CN104860795A - Preparation method for 3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyl-1-ol - Google Patents
Preparation method for 3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyl-1-ol Download PDFInfo
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- CN104860795A CN104860795A CN201510189142.1A CN201510189142A CN104860795A CN 104860795 A CN104860795 A CN 104860795A CN 201510189142 A CN201510189142 A CN 201510189142A CN 104860795 A CN104860795 A CN 104860795A
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- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
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Abstract
The invention relates to a preparation method for 3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyl-1-ol. The method comprises the following steps: pouring an anhydrous tetrahydrofuran solvent into a three-necked bottle, adding magnesium powder with nitrogen as protective gas, and adding iodine as an initiator at the same time, then carrying out magnetic stirring, dropwise adding 2-bromoheptafluoropropane under heating, and carrying out magnetic stirring reaction so as to prepare a Grignard reagent; and adding a tetrahydrofuran solvent and ethylene oxide as raw materials into a four-necked bottle, dropwise adding the prepared Grignard reagent and carrying out magnetic stirring reaction, then carrying out reflux reaction, distilling the obtained product so as to obtain a final product--the 3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyl-1-ol. The preparation method for the 3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyl-1-ol provided by the invention has the advantages of simple principle and synthetic process, low requirements on reaction conditions, convenient and safe operation, low requirement on production equipment, applicability to large-scale production and high yield of 95.5%.
Description
Technical field
The present invention relates to chemical production field, refer in particular to the method that one prepares the fluoro-3-of 3,4,4,4-tetra-(trifluoromethyl) fourth-1-alcohol.
Background technology
Fluorocarbon alcohol, as the important intermediate of organic fluorine chemical industry, has unique chemical stability, rotproofness, flame retardant resistance, hydro-oleophobicity, didirtresistance etc. various features; Its application has been deep into all kinds of social production, the sphere of lifes such as weaving, military project, electronics, space flight, anticorrosion, chemical industry, surfacecti proteon, be widely used in the industry such as high-grade clothing, senior building, aircraft manufacturing, precision sizing, historical relic's protection, High-Voltage Insulation, ocean exploitation, coated coating, business activity, immeasurable effect is played to the production of the mankind, life;
At present, fluorocarbon alcohol is produced and is mainly contained electrofluorination method, oligomerisation method and telomerization method three kinds of techniques, and first two method exists the deficiencies such as by product is many, yield is low, pollution is difficult to resolve certainly, surfactivity difference; Telomerization method by product is few, yield is high, and always by the several transnational such as Du Pont, great Jin company monopolizing, current domestic employing does not extract the low-temp low-pressure telomerization method of PFEI out to produce fluorocarbon alcohol, but production capacity wretched insufficiency, domestic needs is main dependence on import still, and for this reason, we have developed one and prepare 3,4, the method of the fluoro-3-of 4,4-tetra-(trifluoromethyl) fourth-1-alcohol, reaction conditions requires low, easy to operate, and improve productivity.
Summary of the invention
The present invention seeks to provide one to prepare the method for 3,4,4,4-tetra-fluoro-3-(trifluoromethyl) fourth-1-alcohol to overcome the deficiencies in the prior art, reaction conditions requires low, easy to operate, and improves productivity.
For achieving the above object, the technical solution used in the present invention is: one prepares 3,4,4, the method of the fluoro-3-of 4-tetra-(trifluoromethyl) fourth-1-alcohol, first anhydrous tetrahydro furan solvent is poured in three-necked bottle, with nitrogen as protection gas, add magnesium powder, add iodine simultaneously and make initiator, and carry out magnetic agitation, drip 2-bromine heptafluoro-propane in a heated condition, the obtained Grignard reagent of magnetic agitation reaction; Join in four-necked bottle using tetrahydrofuran solvent and oxyethane as raw material again, the grignard reagent that dropping prepares also carries out magnetic agitation reaction, and then carry out back flow reaction, products therefrom obtains final product 3 through distillation, the fluoro-3-of 4,4,4-tetra-(trifluoromethyl) fourth-1-alcohol.
Preferably, described grignard reagent slowly drips at-5 DEG C in temperature between 10 DEG C.
Preferably, the time of described back flow reaction is 0.5 to 2 hours.
Preferably, the input amount of described oxyethane is 0.85g to 0.9g.
Due to the utilization of technique scheme, the present invention compared with prior art has following advantages:
Preparation 3 of the present invention, 4, 4, the method of the fluoro-3-of 4-tetra-(trifluoromethyl) fourth-1-alcohol with 2-bromine heptafluoro-propane for initial feed, Grignard reagent is made by 2-bromine heptafluoro-propane and reactive magnesium, C-Mg key is wherein the covalent linkage of high-polarity, electron rich carbon has very strong nucleophilicity, living, it is very active to learn character, do nucleophilic addition occurs with oxyethane, synthesize 3, 4, 4, the fluoro-3-of 4-tetra-(trifluoromethyl) fourth-1-alcohol, principle and synthesis technique simple, reaction conditions requires low, easy and safe to operate, require low to production unit, be applicable to scale operation and productive rate is high, can 95.5% be reached.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, technical solution of the present invention is described further:
Accompanying drawing 1 is the chemical equation of the method for preparation 3,4,4,4-tetra-of the present invention fluoro-3-(trifluoromethyl) fourth-1-alcohol;
Embodiment
Below in conjunction with drawings and the specific embodiments, the present invention is described in further detail.
Accompanying drawing 1 is the method for preparation 3,4,4,4-tetra-of the present invention fluoro-3-(trifluoromethyl) fourth-1-alcohol:
First Grignard reagent is prepared; the anhydrous tetrahydro furan solvent getting 20ml is poured in three-necked bottle; with nitrogen as protection gas; add the magnesium powder of 0.022mol (0.528g); add a small amount of iodine and make initiator; carry out magnetic agitation, drip the 2-bromine heptafluoro-propane of 0.02mol (4.98g) under suitable heating condition, magnetic agitation reacts for some time, and namely to obtain Grignard reagent stand-by.
Example 1 (temperature of reaction T=10 DEG C):
Get four-necked bottle, get the tetrahydrofuran solvent of 50ml, add the oxyethane of 0.02mol (0.88g), install thermometer and condensation reflux unit, temperature controls under 10 DEG C of conditions, the grignard reagent that slow dropping 0.03mol prepares also carries out magnetic agitation reaction, after dropping terminates under 10 DEG C of conditions back flow reaction 0.5h, reaction terminates rear first intensification and to be steamed by solvent, after again 80 DEG C of underpressure distillation by product 3,4,4, the fluoro-3-of 4-tetra-(trifluoromethyl) fourth-1-alcohol steams and can claim quality is 3.62g, and productive rate (calculating with theoretical yield) is for 84.50%.
Embodiment 2-16, reaction response temperature is 10 DEG C, the fluoro-3-of 3,4,4,4-tetra-(trifluoromethyl) fourth-1-alcohol, and the raw material of employing and reagent are as following table:
| Example | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Oxyethane/g | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 |
| 2-bromine heptafluoro-propane/g | 9.96 | 12.45 | 14.94 | 7.47 | 9.96 | 12.45 | 14.94 |
| Temperature of reaction/DEG C | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Time/h | 0.5 | 0.5 | 0.5 | 1 | 1 | 1 | 1 |
| Product quality/g | 3.67 | 3.75 | 3.75 | 3.64 | 3.69 | 3.77 | 3.76 |
| Productive rate/% | 85.67 | 87.58 | 87.62 | 85.05 | 86.32 | 88.09 | 87.92 |
| Example | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 |
| Oxyethane/g | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 |
| 2-bromine heptafluoro-propane/g | 7.47 | 9.96 | 12.45 | 14.94 | 7.47 | 9.96 | 12.45 | 14.94 |
| Temperature of reaction/DEG C | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Time/h | 1.5 | 1.5 | 1.5 | 1.5 | 2 | 2 | 2 | 2 |
| Product quality/g | 3.67 | 3.73 | 3.81 | 3.80 | 3.67 | 3.75 | 3.81 | 3.82 |
| Productive rate/% | 85.82 | 87.20 | 89.09 | 88.89 | 85.68 | 87.58 | 88.93 | 89.29 |
Example 17 (temperature of reaction T=5 DEG C):
Get four-necked bottle, the tetrahydrofuran (THF) getting 50ml makees solvent, add the oxyethane of 0.02mol (0.88g), frame installs thermometer and condensation reflux unit, system temperature controls under 5 DEG C of conditions, the grignard reagent that slow dropping 0.03mol prepares also carries out magnetic agitation reaction, after dropping terminates under 5 DEG C of conditions back flow reaction 0.5h, reaction terminates rear first intensification and to be steamed by solvent, after again 80 DEG C of underpressure distillation by product 3, 4, 4, the fluoro-3-of 4-tetra-(trifluoromethyl) fourth-1-alcohol steams and can claim quality is 3.74g, productive rate (calculating with theoretical yield) is for 87.37%.
Embodiment 18-32, reaction response temperature is 5 DEG C, the fluoro-3-of 3,4,4,4-tetra-(trifluoromethyl) fourth-1-alcohol, and the raw material of employing and reagent are as following table:
Example 33 (temperature of reaction T=0 DEG C):
Get four-necked bottle, the tetrahydrofuran (THF) getting 50ml makees solvent, add the oxyethane of 0.02mol (0.88g), frame installs thermometer and condensation reflux unit, system temperature controls under 0 DEG C of condition, the grignard reagent that slow dropping 0.03mol prepares also carries out magnetic agitation reaction, after dropping terminates under 0 DEG C of condition back flow reaction 0.5h, reaction terminates rear first intensification and to be steamed by solvent, after again 80 DEG C of underpressure distillation by product 3, 4, 4, the fluoro-3-of 4-tetra-(trifluoromethyl) fourth-1-alcohol steams and can claim quality is 3.65g, productive rate (calculating with theoretical yield) is for 85.30%.
Embodiment 34-48, reaction response temperature is 0 DEG C, the fluoro-3-of 3,4,4,4-tetra-(trifluoromethyl) fourth-1-alcohol, and the raw material of employing and reagent are as following table:
| Example | 34 | 35 | 36 | 37 | 38 | 39 | 40 |
| Oxyethane/g | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 |
| 2-bromine heptafluoro-propane/g | 9.96 | 12.45 | 14.94 | 7.47 | 9.96 | 12.45 | 14.94 |
| Temperature of reaction/DEG C | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Time/h | 0.5 | 0.5 | 0.5 | 1 | 1 | 1 | 1 |
| Product quality/g | 3.75 | 3.84 | 3.85 | 3.68 | 3.80 | 3.95 | 3.93 |
| Productive rate/% | 87.73 | 89.75 | 89.97 | 86.06 | 88.82 | 92.51 | 91.80 |
| Example | 41 | 42 | 43 | 44 | 45 | 46 | 47 | 48 |
| Oxyethane/g | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 |
| 2-bromine heptafluoro-propane/g | 7.47 | 9.96 | 12.45 | 14.94 | 7.47 | 9.96 | 12.45 | 14.94 |
| Temperature of reaction/DEG C | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Time/h | 1.5 | 1.5 | 1.5 | 1.5 | 2 | 2 | 2 | 2 |
| Product quality/g | 3.71 | 3.83 | 3.97 | 3.98 | 3.72 | 3.86 | 3.95 | 3.93 |
| Productive rate/% | 86.76 | 89.56 | 92.82 | 93.09 | 86.97 | 90.12 | 92.30 | 91.84 |
Example 49 (temperature of reaction T=-5 DEG C):
Get four-necked bottle, the tetrahydrofuran (THF) getting 50ml makees solvent, add the oxyethane of 0.02mol (0.88g), frame installs thermometer and condensation reflux unit, system temperature controls under-5 DEG C of conditions, the grignard reagent that slow dropping 0.03mol prepares also carries out magnetic agitation reaction, after dropping terminates under-5 DEG C of conditions back flow reaction 0.5h, reaction terminates rear first intensification and to be steamed by solvent, after again 80 DEG C of underpressure distillation by product 3, 4, 4, the fluoro-3-of 4-tetra-(trifluoromethyl) fourth-1-alcohol steams and can claim quality is 3.68g, productive rate (calculating with theoretical yield) is for 85.91%.
Embodiment 50-64, reaction response temperature is-5 DEG C, the fluoro-3-of 3,4,4,4-tetra-(trifluoromethyl) fourth-1-alcohol, and the raw material of employing and reagent are as following table:
| Example | 50 | 51 | 52 | 53 | 54 | 55 | 56 |
| Oxyethane/g | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 |
| 2-bromine heptafluoro-propane/g | 9.96 | 12.45 | 14.94 | 7.47 | 9.96 | 12.45 | 14.94 |
| Temperature of reaction/DEG C | -5 | -5 | -5 | -5 | -5 | -5 | -5 |
| Time/h | 0.5 | 0.5 | 0.5 | 1 | 1 | 1 | 1 |
| Product quality/g | 3.75 | 3.85 | 3.85 | 3.72 | 3.80 | 3.92 | 3.94 |
| Productive rate/% | 87.53 | 90.02 | 89.92 | 86.90 | 88.82 | 91.60 | 92.00 |
| Example | 57 | 58 | 59 | 60 | 61 | 62 | 63 | 64 |
| Oxyethane/g | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 | 0.88 |
| 2-bromine heptafluoro-propane/g | 7.47 | 9.96 | 12.45 | 14.94 | 7.47 | 9.96 | 12.45 | 14.94 |
| Temperature of reaction/DEG C | -5 | -5 | -5 | -5 | -5 | -5 | -5 | -5 |
| Time/h | 1.5 | 1.5 | 1.5 | 1.5 | 2 | 2 | 2 | 2 |
| Product quality/g | 3.64 | 3.78 | 3.98 | 3.97 | 3.74 | 3.82 | 3.98 | 3.99 |
| Productive rate/% | 85.08 | 88.21 | 93.08 | 92.87 | 87.34 | 89.23 | 92.97 | 93.12 |
Due to the utilization of technique scheme, the present invention compared with prior art has following advantages:
Preparation 3 of the present invention, 4,4, the method of the fluoro-3-of 4-tetra-(trifluoromethyl) fourth-1-alcohol for initial feed, makes Grignard reagent by 2-bromine heptafluoro-propane and reactive magnesium with 2-bromine heptafluoro-propane, and C-Mg key is wherein the covalent linkage of high-polarity, electron rich carbon has very strong nucleophilicity, living, it is very active to learn character, does nucleophilic addition occurs with oxyethane
Synthesize the fluoro-3-of 3,4,4,4-tetra-(trifluoromethyl) fourth-1-alcohol, principle and synthesis technique are simple, and reaction conditions requires low, easy and safe to operate, require low to production unit, are applicable to scale operation and productive rate is high, can reach 95.5%.
Below be only embody rule example of the present invention, protection scope of the present invention is not constituted any limitation.The technical scheme that all employing equivalents or equivalence are replaced and formed, all drops within rights protection scope of the present invention.
Claims (4)
1. prepare 3 for one kind, 4, the fluoro-3-(trifluoromethyl of 4,4-tetra-) method of fourth-1-alcohol, it is characterized in that: first anhydrous tetrahydro furan solvent is poured in three-necked bottle, with nitrogen as protection gas, add magnesium powder, add iodine simultaneously and make initiator, and carry out magnetic agitation, drip 2-bromine heptafluoro-propane in a heated condition, the obtained Grignard reagent of magnetic agitation reaction; Join in four-necked bottle using tetrahydrofuran solvent and oxyethane as raw material again, the grignard reagent that dropping prepares also carries out magnetic agitation reaction, and then carry out back flow reaction, products therefrom obtains final product 3 through distillation, the fluoro-3-(trifluoromethyl of 4,4,4-tetra-) fourth-1-alcohol.
2. the fluoro-3-(trifluoromethyl of preparation 3,4,4,4-tetra-according to claim 1) method of fourth-1-alcohol, it is characterized in that: described grignard reagent slowly drips at-5 DEG C in temperature between 10 DEG C.
3. the fluoro-3-(trifluoromethyl of preparation 3,4,4,4-tetra-according to claim 1) method of fourth-1-alcohol, it is characterized in that: the time of described back flow reaction is 0.5 to 2 hours.
4. the fluoro-3-(trifluoromethyl of preparation 3,4,4,4-tetra-according to claim 1) method of fourth-1-alcohol, it is characterized in that: the input amount of described oxyethane is 0.85g to 0.9g.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108715573A (en) * | 2018-08-02 | 2018-10-30 | 江西力田维康科技有限公司 | A kind of preparation method of 3- butene-1-ols |
| CN113943208A (en) * | 2021-12-07 | 2022-01-18 | 山东华安新材料有限公司 | Preparation method of 3,3, 3-trifluoropropanol |
| CN114560754A (en) * | 2022-02-25 | 2022-05-31 | 滁州学院 | Preparation method of alkyl alcohol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102531838A (en) * | 2012-01-18 | 2012-07-04 | 常州市牛塘化工厂有限公司 | Method for preparing 3,3-dimethyl-1-butanol |
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2015
- 2015-04-21 CN CN201510189142.1A patent/CN104860795A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102531838A (en) * | 2012-01-18 | 2012-07-04 | 常州市牛塘化工厂有限公司 | Method for preparing 3,3-dimethyl-1-butanol |
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| D. D. DENSON,ET AL: "SYNTHESIS OF PERFLUOROALIPHATIC GRIGNARD REAGENTS", 《JOURNAL OF FLUORINE CHEMISTRY》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108715573A (en) * | 2018-08-02 | 2018-10-30 | 江西力田维康科技有限公司 | A kind of preparation method of 3- butene-1-ols |
| CN113943208A (en) * | 2021-12-07 | 2022-01-18 | 山东华安新材料有限公司 | Preparation method of 3,3, 3-trifluoropropanol |
| CN114560754A (en) * | 2022-02-25 | 2022-05-31 | 滁州学院 | Preparation method of alkyl alcohol |
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