chlorine introduction time is about 8 hours.
86.04g of p-toluenesulfonamide (content: 99.5%, 0.5mol, p-toluenesulfonamide: dimethyl carbonate = 1: 1) and 86g of chlorobenzene were dissolved with stirring, and added to a constant pressure dropping funnel.
After the chlorine introducing reaction is finished, adding the p-toluenesulfonamide chlorobenzene solution into a four-mouth bottle, stirring and heating to above 90 ℃, controlling the temperature to be 100 ℃ for reaction for 4 hours, sampling and detecting that the raw materials are completely reacted, connecting a condensing tube and a receiving bottle, starting to recover the solvent chlorobenzene, and controlling the vacuum degree to be-0.07 Mpa and the recovery temperature to be 100 ℃.
After the solvent chlorobenzene is recovered, transferring the material into a distillation flask, vacuumizing to be below-0.095 Mpa by using a vacuum pump, heating and distilling to obtain 95.73 g of p-toluenesulfonyl isocyanate, wherein the detection content is 99.39%, and the experimental yield is 95.19%.
Example 3
50.04g (content: 99%, 0.55 mol) of dimethyl carbonate is added into a 500ml four-product bottle, 232.53g (content: 99.9%, 3.3mol, dimethyl carbonate: chlorine = 1: 6) of chlorine is introduced into the bottle with stirring, the chlorine is slowly introduced, the temperature is gradually increased along with the reaction, a water bath is added, the temperature is controlled at 50 ℃, and the chlorine introduction time is finished for about 8 hours.
86.04g of p-toluenesulfonamide (content: 99.5%, 0.5mol, p-toluenesulfonamide: dimethyl carbonate = 1: 1.1) and 86g of chlorobenzene were dissolved with stirring, and added to a constant pressure dropping funnel.
After the chlorine introducing reaction is finished, adding the p-toluenesulfonamide chlorobenzene solution into a four-mouth bottle, stirring and heating to above 90 ℃, controlling the temperature to be 105 ℃ for reaction for 4 hours, sampling and detecting that the raw materials are completely reacted, connecting a condensing tube and a receiving bottle, starting to recover the solvent chlorobenzene, and controlling the vacuum degree to be-0.08 Mpa and the recovery temperature to be 105 ℃.
After the solvent chlorobenzene is recovered, transferring the material into a distillation flask, vacuumizing to below-0.095 Mpa by using a vacuum pump, heating and distilling to obtain 97.73 g of p-toluenesulfonyl isocyanate, wherein the detection content is 99.19 percent, and the experimental yield is 98.33 percent.
Example 4
46.85g (content: 99%, 0.515 mol) of dimethyl carbonate is added into a 500ml four-product bottle, 230.59g (content: 99.9%, 3.244mol, dimethyl carbonate: chlorine = 1: 6.3) of chlorine is introduced into the bottle with stirring, the chlorine is slowly introduced, the temperature is gradually increased along with the reaction, a water bath is added, the temperature is controlled to be 60 ℃, and the chlorine introduction time is about 8 hours.
86.04g of p-toluenesulfonamide (content: 99.5%, 0.5mol, p-toluenesulfonamide: dimethyl carbonate = 1: 1.03) and 86g of chlorobenzene were dissolved with stirring, and added to a constant pressure dropping funnel.
After the chlorine introducing reaction is finished, adding the p-toluenesulfonamide chlorobenzene solution into a four-mouth bottle, stirring and heating to above 90 ℃, controlling the temperature to be 110 ℃ for reaction for 4 hours, sampling and detecting that the raw materials are completely reacted, connecting a condensing tube and a receiving bottle, starting to recover the solvent chlorobenzene, and controlling the vacuum degree to be-0.08 Mpa and the recovery temperature to be 110 ℃.
After the solvent chlorobenzene is recovered, transferring the material into a distillation flask, vacuumizing to below-0.095 Mpa by using a vacuum pump, heating and distilling to obtain 98.01 g of p-toluenesulfonyl isocyanate, wherein the detection content is 99.06%, and the experimental yield is 97.85%.
Example 5
48.67g (content: 99%, 0.535 mol) of dimethyl carbonate was put into a 500ml four-product bottle, 239.55g (content: 99.9%, 3.371mol, dimethyl carbonate: chlorine = 1: 6.3) of chlorine was introduced with stirring, the mixture was slowly introduced, the temperature was gradually increased with the reaction, a water bath was added, the temperature was controlled at 80 ℃, and the chlorine introduction time was completed for about 8 hours.
86.04g of p-toluenesulfonamide (content: 99.5%, 0.5mol, p-toluenesulfonamide: dimethyl carbonate = 1: 1.07) and 86g of chlorobenzene were dissolved with stirring, and added to a constant-pressure dropping funnel.
After the chlorine introducing reaction is finished, adding the p-toluenesulfonamide chlorobenzene solution into a four-mouth bottle, stirring and heating to above 90 ℃, controlling the temperature to be 100 ℃ for reaction for 4 hours, sampling and detecting that the raw materials are completely reacted, connecting a condensing tube and a receiving bottle, starting to recover the solvent chlorobenzene, and controlling the vacuum degree to be-0.06 Mpa and the recovery temperature to be 100 ℃.
After the solvent chlorobenzene is recovered, transferring the material into a distillation flask, vacuumizing to below-0.095 Mpa by using a vacuum pump, heating and distilling to obtain 97.66 g of p-toluenesulfonyl isocyanate, wherein the detection content is 99.08 percent, and the experimental yield is 97.88 percent.
Example 6
47.76g (content: 99%, 0.525 mol) of dimethyl carbonate is added into a 500ml four-product bottle, 231.34g (content: 99.9%, 3.355mol, dimethyl carbonate: chlorine = 1: 6.2) of chlorine is introduced into the bottle with stirring, the chlorine is slowly introduced, the temperature is gradually increased along with the reaction, a water bath is added, the temperature is controlled to be 90 ℃, and the chlorine introduction time is about 8 hours.
86.04g of p-toluenesulfonamide (content: 99.5%, 0.5mol, p-toluenesulfonamide: dimethyl carbonate = 1: 1.07) and 86g of chlorobenzene were dissolved with stirring, and added to a constant-pressure dropping funnel.
After the chlorine introducing reaction is finished, adding the p-toluenesulfonamide chlorobenzene solution into a four-mouth bottle, stirring and heating to above 90 ℃, controlling the temperature to be 95 ℃ for reaction for 4 hours, sampling and detecting that the raw materials are completely reacted, connecting a condensing tube and a receiving bottle, starting to recover the solvent chlorobenzene, and controlling the vacuum degree to be-0.06 Mpa and the recovery temperature to be 95 ℃.
After the solvent chlorobenzene is recovered, transferring the material into a distillation flask, vacuumizing to be below-0.095 Mpa by a vacuum pump, heating and distilling to obtain 96.99 g of p-toluenesulfonyl isocyanate, wherein the detection content is 99.38%, and the experimental yield is 97.39%.
The p-toluenesulfonyl isocyanate samples prepared in the above examples 1 to 6 were taken and tested by gas chromatography:
1. pretreatment of samples
Preparing a sample: according to the formula of p-toluenesulfonic acid isonitrile: acetone = 1: dissolving by 30 volume ratio, filtering by using an organic filter membrane of 0.45 mu m after dissolving, and then injecting a sample;
preparing a standard substance: according to the standard product of p-toluenesulfonic acid isonitrile ester: acetone = 1: dissolving the mixture by 30 volume ratio, filtering the dissolved mixture by using a 0.45 mu m organic filter membrane, and then injecting a sample.
2. Gas chromatography conditions:
a detector: hydrogen flame ionization detector, chromatographic column: capillary column, ae.ov-1701, 30m 0.25mm 0.25 μm, injection port temperature: 250 ℃, carrier gas: high purity (99.999%) nitrogen, carrier gas flow 0.9ml/min, calibration: 0.3ul, temperature programming: the initial temperature is 150 ℃, the temperature is kept for 3.0min, the temperature is raised to 280 ℃ at the speed of 15 ℃/min, and the holding time is 30 min.
3. Establishment of fingerprint and result analysis
Analyzing and recording the gas fingerprint chromatogram of the p-toluenesulfonic acid isonitrile acid ester sample and the standard substance by using gas chromatography workstation software, and calculating the relative content of each chromatographic peak by adopting an area normalization method.
The specific results are shown in FIGS. 2-8.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (7)
1. A preparation method of p-toluenesulfonyl isocyanate is characterized by comprising the following steps:
(1) chlorination reaction: adding dimethyl carbonate into a reaction kettle, and introducing chlorine gas to carry out chlorination reaction;
(2) esterification reaction: dissolving p-toluenesulfonamide in chlorobenzene to form a p-toluenesulfonamide chlorobenzene solution, adding the p-toluenesulfonamide chlorobenzene solution into the reaction kettle, and carrying out reflux reaction at 90-110 ℃ for 3-5 h;
(3) refining: and after the esterification reaction is finished, decompressing the reaction product to recover chlorobenzene, and distilling the reaction product after recovering the chlorobenzene in high vacuum to obtain the p-toluenesulfonyl isocyanate.
2. The method for preparing p-toluenesulfonyl isocyanate according to claim 1, wherein in step (1), the molar ratio of the dimethyl carbonate to the chlorine gas is 1: 6 to 6.6.
3. The method for preparing p-toluenesulfonyl isocyanate according to claim 1, wherein the temperature of introducing said chlorine gas in step (1) is 30 to 90 ℃.
4. The method for producing p-toluenesulfonyl isocyanate according to claim 1, wherein in step (2), the molar ratio of the p-toluenesulfonamide to the dimethyl carbonate is 1: 1 to 1.1.
5. The method for preparing p-toluenesulfonyl isocyanate according to claim 1, wherein in the step (3), the pressure for recovering chlorobenzene under reduced pressure is-0.06 to-0.08 Mpa, and the recovery temperature is 90 to 110 ℃.
6. The process for producing p-toluenesulfonyl isocyanate according to claim 1, wherein in step (3), the recovered chlorobenzene is fed back to step (2).
7. The process for producing p-toluenesulfonyl isocyanate according to claim 1, wherein in the step (3), the degree of vacuum of said high vacuum distillation is not more than-0.095 MPa.
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| WO2024200331A3 (en) * | 2023-03-29 | 2024-11-21 | Bayer Aktiengesellschaft | Method for producing methyl-4-isocyanatosulfonyl-5-methyl-thiophene-3-carboxylate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024200331A3 (en) * | 2023-03-29 | 2024-11-21 | Bayer Aktiengesellschaft | Method for producing methyl-4-isocyanatosulfonyl-5-methyl-thiophene-3-carboxylate |
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