CN114105728A - Method for simultaneously preparing E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene - Google Patents
Method for simultaneously preparing E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene Download PDFInfo
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Abstract
The invention discloses a method for simultaneously preparing E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, which comprises the following steps: in the presence of an aprotic polar solvent, 1,1,1,3, 3-pentachloropropane and an alkali metal salt are reacted to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, the obtained E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene have high selectivity, the selectivity of the E-1,3,3, 3-tetrachloropropene is in the range of 35-45%, the selectivity of the 1,1,3, 3-tetrachloropropene is in the range of 55-65%, the sum of the selectivity of the two is close to 100%, the conversion rate of the 1,1,1,3, 3-pentachloropropane is high, the synthesis conditions of the method are mild, the operation is convenient, and the raw materials are easy to obtain.
Description
Technical Field
The invention relates to the technical field of chloropropene production, and particularly relates to a method for simultaneously preparing E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene.
Background
E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene are raw materials for synthesizing environmentally friendly chlorofluorocarbon substitutes such as E-1-chloro-3, 3, 3-trifluoropropene, Z-1-chloro-3, 3, 3-trifluoropropene, E-1,3,3, 3-tetrafluoropropene, Z-1,3,3, 3-tetrafluoropropene, 1,1,1,3, 3-pentafluoropropane, and the like.
At present, the synthesis method of E-1,3,3, 3-tetrachloropropene is rarely reported, and the following two methods are mainly adopted:
(1) high-temperature pyrolysis reaction: 3-chloro-4- (trichloromethyl) oxetane-2-butanone is pyrolyzed in a ketene generator to obtain E/Z-1,3,3, 3-tetrachloropropene with a yield of 80%.
(2) Chlorination reaction: E/Z-1, 3-dichloropropene in FeCl3Reacting with chlorine in the presence of a catalyst at 210 ℃ for 1 s to obtain the E/Z-1,3,3, 3-tetrachloropropene with the yield of 80.65 percent.
The mainstream synthesis method of 1,1,3, 3-tetrachloropropene is obtained by dehydrochlorination reaction of 1,1,1,3, 3-pentachloropropane as a raw material, and specifically comprises the following steps:
(1) patent application WO2017183501A1 discloses that 1,1,1,3, 3-pentachloropropane with a mass ratio of 40: 1 is reacted with ferric chloride at 80 ℃ for 4 h, with a conversion of 1,1,1,3, 3-pentachloropropane of 97.1% and a selectivity of 1,1,3, 3-tetrachloropropene of 97.2%.
(2) Patent application CN109608302A discloses adding 694.2 g of 80% KOH solution, 1619.8 g of 1,1,1,3, 3-pentachloropropane into a 5L hastelloy material autoclave, passing through N2Controlling the pressure of the reaction kettle; controlling the pressure of the reaction kettle to be 4 bar and the temperature to be 140 ℃, stirring and reacting for 8 h under the condition, and collecting 1,1,3, 3-tetrachloropropene 1212, l g after the reaction.
(3) Patent application CN107646029A discloses that 1626.5 g of 1,1,1,3, 3-pentachloropropane is reacted in the presence of 17g of anhydrous ferric chloride at 80 ℃ for 5 h, and crude 1,1,3, 3-tetrachloropropene is collected in 1338.1 g with a purity of 92.25%.
(4) Patent application CN111454122A discloses that 1,1,1,3, 3-pentachloropropane with a liquid hourly space velocity of 2.5 mL/(h.g-catalyst) in the presence of nitrogen doped carbon catalyst C-1 reacts at 280 ℃ with a conversion of 1,1,1,3, 3-pentachloropropane of 98.5% and a selectivity of 1,1,3, 3-tetrachloropropene of 40.8%.
(5) Patent application CN102177120A discloses that 1,1,1,3, 3-pentachloropropane is preheated to 200 ℃ for gasification, and enters a reaction tube at 500 ℃ for reaction, and the residence time is 2.5 s, so that the conversion rate of 1,1,1,3, 3-pentachloropropane is 99.1%, and the selectivity of 1,1,3, 3-tetrachloropropene is 98.0%.
(6) Patent application CN 110483233a discloses charging a bottom flask with 0.26 g anhydrous ferric chloride and 290.7 g1,1,1,3, 3-pentachloropropane, and heating to reflux. The overhead product fraction was started using a 0.7: 1 reflux ratio. During 292 min of continuous operation, the overhead temperature was gradually increased from 82 ℃ to 103 ℃ while the bottoms were increased from 92 ℃ to 113 ℃. Collecting an overhead distillate sample, wherein when the running time is 24 min, the cumulative feeding of 1,1,1,3, 3-pentachloropropane is 0.8 mol, the purity of the overhead distillate 1,1,3, 3-tetrachloropropene is 99.2%, the content of 1,1,1,3, 3-pentachloropropane is 0.8%, and the cumulative extraction of 0.282 mol of 1,1,3, 3-tetrachloropropene is obtained; when the running time was 294 min, the cumulative amount of 1,1,1,3, 3-pentachloropropane fed was 4.89 mol, the purity of the overhead fraction containing 1,1,3, 3-tetrachloropropene was 33.7%, the purity of the overhead fraction containing 1,1,1,3, 3-pentachloropropane was 66.3%, and the cumulative amount of 1,1,3, 3-tetrachloropropene was 2.523 mol.
(7) Patent application CN 108026001A discloses the use of a Ni/Cr/AlF alloy in a steel casting3In the presence of the catalyst, 1,1,1,3, 3-pentachloropropane is continuously reacted for 24 hours at 250 ℃ and with the contact time of 60 s, so that the conversion rate of the 1,1,1,3, 3-pentachloropropane is 98.7 percent, and the selectivity of the 1,1,3, 3-tetrachloropropene is 99 percent.
(8) Patent application CN 110746266a discloses that 1,1,1,3, 3-pentachloropropane reacts at 75-80 ℃ for about 4 h in the presence of anhydrous ferric chloride, and that the conversion of 1,1,1,3, 3-pentachloropropane is 93.9% and the selectivity of 1,1,3, 3-tetrachloropropene is 98.6%.
(9) Patent application WO2020041731A1 discloses that in a reaction rectification system, carbon tetrachloride is used as a solvent, 1,1,1,3, 3-pentachloropropane is reacted at 154 ℃ in the presence of anhydrous gallium chloride, and when the reaction rectification system is continuously operated for 120 min, the fraction cumulatively extracted from the tower top contains 78% of 1,1,3, 3-tetrachloropropene and 22% of 1,1,1,3, 3-pentachloropropane; when the operation was continued for 458 min, the cumulative distillate from the column top had a purity of 61% for 1,1,3, 3-tetrachloropropene and 38% for 1,1,1,3, 3-pentachloropropane.
In the above publications, the synthesis method of E-1,3,3, 3-tetrachloropropene has the disadvantages of difficulty in obtaining raw materials, relatively severe synthesis method (high-temperature pyrolysis reaction or chlorination reaction), and low safety factor; however, in the method of synthesizing 1,1,3, 3-tetrachloropropene by dehydrochlorinating 1,1,1,3, 3-pentachloropropane, 1,1,3, 3-tetrachloropropene is mainly obtained as a product, and a method of selectively dehydrochlorinating to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene has not been reported.
Disclosure of Invention
The invention provides a method for preparing E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene with high conversion rate and high selectivity.
The specific technical scheme of the invention is as follows:
1. a process for the simultaneous preparation of E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene comprising:
reacting 1,1,1,3, 3-pentachloropropane with an alkali metal salt in the presence of an aprotic polar solvent to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene.
2. The method according to item 1, wherein the aprotic polar solvent is selected from one or two or more of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylisobutyramide, N-diethylformamide, N-diisopropylformamide, dimethyl sulfoxide and sulfolane, preferably N, N-dimethylformamide or N, N-dimethylacetamide.
3. The method according to item 1 or 2, wherein the alkali metal salt is a salt containing lithium, sodium, potassium, rubidium or cesium, preferably, the alkali metal salt is one or more selected from fluoride salt, chloride salt, bromide salt, iodide salt, nitrite salt, thiocyanate salt and cyanate salt.
4. The process according to any of items 1 to 3, wherein the amount ratio of 1,1,1,3, 3-pentachloropropane to alkali metal salt of the substance is 1: 1 to 5, preferably 1: 1.5 to 5.
5. The process according to any of items 1 to 4, wherein the volume ratio of the amount of substance of 1,1,1,3, 3-pentachloropropane to the aprotic polar solvent is 1: 0.4 to 4 mol/L, preferably 1: 0.8 to 2 mol/L.
6. The process according to any of claims 1 to 5, wherein the reaction time is from 2 to 20 h, preferably from 4 to 10 h.
7. The process according to any one of items 1 to 6, wherein the reaction temperature is 20 to 120 ℃, preferably 70 to 90 ℃.
8. The process according to any one of items 1 to 7, wherein the reaction pressure is 0.1 to 0.5 MPa, preferably 0.1 MPa.
9. The process of any one of items 1-8, wherein the selectivity to E-1,3,3, 3-tetrachloropropene is 35-45% and the selectivity to 1,1,3, 3-tetrachloropropene is 55-65%.
ADVANTAGEOUS EFFECTS OF INVENTION
The method can simultaneously obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, the obtained E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene have high selectivity, the selectivity of the E-1,3,3, 3-tetrachloropropene is in the range of 35-45%, the selectivity of the 1,1,3, 3-tetrachloropropene is in the range of 55-65%, the sum of the two selectivities is close to 100%, the conversion rate of the 1,1,1,3, 3-pentachloropropane is high, the synthesis conditions of the method are mild, the operation is convenient, and the raw materials are easy to obtain.
Detailed Description
The embodiments described below explain the present invention in detail. While specific embodiments of the invention have been shown, it should be understood that the invention may be embodied in various forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
It should be noted that certain terms are used throughout the description and claims to refer to particular components. As one skilled in the art will appreciate, various names may be used to refer to a component. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. The description which follows is a preferred embodiment of the invention, however, the description is given for the purpose of illustrating the general principles of the invention and not for the purpose of limiting the scope of the invention. The scope of the present invention is defined by the appended claims.
The invention provides a method for simultaneously preparing E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, which comprises the following steps:
reacting 1,1,1,3, 3-pentachloropropane with an alkali metal salt in the presence of an aprotic polar solvent to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, the reaction scheme is as follows:
the invention uses anion X provided by alkali metal salt MX (M is alkali metal) in the presence of aprotic polar solvent-Promoting the dehydrochlorination reaction of the 1,1,1,3, 3-pentachloropropane to synthesize E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, and simultaneously obtaining alkali metal chloride MCl and HX.
In one embodiment, the aprotic polar solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylisobutyramide, N-diethylformamide, N-diisopropylformamide, dimethyl sulfoxide, and sulfolane, and is preferably N, N-dimethylformamide or N, N-dimethylacetamide.
In one embodiment, the alkali metal salt is a salt containing lithium, sodium, potassium, rubidium or cesium, preferably, the alkali metal salt is one or more selected from fluoride, chloride, bromide, iodide, nitrite, thiocyanate and cyanate, i.e., in the above reaction scheme, X is-One or more selected from fluorine ion, chlorine ion, bromine ion, iodine ion, nitrite ion, thiocyanate ion and cyanate ion.
During the reaction, the byproduct HX preferentially reacts with the excessive raw material alkali metal salt MX (M is alkali metal) to generate acid salt MHX2For example: KF reacts with HF to form KHF2. When MX is completely consumed or HX and MX are not sufficiently reacted, HX may react with amide or sulfone to form acid adduct, such as dmf.hf from DMF and HF, dmf.hcl from DMF and HCl, DMSO and HCl to dmso.hcl, etc., such adducts are disclosed in "jimura, endonex, KAGAKU, vol. 26 (1977): 785-789". Therefore, the byproduct HX generated in the reaction process has enough acid-binding agent to adsorb and fix the byproduct HX, thereby increasing the safety of the reaction process.
In one embodiment, the amount ratio of 1,1,1,3, 3-pentachloropropane to alkali metal salt is 1: 1 to 5, preferably 1: 1.5 to 5, more preferably 1: 2 to 3.
For example, the ratio of the amounts of 1,1,1,3, 3-pentachloropropane and alkali metal salt of the substance (n)1,1,1,3, 3-pentachloropropane∶nAlkali metal salts) Can be 1: 1, 1: 1.5, 1: 2, 1: 2.5, 1: 3, 1: 3.5, 1: 4, 1: 4.5, 1: 5, etc.
In one embodiment, the amount of 1,1,1,3, 3-pentachloropropane is 1: 0.4 to 4 mol/L, preferably 1: 0.8 to 2 mol/L, by volume, based on the aprotic polar solvent.
For example, the volume ratio of the amount of 1,1,1,3, 3-pentachloropropane to the aprotic polar solvent (n)1,1,1,3, 3-pentachloropropane∶vAprotic polar solvent) May be 1: 0.4 mol/L, 1: 0.5 mol/L, 1: 0.6 mol/L, 1: 0.7 mol/L, 1: 0.8 mol/L, 1: 0.9 mol/L, 1: 1 mol/L, 1: 2 mol/L, 1: 3 mol/L, 1: 4 mol/L, etc.
In one embodiment, the reaction time is 2 to 20 h, preferably 4 to 10 h, preferably the reaction temperature is 20 to 120 ℃, preferably 70 to 90 ℃.
For example, the reaction time may be 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, etc., and the reaction temperature may be 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, etc.
In one embodiment, the reaction pressure is from 0.1 to 0.5 MPa, preferably 0.1 MPa.
For example, the reaction pressure may be 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, or the like.
In one embodiment, the selectivity to E-1,3,3, 3-tetrachloropropene ranges from 35 to 45% and the selectivity to 1,1,3, 3-tetrachloropropene ranges from 55 to 65%.
The selectivity refers to the percentage of the target product to the converted reaction raw material.
In one embodiment, the method comprises:
reacting 1,1,1,3, 3-pentachloropropane with an alkali metal salt in the presence of an aprotic polar solvent to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, wherein the aprotic polar solvent is one or more selected from N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylisobutyramide, N-diethylformamide, N-diisopropylformamide, dimethyl sulfoxide and sulfolane, and preferably is N, N-dimethylformamide or N, N-dimethylacetamide.
In one embodiment, the method comprises:
reacting 1,1,1,3, 3-pentachloropropane with an alkali metal salt in the presence of an aprotic polar solvent to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, wherein the aprotic polar solvent is one or more selected from N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylisobutyramide, N-diethylformamide, N-diisopropylformamide, dimethyl sulfoxide and sulfolane, preferably N, N-dimethylformamide or N, N-dimethylacetamide, and the alkali metal salt is a salt containing lithium, sodium, potassium, rubidium or cesium, preferably the alkali metal salt is selected from fluoride salt, chloride salt, bromide salt, fluoride salt, rubidium salt, or cesium salt, One or more of iodide, nitrite, thiocyanate and cyanate.
In one embodiment, the method comprises:
reacting 1,1,1,3, 3-pentachloropropane with an alkali metal salt in the presence of an aprotic polar solvent to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, wherein the aprotic polar solvent is one or more selected from N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylisobutyramide, N-diethylformamide, N-diisopropylformamide, dimethyl sulfoxide and sulfolane, preferably N, N-dimethylformamide or N, N-dimethylacetamide, and the alkali metal salt is a salt containing lithium, sodium, potassium, rubidium or cesium, preferably the alkali metal salt is selected from fluoride salt, chloride salt, bromide salt, fluoride salt, rubidium salt, or cesium salt, One or more of iodide, nitrite, thiocyanate and cyanate, and the amount ratio of 1,1,1,3, 3-pentachloropropane to alkali metal salt is 1: 1-5, preferably 1: 1.5-5.
In one embodiment, the method comprises:
reacting 1,1,1,3, 3-pentachloropropane with an alkali metal salt in the presence of an aprotic polar solvent to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, wherein the aprotic polar solvent is one or more selected from N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylisobutyramide, N-diethylformamide, N-diisopropylformamide, dimethyl sulfoxide and sulfolane, preferably N, N-dimethylformamide or N, N-dimethylacetamide, and the alkali metal salt is a salt containing lithium, sodium, potassium, rubidium or cesium, preferably the alkali metal salt is selected from fluoride salt, chloride salt, bromide salt, fluoride salt, rubidium salt, or cesium salt, One or more of iodide, nitrite, thiocyanate and cyanate, wherein the ratio of the amount of the 1,1,1,3, 3-pentachloropropane to the amount of the alkali metal salt is 1: 1-5, preferably 1: 1.5-5, and the volume ratio of the amount of the 1,1,1,3, 3-pentachloropropane to the amount of the aprotic polar solvent is 1: 0.4-4 mol/L, preferably 1: 0.8-2 mol/L.
In one embodiment, the method comprises:
reacting 1,1,1,3, 3-pentachloropropane with an alkali metal salt in the presence of an aprotic polar solvent to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, wherein the aprotic polar solvent is one or more selected from N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylisobutyramide, N-diethylformamide, N-diisopropylformamide, dimethyl sulfoxide and sulfolane, preferably N, N-dimethylformamide or N, N-dimethylacetamide, and the alkali metal salt is a salt containing lithium, sodium, potassium, rubidium or cesium, preferably the alkali metal salt is selected from fluoride salt, chloride salt, bromide salt, fluoride salt, rubidium salt, or cesium salt, One or more of iodide, nitrite, thiocyanate and cyanate, wherein the ratio of the amount of the 1,1,1,3, 3-pentachloropropane to the amount of the alkali metal salt is 1: 1-5, preferably 1: 1.5-5, the volume ratio of the amount of the 1,1,1,3, 3-pentachloropropane to the amount of the aprotic polar solvent is 1: 0.4-4 mol/L, preferably 1: 0.8-2 mol/L, and the reaction time is 2-20 h, preferably 4-10 h.
In one embodiment, the method comprises:
reacting 1,1,1,3, 3-pentachloropropane with an alkali metal salt in the presence of an aprotic polar solvent to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, wherein the aprotic polar solvent is one or more selected from N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylisobutyramide, N-diethylformamide, N-diisopropylformamide, dimethyl sulfoxide and sulfolane, preferably N, N-dimethylformamide or N, N-dimethylacetamide, and the alkali metal salt is a salt containing lithium, sodium, potassium, rubidium or cesium, preferably the alkali metal salt is selected from fluoride salt, chloride salt, bromide salt, fluoride salt, rubidium salt, or cesium salt, One or more than two of iodide, nitrite, thiocyanate and cyanate, the ratio of the amount of the 1,1,1,3, 3-pentachloropropane to the amount of the alkali metal salt is 1: 1-5, preferably 1: 1.5-5, the volume ratio of the amount of the 1,1,1,3, 3-pentachloropropane to the amount of the aprotic polar solvent is 1: 0.4-4 mol/L, preferably 1: 0.8-2 mol/L, the reaction time is 2-20 h, preferably 4-10 h, and the reaction temperature is 20-120 ℃, preferably 70-90 ℃.
In one embodiment, the method comprises:
reacting 1,1,1,3, 3-pentachloropropane with an alkali metal salt in the presence of an aprotic polar solvent to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, wherein the aprotic polar solvent is one or more selected from N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylisobutyramide, N-diethylformamide, N-diisopropylformamide, dimethyl sulfoxide and sulfolane, preferably N, N-dimethylformamide or N, N-dimethylacetamide, and the alkali metal salt is a salt containing lithium, sodium, potassium, rubidium or cesium, preferably the alkali metal salt is selected from fluoride salt, chloride salt, bromide salt, fluoride salt, rubidium salt, or cesium salt, One or more than two of iodide, nitrite, thiocyanate and cyanate, wherein the volume ratio of the 1,1,1,3, 3-pentachloropropane to the alkali metal salt is 1: 1-5, preferably 1: 1.5-5, and the volume ratio of the 1,1,1,3, 3-pentachloropropane to the aprotic polar solvent is 1: 0.4-4 mol/L, preferably 1: 0.8-2 mol/L, the reaction time is 2-20 h, preferably 4-10 h, the reaction temperature is 20-120 ℃, preferably 70-90 ℃, and the reaction pressure is 0.1-0.5 MPa, preferably 0.1 MPa.
In one embodiment, the method comprises:
reacting 1,1,1,3, 3-pentachloropropane with an alkali metal salt in the presence of an aprotic polar solvent to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, wherein the aprotic polar solvent is one or more selected from N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylisobutyramide, N-diethylformamide, N-diisopropylformamide, dimethyl sulfoxide and sulfolane, preferably N, N-dimethylformamide or N, N-dimethylacetamide, and the alkali metal salt is a salt containing lithium, sodium, potassium, rubidium or cesium, preferably the alkali metal salt is selected from fluoride salt, chloride salt, bromide salt, fluoride salt, rubidium salt, or cesium salt, An iodide salt, a nitrite salt, one or more of thiocyanate and cyanate, wherein the volume ratio of the 1,1,1,3, 3-pentachloropropane to the alkali metal salt is 1: 1-5, preferably 1: 1.5-5, the volume ratio of the 1,1,1,3, 3-pentachloropropane to the aprotic polar solvent is 1: 0.4-4 mol/L, preferably 1: 0.8-2 mol/L, the reaction time is 2-20 h, preferably 4-10 h, the reaction temperature is 20-120 ℃, preferably 70-90 ℃, the reaction pressure is 0.1-0.5 MPa, preferably 0.1 MPa, the selectivity of E-1,3,3, 3-tetrachloropropene is 35-45%, and the selectivity of 1,1,3, 3-tetrachloropropene is 55-65%.
For the reaction product obtained by the present invention, because the boiling point difference between the raw material and the reaction product is large, the raw material and the product can be effectively separated by adopting a simple distillation mode. Wherein the boiling point of the E-1,3,3, 3-tetrachloropropene is 140 ℃ (760 mmHg); the boiling point of the 1,3, 3-tetrachloropropene is 151.4 ℃ (760 mmHg); the boiling point of the 1,1,1,3, 3-pentachloropropane is 178.5-179.0 ℃ (760 mmHg).
By adopting the method, the E-1,3,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene can be obtained simultaneously, the selectivity of the two substances is high, the selectivity of the E-1,3,3, 3-tetrachloropropene is 35-45%, the selectivity of the 1,1,3, 3-tetrachloropropene is 55-65%, and the conversion rate of the 1,1,1,3, 3-pentachloropropane is high.
In the process of the present invention for preparing E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, the reactor used is a reactor commonly used in the art, and may be, for example, an autoclave, a glass flask, an enamel kettle, a reaction tank, or the like.
Examples
The invention is described generally and/or specifically for the materials used in the tests and the test methods, in the following examples,% means wt%, i.e. percent by weight, unless otherwise specified. The reagents or equipment used, not indicated by the manufacturer, were all conventional reagent products available commercially, with the GC analysis product having the instrument model Shimadzu GC-2010 and the column model InterCap1 (i.d. 0.25 mm; length 60 m; J & W Scientific Inc.).
Gas chromatographic analysis method: high purity helium and hydrogen were used as carrier gases. The temperature of the detector is 240 ℃, the temperature of the vaporization chamber is 150 ℃, the initial temperature of the column is 40 ℃, the temperature is kept for 10 min, the temperature is raised to 240 ℃ at the rate of 20 ℃/min, and the temperature is kept for 10 min.
Example 1
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 7 hours, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing the water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 98.25%, the selectivity to E-1,3,3, 3-tetrachloropropene was 39.1%, and the selectivity to 1,1,3, 3-tetrachloropropene was 58.2%.
Example 2
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is-20 ℃, the reaction time is 7h, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing the water, and the results are as follows after GC detection and analysis: the conversion of 1,1,1,3, 3-pentachloropropane was 45.4%, the selectivity for E-1,3,3, 3-tetrachloropropene was 38.6%, and the selectivity for 1,1,3, 3-tetrachloropropene was 57.9%.
Example 3
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 0 ℃, the reaction time is 7 hours, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing the water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 69.2%, the selectivity to E-1,3,3, 3-tetrachloropropene was 38.8%, and the selectivity to 1,1,3, 3-tetrachloropropene was 58.6%.
Example 4
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 30 ℃, the reaction time is 7 hours, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing the water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 78.0%, the selectivity to E-1,3,3, 3-tetrachloropropene was 39.1%, and the selectivity to 1,1,3, 3-tetrachloropropene was 57.4%.
Example 5
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 50 ℃, the reaction time is 7 hours, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing the water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 84.8%, the selectivity for E-1,3,3, 3-tetrachloropropene was 38.4%, and the selectivity for 1,1,3, 3-tetrachloropropene was 58.4%.
Example 6
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 90 ℃, the reaction time is 7 hours, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing the water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity to E-1,3,3, 3-tetrachloropropene was 39.5%, and the selectivity to 1,1,3, 3-tetrachloropropene was 59.6%.
Example 7
0.05mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 1, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 7 hours, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing the water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 67.8%, the selectivity to E-1,3,3, 3-tetrachloropropene was 39.2%, and the selectivity to 1,1,3, 3-tetrachloropropene was 59.2%.
Example 8
0.15 mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 3, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 7 hours, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing the water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity to E-1,3,3, 3-tetrachloropropene was 39.5%, and the selectivity to 1,1,3, 3-tetrachloropropene was 59.6%.
Example 9
0.25 mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 5, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 7 hours, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing the water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity to E-1,3,3, 3-tetrachloropropene was 39.7%, and the selectivity to 1,1,3, 3-tetrachloropropene was 60.0%.
Example 10
Sequentially adding 0.1mol of sodium nitrite, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the sodium nitrite is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 3 hours, returning the reaction system to room temperature, washing off the solvent and alkali metal salt by water, drying and removing water to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, and detecting by GC, the results are as follows: the conversion of 1,1,1,3, 3-pentachloropropane was 62.6%, the selectivity for E-1,3,3, 3-tetrachloropropene was 38.7%, and the selectivity for 1,1,3, 3-tetrachloropropene was 58.9%.
Example 11
Sequentially adding 0.1mol of potassium thiocyanate, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide into a three-neck flask with a water condensation tube, wherein the ratio of the amount of the substances of the 1,1,1,3, 3-pentachloropropane to the amount of the potassium thiocyanate is 1: 2, the ratio of the amount of the substances of the 1,1,1,3, 3-pentachloropropane to the volume of the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 5 hours, returning the reaction system to room temperature, washing away the solvent and the alkali metal salt with water, drying and removing water to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, and detecting and analyzing by GC, wherein the results are as follows: the conversion of 1,1,1,3, 3-pentachloropropane was 82.4%, the selectivity to E-1,3,3, 3-tetrachloropropene was 38.5%, and the selectivity to 1,1,3, 3-tetrachloropropene was 58.6%.
Example 12
Sequentially adding 0.1mol of rubidium fluoride, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide into a three-neck flask with a water condensation tube, wherein the amount ratio of the 1,1,1,3, 3-pentachloropropane to the rubidium fluoride is 1: 2, the amount ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 5 hours, returning the reaction system to room temperature, washing with water to remove a solvent and an alkali metal salt, drying to remove water, obtaining E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, and detecting and analyzing by GC, wherein the results are as follows: the conversion of 1,1,1,3, 3-pentachloropropane was 90.3%, the selectivity to E-1,3,3, 3-tetrachloropropene was 42.1%, and the selectivity to 1,1,3, 3-tetrachloropropene was 56.2%.
Example 13
0.1mol of cesium fluoride, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the cesium fluoride is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 5 hours, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene are obtained by drying and removing water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 99.9%, the selectivity for E-1,3,3, 3-tetrachloropropene was 41.4%, and the selectivity for 1,1,3, 3-tetrachloropropene was 55.8%.
Example 14
Sequentially adding 0.1mol of sodium cyanate, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the sodium cyanate is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 5 hours, returning the reaction system to room temperature, washing with water to remove a solvent and an alkali metal salt, drying to remove water, obtaining E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, and detecting and analyzing by GC, wherein the results are as follows: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity to E-1,3,3, 3-tetrachloropropene was 40.5%, and the selectivity to 1,1,3, 3-tetrachloropropene was 56.7%.
Example 15
Sequentially adding 0.1mol of sodium nitrite, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the sodium nitrite is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 5 hours, returning the reaction system to room temperature, washing off the solvent and alkali metal salt by water, drying and removing water to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, and detecting by GC, the results are as follows: the conversion of 1,1,1,3, 3-pentachloropropane was 98.1%, the selectivity for E-1,3,3, 3-tetrachloropropene was 32.0%, and the selectivity for 1,1,3, 3-tetrachloropropene was 62.1%.
Example 16
Sequentially adding 0.1mol of potassium nitrite, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the potassium nitrite is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 5 hours, returning the reaction system to room temperature, washing off the solvent and alkali metal salt by water, drying and removing water to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, and detecting by GC, the results are as follows: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity for E-1,3,3, 3-tetrachloropropene was 32.5%, and the selectivity for 1,1,3, 3-tetrachloropropene was 64.6%.
Example 17
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 20 hours, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing the water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity for E-1,3,3, 3-tetrachloropropene was 38.6%, and the selectivity for 1,1,3, 3-tetrachloropropene was 60.1%.
Example 18
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylacetamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylacetamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 7h, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 98.0%, the selectivity to E-1,3,3, 3-tetrachloropropene was 40.1%, and the selectivity to 1,1,3, 3-tetrachloropropene was 58.9%.
Example 19
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylpropionamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylpropionamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 7h, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing the water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 57.5%, the selectivity to E-1,3,3, 3-tetrachloropropene was 39.2%, and the selectivity to 1,1,3, 3-tetrachloropropene was 57.9%.
Example 20
Sequentially adding 0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethyl isobutyramide into a three-neck flask with a water condensation tube, wherein the ratio of the amount of the substances of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the ratio of the amount of the substances of the 1,1,1,3, 3-pentachloropropane to the volume of the N, N-dimethyl isobutyramide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 7h, returning the reaction system to room temperature, washing off a solvent and an alkali metal salt by water, drying and removing water to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, and carrying out GC detection and analysis, wherein the results are as follows: the conversion of 1,1,1,3, 3-pentachloropropane was 84.2%, the selectivity to E-1,3,3, 3-tetrachloropropene was 37.4%, and the selectivity to 1,1,3, 3-tetrachloropropene was 56.7%.
Example 21
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-diethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-diethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 7h, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing the water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 62.5%, the selectivity for E-1,3,3, 3-tetrachloropropene was 37.9%, and the selectivity for 1,1,3, 3-tetrachloropropene was 60.8%.
Example 22
Sequentially adding 0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-diisobutylformamide into a three-neck flask with a water condensation tube, wherein the ratio of the amount of the substances of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the ratio of the amount of the substances of the 1,1,1,3, 3-pentachloropropane to the volume of the N, N-diisobutylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 7h, returning the reaction system to room temperature, washing off a solvent and an alkali metal salt by water, drying and removing water to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene, and detecting and analyzing by GC, wherein the results are as follows: the conversion of 1,1,1,3, 3-pentachloropropane was 38.0%, the selectivity to E-1,3,3, 3-tetrachloropropene was 35.5%, and the selectivity to 1,1,3, 3-tetrachloropropene was 63.4%.
Example 23
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 90 ℃, the reaction time is 2 hours, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing the water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 75.4%, the selectivity to E-1,3,3, 3-tetrachloropropene was 42.4%, and the selectivity to 1,1,3, 3-tetrachloropropene was 56.3%.
Example 24
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 90 ℃, the reaction time is 10 hours, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing the water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity to E-1,3,3, 3-tetrachloropropene was 42.8%, and the selectivity to 1,1,3, 3-tetrachloropropene was 56.7%.
Example 25
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 120 ℃, the reaction time is 7h, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity for E-1,3,3, 3-tetrachloropropene was 45.0%, and the selectivity for 1,1,3, 3-tetrachloropropene was 54.7%.
Example 26
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 100 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 2 mol/L, the reaction pressure is normal pressure, the reaction temperature is 90 ℃, the reaction time is 7h, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing water, and the results are as follows after GC detection and analysis: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity to E-1,3,3, 3-tetrachloropropene was 42.6%, and the selectivity to 1,1,3, 3-tetrachloropropene was 56.2%.
Example 27
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 50 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 1 mol/L, the reaction pressure is normal pressure, the reaction temperature is 90 ℃, the reaction time is 7h, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing water, and the results are as follows after GC detection and analysis: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity for E-1,3,3, 3-tetrachloropropene was 41.5%, and the selectivity for 1,1,3, 3-tetrachloropropene was 57.5%.
Example 28
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 20 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 0.4 mol/L, the reaction pressure is normal pressure, the reaction temperature is 90 ℃, the reaction time is 7 hours, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing the water, and the results are as follows after GC detection: the conversion of 1,1,1,3, 3-pentachloropropane was 91.5%, the selectivity to E-1,3,3, 3-tetrachloropropene was 42.3%, and the selectivity to 1,1,3, 3-tetrachloropropene was 56.4%.
Example 29
0.1mol of KF, 0.05mol of 1,1,1,3, 3-pentachloropropane and 200 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, wherein the mass ratio of the 1,1,1,3, 3-pentachloropropane to the KF is 1: 2, the mass ratio of the 1,1,1,3, 3-pentachloropropane to the N, N-dimethylformamide is 1: 4 mol/L, the reaction pressure is normal pressure, the reaction temperature is 90 ℃, the reaction time is 7h, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, and the E-1,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene are obtained by drying and removing water, and the results are as follows after GC detection and analysis: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity for E-1,3,3, 3-tetrachloropropene was 43.4%, and the selectivity for 1,1,3, 3-tetrachloropropene was 55.0%.
Comparative example
0.05mol of 1,1,1,3, 3-pentachloropropane and 40 mL of N, N-dimethylformamide are sequentially added into a three-neck flask with a water condensation tube, the ratio of the amount of the 1,1,1,3, 3-pentachloropropane to the volume of the N, N-dimethylformamide is 1: 0.8 mol/L, the reaction pressure is normal pressure, the reaction temperature is 70 ℃, the reaction time is 7 hours, the reaction system is returned to room temperature, the solvent and the alkali metal salt are removed by washing, the water and the water are removed by drying, and the results are as follows by GC detection analysis: the conversion of 1,1,1,3, 3-pentachloropropane is 0.
TABLE 1 reaction conditions
In conclusion, the method can be used for simultaneously preparing the E-1,3,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene, the obtained E-1,3,3, 3-tetrachloropropene and the 1,1,3, 3-tetrachloropropene have high selectivity, the conversion rate of the 1,1,1,3, 3-pentachloropropane is high, the synthesis conditions of the method are mild, the operation is convenient, and the raw materials are easy to obtain.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (15)
1. A process for the simultaneous preparation of E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene comprising:
reacting 1,1,1,3, 3-pentachloropropane with an alkali metal salt in the presence of an aprotic polar solvent to obtain E-1,3,3, 3-tetrachloropropene and 1,1,3, 3-tetrachloropropene.
2. The method according to claim 1, wherein the aprotic polar solvent is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylisobutyramide, N-diethylformamide, N-diisopropylformamide, dimethyl sulfoxide, and sulfolane.
3. The process according to claim 1, wherein the aprotic polar solvent is N, N-dimethylformamide or N, N-dimethylacetamide.
4. The method of claim 1 or 2, wherein the alkali metal salt is a salt containing lithium, sodium, potassium, rubidium, or cesium.
5. The method according to claim 1 or 2, wherein the alkali metal salt is selected from one or more of fluoride salt, chloride salt, bromide salt, iodide salt, nitrite salt, thiocyanate salt and cyanate salt.
6. The process according to claim 1 or 2, wherein the amount of 1,1,1,3, 3-pentachloropropane to alkali metal salt of the substance is in a ratio of 1: 1-5.
7. The process according to claim 1 or 2, wherein the amount of 1,1,1,3, 3-pentachloropropane to alkali metal salt of the substance is in the ratio of 1: 1.5-5.
8. The process according to claim 1 or 2, wherein the amount of substance of 1,1,1,3, 3-pentachloropropane and the volume ratio of aprotic polar solvent are 1: 0.4-4 mol/L.
9. The process according to claim 1 or 2, wherein the amount of substance of 1,1,1,3, 3-pentachloropropane and the volume ratio of aprotic polar solvent are 1: 0.8-2 mol/L.
10. The process according to claim 1 or 2, wherein the reaction time is 2-20 h.
11. The process according to claim 1 or 2, wherein the reaction time is 4-10 h.
12. The process according to claim 1 or 2, wherein the reaction temperature is 20-120 ℃.
13. The process according to claim 1 or 2, wherein the reaction temperature is 70-90 ℃.
14. The process according to claim 1 or 2, wherein the reaction pressure is from 0.1 to 0.5 MPa.
15. The process of claim 1 or 2, wherein the selectivity to E-1,3,3, 3-tetrachloropropene is from 35 to 45% and the selectivity to 1,1,3, 3-tetrachloropropene is from 55 to 65%.
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