CN102219636A - Synthesizing method of fluorine-containing iodoalkane - Google Patents
Synthesizing method of fluorine-containing iodoalkane Download PDFInfo
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- CN102219636A CN102219636A CN2011101053252A CN201110105325A CN102219636A CN 102219636 A CN102219636 A CN 102219636A CN 2011101053252 A CN2011101053252 A CN 2011101053252A CN 201110105325 A CN201110105325 A CN 201110105325A CN 102219636 A CN102219636 A CN 102219636A
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- sodium iodide
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Abstract
The invention discloses a synthesizing method of fluorine-containing iodoalkane. The synthesis is carried out under the effect of a phase-transfer catalyst, and/or in a polar aprotic ketone solvent. A compound with a general formula of CFmH3-m(CH2)nX is subject to a halogen exchange reaction with sodium iodide or potassium iodide, such that a compound with a general formula of CFmH3-m(CH2)nI is synthesized, wherein m=2 to 3, n=2 to 5, and X represents Cl or Br. The reaction temperature is 20 DEG C to 140 DEG C. The mass ratio of the phase-transfer catalyst to CFmH3-m(CH2)nX is 0.0005:1 to 0.05:1. The molar ratio of CFmH3-m(CH2)nX to sodium iodide or potassium iodide is 0.5:1 to 5:1. The method provided by the present invention has substantial advantages of short process procedures, and low raw material cost.
Description
Technical field
The present invention relates to synthesis technical field, relate in particular to a kind of synthetic method of fluorine-containing idoalkane.
Background technology
C-I key in the fluorine-containing idoalkane is more active, makes it can easier synthesize other chemical.Therefore become a kind of important fluoro-building block reagent, main as medicine, medical synthetic intermediate.
Disclosing a kind of trifluoro-chloroethane and sodium iodide or potassiumiodide among the CN 1182092 is main raw material, in the presence of quaternary ammonium salt or polyoxyethylene glycol phase-transfer catalyst and in the aprotic polar solvent, synthesized the trifluoro iodoethane, but yield is lower.
In this method, phase-transfer catalyst and aprotic solvent are the essential conditions of fluorine chlorine permutoid reaction, used solvent is N, dinethylformamide, dimethyl sulfoxide (DMSO) and N-Methyl pyrrolidone etc., required temperature is at 100 ℃～150 ℃, and the reaction required time is 12～20h, and yield only is 51～74% then.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of synthetic method of fluorine-containing idoalkane is provided.
The objective of the invention is to be achieved through the following technical solutions: a kind of synthetic method of fluorine-containing idoalkane, the general formula of fluorine-containing idoalkane are CF
mH
3-m(CH
2)
nI, this method is: under the effect of phase-transfer catalyst, and/or in polar protic inert ketones solvent, general formula is CF
mH
3-m(CH
2)
nThe compound of X is with sodium iodide or potassiumiodide generation halogen exchange reaction, and synthetic general formula is CF
mH
3-m(CH
2)
nThe compound of I; Wherein, m=2～3, n=2～5, X is Cl or Br, temperature of reaction is 20 ℃～140 ℃, phase-transfer catalyst and CF
mH
3-m(CH
2)
nThe mass ratio of X is 0.0005～0.05: 1, CF
mH
3-m(CH
2)
nX is 0.5～5: 1 with the mol ratio of sodium iodide or potassiumiodide.
Further, described phase-transfer catalyst is R
1R
2R
3R
4NX, R-C
6H
4-SO
3Na or crown ether, wherein, R
1-R
4Be C
1-C
16Alkyl or benzyl; R is C
6-C
16Alkyl, C
6-C
9Perfluoroalkyl or R
5SO
3Na, R
5Be C
4-C
12Alkyl.
Further, described polar protic inert ketones solvent is the ketone compounds of acetone, butanone, hexanone or pimelinketone.
Further, described temperature of reaction is preferably 70 ℃～110 ℃.
Further, described phase-transfer catalyst and CF
mH
3-m(CH
2)
nThe mass ratio of X is preferably 0.005～0.03: 1, and CF
mH
3-m(CH
2)
nX is preferably 1～3 with the mol ratio of sodium iodide or potassiumiodide: 1.
The invention has the beneficial effects as follows, it is simple that the present invention has a production unit, complicated after-treatment device is lacked, be need not in technical process, and processing parameter control is easy, and processing safety is better, the phase-transfer catalyst consumption is less, price is more honest and cleaner relatively, good reaction selectivity, the product purity height, energy consumption is low, the three wastes are few, environmental pollution is little, invest characteristics such as less.
Embodiment
It is short that the present invention aims to provide a kind of technical process, and the general formula that raw materials cost is low is CF
mH
3-m(CH
2)
nThe synthetic method of the compound of I.
Fluorine-containing idoalkane general formula is CF
mH
3-m(CH
2)
nI, the synthetic method of the fluorine-containing idoalkane of the present invention is under the effect of phase-transfer catalyst, and/or in polar protic inert ketones solvent, is CF by general formula
mH
3-m(CH
2)
nThe compound of X is with sodium iodide or potassiumiodide generation halogen exchange reaction, and synthetic general formula is CF
mH
3-m(CH
2)
nThe compound of I, m=2～3 wherein, n=2～5, X is Cl or Br.Temperature of reaction is 20 ℃～140 ℃, phase-transfer catalyst and CF
mH
3-m(CH
2)
nThe mass ratio of X is 0.0005～0.05: 1, CF
mH
3-m(CH
2)
nX is 0.5～5: 1 with the mol ratio of sodium iodide or potassiumiodide.
Under the condition that phase-transfer catalyst exists, whether no matter solvent arranged, general formula is CF
mH
3-m(CH
2)
nThe compound of X can be CF with sodium iodide or the synthetic general formula of potassiumiodide reaction all
mH
3-m(CH
2)
nThe compound of I, but the reaction times need proper extension, the selectivity of reaction also has certain reduction.Equally, under the condition that has polar protic inert ketones solvent to exist, whether no matter phase-transfer catalyst arranged, general formula is CF
mH
3-m(CH
2)
nThe compound of X can be CF with sodium iodide or the synthetic general formula of potassiumiodide reaction all also
mH
3-m(CH
2)
nThe compound of I, but the reaction times need proper extension.At existing phase-transfer catalyst, have again under the condition of polar protic inert ketones solvent existence, general formula is CF
mH
3-m(CH
2)
nThe compound of X is CF with sodium iodide or the synthetic general formula of potassiumiodide reaction
mH
3-m(CH
2)
nRequired reaction times of the compound of I is the shortest, and selectivity is the highest.
Phase-transfer catalyst is R
1R
2R
3R
4NX, R-C
6H
4-SO
3Na or crown ether, wherein, R
1-R
4Be C
1-C
16Alkyl or benzyl; R is C
6-C
16Alkyl, C
6-C
9Perfluoroalkyl or R
5SO
3Na, R
5Be C
4-C
12Alkyl.
Polar protic inert ketones solvent is ketone compounds such as acetone, butanone, hexanone, pimelinketone.
Temperature of reaction is 20 ℃～140 ℃, preferred 70 ℃～110 ℃.
Phase-transfer catalyst and CF
mH
3-m(CH
2)
nThe mass ratio of X is 0.0005～0.05: 1, preferred 0.005～0.03: 1, and CF
mH
3-m(CH
2)
nX is 0.5～5: 1 with the mol ratio of sodium iodide or potassiumiodide, preferred 1～3: 1.
By the following examples the present invention is carried out more specific description, but the present invention is not limited to described embodiment.
Embodiment 1
In 1.0 L reactors, add 4 g 18-hat-6,3 mol CF
2HCH
2CH
2CH
2Behind the sodium iodide of Cl and 1 mol, sealed reactor.Start stirring, reactor is warming up to 85 ℃, and isothermal reaction 5 h.Reactant after filtration, rectifying obtains CF
3CH
2CH
2CH
2I is 94.3% based on the yield of sodium iodide.
Embodiment 2
In 1.0 L reactors, add 5.5 mol CF
3CH
2CH
2CH
2CH
2Br, behind the sodium iodide of 2 mol and the 500ml acetone, sealed reactor.Start stirring, reactor is warming up to 70 ℃, and isothermal reaction 6 h.Reactant after filtration, rectifying obtains CF
3CH
2CH
2CH
2CH
2I is 80.5% based on the yield of sodium iodide.
Embodiment 3
In 1.0 L reactors, add 1.5g tetramethyl-amine bromide, 3 mol CF
2HCH
2CH
2Cl, 3mol sodium iodide and 500 ml butanone, sealed reactor.Start stirring, reactor is warming up to 75 ℃, and stopped reaction behind isothermal reaction 6 h.Reactant after filtration, rectifying obtains CF
2HCH
2CH
2I is 88.9% based on the yield of sodium iodide.
Embodiment 4
In 1.0 L reactors, add 3.5g nona oxy benzene sulfonic acid sodium salt of perfluoro, 2.5mol potassiumiodide, 500 ml hexanones and 3 mol CF
3CH
2CH
2CH
2CH
2Cl, sealed reactor.Start stirring, reactor is warming up to 85 ℃, and stopped reaction behind isothermal reaction 2.5 h.Reactant after filtration, rectifying obtains CF
3CH
2CH
2CH
2CH
2I is 92.7% based on the yield of potassiumiodide.
Embodiment 5
In 1.0 L reactors, add 2g 18-hat-6,3 mol CF
3CH
2CH
2Cl, behind the sodium iodide of 2 mol and the 500ml pimelinketone, sealed reactor.Start stirring, reactor is warming up to 110 ℃, and isothermal reaction 3h.Reactant after filtration, rectifying obtains CF
3CH
2CH
2I is 95.8% based on the yield of sodium iodide.
Embodiment 6
In 1.0 L reactors, add 0.8g 18-hat-6,3 mol CF
3CH
2CH
2CH
2Cl, behind the potassiumiodide of 1.5 mol and the 500ml acetone, sealed reactor.Start stirring, reactor is warming up to 90 ℃, and isothermal reaction 6 h.Reactant after filtration, rectifying obtains CF
3CH
2CH
2CH
2I is 93.4% based on the yield of potassiumiodide.
Embodiment 7
In 1.0 L reactors, add 5g 18-hat-6,3 mol CF
3CH
2CH
2Cl, behind the sodium iodide of 2 mol and the 500ml acetone, sealed reactor.Start stirring, reactor is controlled at 25 ℃, and isothermal reaction 50h.Reactant after filtration, rectifying obtains CF
3CH
2CH
2I is 43.5% based on the yield of sodium iodide.
Embodiment 8
In 1.0 L reactors, add 1.5g 18-hat-6,3 mol CF
3CH
2CH
2CH
2CH
2Br, behind the sodium iodide of 2 mol and the 500ml acetone, sealed reactor.Start stirring, reactor is controlled at 140 ℃, and isothermal reaction 1.5h.Reactant after filtration, rectifying obtains CF
3CH
2CH
2CH
2CH
2I is 89.5% based on the yield of sodium iodide.
The foregoing description is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (5)
1. the synthetic method of a fluorine-containing idoalkane, the general formula of fluorine-containing idoalkane is CF
mH
3-m(CH
2)
nI is characterized in that, this method is: under the effect of phase-transfer catalyst, and/or in polar protic inert ketones solvent, general formula is CF
mH
3-m(CH
2)
nThe compound of X is with sodium iodide or potassiumiodide generation halogen exchange reaction, and synthetic general formula is CF
mH
3-m(CH
2)
nThe compound of I; Wherein, m=2～3, n=2～5, X is Cl or Br, temperature of reaction is 20 ℃～140 ℃, phase-transfer catalyst and CF
mH
3-m(CH
2)
nThe mass ratio of X is 0.0005～0.05: 1, CF
mH
3-m(CH
2)
nX is 0.5～5: 1 with the mol ratio of sodium iodide or potassiumiodide.
2. general formula according to claim 1 is CF
mH
3-m(CH
2)
nThe synthetic method of the compound of I is characterized in that, described phase-transfer catalyst is R
1R
2R
3R
4NX, R-C
6H
4-SO
3Na or crown ether, wherein, R
1-R
4Be C
1-C
16Alkyl or benzyl; R is C
6-C
16Alkyl, C
6-C
9Perfluoroalkyl or R
5SO
3Na, R
5Be C
4-C
12Alkyl.
3. general formula according to claim 1 is CF
mH
3-m(CH
2)
nThe synthetic method of the compound of I is characterized in that, described polar protic inert ketones solvent is the ketone compounds of acetone, butanone, hexanone or pimelinketone.
4. general formula according to claim 1 is CF
mH
3-m(CH
2)
nThe synthetic method of the compound of I is characterized in that, described temperature of reaction is preferably 70 ℃～110 ℃.
5. general formula according to claim 1 is CF
mH
3-m(CH
2)
nThe synthetic method of the compound of I is characterized in that, described phase-transfer catalyst and CF
mH
3-m(CH
2)
nThe mass ratio of X is preferably 0.005～0.03: 1, and CF
mH
3-m(CH
2)
nX is preferably 1～3 with the mol ratio of sodium iodide or potassiumiodide: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101053252A CN102219636A (en) | 2011-04-26 | 2011-04-26 | Synthesizing method of fluorine-containing iodoalkane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101053252A CN102219636A (en) | 2011-04-26 | 2011-04-26 | Synthesizing method of fluorine-containing iodoalkane |
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|---|---|
| CN102219636A true CN102219636A (en) | 2011-10-19 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107857691A (en) * | 2017-10-30 | 2018-03-30 | 大丰跃龙化学有限公司 | New method prepared by a kind of iodomethane of a fluorine one |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085897A (en) * | 1992-06-03 | 1994-04-27 | 伊莱利利公司 | Angiotension II antagonists |
| CN1982268A (en) * | 2005-12-14 | 2007-06-20 | 上海申大科技公司 | Production of alkyl iodide by halogen exchange reaction |
| JP2010001272A (en) * | 2008-06-23 | 2010-01-07 | Central Glass Co Ltd | Method of preparing ethyl iodides substituted with fluorine-containing alkyl |
-
2011
- 2011-04-26 CN CN2011101053252A patent/CN102219636A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085897A (en) * | 1992-06-03 | 1994-04-27 | 伊莱利利公司 | Angiotension II antagonists |
| CN1982268A (en) * | 2005-12-14 | 2007-06-20 | 上海申大科技公司 | Production of alkyl iodide by halogen exchange reaction |
| JP2010001272A (en) * | 2008-06-23 | 2010-01-07 | Central Glass Co Ltd | Method of preparing ethyl iodides substituted with fluorine-containing alkyl |
Non-Patent Citations (1)
| Title |
|---|
| VIACHESLAV: "Direct Synthesis of polyfluorinated allyl halides from fluoroolefins and AlX3", 《JOURNAL OF FLUORINE CHEMISTRY》, vol. 117, 31 December 2002 (2002-12-31) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107857691A (en) * | 2017-10-30 | 2018-03-30 | 大丰跃龙化学有限公司 | New method prepared by a kind of iodomethane of a fluorine one |
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Application publication date: 20111019 |