CN114014817A - Synthesis method of mesityl-2-sulfonyl triazole - Google Patents
Synthesis method of mesityl-2-sulfonyl triazole Download PDFInfo
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- CN114014817A CN114014817A CN202111625373.4A CN202111625373A CN114014817A CN 114014817 A CN114014817 A CN 114014817A CN 202111625373 A CN202111625373 A CN 202111625373A CN 114014817 A CN114014817 A CN 114014817A
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- 238000001308 synthesis method Methods 0.000 title description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 20
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010189 synthetic method Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 229940126062 Compound A Drugs 0.000 claims description 9
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- 235000010288 sodium nitrite Nutrition 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 claims 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000543 intermediate Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 3
- 150000003852 triazoles Chemical class 0.000 description 3
- YNWVFADWVLCOPU-MDWZMJQESA-N (1E)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-ol Chemical compound C1=NC=NN1/C(C(O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1 YNWVFADWVLCOPU-MDWZMJQESA-N 0.000 description 2
- RMOGWMIKYWRTKW-UONOGXRCSA-N (S,S)-paclobutrazol Chemical compound C([C@@H]([C@@H](O)C(C)(C)C)N1N=CN=C1)C1=CC=C(Cl)C=C1 RMOGWMIKYWRTKW-UONOGXRCSA-N 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 2
- 239000005985 Paclobutrazol Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- FBOUIAKEJMZPQG-BLXFFLACSA-N diniconazole-M Chemical compound C1=NC=NN1/C([C@H](O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl FBOUIAKEJMZPQG-BLXFFLACSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of chemical intermediates, and particularly relates to a synthetic method of mesityl-2-sulfonyl triazole. According to the invention, formamide, thiosemicarbazide and the like are used as starting raw materials, and mesityl-2-sulfonyl triazole is synthesized through three steps.
Description
Technical Field
The invention belongs to the technical field of chemical intermediates, and particularly relates to a synthetic method of mesityl-2-sulfonyl triazole.
Background
Triazole is an organic matter, has a chemical formula of CHN, is widely applied to synthesis of pesticides such as triadimefon, paclobutrazol, uniconazole and diniconazole, is a white needle crystal, is a light yellow or brown needle crystal as an industrial product, and has strong water absorption. The application is a pesticide and a medical intermediate, and is widely applied to the synthesis of pesticides such as triadimefon, paclobutrazol, uniconazole and diniconazole.
Mesityl-2-sulfonyl triazole is a derivative of triazole, no report on a synthesis method of the triazole is found in the prior art, and a method for efficiently synthesizing mesityl-2-sulfonyl triazole is urgently needed at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for synthesizing mesityl-2-sulfonyl triazole.
The synthesis method of the mesityl-2-sulfonyl triazole comprises the following steps:
(1) adding formamide and thiosemicarbazide into a reactor, stirring, heating to 100 ℃, carrying out heat preservation reaction, cooling to 25-30 ℃, adding methanol, stirring, adding potassium hydroxide, controlling the temperature to 30-35 ℃, carrying out heat preservation stirring reaction to obtain a compound A
(2) Stirring and mixing the hydrochloric acid solution and the sym-tritolylamine at 0-5 ℃, adding the sodium nitrite aqueous solution, keeping the temperature and stirring for reaction, adding the compound A, controlling the temperature to be 30-35 ℃, stirring for reaction, adjusting the pH to 7, separating out solids, carrying out suction filtration and centrifugation to obtain a compound B
(3) Putting water, liquid caustic soda and a compound B into a reactor, controlling the temperature to be 60-65 ℃, dropwise adding a sodium hypochlorite aqueous solution, after dropwise adding, heating to 90-95 ℃, carrying out heat preservation reaction, cooling to 25-30 ℃, adding water and sodium sulfite, stirring for dissolving, controlling the temperature to be 50-55 ℃, carrying out heat preservation reaction, adjusting the pH value, stirring and centrifuging to obtain the mesityl-2-sulfonyl triazole
Preferably, in the step (1), the mass ratio of formamide to thiosemicarbazide to potassium hydroxide is 2: 3-5: 4, and the addition amount of methanol is 6 times of the mass of formamide.
Preferably, the mass ratio of the sym-tritoluidine to the compound A to the sodium nitrite in the step (2) is 5: 20-25: 3.
Preferably, the mass ratio of the compound B, the caustic soda liquid, the sodium sulfite and the sodium hypochlorite in the step (3) is 1: 1-2: 0.5: 5.
According to the invention, formamide, thiosemicarbazide and the like are used as starting raw materials, and mesityl-2-sulfonyl triazole is synthesized through three steps.
Detailed Description
Example 1
A method for synthesizing mesityl-2-sulfuryl triazole comprises the following steps:
(1) adding 200kg of formamide into a cyclization kettle, starting stirring, adding 500kg of thiosemicarbazide, stirring for 30min, starting a reaction kettle jacket, raising the temperature to 100 ℃ by steam, carrying out heat preservation reaction for 4h, starting circulating water after the reaction is qualified, cooling to 25 ℃, adding 1200kg of methanol, starting stirring, adding 400kg of potassium hydroxide in batches, controlling the temperature to be 40 ℃, and stirring to obtain 2412kg of compound A;
(2) adding 700kg of hydrochloric acid into a reaction kettle, adding 500kg of water, starting frozen brine to start cooling, cooling to 3 ℃, then starting adding 500kg of sym-tritoluidine as a raw material, stirring for 0.5h, slowly adding 300kg of sodium nitrite, finishing dripping, keeping the temperature and stirring for reaction for 2h to obtain diazo liquid for later use, checking that metering pumps of a diazo liquid kettle and a sylvite kettle work normally, setting the flow rates of the two pumps, starting to simultaneously start the two metering pumps, adding 2000kg of compound A into a spiral pipeline reaction, controlling the temperature of a material in the reactor to be 30 ℃, adding the material at a discharge end into an acidification kettle, dripping hydrochloric acid into the acidification kettle, adjusting the pH =7, separating out a solid, and performing centrifugal suction filtration to obtain 934kg of compound B;
(3) adding 300kg of water and 100kg of liquid caustic soda into an oxidation kettle, starting stirring, adding 100kg of compound B in batches, stirring and heating to 60 ℃, starting slowly dropwise adding 700kg of sodium hypochlorite aqueous solution, heating to 90 ℃, keeping the temperature and reacting for 6h, cooling to 25 ℃, transferring the material into a crystallization kettle, adding 500kg of water and 50kg of sodium sulfite into a blending kettle, stirring and dissolving, controlling the temperature in the crystallization kettle to be 50 ℃, slowly adding the material liquid in the blending kettle into the crystallization kettle, keeping the temperature and reacting for 1h, dropwise adding hydrochloric acid to adjust the pH to be =4, stirring, centrifuging, and drying to obtain 115kg of mesityl-2-sulfonyl triazole with the purity of 97.8%.
Example 2
A method for synthesizing mesityl-2-sulfuryl triazole comprises the following steps:
(1) adding 200kg of formamide into a cyclization kettle, starting stirring, adding 300kg of thiosemicarbazide, stirring for 30min, starting a reaction kettle jacket, raising the temperature to 100 ℃ by steam, carrying out heat preservation reaction for 4h, starting circulating water after the reaction is qualified, cooling to 25 ℃, adding 1200kg of methanol, starting stirring, adding 400kg of potassium hydroxide in batches, controlling the temperature to be 40 ℃, and stirring to obtain 2503kg of compound A;
(2) adding 700kg of hydrochloric acid into a reaction kettle, adding 500kg of water, starting frozen brine to cool to 3 ℃, then starting adding the raw material of sym-tritoluidine, stirring for 0.5h, slowly adding 300kg of sodium nitrite, finishing dripping, keeping the temperature and stirring for reaction for 2h to obtain diazo liquid for later use, checking that metering pumps of a diazo liquid kettle and a sylvite kettle work normally, setting two pump flow rates, starting to simultaneously start two metering pumps, adding 2500kg of compound B feed liquid into a spiral pipeline reaction, controlling the temperature of the reactor material to be 30 ℃, adding the material at a discharge end into an acidification kettle, dripping hydrochloric acid into the acidification kettle, adjusting the pH =7, precipitating solids, and performing suction filtration to obtain 947kg of compound B;
(3) adding 300kg of water and 200kg of liquid caustic soda into an oxidation kettle, starting stirring, adding 100kg of compound B in batches, stirring and heating to 60 ℃, starting slowly dropwise adding 700kg of sodium hypochlorite aqueous solution, heating to 90 ℃, keeping the temperature and reacting for 6h, cooling to 25 ℃, transferring the material into a crystallization kettle, adding 500kg of water and 50kg of sodium sulfite into a blending kettle, stirring and dissolving, controlling the temperature in the crystallization kettle to be 50 ℃, slowly adding the material liquid in the blending kettle into the crystallization kettle, keeping the temperature and reacting for 1h, dropwise adding hydrochloric acid to adjust the pH to be =4, stirring, centrifuging, and drying to obtain 121kg of mesityl-2-sulfonyl triazole with the purity of 98.3%.
Claims (4)
1. A synthetic method of mesityl-2-sulfuryl triazole is characterized by comprising the following steps:
(1) adding formamide and thiosemicarbazide into a reactor, stirring, heating to 100 ℃, carrying out heat preservation reaction, cooling to 25-30 ℃, adding methanol, stirring, adding potassium hydroxide, controlling the temperature to 30-35 ℃, carrying out heat preservation stirring reaction to obtain a compound A
(2) Stirring and mixing the hydrochloric acid solution and the sym-tritolylamine at 0-5 ℃, adding the sodium nitrite aqueous solution, keeping the temperature and stirring for reaction, adding the compound A, controlling the temperature to be 30-35 ℃, stirring for reaction, adjusting the pH to 7, separating out solids, carrying out suction filtration and centrifugation to obtain a compound B
(3) Putting water, liquid caustic soda and a compound B into a reactor, controlling the temperature to be 60-65 ℃, dropwise adding a sodium hypochlorite aqueous solution, after dropwise adding, heating to 90-95 ℃, carrying out heat preservation reaction, cooling to 25-30 ℃, adding water and sodium sulfite, stirring for dissolving, controlling the temperature to be 50-55 ℃, carrying out heat preservation reaction, adjusting the pH value, stirring and centrifuging to obtain the mesityl-2-sulfonyl triazole
2. The method for synthesizing mesityl-2-sulfonyl triazole as claimed in claim 1, wherein the mass ratio of formamide to thiosemicarbazide to potassium hydroxide in the step (1) is 2:3 to 5:4, and the addition amount of methanol is 6 times of the mass of formamide.
3. The method for synthesizing mesityl-2-sulfonyl triazole as claimed in claim 1, wherein the mass ratio of the mesityl oxide to the compound A to the sodium nitrite in the step (2) is 5:20 to 25: 3.
4. The method for synthesizing mesityl-2-sulfonyl triazole as claimed in claim 1, wherein the mass ratio of the compound B, the caustic soda liquid, the sodium sulfite and the sodium hypochlorite in the step (3) is 1: 1-2: 0.5: 5.
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| CN202111625373.4A CN114014817A (en) | 2021-12-29 | 2021-12-29 | Synthesis method of mesityl-2-sulfonyl triazole |
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| CN202111625373.4A CN114014817A (en) | 2021-12-29 | 2021-12-29 | Synthesis method of mesityl-2-sulfonyl triazole |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0680651A (en) * | 1991-06-06 | 1994-03-22 | Chugai Pharmaceut Co Ltd | Production of triazole-based compound |
| JPH06340638A (en) * | 1993-06-01 | 1994-12-13 | Nippon Peroxide Co Ltd | Process for producing 3- (phenylsulfonyl) -1,2,4-triazoles |
| JPH0753529A (en) * | 1993-08-10 | 1995-02-28 | Taoka Chem Co Ltd | Method for producing sulfone derivative |
| US20030060494A1 (en) * | 2001-05-18 | 2003-03-27 | Nobuyuki Yasuda | Pharmaceutical use of N-carbamoylazole derivatives |
| CN111690033A (en) * | 2020-07-05 | 2020-09-22 | 沈阳药科大学 | Dammarane sapogenin derivative, preparation method and application |
-
2021
- 2021-12-29 CN CN202111625373.4A patent/CN114014817A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0680651A (en) * | 1991-06-06 | 1994-03-22 | Chugai Pharmaceut Co Ltd | Production of triazole-based compound |
| JPH06340638A (en) * | 1993-06-01 | 1994-12-13 | Nippon Peroxide Co Ltd | Process for producing 3- (phenylsulfonyl) -1,2,4-triazoles |
| JPH0753529A (en) * | 1993-08-10 | 1995-02-28 | Taoka Chem Co Ltd | Method for producing sulfone derivative |
| US20030060494A1 (en) * | 2001-05-18 | 2003-03-27 | Nobuyuki Yasuda | Pharmaceutical use of N-carbamoylazole derivatives |
| CN111690033A (en) * | 2020-07-05 | 2020-09-22 | 沈阳药科大学 | Dammarane sapogenin derivative, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 李正化: "有机药物合成原理", 北京：人民卫生出版社, pages: 809 * |
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Application publication date: 20220208 |
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