CN102659520A - Synthetic method of 2,3,5,6-tetrafluorobenzyl alcohol - Google Patents
Synthetic method of 2,3,5,6-tetrafluorobenzyl alcohol Download PDFInfo
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- CN102659520A CN102659520A CN2012101003879A CN201210100387A CN102659520A CN 102659520 A CN102659520 A CN 102659520A CN 2012101003879 A CN2012101003879 A CN 2012101003879A CN 201210100387 A CN201210100387 A CN 201210100387A CN 102659520 A CN102659520 A CN 102659520A
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Abstract
The invention which discloses a synthetic method of 2,3,5,6-tetrafluorobenzyl alcohol belongs to the field of the synthetic technology of 2,3,5,6-tetrafluorobenzyl alcohol. The synthetic method is characterized in that 2,3,5,6-tetrafluorobenzyl alcohol is obtained through reacting a raw material 1,2,4,5-tetrafluorobenzene with an organic lithium reagent, and reacting by letting a formaldehyde gas in after above reaction is finished. The synthetic method of the invention, which allows final products to be obtained through a one-step reaction (two stages), has the advantages of avoiding of multi-step reactions of traditional methods, synthetic cost reduction, production period shortening, high reaction yield, and high product purity; and the target products are generated through above almost quantitative reaction, the finished products are obtained through distillation, and the total reaction yield can reach above 90%.
Description
Technical field:
The present invention relates to a kind of 2,3,5, the compound method of 6-tetrafluorobenzyl alcohol, specifically, relate to a kind of from 1,2,4,5-tetra fluoro benzene preparation 2,3,5, the method for 6-tetrafluorobenzyl alcohol.
Background technology:
2,3,5, the 6-tetrafluorobenzyl alcohol is the key intermediate of synthetic transfluthrin.Transfluthrin is to use pyrethroid insecticides by the health of a kind of high-efficiency low-toxicity of Bayer A.G's exploitation the eighties in 20th century; Mainly as the raw material of mosquito-repellent incense, the mothproof product of family expenses, be a pyrethroid insecticides with wide market outlook.Along with Chinese patent expired in 2008, its consumption will obtain very big growth, thereby drives 2,3,5, the fast rise of 6-tetrafluorobenzyl alcohol market demand.
2,3,5 of bibliographical information is arranged at present, and 6-tetrafluorobenzyl alcohol compound method mainly contains following several kinds:
(1) is raw material with the tetrafluoro Terephthalodinitrile,, obtains 2,3,5 through reactions such as hydrolysis, decarboxylation, reduction; The 6-tetrafluorobenzyl alcohol perhaps earlier through decyanation, again through reactions such as hydrolysis, reduction, obtains 2,3; 5, the 6-tetrafluorobenzyl alcohol also can be after removing an itrile group, and reduction earlier obtains tetrafluorobenzene carbaldehyde; Continue to revert to 2,3,5 again, the 6-tetrafluorobenzyl alcohol.
(2) be raw material with the penta fluoro benzene formonitrile HCN, obtain 2,3,5 through reduction, diazotization/hydrolysis, defluorination reaction, the 6-tetrafluorobenzyl alcohol perhaps earlier through defluorinate, obtains 2,3,5, the 6-tetrafluorobenzyl alcohol through reduction, diazotization/hydrolysis reaction again.
。
(3) with the pentafluorobenzoic acid be raw material, obtain 2,3,5 through reduction, defluorination reaction, the 6-tetrafluorobenzyl alcohol perhaps earlier through defluorination reaction, obtains 2,3,5, the 6-tetrafluorobenzyl alcohol through reduction again.
In the above-mentioned compound method, though part has realized industrial applications, part all comes with some shortcomings: at first, reactions step is longer, and most synthetic routes need just can obtain product through three above reactions of step; Secondly, Atom economy is relatively poor, and raw material need remove part molecule sheet and have no progeny and just can obtain product.
Summary of the invention:
The object of the present invention is to provide 2,3,5 of a kind of novelty, the compound method of 6-tetrafluorobenzyl alcohol; With 1,2,4, the 5-tetra fluoro benzene is a raw material; Through single step reaction (two stages) Synthetic 2,3,5,6-tetrafluorobenzyl alcohol; Advantages such as it is short to have reactions step, and Atom economy is good, and reaction yield is high, and product purity is good.
The technical scheme that the present invention adopts is following: a kind of 2,3,5, the compound method of 6-tetrafluorobenzyl alcohol is characterized in that:
Fs: with 1,2,4, the 5-tetra fluoro benzene is a raw material, with the organolithium reagent reaction,
Subordinate phase: after the fs, reaction finished, feed the formaldehyde gas reaction, get 2,3,5, the 6-tetrafluorobenzyl alcohol.
The reaction equation that the present technique scheme relates to is following:
Be provided with further and be:
A kind of 2,3,5, the compound method of 6-tetrafluorobenzyl alcohol, its characteristic is following: raw material 1,2,4, the 5-tetra fluoro benzene is dissolved in the inert solvent, is cooled to 0～-78
oC drips organolithium reagent, dropwises the continued stirring reaction 0.5-3 hour; In reaction system, feed exsiccant formaldehyde gas, stirring reaction 0.5-3 hour; Reaction system is warming up to 0
oC drips protic solvent cancellation reaction to room temperature, and reaction system gets 2,3,5,6-tetrafluorobenzyl alcohol finished product through extraction, distillation.
Inert solvent of the present invention is following one or more mixing: ether, isopropyl ether, MTBE, THF, 2-methyltetrahydrofuran, glycol dimethyl ether, diethylene glycol dimethyl ether, normal hexane, hexanaphthene, normal heptane, benzene,toluene,xylene; The inert solvent consumption is a raw material 1,2,4,0.5～10 times of 5-tetra fluoro benzene quality.
Organolithium reagent of the present invention is following one or more mixing: n-Butyl Lithium, isobutyl-lithium, s-butyl lithium, tert-butyl lithium, n-propyl lithium, sec.-propyl lithium, lithium methide, diisopropylamine lithium (LDA), hexamethyl two silica-based amido lithiums (LHMDS); The effective concentration of organolithium reagent is pressed commodity mark concentration and is calculated, and need not to carry out any dilution or concentrated during use; Organolithium reagent and raw material 1,2,4, the ratio of the amount of substance of 5-tetra fluoro benzene is: 1:1～1.2:1; The rate of addition of organolithium reagent is so that the interior temperature control of reaction system comes definite in the range of reaction temperature that requires.
Temperature of reaction of the present invention is 0～-78
oC, preferred temperature of reaction is-20～-50
oC.
The reaction times of fs reaction according to the invention is 0.5-3 hour, and the preferred reaction times is 0.5-1 hour.
Exsiccant formaldehyde gas of the present invention, can adopt following mode to prepare: heating Paraformaldehyde 96, trioxymethylene, formalin produce formaldehyde gas, and after dry, obtain; Formaldehyde gas can directly feed reaction system, also can get into reaction system through the mode that rare gas element carries; If adopted the mode of carrying, the rare gas element of being selected for use is a kind of mixing for several kinds below being: nitrogen, helium; Formaldehyde and raw material 1,2,4, the ratio of the amount of substance of 5-tetra fluoro benzene is 1:1～3:1; The feeding speed of formaldehyde gas is so that the interior temperature control of reaction system comes definite in the range of reaction temperature that requires.
The reaction times of subordinate phase reaction according to the invention is 0.5-3 hour, and preferred soaking time is 0.5-2 hour.
Temperature during subordinate phase reaction system cancellation of the present invention is 0
oC is to room temperature, and preferred temperature is 0-10
oC.
Subordinate phase reaction system cancellation reagent of the present invention is protic solvent, is preferably following one or more mixing: water, methyl alcohol, ethanol, formic acid, acetate.
The present invention compared with prior art, its beneficial effect is following:
(1), reactions step is short: can obtain the finished product through single step reaction (two stages), avoid the polystep reaction of traditional method, reduce synthetic cost, shorten the production cycle;
(2), the Atom economy of reaction is good: expect that from former the process of product is the process that compound molecular weight increases;
(3), reaction yield is high, product purity is good: reaction almost quantitatively generates title product, through distillation get final product finished product, overall yield of reaction can reach more than 90%.
Further specify technical scheme of the present invention with specific embodiment below, but protection scope of the present invention is not limited thereto.
Embodiment:
Embodiment one:
In 500 milliliters of four-hole boiling flasks that mechanical stirring, TM, constant pressure funnel are housed, add 1,2,4,5-tetra fluoro benzene 50 grams, anhydrous 2-methyltetrahydrofuran 100 grams stir under nitrogen protection and are cooled to-50
oC, 220 milliliters of the hexane solutions (1.6 mol/L) of dropping n-Butyl Lithium are after dropwising; Continue to stir 0.5 hour; In system, feed formaldehyde gas (generated after adding thermal depolymerization by 20 gram Paraformaldehyde 96s, and slowly brought into by nitrogen gas stream), the logical continued that finishes stirred 0.5 hour.Reaction system is warming up to 5
oC drips 100 gram water, filters, and removes insolubles, and filtrating is told organic phase, and water merges organic phase with 2-methyltetrahydrofuran 40 gram extractions 2 times, through drying, precipitation, distill 2,3,5,6-tetrafluorobenzyl alcohol 56.4 restrains purity 99.3 %.
Embodiment two:
In 500 milliliters of four-hole boiling flasks that mechanical stirring, TM, constant pressure funnel are housed, add 1,2,4,5-tetra fluoro benzene 30 grams, anhydrous tetrahydro furan 80 grams stir under nitrogen protection and are cooled to-40
oC, 130 milliliters of the hexane solutions (1.6 mol/L) of dropping n-Butyl Lithium are after dropwising; Continue to stir 0.5 hour; In system, feed formaldehyde gas (generated after adding thermal depolymerization by 12 gram Paraformaldehyde 96s, and slowly brought into by nitrogen gas stream), the logical continued that finishes stirred 1 hour.Reaction system is warming up to 10
oC drips 80 gram water, filters, and removes insolubles, and filtrating is told organic phase, and water merges organic phase with ETHYLE ACETATE 30 gram extractions 2 times, through drying, precipitation, distill 2,3,5,6-tetrafluorobenzyl alcohol 32.9 restrains purity 99.1 %.
Embodiment three:
In 500 milliliters of four-hole boiling flasks that mechanical stirring, TM, constant pressure funnel are housed, add 1,2,4,5-tetra fluoro benzene 30 grams, anhydrous tetrahydro furan 70 grams stir under nitrogen protection and are cooled to-30
oC drips diisopropylamine lithium solution (2.0 mol/L) 105 milliliters, after dropwising; Continue to stir 1 hour; In system, feed formaldehyde gas (generated after adding thermal depolymerization by 10 gram Paraformaldehyde 96s, and slowly brought into by nitrogen gas stream), the logical continued that finishes stirred 1 hour.Reaction system is warming up to 10
oC drips 80 gram water, filters, and removes insolubles, and filtrating is told organic phase, and water merges organic phase with ETHYLE ACETATE 20 gram extractions 2 times, through drying, precipitation, distill 2,3,5,6-tetrafluorobenzyl alcohol 32.4 restrains purity 99.0 %.
Embodiment four:
In 500 milliliters of four-hole boiling flasks that mechanical stirring, TM, constant pressure funnel are housed, add 1,2,4,5-tetra fluoro benzene 45 grams, anhydrous glycol dimethyl ether 100 grams stir under nitrogen protection and are cooled to-40
oC, 200 milliliters of the hexane solutions (1.6 mol/L) of dropping n-Butyl Lithium are after dropwising; Continue to stir 0.5 hour; In system, feed formaldehyde gas (generated after adding thermal depolymerization by 18 gram Paraformaldehyde 96s, and slowly brought into by nitrogen gas stream), the logical continued that finishes stirred 0.5 hour.Reaction system is warming up to 0
oC drips 100 gram water, filters, and removes insolubles, and filtrating is told organic phase, and water merges organic phase with ETHYLE ACETATE 40 gram extractions 2 times, through drying, precipitation, distill 2,3,5,6-tetrafluorobenzyl alcohol 49.7 restrains purity 99.4 %.
Embodiment five:
In 500 milliliters of four-hole boiling flasks that mechanical stirring, TM, constant pressure funnel are housed, add 1,2,4,5-tetra fluoro benzene 45 grams, anhydrous diethylene glycol dimethyl ether 120 grams stir under nitrogen protection and are cooled to-40
oC, 200 milliliters of the hexane solutions (1.6 mol/L) of dropping n-Butyl Lithium are after dropwising; Continue to stir 0.5 hour; In system, feed formaldehyde gas (generated after adding thermal depolymerization by 18 gram Paraformaldehyde 96s, and slowly brought into by nitrogen gas stream), the logical continued that finishes stirred 0.5 hour.Reaction system is warming up to 5
oC drips 100 gram water, filters, and removes insolubles, and filtrating is told organic phase, and water merges organic phase with ETHYLE ACETATE 40 gram extractions 2 times, through drying, precipitation, distill 2,3,5,6-tetrafluorobenzyl alcohol 48.7 restrains purity 99.0 %.
Embodiment six:
In 500 milliliters of four-hole boiling flasks that mechanical stirring, TM, constant pressure funnel are housed, add 1,2,4,5-tetra fluoro benzene 45 grams, anhydrous 2-methyltetrahydrofuran 100 grams stir under nitrogen protection and are cooled to-40
oC, 200 milliliters of the hexane solutions (1.6 mol/L) of dropping isobutyl-lithium are after dropwising; Continue to stir 0.5 hour; In system, feed formaldehyde gas (generated after adding thermal depolymerization by 18 gram Paraformaldehyde 96s, and slowly brought into by nitrogen gas stream), the logical continued that finishes stirred 0.5 hour.Reaction system is warming up to 5
oC drips 100 gram water, filters, and removes insolubles, and filtrating is told organic phase, and water merges organic phase with 2-methyltetrahydrofuran 30 gram extractions 2 times, through drying, precipitation, distill 2,3,5,6-tetrafluorobenzyl alcohol 50.5 restrains purity 99.3 %.
Embodiment seven:
In 500 milliliters of four-hole boiling flasks that mechanical stirring, TM, constant pressure funnel are housed, add 1,2,4,5-tetra fluoro benzene 30 grams, anhydrous tetrahydro furan 80 grams stir under nitrogen protection and are cooled to-40
oC, 130 milliliters of the hexane solutions (1.6 mol/L) of dropping n-Butyl Lithium are after dropwising; Continue to stir 0.5 hour; In system, feed formaldehyde gas (generated after adding thermal depolymerization by 12 gram trioxymethylenes, and slowly brought into by nitrogen gas stream), the logical continued that finishes stirred 1 hour.Reaction system is warming up to 10
oC, Dropwise 50 gram water filters, and removes insolubles, filtrating is told organic phase, water merges organic phase with ETHYLE ACETATE 30 gram extractions 2 times, through drying, precipitation, distill 2,3,5,6-tetrafluorobenzyl alcohol 32.9 restrains purity 99.1 %.
Claims (10)
1. one kind 2,3,5, the compound method of 6-tetrafluorobenzyl alcohol is characterized in that: with 1,2,4, the 5-tetra fluoro benzene is a raw material, with the organolithium reagent reaction, after reaction finishes, feeds the formaldehyde gas reaction, gets 2,3,5, the 6-tetrafluorobenzyl alcohol.
2. according to claim 1 a kind of 2,3,5, the compound method of 6-tetrafluorobenzyl alcohol is characterized in that: with raw material 1,2,4, the 5-tetra fluoro benzene is dissolved in the inert solvent, is cooled to 0～-78
oC drips organolithium reagent, after dropwising, continues stirring reaction 0.5-3 hour; In reaction system, feed exsiccant formaldehyde gas, stirring reaction 0.5-3 hour then; Be warming up to 0
oC～room temperature drips protic solvent cancellation reaction, through extraction, distill 2,3,5,6-tetrafluorobenzyl alcohol finished product.
3. according to claim 2 a kind of 2; 3; 5; The compound method of 6-tetrafluorobenzyl alcohol is characterized in that: inert solvent is one or more of ether, isopropyl ether, MTBE, THF, 2-methyltetrahydrofuran, glycol dimethyl ether, diethylene glycol dimethyl ether, normal hexane, hexanaphthene, normal heptane, benzene,toluene,xylene; The inert solvent consumption is a raw material 1,2,4,0.5～10 times of 5-tetra fluoro benzene quality.
4. according to claim 2 a kind of 2; 3; 5; The compound method of 6-tetrafluorobenzyl alcohol is characterized in that: organolithium reagent is one or more of n-Butyl Lithium, isobutyl-lithium, s-butyl lithium, tert-butyl lithium, n-propyl lithium, sec.-propyl lithium, lithium methide, diisopropylamine lithium, hexamethyl two silica-based amido lithiums; Organolithium reagent and raw material 1,2,4, the ratio of the amount of substance of 5-tetra fluoro benzene is: 1:1～1.2:1.
5. according to claim 2 a kind of 2,3,5, the compound method of 6-tetrafluorobenzyl alcohol is characterized in that: 1,2,4, and the temperature of reaction of 5-tetra fluoro benzene and organolithium reagent reaction is-20～-50
oC, the reaction times is 0.5-1 hour.
6. according to claim 2 a kind of 2,3,5, the compound method of 6-tetrafluorobenzyl alcohol is characterized in that: formaldehyde and raw material 1,2,4, the ratio of the amount of substance of 5-tetra fluoro benzene is 1:1～3:1.
7. according to claim 2 or 6 described a kind of 2; 3,5, the compound method of 6-tetrafluorobenzyl alcohol; It is characterized in that: the exsiccant formaldehyde gas adopts following method preparation: heating Paraformaldehyde 96, trioxymethylene or formalin obtain formaldehyde gas, then formaldehyde gas are carried out drying.
8. according to claim 2 a kind of 2,3,5, the compound method of 6-tetrafluorobenzyl alcohol is characterized in that: formaldehyde gas gets into reaction system through the mode that rare gas element carries.
9. according to claim 8 a kind of 2,3,5, the compound method of 6-tetrafluorobenzyl alcohol is characterized in that: rare gas element is one or both of nitrogen, helium.
10. according to claim 2 a kind of 2,3,5, the compound method of 6-tetrafluorobenzyl alcohol is characterized in that: protic solvent is one or more of water, methyl alcohol, ethanol, formic acid, acetate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292399A (en) * | 2021-04-30 | 2021-08-24 | 浙江中欣氟材股份有限公司 | Synthetic method of transfluthrin intermediate |
| CN115259996A (en) * | 2022-08-29 | 2022-11-01 | 浙江中欣氟材股份有限公司 | Synthetic method of transfluthrin intermediate |
Citations (4)
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| EP0060617A1 (en) * | 1981-03-18 | 1982-09-22 | Imperial Chemical Industries Plc | Fluorobenzyl cyclopropane carboxylates, their preparation, compositions and use as insecticides |
| JPH0840958A (en) * | 1994-03-04 | 1996-02-13 | Hoechst Schering Agrevo Gmbh | New production of 2,6-bis(trifluoromethyl)benzyl alcohol |
| CN1503772A (en) * | 2001-04-23 | 2004-06-09 | 石原产业株式会社 | Process for the preparation of benzyl alcohols |
| CN1989105A (en) * | 2004-07-19 | 2007-06-27 | 辉瑞产品有限公司 | Preparation of novel substituted haloarene compounds |
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2012
- 2012-04-09 CN CN201210100387.9A patent/CN102659520B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0060617A1 (en) * | 1981-03-18 | 1982-09-22 | Imperial Chemical Industries Plc | Fluorobenzyl cyclopropane carboxylates, their preparation, compositions and use as insecticides |
| JPH0840958A (en) * | 1994-03-04 | 1996-02-13 | Hoechst Schering Agrevo Gmbh | New production of 2,6-bis(trifluoromethyl)benzyl alcohol |
| CN1503772A (en) * | 2001-04-23 | 2004-06-09 | 石原产业株式会社 | Process for the preparation of benzyl alcohols |
| CN1989105A (en) * | 2004-07-19 | 2007-06-27 | 辉瑞产品有限公司 | Preparation of novel substituted haloarene compounds |
Non-Patent Citations (2)
| Title |
|---|
| 唐渝等: "2,3,5,6-四氟苯甲醇的合成", 《有机化学》, vol. 25, no. 09, 25 September 2005 (2005-09-25) * |
| 梁强等: "有机锂化合物及其在有机合成中的应用", 《晋东南师范专科学校学报》, vol. 20, no. 05, 30 October 2003 (2003-10-30) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292399A (en) * | 2021-04-30 | 2021-08-24 | 浙江中欣氟材股份有限公司 | Synthetic method of transfluthrin intermediate |
| CN115259996A (en) * | 2022-08-29 | 2022-11-01 | 浙江中欣氟材股份有限公司 | Synthetic method of transfluthrin intermediate |
| CN115259996B (en) * | 2022-08-29 | 2024-02-02 | 浙江中欣氟材股份有限公司 | Synthesis method of 2,3,5, 6-tetrafluorobenzyl alcohol |
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Address after: 312000 Hangzhou Bay Shangyu economic and Technological Development Zone, Zhejiang, Shaoxing Patentee after: ZHEJIANG ZHONGXIN FLUORINE MATERIALS CO., LTD. Address before: 312000 Zhejiang city of Shaoxing province Shangyu city Hangzhou Bay Industrial Park, Shangyu Road No. 2 Patentee before: Zhejiang Zhongxin Chemical Co., Ltd. |