CN111004091A - Method for preparing 4,4,5,5, 5-penta-fluoropentanol - Google Patents
Method for preparing 4,4,5,5, 5-penta-fluoropentanol Download PDFInfo
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- CN111004091A CN111004091A CN201911276485.6A CN201911276485A CN111004091A CN 111004091 A CN111004091 A CN 111004091A CN 201911276485 A CN201911276485 A CN 201911276485A CN 111004091 A CN111004091 A CN 111004091A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
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Abstract
The invention discloses a method for preparing 4,4,5,5, 5-penta-fluoropentanol, which is used for preparing 4,4,5,5, 5-penta-fluoropentanol by one-step catalytic oxidation of 1,1,1,2, 2-penta-fluoropentane in the presence of a supported noble metal composite catalyst, a solvent and an oxidant, wherein the solvent is water, acetonitrile, isopropanol, dimethylformamide and N-methylpyrrolidone, and the oxidant is organic peroxide, and the method comprises the following steps: cumene hydroperoxide, tert-butyl hydroperoxide, acetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, cyclohexanone peroxide, iodosobenzene (PhIO), m-chloroperbenzoic acid, 1,1,1,2, 2-pentafluoropropane: catalyst: solvent: the mass ratio of the oxidant is 1: 0.01-0.1: 0.5-2: 0.05-0.5, and the method for preparing 4,4,5,5, 5-penta-fluoropentanol has the advantages of simple reaction operation, high selectivity and mild reaction conditions.
Description
Technical Field
The invention belongs to the field of fluorine chemical industry, and relates to a preparation method of 4,4,5,5, 5-penta-fluoropentanol.
Background
Penta-fluoropentanol of formula C5H7F5And O, the main application is an antitumor drug intermediate and the production of pentafluoro-pentanethiol, and in recent years, the pentafluropentanol is widely used as an intermediate for the synthesis of surfactants, functional materials, inert liquids and dye industries.
The synthesis method of 4,4,5,5, 5-penta-fluoropentanol mainly comprises the following steps: (1) reacting pentafluoroethyl iodide with allyl acetate to generate 2-iodo-4, 4,5,5, 5-pentafluoro-2-pentyl acetate, and reducing and hydrolyzing to obtain pentafluoropentanol; (2) synthesizing 2-iodo-4, 4,5,5, 5-pentafluoro-2-pentenyl-1-ol by pentafluoroethyl iodide and propargyl alcohol, and reducing to obtain pentafluropentanol; (3) reacting pentafluoroethyl iodide with allyl alcohol to generate 2-iodo-5, 5,5,5, 5-pentafluoro-2-pentyl-1-alcohol, and reducing to obtain pentafluropentanol. All the problems of multiple synthesis steps, complex operation, expensive price of all reagents, low yield and the like exist.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a preparation method of 4,4,5,5, 5-penta-fluoropentanol, which is simple to operate and mild in reaction.
In order to realize the purpose of the invention, the invention takes 1,1,1,2, 2-pentafluoropentane as a raw material to prepare 4,4,5,5, 5-pentafluoropentanol by one-step catalytic oxidation in the presence of a catalyst, an oxidant and a solvent, wherein the reaction temperature is 60-100 ℃, and the reaction time is 1-8 h; the catalyst is a noble metal composite catalyst, the solvent is acetonitrile, isopropanol, dimethylformamide and N-methylpyrrolidone, and the oxidant is organic peroxide.
The noble metal composite catalyst of the present invention comprises: the catalyst comprises active noble metal, a carrier and an auxiliary metal, wherein the active noble metal is silver, gold or platinum, the carrier is inorganic fluoride and comprises: aluminum fluoride, magnesium fluoride and ferric fluoride, wherein the auxiliary metal is iron, nickel, copper, cobalt, bismuth, lanthanum, manganese, cerium or magnesium, and the organic peroxide comprises: cumene hydroperoxide, tert-butyl hydroperoxide, acetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, cyclohexanone peroxide, iodosobenzene (PhIO) and m-chloroperbenzoic acid.
The method for preparing the 2,2,3,3, 3-pentafluoropropanol is carried out by a batch method, 1,1,1,2, 2-pentafluoropentane, a catalyst, a solvent and an oxidant are added into a reactor at one time, the reaction temperature is increased to be 60-120 ℃, the reaction time is 1-8 h, and the reaction pressure is 1.0-2.0 MPA. 1,1,1,2, 2-pentafluoropentane: catalyst: solvent: the mass ratio of the oxidant is 1: 0.01-0.1: 0.5-2: 0.05 to 0.5.
The invention has the beneficial effects that:
the invention develops a new route for synthesizing 4,4,5,5, 5-penta-fluoropentanol. The route takes 1,1,1,2, 2-pentafluoropentane as a raw material, and prepares 4,4,5,5, 5-pentafluoropentanol through one-step catalytic oxidation. The synthetic route has the advantages of simple steps, low raw material cost, convenient operation, high reaction yield and less generation of three wastes, and is a process route suitable for industrial production.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way.
Example 1
Batch liquid phase fluorination reactions were carried out in a stirred 300mL stainless steel autoclave. 1g of Pt/AlF3 catalyst, 100g of isopropanol, 5g of cumene hydroperoxide and 80g of 1,1,1,2, 2-pentafluoropentane are sequentially put into a reaction kettle, the temperature is increased to 80 ℃, the temperature is reduced after the reaction is carried out for 2 hours, and the gas chromatography analysis on an organic phase shows that the conversion rate of the 1,1,1,2, 2-pentafluoropentane is 77.5 percent and the selectivity of the 4,4,5,5, 5-pentafluoropentanol is 79.8 percent.
Examples 2 to 5
Examples 2 to 5 the process for preparing 4,4,5,5, 5-pentafluoropentanol was the same as in example 1 except that the reaction time was changed and the reaction results were as shown in Table 1.
TABLE 1
| Examples | Reaction time/h | 1,1,1,2, 2-pentafluoropentane/%) | 4,4,5,5, 5-penta-fluoropentanol/% ] |
| 2 | 1 | 70.2 | 79.4 |
| 3 | 3 | 77.1 | 77.9 |
| 4 | 6 | 77.6 | 76.5 |
| 5 | 8 | 77.8 | 76.1 |
Examples 6 to 10
Examples 6 to 10 the process for preparing 4,4,5,5, 5-pentafluoropentanol was the same as in example 1 except that the reaction temperature was changed and the reaction results were as shown in Table 2.
TABLE 2
Examples 11 to 13
Examples 11 to 13 4,4,5,5, 5-Pentafluoropentanol preparation was carried out in the same manner as in example 1 except that the solvent was changed and the results of the reaction were as shown in Table 3.
TABLE 3
| Examples | Solvent(s) | 1,1,1,2, 2-pentafluoropentane/%) | 4,4,5,5, 5-penta-fluoropentanol/% ] |
| 11 | Acetonitrile | 74.6 | 71.3 |
| 12 | Dimethyl formamide | 79.9 | 81.2 |
| 13 | N-methyl pyrrolidone | 81.0 | 82.2 |
Examples 14 to 20
Examples 14 to 20 the process for preparing 4,4,5,5, 5-pentafluoropentanol was the same as in example 1 except that the oxidizing agent was changed and the results are shown in Table 4.
TABLE 4
| Examples | Oxidizing agent | 1,1,1,2, 2-pentafluoropentane/%) | 4,4,5,5, 5-penta-fluoropentanol/% ] |
| 14 | Peroxyacetyl | 76.3 | 74.2 |
| 15 | Tert-butyl hydroperoxide | 78.1 | 78.4 |
| 16 | Iodosobenzene (PhIO) | 71.4 | 72.2 |
| 17 | Benzoyl peroxide | 81.7 | 74.7 |
| 18 | Meta-chloroperbenzoic acid | 80.4 | 72.4 |
| 19 | Dibenzoyl peroxide | 68.4 | 67.5 |
| 20 | Cyclohexanone peroxide | 70.3 | 68.3 |
Examples 21 to 38
Examples 21 to 38 the process for preparing 4,4,5,5, 5-pentafluoropentanol was the same as in example 1 except that the catalyst was changed and the results are shown in Table 5.
TABLE 5
Claims (7)
1. The method for preparing 4,4,5,5, 5-penta-fluoropentanol is characterized in that 1,1,1,2, 2-pentafluoropentane is used as a raw material to prepare 4,4,5,5, 5-penta-fluoropentanol through one-step catalytic oxidation in the presence of a catalyst, an oxidant and a solvent, the reaction temperature is 60-120 ℃, and the reaction time is 1-8 hours.
2. The process for preparing 4,4,5,5, 5-pentafluoropentanol according to claim 1, wherein the solvent is one of acetonitrile, isopropanol, dimethylformamide, N-methylpyrrolidone.
3. The process for producing 4,4,5,5, 5-pentafluoropentanol according to claim 1, wherein said oxidizing agent is an organic peroxide.
4. The process for producing 4,4,5,5, 5-pentafluoropentanol according to claim 3, wherein said organic peroxide is: cumene hydroperoxide, tert-butyl hydroperoxide, acetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, cyclohexanone peroxide, iodosobenzene and m-chloroperbenzoic acid.
5. The method of claim 1, wherein the catalyst is a mixture of an active noble metal, a carrier, and an auxiliary metal, and the active noble metal is silver, gold, or platinum; the carrier is inorganic fluoride; the metal of the auxiliary agent is iron, nickel, copper, cobalt, bismuth, lanthanum, manganese, cerium or magnesium.
6. The process for preparing 4,4,5,5, 5-pentafluoropentanol according to claim 5, wherein said inorganic fluoride is aluminum fluoride, magnesium fluoride or iron fluoride.
7. The process for the preparation of 4,4,5,5, 5-pentafluoropentanol according to claim 1 wherein the ratio of 1,1,1,2, 2-pentafluoropentane: catalyst: solvent: the mass ratio of the oxidant is 1: 0.01-0.1: 0.5-2: 0.05 to 0.5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853568A (en) * | 2022-03-16 | 2022-08-05 | 辽宁迪诺医药科技有限公司 | Preparation method of 4,4,5,5, 5-penta-fluoropentanol |
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| US5629458A (en) * | 1996-07-26 | 1997-05-13 | Alliedsignal Inc. | Process for the preparation of 2 2 2 trifluoroethanol |
| CN102648172A (en) * | 2009-10-29 | 2012-08-22 | 卡迪夫大学学院顾问有限公司 | Hydrocarbon selective oxidation with heterogenous gold catalysts |
| CN107501044A (en) * | 2017-08-31 | 2017-12-22 | 天津长芦华信化工股份有限公司 | The preparation method of Pentafluorobenzyl pentanol |
| CN107915581A (en) * | 2017-12-08 | 2018-04-17 | 西安近代化学研究所 | A kind of preparation method of 2,2,3,3,3 5 fluorine propyl alcohol |
| CN107954833A (en) * | 2017-12-08 | 2018-04-24 | 西安近代化学研究所 | A kind of method for preparing five fluorine propyl alcohol of 2,2,3,3,3- |
| CN109534953A (en) * | 2018-12-17 | 2019-03-29 | 西安近代化学研究所 | A method of preparing five fluorine propyl alcohol of 2,2,3,3,3- |
-
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- 2019-12-12 CN CN201911276485.6A patent/CN111004091A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5629458A (en) * | 1996-07-26 | 1997-05-13 | Alliedsignal Inc. | Process for the preparation of 2 2 2 trifluoroethanol |
| CN102648172A (en) * | 2009-10-29 | 2012-08-22 | 卡迪夫大学学院顾问有限公司 | Hydrocarbon selective oxidation with heterogenous gold catalysts |
| CN107501044A (en) * | 2017-08-31 | 2017-12-22 | 天津长芦华信化工股份有限公司 | The preparation method of Pentafluorobenzyl pentanol |
| CN107915581A (en) * | 2017-12-08 | 2018-04-17 | 西安近代化学研究所 | A kind of preparation method of 2,2,3,3,3 5 fluorine propyl alcohol |
| CN107954833A (en) * | 2017-12-08 | 2018-04-24 | 西安近代化学研究所 | A kind of method for preparing five fluorine propyl alcohol of 2,2,3,3,3- |
| CN109534953A (en) * | 2018-12-17 | 2019-03-29 | 西安近代化学研究所 | A method of preparing five fluorine propyl alcohol of 2,2,3,3,3- |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853568A (en) * | 2022-03-16 | 2022-08-05 | 辽宁迪诺医药科技有限公司 | Preparation method of 4,4,5,5, 5-penta-fluoropentanol |
| CN114853568B (en) * | 2022-03-16 | 2023-09-22 | 辽宁孚音生物科技有限公司 | Preparation method of 4, 5-pentafluoropentanol |
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