Synthesis method of 1, 1, 1, 2, 2, 5, 5, 6, 6, 6-decafluoro-3-hexene

Abstract

The invention belongs to the field of fluorine chemical industry, and particularly relates to a synthesis method of 1, 1, 1, 2, 2, 5, 5, 6, 6, 6-decafluoro-3-hexene. The preparation method comprises the following steps: 1, carrying out addition reaction on pentafluoro halogenated hydrocarbon such as pentafluoro iodoethane or pentafluoro bromoethane serving as a raw material and ethylene, carrying out dehydrohalogenation to obtain 3, 3, 4, 4, 4-pentafluoro butene, carrying out addition reaction on the 3, 3, 4, 4, 4-pentafluoro butene and the pentafluoro halogenated hydrocarbon, and carrying out dehydrohalogenation to obtain 1, 1, 1, 2, 2, 5, 5, 6, 6, 6-decafluoro-3-hexene. And the other method comprises the following steps of: reacting pentafluoro halogenated hydrocarbon serving as a raw material with acetylene to obtain 3, 4-dibromo (diiodo)-1, 1, 1, 2, 2, 5, 5, 6, 6, 6-decafluoro-hexane, and removing bromine or iodine to obtain 1, 1, 1, 2, 2, 5, 5, 6, 6, 6-decafluoro-3-hexene. The synthesis method provided by the invention has the advantages of easily available raw materials, simple operation, convenient purification and easy large-scale production.

Description

Technical Field

[0001] The present invention belongs to the field of fluorine chemical industry, and specifically relates to a method for synthesizing 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene. Background Art

[0002] 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene is a hydrofluoroolefin,

[0003] HFO-153-10mczz, with the chemical formula CF3CF2CH=CHCF2CF3 and a normal-pressure boiling point of 48.8°C, has a small dielectric constant and high volume resistivity, and a GWP of <20. It is an ideal immersion cooling working fluid and also has broad application prospects in the field of environmentally friendly cleaning agents. Currently, there are few reports on the synthesis of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene. Patents WO2023164093A3 and WO2023164153A2 describe methods for using 3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca) as a raw material and catalytically coupling to produce 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene. Alternatively, methods for using 1,1,1-trichloropentafluoropropane (CFC-215cb) as a raw material and catalytically coupling and then hydrogenating to produce 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene are described. The technical routes are as follows:

[0004] C2F5HCl2+C2F5HCl2→C2F5CH=CHC2F5

[0005] C2F5Cl3+C2F5Cl3→C2F5CCl=CClC2F5

[0006] C2F5CCl=CClC2F5+H2→C2F5CH=CHC2F5

[0007] This method has high reaction temperature, complicated operation, difficult to obtain raw materials and dangerous process. Summary of the Invention

[0008] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a method for synthesizing 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0009] To achieve the above object, the technical solution adopted by the present invention is:

[0010] A method for synthesizing 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, using formula (I) or formula (II);

[0011]

[0012] Wherein, X is a halogen; preferably, X is bromine or iodine.

[0013] Formula (I) specifically includes the following steps: 11) using pentafluorohalogenated ethane as a raw material, first adding olefin ethylene; 12) dehydrohalogenating to obtain 3,3,4,4,4-pentafluorobutene; 13) further adding pentafluorohalogenated ethane to the olefin 3,3,4,4,4-pentafluorobutene; 14) dehydrohalogenating to obtain 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0014] Steps 11) and 13) are independently as follows: adding pentafluorohaloethane, olefin and catalyst to a reaction vessel, heating for reaction, and distilling to obtain a product; preferably, the reaction temperature is 70°C-200°C, preferably 80-110°C; preferably, the catalyst is benzoyl peroxide; preferably, the molar ratio of pentafluorochloroethane to olefin is 1:(0.1-1), preferably 1:(0.25-0.4); preferably, the amount of catalyst added is 0.5-5% of the molar number of the olefin monomer, preferably 1-1.5%.

[0015] Steps 12) and 14) are independently as follows: adding a halogenated hydrocarbon to an alkaline solution for dehydrohalogenation; preferably, the alkaline solution is an ethanol aqueous solution of potassium hydroxide; preferably, the concentration of potassium hydroxide is 25%, the ratio of water to ethanol is 10:3, and the reaction temperature is 40°C-80°C; preferably, 60°C.

[0016] Formula (II) specifically comprises the following steps: 21) using pentafluorohalogenated ethane as a raw material, reacting with acetylene to obtain 3,4-dihalogenated-1,1,1,2,2,5,5,6,6,6-decafluoro-hexane; 22) dehalogenating to obtain

[0017] 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0018] The specific steps of step 21) are: adding pentafluorohaloethane, alkyne and catalyst to a reaction vessel, heating the reaction, and distilling to obtain a product; preferably, the reaction temperature is 70°C-200°C, preferably 80-110°C; preferably, the catalyst is benzoyl peroxide; preferably, the molar ratio of pentafluorochloroethane to alkyne is 1:(0.05-0.5), preferably 1:(0.1-0.2); preferably, the amount of catalyst added is 0.5-5% of the molar number of the olefin monomer, preferably 2-2.5%.

[0019] The specific steps of step 22) are: adding ethanol and zinc powder to the reaction vessel, preferably, the mass ratio of zinc powder to ethanol is (0.5-2): (1-3); preferably 1:1.5; heating to boiling, slowly adding 3,4-dihalo-1,1,1,2,2,5,5,6,6,6-decafluoro-hexane, controlling the reaction temperature to 40°C-80°C; preferably 60°C, pouring into water after the reaction is completed, and separating the liquid to obtain 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The technical solution of the present application provides two methods for synthesizing 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene;

[0022] One method is to use pentafluorohalogenated hydrocarbons, such as pentafluoroiodoethane or pentafluorobromoethane, as raw materials, first add ethylene and then dehydrohalogenate to obtain 3,3,4,4,4-pentafluorobutene, and then continue to add pentafluorohalogenated hydrocarbons and then dehydrohalogenate to obtain 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0023] The second method uses pentafluorohalogenated hydrocarbons as raw materials, which are first reacted with acetylene to obtain 3,4-dibromo(diiodo)-1,1,1,2,2,5,5,6,6,6-decafluoro-hexane, and then debrominated or iodinated to obtain 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0024] The synthetic method of the present application has readily available raw materials, simple operation, convenient purification, and is easy to scale up for production. DETAILED DESCRIPTION

[0025] In order to enable those skilled in the art to better understand the technical solutions of the present invention, the present invention is further described in detail below with reference to the embodiments.

[0026] Example 1

[0027] A method for synthesizing 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, using formula (I);

[0028]

[0029] The specific steps include:

[0030] 11) 100 g (0.5 mol) of bromopentafluoroethane, 0.58 g (0.0024 mol) of benzoyl peroxide, and 5.6 g (0.2 mol) of ethylene were added to a 1 L reactor, and then stirred and heated to 100°C. After reacting for 10 h, the liquid in the reactor was discharged and then distilled to obtain 36.32 g of a 1:1 addition product 4-bromo-1,1,1,2,2-pentafluorobutane and 9.08 g of a 1:2 addition product 6-bromo-1,1,1,2,2-pentafluorohexane.

[0031] 12) 4-bromo-1,1,1,2,2-pentafluorobutane was slowly added dropwise to a hot aqueous solution of potassium hydroxide and ethanol (including 28 g of potassium hydroxide, 34.5 g of ethanol, and 45 g of deionized water). The reaction temperature was controlled to 60°C. After the addition was completed, stirring was continued for 30 minutes. The mixture was then poured into deionized water, and the lower layer was separated. The mixture was then washed with water and dried to obtain 22.89 g of 3,3,4,4,4-pentafluorobutene.

[0032] 13) 29.2 g (0.2 mol) of 3,3,4,4,4-pentafluorobutene, 0.63 g (0.0026 mol) of benzoyl peroxide, and 100 g of bromopentafluoroethane (0.5 mol) were added to a 1 L reactor, and then stirred and heated to 100°C. After reacting for 8 h, the liquid in the reactor was released and then distilled to obtain 65.55 g of 3-bromo-1,1,1,2,2,5,5,6,6,6-decafluorohexane.

[0033] 14) 3-bromo-1,1,1,2,2,5,5,6,6,6-decafluorohexane was slowly added dropwise to a hot aqueous solution of potassium hydroxide and ethanol (including 33.6 g of potassium hydroxide, 41.4 g of ethanol, and 54 g of deionized water). The reaction temperature was controlled to 80°C. After the addition was completed, stirring was continued for 30 minutes. The mixture was then poured into deionized water, and the lower layer was separated and then washed with water and dried to obtain 49.16 g of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0034] Example 2

[0035] The synthesis method of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene is shown in Example 1 using formula (I);

[0036] The specific steps include:

[0037] 11) 100 g (0.4 mol) of pentafluoroiodoethane, 0.50 g of benzoyl peroxide (0.0021 mol), and 4.55 g (0.16 mol) of ethylene were added to a 1 L reactor, and then stirred and heated to 90°C. After reacting for 10 h, the liquid in the reactor was discharged and then distilled to obtain 33.39 g of a 1:1 addition product 4-iodo-1,1,1,2,2-pentafluorobutane and 12.27 g of a 1:2 addition product 6-iodo-1,1,1,2,2-pentafluorohexane.

[0038] 12) 4-iodo-1,1,1,2,2-pentafluorobutane was slowly added dropwise to a hot aqueous solution of potassium hydroxide and ethanol (including 20.16 g of potassium hydroxide, 24.84 g of ethanol, and 32.4 g of deionized water). The reaction temperature was controlled to 70°C. After the addition was completed, stirring was continued for 30 minutes. The mixture was then poured into deionized water, and the lower layer was separated. The mixture was then washed with water and dried to obtain 17.61 g of 3,3,4,4,4-pentafluorobutene.

[0039] 13) 23.94 g (0.18 mol) of 3,3,4,4,4-pentafluorobutene, 0.52 g (0.00215 mol) of benzoyl peroxide, and 100 g of pentafluoroiodoethane were added to a 1 L reactor, and then stirred and heated to 100°C. After reacting for 8 h, the liquid in the reactor was released and then distilled to obtain 57.84 g of 3-iodo-1,1,1,2,2,5,5,6,6,6-decafluorohexane.

[0040] 14) 3-iodo-1,1,1,2,2,5,5,6,6,6-decafluorohexane was slowly added dropwise to a hot aqueous solution of potassium hydroxide and ethanol (including 25.2 g of potassium hydroxide, 3.05 g of ethanol, and 40.5 g of deionized water). The reaction temperature was controlled to 80° C. After the addition was completed, stirring was continued for 30 minutes. The mixture was then poured into deionized water, the lower layer was separated, and then washed with water and dried to obtain 38.38 g of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0041] Example 3

[0042] A method for synthesizing 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, characterized by using formula (II);

[0043]

[0044] The specific steps include:

[0045] 21) 100 g of pentafluorobromoethane (0.5 mol), 0.65 g (0.0027 ml) of benzoyl peroxide, and 2.61 g (0.1 mol) of acetylene were added to a 1 L reactor, then stirred and heated to 100°C. After reacting for 12 h, the liquid in the reactor was released and then distilled to obtain 38.31 g of 3,4-dibromo-1,1,1,2,2,5,5,6,6,6-decafluorohexane.

[0046] 22) In a 250 ml flask, 20.60 g of ethanol and 30.89 g of zinc powder were added and heated to boiling. Then, 100 g of 3,4-dibromo-1,1,1,2,2,5,5,6,6,6-decafluorohexane was slowly added dropwise. The reaction temperature was controlled at 60°C. After the addition was completed, stirring was continued for 30 minutes. The mixture was then poured into deionized water, and the lower layer was separated. The mixture was then washed with water and dried to obtain 56.04 g of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0047] Example 4

[0048] The synthesis method of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene is shown in Example 3 using formula (II);

[0049] The specific steps include:

[0050] 21) 100 g (0.4255 mol) of pentafluoroiodoethane, 0.62 g of benzoyl peroxide (0.00256 mol), and 2.11 g (0.08 mol) of acetylene were added to a 1 L reactor, then stirred and heated to 90°C. After reacting for 12 h, the liquid in the reactor was released and then distilled to obtain 38.74 g of 3,4-diiodo-1,1,1,2,2,5,5,6,6,6-decafluorohexane.

[0051] 22) In a 250 ml flask, 17 g of ethanol and 25.51 g of zinc powder were added and heated to boiling. Then, 100 g of 3,4-diiodo-1,1,1,2,2,5,5,6,6,6-decafluorohexane was slowly added dropwise. The reaction temperature was controlled at 60°C. After the addition was completed, stirring was continued for 30 minutes. The mixture was then poured into deionized water, and the lower layer was separated. The mixture was then washed with water and dried to obtain 48.44 g of 3,3,4,4,4-pentafluorobutene.

[0052] In summary, the technical solution of the present application provides two methods for synthesizing 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene;

[0053] One method is to use pentafluorohalogenated hydrocarbons, such as pentafluoroiodoethane or pentafluorobromoethane, as raw materials, first add ethylene and then dehydrohalogenate to obtain 3,3,4,4,4-pentafluorobutene, and then continue to add pentafluorohalogenated hydrocarbons and then dehydrohalogenate to obtain 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0054] The second method uses pentafluorohalogenated hydrocarbons as raw materials, which are first reacted with acetylene to obtain 3,4-dibromo(diiodo)-1,1,1,2,2,5,5,6,6,6-decafluoro-hexane, and then debrominated or iodinated to obtain 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0055] The synthetic method of the present application has readily available raw materials, simple operation, convenient purification, and is easy to scale up for production.

[0056] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for synthesizing 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, characterized in that: Using formula (I) or formula (II); Wherein, X is a halogen; preferably, X is bromine or iodine.

2. The method for synthesizing 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene according to claim 1, characterized in that Formula (I) specifically includes the following steps: 11) using pentafluorohalogenated ethane as a raw material, first adding olefin ethylene; 12) dehydrohalogenating to obtain 3,3,4,4,4-pentafluorobutene; 13) further adding pentafluorohalogenated ethane to the olefin 3,3,4,4,4-pentafluorobutene; 14) dehydrohalogenating to obtain 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

3. The method for synthesizing 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene according to claim 2, characterized in that: Steps 11) and 13) are independently as follows: adding pentafluorohaloethane, olefin and catalyst to a reaction vessel, heating for reaction, and distilling to obtain a product; preferably, the reaction temperature is 70°C-200°C, preferably 80-110°C; preferably, the catalyst is benzoyl peroxide; preferably, the molar ratio of pentafluorochloroethane to olefin is 1:(0.1-1), preferably 1:(0.25-0.4); preferably, the amount of catalyst added is 0.5-5% of the molar number of the olefin monomer, preferably 1-1.5%.

4. The method for synthesizing 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene according to claim 2, characterized in that: Steps 12) and 14) are independently as follows: adding a halogenated hydrocarbon to an alkaline solution for dehydrohalogenation; preferably, the alkaline solution is an ethanol aqueous solution of potassium hydroxide; preferably, the concentration of potassium hydroxide is 25%, the ratio of water to ethanol is 10:3, and the reaction temperature is 40°C-80°C; preferably, 60°C.

5. The method for synthesizing 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene according to claim 1, characterized in that Formula (II) specifically includes the following steps: 21) using pentafluorohalogenated ethane as a raw material and reacting it with acetylene to obtain 3,4-dihalogenated-1,1,1,2,2,5,5,6,6,6-decafluoro-hexane; 22) dehalogenating to obtain 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

6. The method for synthesizing 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene according to claim 5, characterized in that: The specific steps of step 21) are: adding pentafluorohaloethane, alkyne and catalyst to a reaction vessel, heating the reaction, and distilling to obtain a product; preferably, the reaction temperature is 70°C-200°C, preferably 80-110°C; preferably, the catalyst is benzoyl peroxide; preferably, the molar ratio of pentafluorochloroethane to alkyne is 1:(0.05-0.5), preferably 1:(0.1-0.2); preferably, the amount of catalyst added is 0.5-5% of the molar number of the olefin monomer, preferably 2-2.5%.

7. The method for synthesizing 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene according to claim 5, characterized in that: The specific steps of step 22) are as follows: add ethanol and zinc powder to the reaction vessel, preferably, the mass ratio of zinc powder to ethanol is (0.5-2): (1-3); preferably 1:1.5; heat to boiling, slowly add 3,4-dihalo-1,1,1,2,2,5,5,6,6,6-decafluoro-hexane, and control the reaction temperature to 40°C -80°C; preferably 60°C. After the reaction is complete, pour into water and separate the liquid to obtain 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

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