CN118598752A - Synthesis method of 1, 1-dichloro-2-nitroethylene - Google Patents
Synthesis method of 1, 1-dichloro-2-nitroethylene Download PDFInfo
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- CN118598752A CN118598752A CN202310979032.XA CN202310979032A CN118598752A CN 118598752 A CN118598752 A CN 118598752A CN 202310979032 A CN202310979032 A CN 202310979032A CN 118598752 A CN118598752 A CN 118598752A
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- Prior art keywords
- nitroethylene
- dichloro
- vinylidene chloride
- synthesis method
- nitrogen dioxide
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- CTFMCQGUXONREY-UHFFFAOYSA-N 1,1-dichloro-2-nitroethene Chemical group [O-][N+](=O)C=C(Cl)Cl CTFMCQGUXONREY-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000001308 synthesis method Methods 0.000 title claims abstract description 18
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- OUMZKMRZMVDEOF-UHFFFAOYSA-N tris(trimethylsilyl)phosphane Chemical compound C[Si](C)(C)P([Si](C)(C)C)[Si](C)(C)C OUMZKMRZMVDEOF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 238000011534 incubation Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims 4
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 5
- 230000002950 deficient Effects 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- CFRPSFYHXJZSBI-DHZHZOJOSA-N (E)-nitenpyram Chemical compound [O-][N+](=O)/C=C(\NC)N(CC)CC1=CC=C(Cl)N=C1 CFRPSFYHXJZSBI-DHZHZOJOSA-N 0.000 description 1
- SBFICQFUERLNDG-UHFFFAOYSA-N 1,1,1-trichloro-2-nitroethane Chemical compound [O-][N+](=O)CC(Cl)(Cl)Cl SBFICQFUERLNDG-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- NDHXMRFNYMNBKO-PWSUYJOCSA-N chembl2227757 Chemical compound [O-][N+](=O)C([C@H]1CC[C@H](O1)N1CC2)=C1N2CC1=CC=C(Cl)N=C1 NDHXMRFNYMNBKO-PWSUYJOCSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229940079888 nitenpyram Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a synthesis method of 1, 1-dichloro-2-nitroethylene, which comprises the steps of adding vinylidene chloride, a solvent and a catalyst into a reactor, introducing nitrogen dioxide gas, controlling a certain temperature and carrying out heat preservation reaction to obtain the 1, 1-dichloro-2-nitroethylene. The synthesis method of 1, 1-dichloro-2-nitroethylene provided by the invention uses vinylidene chloride as a raw material, adopts a electron-deficient system tri (trimethylsilyl) phosphorus as a catalyst, and directly reacts with nitrogen dioxide to obtain 1, 1-dichloro-2-nitroethylene; compared with the traditional process, the method has the advantages of low cost and availability of raw materials, less three wastes, no pollution and high yield, and the process is simple and smooth, mild in reaction condition and high in yield, and is worthy of large-scale popularization and application.
Description
Technical Field
The invention relates to the technical field of pesticide intermediate synthesis, in particular to a synthesis method of 1, 1-dichloro-2-nitroethylene.
Background
1, 1-Dichloro-2-nitroethylene (formula 1 below) is an important intermediate for synthesizing pesticides cycloxaprid, piprolin and nitenpyram, and the traditional process is to nitrify and add mixed acid such as vinylidene chloride, hydrochloric acid and nitric acid at normal temperature to obtain trichloronitroethane, and then eliminate one molecule of hydrogen chloride to obtain 1, 1-dichloro-2-nitroethylene. As shown in Gu Zhenggui et al (synthesis of 1, 1-dichloro-2-nitroethylene), chemical engineering is applied, 2004, 33 (3), 39-46), the reported synthesis method is that 1, 2-trichloroethane is taken as a raw material, vinylidene chloride is obtained by eliminating under alkaline condition, then the vinylidene chloride is reacted with mixed acid, and then hydrogen chloride is removed by dilute alkali, so that the 1, 1-dichloro-2-nitroethylene is obtained. The synthesis method disclosed in Chinese patent CN107382736 still comprises the steps of reacting vinylidene chloride with hydrochloric acid and nitric acid, and eliminating under alkaline conditions to obtain 1, 1-dichloro-2-nitroethylene.
The method has the advantages that the unsaturated double bond and the hydrochloric acid can undergo addition reaction, the synthesis yield is low when hydrogen chloride is eliminated, a large amount of waste acid water is generated by the process, the waste acid water is difficult to treat, the environment is polluted, and the environmental protection cost is increased.
Therefore, the search for a method for synthesizing 1, 1-dichloro-2-nitroethylene, which is economical, environment-friendly, safe and stable in process, is the focus of research in the field.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a synthesis method of 1, 1-dichloro-2-nitroethylene, which is characterized in that under the condition of no acid water, a trace amount of catalyst tri (trimethylsilyl) phosphorus is added, nitrogen dioxide gas is introduced in the stirring of a solvent, the solvent is distilled off after a certain time of thermal insulation reaction, and the 1, 1-dichloro-2-nitroethylene can be obtained.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a synthesis method of 1, 1-dichloro-2-nitroethylene, which comprises the following steps:
vinylidene chloride, a solvent and a catalyst are added into a reactor, nitrogen dioxide gas is introduced, and the temperature is controlled to keep the temperature for reaction to obtain 1, 1-dichloro-2-nitroethylene.
Further, the catalyst is tris (trimethylsilyl) phosphorus.
Further, the molar ratio of vinylidene chloride to tris (trimethylsilyl) phosphorus is 1:0.01-0.1, preferably 1:0.01-0.02.
Further, the solvent is selected from one or more of dichloromethane, dichloroethane, ethyl acetate and methyl acetate, preferably dichloromethane.
Further, the molar ratio of vinylidene chloride to nitrogen dioxide is 1:1.0 to 3.0, preferably 1:1.1-1.3.
Further, the above synthesis method further comprises: after the reaction is finished, concentrating and recovering the solvent, and then distilling under reduced pressure to obtain the 1, 1-dichloro-2-nitroethylene.
Further, the reaction conditions are: the temperature is kept at 0-30deg.C, preferably 0-5deg.C; the incubation time is 1 to 6 hours, preferably 2 to 3 hours.
Compared with the prior art, the invention has the following technical effects:
the synthesis method of 1, 1-dichloro-2-nitroethylene provided by the invention uses vinylidene chloride as a raw material, adopts a electron-deficient system tri (trimethylsilyl) phosphorus as a catalyst, and directly reacts with nitrogen dioxide to obtain 1, 1-dichloro-2-nitroethylene; compared with the traditional process, the method has the advantages of low cost and availability of raw materials, less three wastes, no pollution and high yield, and the process is simple and smooth, mild in reaction condition and high in yield, and is worthy of large-scale popularization and application.
Detailed Description
The invention provides a synthesis method of 1, 1-dichloro-2-nitroethylene, which uses raw materials of vinylidene chloride, nitrogen dioxide and a catalyst of tri (trimethylsilyl) phosphine which are cheap and easy to obtain, can greatly reduce three wastes, lighten environmental protection pressure and reduce cost.
Specifically, the synthesis method provided by the invention comprises the following steps:
vinylidene chloride, a solvent and a catalyst are added into a reactor, nitrogen dioxide gas is introduced, and the temperature is controlled to keep the temperature for reaction to obtain 1, 1-dichloro-2-nitroethylene.
In a preferred embodiment of the present invention, the catalyst is tris (trimethylsilyl) phosphorus.
In a preferred embodiment of the invention, the molar ratio of vinylidene chloride to tris (trimethylsilyl) phosphorus is 1:0.01-0.1, preferably 1:0.01-0.02.
In a preferred embodiment of the present invention, the solvent is selected from one or more of dichloromethane, dichloroethane, ethyl acetate, and methyl acetate, preferably dichloromethane.
In a preferred embodiment of the invention, the molar ratio of vinylidene chloride to nitrogen dioxide is 1:1.0 to 3.0, preferably 1:1.1-1.3.
In a preferred embodiment of the present invention, the above synthesis method further includes: after the reaction is finished, concentrating and recovering the solvent, and then distilling under reduced pressure to obtain the 1, 1-dichloro-2-nitroethylene.
In a preferred embodiment of the invention, the reaction conditions are: the temperature is kept at 0-30 ℃, preferably 0-5 ℃; the incubation time is 1 to 6 hours, preferably 2 to 3 hours.
The present invention will be described in detail and in detail by way of the following examples, which are not intended to limit the scope of the invention, for better understanding of the invention.
The methods described in the examples are carried out using conventional methods, if not specified, and the reagents used are, if not specified, conventional commercially available reagents or reagents formulated by conventional methods.
Example 1
The embodiment provides a synthesis method of 1, 1-dichloro-2-nitroethylene, which comprises the following steps:
100.0g of methylene chloride (100.0 g, 1.01 mol) of vinylidene chloride (98%) and 5.01 g (0.015 mol) of tris (trimethylsilyl) phosphorus (95%) are added into a 500 ml four-necked flask, stirring is kept, 52 g (1.13 mol) of nitrogen dioxide gas is introduced at 5 ℃, the temperature is kept for 3 hours, the reaction is finished, the methylene chloride is concentrated and recovered, 141.5 g of 1, 1-dichloro-2-nitroethylene is obtained by reduced pressure distillation, the content is 99%, and the yield is 97.6%.
Example 2
The embodiment provides a synthesis method of 1, 1-dichloro-2-nitroethylene, which comprises the following steps:
100.0 g of methylene chloride (100.0 g, 1.01 mol) of vinylidene chloride (98%) and 5.01 g (0.015 mol) of tris (trimethylsilyl) phosphorus (95%) are added into a 500 ml four-necked flask, stirring is kept, 58 g (1.25 mol) of nitrogen dioxide gas is introduced at 15 ℃, the temperature is kept for 1 hour, after the reaction is finished, the methylene chloride is concentrated and recovered, 143.8 g of 1, 1-dichloro-2-nitroethylene is obtained by vacuum distillation, the content is 95.3%, and the yield is 95.6%.
Example 3
The embodiment provides a synthesis method of 1, 1-dichloro-2-nitroethylene, which comprises the following steps:
100.0 g of ethyl acetate, 100.0 (98%) (1.01 mol) of vinylidene chloride, 5.35 g (0.016 mol) of tris (trimethylsilyl) phosphorus (95%) were put into a 500 ml four-necked flask, the mixture was stirred, 53.44 g (1.16 mol) of nitrogen dioxide gas was introduced at 25℃and the mixture was kept warm for 3 hours, and after completion of the reaction, methylene chloride was recovered by concentration and distillation under reduced pressure to obtain 139.8 g of 1, 1-dichloro-2-nitroethylene, the content of which was 94.6% and the yield of which was 92.3%.
The above description of the specific embodiments of the present invention has been given by way of example only, and the present invention is not limited to the above described specific embodiments. It will be apparent to those skilled in the art that any equivalent modifications and substitutions of the present invention are intended to be within the scope of the present invention. Accordingly, equivalent changes and modifications are intended to be included within the scope of the present invention without departing from the spirit and scope thereof.
Claims (7)
1. The synthesis method of the 1, 1-dichloro-2-nitroethylene is characterized by comprising the following steps of:
vinylidene chloride, a solvent and a catalyst are added into a reactor, nitrogen dioxide gas is introduced, and the temperature is controlled to keep the temperature for reaction to obtain 1, 1-dichloro-2-nitroethylene.
2. The synthetic method of claim 1 wherein the catalyst is tris (trimethylsilyl) phosphorus.
3. The synthetic method according to claim 2, characterized in that the molar ratio of vinylidene chloride to tris (trimethylsilyl) phosphorus is 1:0.01-0.1, preferably 1:0.01-0.02.
4. The synthetic method according to claim 1, characterized in that the solvent is selected from one or more of dichloromethane, dichloroethane, ethyl acetate, methyl acetate, preferably dichloromethane.
5. The method of synthesis according to claim 1, wherein the molar ratio of vinylidene chloride to nitrogen dioxide is 1:1.0 to 3.0, preferably 1:1.1-1.3.
6. The method of synthesizing of claim 1, further comprising: after the reaction is finished, concentrating and recovering the solvent, and then distilling under reduced pressure to obtain the 1, 1-dichloro-2-nitroethylene.
7. The synthetic method of claim 1 wherein the reaction conditions are: the temperature is kept at 0-30deg.C, preferably 0-5deg.C; the incubation time is 1 to 6 hours, preferably 2 to 3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310979032.XA CN118598752A (en) | 2023-08-04 | 2023-08-04 | Synthesis method of 1, 1-dichloro-2-nitroethylene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310979032.XA CN118598752A (en) | 2023-08-04 | 2023-08-04 | Synthesis method of 1, 1-dichloro-2-nitroethylene |
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| CN202310979032.XA Pending CN118598752A (en) | 2023-08-04 | 2023-08-04 | Synthesis method of 1, 1-dichloro-2-nitroethylene |
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- 2023-08-04 CN CN202310979032.XA patent/CN118598752A/en active Pending
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