CN105884589A - Synthetic method of 3,3,3-trifluoropropionaldehyde - Google Patents
Synthetic method of 3,3,3-trifluoropropionaldehyde Download PDFInfo
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- CN105884589A CN105884589A CN201610227949.4A CN201610227949A CN105884589A CN 105884589 A CN105884589 A CN 105884589A CN 201610227949 A CN201610227949 A CN 201610227949A CN 105884589 A CN105884589 A CN 105884589A
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- acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
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Abstract
The invention discloses a synthetic method of 3,3,3-trifluoropropionaldehyde. The synthetic method comprises the following steps: 1,1-dialkyloxy-3,3,3-trifluorophenylpropane (CF3CH2CH(OR)2), water and a catalyst are added to a three-neck flask, heated to the temperature of 90-140 DEG C and subjected to a reaction for 2-8 h under stirring, wherein in 1,1-dialkyloxy-3,3,3-trifluorophenylpropane (CF3CH2CH(OR)2), R is equal to CH3, C2H5, C3H7, C4H9, C5H11, C6H13, C7H15, C8H17, C9H19 or C10H21, and is preferably equal to C5H11, C6H13, C7H15, C8H17, C9H19 or C10H21; the catalyst is selected from sulfuric acid, hydrochloric acid, toluenesulfonic acid, methacrylic acid and trifluoroacetic acid; the mole ratio of 1,1-dialkyloxy-3,3,3-trifluorophenylpropane to water to the catalyst is 1:(0.5-2):(0.1-0.6).
Description
Technical field
The invention belongs to the synthetic method of technical field of chemistry, be specifically related to the synthetic method of a kind of 3,3,3-trifluoro propionic aldehyde.
Background technology
3,3,3-trifluoro propionic aldehyde can be used as synthesis medicine, the intermediate of pesticide, it is possible to as raw material or the synthetic intermediate of synthesized high-performance fluorine material such as fluoropolymer.US2739987 discloses and makes 1-chloro-3,3,3 ,-trifluoropropene and chain alcohol (such as methanol) be synthesized in the presence of a base to obtain vinyl ethers, and then vinyl ethers hydrolyzes generation 3,3,3-trifluoro propionic aldehyde in acid condition.Target product 3,3, the yield of 3-trifluoro propionic aldehyde is far below 50%, and reason is that side reaction a makes the alcohol by-product of hydrolysis and vinyl ethers raw material form 3, the acetal of 3,3-trifluoro propionic aldehyde.For solving this problem, US6111139 discloses and the alkanoic acid of carbon number 3 to 16 coexisting as the alcohol acceptor in reaction system in vinyl ethers hydrolytic process and has shown that, by-product alcohol is trapped by alkanoic acid so that fully suppressing side reaction in hydrolytic process, 3, the yield of 3,3-trifluoro propionic aldehyde brings up to 70%.But needing to use equivalent or the alkanoic acid of excess in the method, the alkanoate of generation equivalent or excess is as unnecessary by-product, and alkanoic acid is expensive.Following formula is existing patent synthetic route:
Summary of the invention
The technical problem to be solved in the present invention is for defect and deficiency present in prior art, it is provided that a kind of reaction yield is higher, the synthetic method of the 3 of low cost, 3,3-trifluoro propionic aldehyde.
The 3 of the present invention, the synthetic method of 3,3-trifluoro propionic aldehyde, comprise the following steps: addition 1,1-dialkoxy-3,3,3-trifluoro propane (CF in there-necked flask3CH2CH(OR)2), water and catalyst, be warming up to 90 DEG C～140 DEG C, stirring lower reaction 2h～8h.Wherein 1,1-dialkoxy-3,3,3-trifluoro propane CF3CH2CH(OR)2In wherein R=CH3,C2H5, C3H7,C4H9,C5H11,C6H13,C7H15,C8H17,C9H19,C10H21, preferably C5H11,C6H13,C7H15,C8H17,C9H19,C10H21；Used catalyst is sulphuric acid, hydrochloric acid, p-methyl benzenesulfonic acid, pyrovinic acid, trifluoroacetic acid；Wherein 1,1-dialkoxy-3,3,3-trifluoro propane: water: mole making a gesture of measuring than for 1:0.5～2:0.1～0.6 of catalyst.
Advantages of the present invention: the 3 of the present invention, the synthetic method yield of 3,3-trifluoro propionic aldehyde is higher, and 3,3,3-trifluoro propionic aldehyde yields are up to 97%；And the 3 of art methods, 3,3-trifluoro propionic aldehyde yields are only 70%；The 3 of the present invention, the synthetic method of 3,3-trifluoro propionic aldehyde uses cheap water to be one of reaction raw materials, and the known method in background technology needs to use high carbon chain acid as higher in caproic acid price, and synthetic route is relatively costly.
Detailed description of the invention
Below by embodiment, the present invention is described in further detail.
Analytical tool: extra large glad GC-930 type gas chromatograph, Agilent company 30m DB-1 (50m × 0.32mm) capillary chromatographic column.
Analysis condition: post stove initial temperature 50 DEG C, 10 DEG C/min temperature programming is to 250 DEG C, and it is 250 DEG C with detector temperature that temperature of vaporization chamber is 280 DEG C.
The following is the embodiment that inventor provides, these embodiments are preferably examples, the invention is not restricted to these embodiments.
Embodiment 1:
By the 1 of 25g under room temperature, 1-bis-amoxy-3,3,3-trifluoro propane, 1.67g water and 1.1g sulphuric acid add in reaction bulb, connect distillation column condensing tube, heated and stirred is warming up to 120 DEG C, distillation limit, limit reaction 3h, collects 50 DEG C～70 DEG C of fractions, obtain the colourless liquid that 9.32g purity is 98%, yield 98.0%
Structural Identification:
MS:m/z 112(M+), 64 (100).
IR (KBr), υ/cm-1: 2948,2877,2810,1741,1383,1254,1154.
13CNMR(CDCl3), δ/ppm:123.95 (CF3), 47.03 (CH2), 191.90 (CHO).
1HNMR(CDCl3), δ/ppm:9.72 (m, 1H), 3.22 (m, 2H).
Said structure appraising datum confirms, above-described embodiment gained material is strictly 3,3,3-trifluoro propionic aldehyde.
Embodiment 2:
By the 1 of 25g under room temperature, 1-bis-hexyloxy-3,3,3-trifluoro propane, 2.268g water and 1.5g hydrochloric acid add in reaction bulb, connect distillation column condensing tube, heated and stirred is warming up to 120 DEG C, distillation limit, limit reaction 2h, collects 50 DEG C～70 DEG C of fractions, obtain the colourless liquid that 8.47g purity is 98%, yield 97.0%.
Embodiment 3:
By the 1 of 25g under room temperature, 1-bis-epoxide in heptan-3,3,3-trifluoro propane, 2.07g water and 4g p-methyl benzenesulfonic acid add in reaction bulb, connect distillation column condensing tube, heated and stirred is warming up to 120 DEG C, distillation limit, limit reaction 5h, collects 50 DEG C～70 DEG C of fractions, obtain the colourless liquid that 7.8g purity is 98%, yield 97.5%.
Embodiment 4:
By the 1 of 25g under room temperature, 1-bis-octyloxy-3,3,3-trifluoro propane, 0.6g water and 3.8g pyrovinic acid add in reaction bulb, connect distillation column condensing tube, heated and stirred is warming up to 120 DEG C, distillation limit, limit reaction 8h, collects 50 DEG C～70 DEG C of fractions, obtain the colourless liquid that 7.22g purity is 98%, yield 97.8%.
Embodiment 5:
By the 1 of 25g under room temperature, 1-bis-nonyl epoxide-3,3,3-trifluoro propane, 2.22g water and 4g trifluoroacetic acid add in reaction bulb, connect distillation column condensing tube, heated and stirred is warming up to 120 DEG C, distillation limit, limit reaction 7h, collects 50 DEG C～70 DEG C of fractions, obtain the colourless liquid that 6.68g purity is 96.8%, yield 98.0%.
Claims (3)
1. one kind 3, the synthetic method of 3,3-trifluoro propionic aldehyde, including: in there-necked flask, add 1,1-dialkoxy
Base-3,3,3-trifluoro propane (CF3CH2CH(OR)2), water and catalyst, be warming up to 90 DEG C～140 DEG C,
Lower reaction 2h～8h of stirring；Wherein 1,1-dialkoxy-3,3,3-trifluoro propane CF3CH2CH(OR)2In
R=CH3,C2H5,C3H7,C4H9,C5H11,C6H13,C7H15,C8H17,C9H19,C10H21；Wherein 1,1-
Dialkoxy-3,3,3-trifluoro propane: water: the mol ratio of catalyst is 1:0.5～2:0.1～0.6.
The synthetic method of 3,3,3-trifluoro propionic aldehyde the most according to claim 1, described catalyst selected from sulphuric acid,
Hydrochloric acid, p-methyl benzenesulfonic acid, pyrovinic acid, trifluoroacetic acid.
The synthetic method of 3,3,3-trifluoro propionic aldehyde the most according to claim 1, described 1,1-dialkoxy
-3,3,3-trifluoro propane CF3CH2CH(OR)2In, R is C5H11,C6H13,C7H15,C8H17,C9H19,
C10H21。
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| CN201610227949.4A CN105884589A (en) | 2016-04-13 | 2016-04-13 | Synthetic method of 3,3,3-trifluoropropionaldehyde |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2739987A (en) * | 1956-03-27 | Production of fluorine-substituted | ||
| CN101277917A (en) * | 2005-09-29 | 2008-10-01 | 中央硝子株式会社 | Method for producing 3,3,3-trifluoropropionaldehyde |
| CN102320937A (en) * | 2011-09-09 | 2012-01-18 | 西安近代化学研究所 | Preparation method for 3,3,3-trifluoropropionaldehyde dimethoxyethane |
-
2016
- 2016-04-13 CN CN201610227949.4A patent/CN105884589A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2739987A (en) * | 1956-03-27 | Production of fluorine-substituted | ||
| CN101277917A (en) * | 2005-09-29 | 2008-10-01 | 中央硝子株式会社 | Method for producing 3,3,3-trifluoropropionaldehyde |
| CN102320937A (en) * | 2011-09-09 | 2012-01-18 | 西安近代化学研究所 | Preparation method for 3,3,3-trifluoropropionaldehyde dimethoxyethane |
Non-Patent Citations (2)
| Title |
|---|
| YU. L. YAGUPOLSKII等: "Alternative synthetic routes to hydrofluoroolefins", 《JOURNAL OF FLUORINE CHEMISTRY》 * |
| 王暖庆等: "酸催化缩醛缩酮水解机理的理论研究", 《第十届全国计算(机)化学学术会议论文摘要集》 * |
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Application publication date: 20160824 |