CN1204104C - Process for preparing 2,3,5,6-Tetrafluoro-para-xylyl alcohol - Google Patents
Process for preparing 2,3,5,6-Tetrafluoro-para-xylyl alcohol Download PDFInfo
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- CN1204104C CN1204104C CN 03129998 CN03129998A CN1204104C CN 1204104 C CN1204104 C CN 1204104C CN 03129998 CN03129998 CN 03129998 CN 03129998 A CN03129998 A CN 03129998A CN 1204104 C CN1204104 C CN 1204104C
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Abstract
The present invention discloses a preparation method of 2, 3, 5, 6-tetrafluoro p-methylbenzyl alcohol, which belohngs to the preparation technology of the 2, 3, 5, 6-tetrafluoro p-methylbenzyl alcohol. In the method, 2, 3, 5, 6-tetrachloroterephthaloyl chloride is used as a raw material, and the 2, 3, 5, 6-tetrafluoro p-methylbenzyl alcohol is prepared by fluorination, esterification, reduction, bromination and reduction. A fluorinating agent in fluorination reactions is potassium fluoride, etc., solvents are sulfolane, etc., catalysts are calixarene, etc., and a reaction temperature is from 40 to 230 DEG C. An esterifying agent of an esterification reaction is fatty alcohol or aromatic alcohol, and the reaction temperature is from 20 to 120 DEG C. A reducing agent of a reduction reaction of ester is sodium borohydride, etc., a solvent is sulfolane, etc., and the reaction temperature is from-10 to 60 DEG C. A brominating agent of a bromination reaction is HBr acid, a solvent is methylene chloride, and the reaction temperature is from 30 to 160 DEG C. The reducing agent of the reduction reaction of bromide is magnesium powder, etc., solvents are fatty alcohol, water, chloride, etc., and the reaction temperature is from-10 to 50 DEG C. The preparation method has the characteristics of simple technology, low production cost and high product yield and the purity and is suitable for industrialized production.
Description
Technical field
The invention relates to 2,3,5, the 6-tetrafluoro is to the new preparation method of xylyl alcohol.Belong to 2,3,5, the 6-tetrafluoro is to the xylyl alcohol technology of preparing.
Background technology
2,3,5, the 6-tetrafluoro is important pesticide intermediate to xylyl alcohol, is used to prepare pyrethroid pesticide etc.The synthetic route of bibliographical information is by 2,3,5, the 6-tetra fluoro benzene be raw material through methylating, carbonylation, reductive synthetic method, concrete route is as follows:
Used reagent such as methyl iodide during the raw material 2,3,5 that this route is used, 6-tetra fluoro benzene reach and synthesize, lithium aluminum hydride costs an arm and a leg, and is not suitable for suitability for industrialized production; And the reaction conditions requirement is harsh, as need be in low temperature-45 ℃ operation down in methylating, and carbonylation then needs to use high pressure, makes 2,3,5, and the 6-tetrafluoro is to xylyl alcohol total recovery very low (having only 1%) (GB2127013 1984-04-04).
Summary of the invention
The object of the present invention is to provide a kind ofly 2,3,5, the 6-tetrafluoro is to the preparation method of xylyl alcohol, and this method has that technology is simple, production cost is low, product yield and the high characteristics of purity.
The present invention is realized by following technical proposals.With 2,3,5,6-tetrachloro-p-phenylene dimethyl chloride be raw material through fluoridize, esterification, reduction, bromination, reduction be prepared from.Reaction formula is as follows:
R=CH in the following formula
3, C
2H
5, C
3H
7Or C
6H
5CH
2
It is characterized in that:
1, the fluorizating agent of fluoridation employing is Potassium monofluoride or Sodium Fluoride, and solvent is tetramethylene sulfone or dimethyl sulfoxide (DMSO).Catalyzer is quaternary amine or calixarene.Its consumption is with 2,3,5 of 1mol, and 6-tetrachloro-p-phenylene dimethyl chloride is that benchmark calculates, and the fluorizating agent consumption is 6mol～20mol, and catalyst levels is 0.01mol～1mol; 2,3,5 of 1g, 6-tetrachloro-p-phenylene dimethyl chloride, needing solvent load is 5mL～30mL; Temperature of reaction is 40 ℃～230 ℃, and the reaction times is 1h～12h.
2, esterification employing esterifying agent is Fatty Alcohol(C12-C14 and C12-C18) or aromatic alcohol, and Fatty Alcohol(C12-C14 and C12-C18) is selected from methyl alcohol, ethanol or propyl alcohol; Aromatic alcohol is a benzylalcohol, and its consumption is with 2,3,5 of 1g, and 6-tetrafluoro terephthaldehyde acyl fluorides is that benchmark calculates, and pure consumption is 2mL～40mL; Temperature of reaction is 20 ℃～120 ℃, and the reaction times is 0.1h～10h.
3, reduction reaction employing sodium borohydride or POTASSIUM BOROHYDRIDE are reductive agent, and solvent is tetramethylene sulfone or diethylene glycol dimethyl ether, and its consumption is with 2,3,5 of 1g, and 6-tetrafluoro terephthalate is that benchmark calculates, and the reductive agent consumption is 0.2g～2g; Solvent load is 2mL～40mL; Temperature of reaction is-10 ℃～60 ℃, and the reaction times is 5h～50h.
4, bromination reaction adopts HBr acid, bromo-succinimide (BNS) or Br
2Be bromizating agent, solvent is benzene, toluene or dimethylbenzene.Its consumption is with 2,3,5 of 1mol, and the 6-tetrafluoro is that benchmark calculates to two benzylalcohols, and the bromizating agent consumption is 1mol～15mol.Temperature of reaction is 30 ℃～160 ℃, and the reaction times is 1h～20h.
5, reduction reaction employing magnesium powder or zinc powder are reductive agent, and solvent is methyl alcohol or ethanol, and its consumption is with 2,3,5 of 1g, and the 6-tetrafluoro is that benchmark calculates to brooethyl benzylalcohol, and the reductive agent consumption is 0.1g～20g, and solvent load is 20mL～100mL; Temperature of reaction is-10 ℃～50 ℃, and the reaction times is 5h～50h.
The temperature of above-mentioned fluoridation is 100 ℃～200 ℃, and the catalyst levels of fluorination process is 0.05mol～0.5mol; Esterification reaction temperature is 50 ℃～100 ℃; The bromination reaction temperature is 50 ℃～120 ℃.
The present invention compares with existing synthetic route, and its enthusiasm is: raw material sources are convenient, low price, and total recovery is greater than 40%, so production cost is low, and because process operation is easy to be reliable, condition is easily controlled, and therefore, can guarantee quality product, the product purity height again.
Embodiment
Example 1
2,3,5, the preparation of 6-tetrafluoro terephthalic acid methyl esters
With 10g anhydrous potassium fluoride powder, 100mL tetramethylene sulfone, 8.75g tetrachloro-p-phenylene dimethyl chloride, 1g cup cyclo catalyst, add in the reactor behind the thorough mixing, be warming up to 220 ℃, be cooled to below 20 ℃ behind the reaction 2h under this temperature, add the 100mL anhydrous methanol, at 60 ℃ of reaction 6h.With the esterification products suction filtration, remove Potassium monofluoride and inorganic salt.Filtrate desolventizes the back and adds in the water of about 50mL, separates out precipitation, and suction filtration, washing, oven dry get product 6.43g, yield 93.87%.The product fusing point: 72 ℃～74 ℃, the liquid-phase chromatographic analysis product purity is 97.01%.
Gas-matter coupling is analyzed, and MS:m/e (relative abundance, %), 266[M, 40], 235[M-OCH
3, 100], 247[M-F, 2].
IR analyzes: 1726.4cm
-1, 1485.3cm
-1, 1217.2cm
-1
Example 2
2,3,5, the 6-tetrafluoro is to the preparation of benzene two benzylalcohols
The 1.90g sodium borohydride is dissolved in the 30mL diethylene glycol dimethyl ether, and slowly adding is dissolved in the tetrafluoro dimethyl terephthalate (DMT) that the 5.00g in the 10mL diethylene glycol dimethyl ether is obtained by example 1, keeps temperature to be lower than 10 ℃, reaction 12h.Use dichloromethane extraction, be cooled to 0 ℃, pickling, alkali cleaning behind the recovery solvent, get the 2.76g product, and fusing point is 122 ℃～124 ℃, and yield is 70.0%.Product is identified through gas-matter coupling.
MS:m/e (relative abundance, %) 210[M, 100], 209[M-H, 25], 193[M-OH, 2] and, 189[M-F-2H, 50], 163[M-CH
2OH-OH+H, 90], 145[M-CH
2OH-F-OH+2H, 75].
Example 3
2,3,5, the 6-tetrafluoro is to the preparation of brooethyl benzylalcohol
1g (4.8mmol) by example 2 obtain 2,3,5, the 6-tetrafluoro joins among the 5mL two benzylalcohols, adds 48% HBr acid 10g (47mmol), 10mL benzene.Reaction mixture is at 65 ℃～70 ℃ heated and stirred 2h.Isolate the upper toluene layer after the reaction mixture cooling.Toluene with anhydrous magnesium sulfate drying after rotary evaporation reclaim toluene and get faint yellow solid 0.7g, yield 54%., identify that through gas-matter coupling liquid phase analysis purity is 94%.
(2 * 10mL) extractions obtain 0.5g raw material, Recycling after ether steams with ether to tell water layer behind the toluene.Calculate total recovery near 100% by raw material consumption.
Example 4
2,3,5, the 6-tetrafluoro is to the preparation of xylyl alcohol
With 1.4g by example 3 obtain 2,3,5, the 6-tetrafluoro is dissolved in the 40mL methyl alcohol brooethyl benzylalcohol, the cooling of outer ice bath adds 2.8g magnesium powder (51.3mmol) and stirs 2h, stirs 14h under the room temperature.Pour in the 20mL water, add hcl acidifying, use extracted with diethyl ether again, steam ether and obtain yellow solid product 0.7g, yield 70%.Liquid phase analysis purity 97%.
MS:m/e (relative abundance, %), 194 (M, 97), 173 (M-F-2H, 100), 163 (M-CH
2OH, 25), 145 (M-F-CH
2OH+H, 80).
Example 5
2,3,5, the preparation of 6-tetrafluoro terephthaldehyde acetoacetic ester
With 15g anhydrous potassium fluoride powder, 100mL dimethyl sulfoxide (DMSO), 8.75g tetrachloro-p-phenylene dimethyl chloride, 1.5g hexadecyl brometo de amonio quaternary ammonium salt catalyst, add in the reactor behind the thorough mixing, be warming up to 200 ℃, be cooled to below 20 ℃ behind the reaction 4h under this temperature, add the 80mL dehydrated alcohol, at 60 ℃ of reaction 4h.With the esterification products suction filtration, filtrate desolventizes the back and adds in the water of about 50mL, separates out precipitation, and suction filtration, washing, oven dry get product 5.80g, yield 81.0%.The product fusing point: 72 ℃～74 ℃, the liquid-phase chromatographic analysis product purity is 97.00%.
Example 6
2,3,5, the 6-tetrafluoro is to the preparation of benzene two benzylalcohols
Take by weighing the 2.0g POTASSIUM BOROHYDRIDE and be dissolved in the 15mL tetramethylene sulfone, adding slowly is dissolved in 5.00g tetrafluoro diethyl terephthalate solution in the 15mL tetramethylene sulfone, keeps temperature less than 10 ℃, reaction 24h.Use dichloromethane extraction, be cooled to 0 ℃, pickling, alkali cleaning behind the recovery solvent, get the 3.07g product, and fusing point is 122 ℃～124 ℃, and yield is 78.0%.
Example 7
2,3,4, the 5-tetrafluoro is to the preparation of brooethyl benzylalcohol
2,3,5 of 1g, the 6-tetrafluoro is added among the 5mL two benzylalcohols, slowly adds 3mLBr
2Solution adds 10mL benzene then.Reaction mixture was 45 ℃～50 ℃ heated and stirred 3 hours.Tell the upper toluene layer after the reaction mixture cooling.Toluene with anhydrous magnesium sulfate drying after rotary evaporation reclaim toluene and get faint yellow solid 0.7g, yield 54%., identify that through gas-matter coupling liquid phase analysis purity is 94%.(2 * 10mL) extractions obtain the 0.5g raw material after ether steams with ether to tell water layer behind the toluene.Recycling, by the raw material consumption total recovery near 100%.
Example 8
2,3,4, the 5-tetrafluoro is to the preparation of xylyl alcohol
With 1.4g by example 7 obtain 2,3,5, the 6-tetrafluoro is dissolved in the 40mL methyl alcohol brooethyl benzylalcohol, and reactor is put into ice bath, adds the 2.8g zinc powder and stirs 2h, stirs 14h under the room temperature.Pour in the 20mL water, add hcl acidifying, use extracted with diethyl ether again, steam ether and obtain yellow solid product 0.7g, yield 70%.Liquid phase analysis purity 95%.
MS:m/e (relative abundance, %), 194 (M, 97), 173 (M-F-2H, 100), 163 (M-CH
2OH, 25), 145 (M-F-CH
2OH+H, 80).
Claims (2)
1. one kind 2,3,5, the 6-tetrafluoro is to the preparation method of xylyl alcohol, and this method is with 2,3,5,6-tetrachloro-p-phenylene dimethyl chloride be raw material through fluoridize, esterification, reduction, bromination, reduction be prepared from, its reaction formula is as follows:
R=CH in the formula
3, C
2H
5, C
3H
7Or C
6H
5CH
2
It is characterized in that:
1) fluorizating agent of fluoridation employing is Potassium monofluoride or Sodium Fluoride, and solvent is tetramethylene sulfone or dimethyl sulfoxide (DMSO); Catalyzer is quaternary amine or calixarene; Consumption is with 2,3,5 of 1mol, and 6-tetrachloro-p-phenylene dimethyl chloride is that benchmark calculates, and the fluorizating agent consumption is 6mol～20mol, and catalyst levels is 0.01mol～1mol; 2,3,5 of 1g, 6-tetrachloro-p-phenylene dioctyl phthalate, solvent load are 5mL～30mL; Temperature of reaction is 40 ℃～230 ℃, and the reaction times is 1h～12h;
2) esterification employing esterifying agent is Fatty Alcohol(C12-C14 and C12-C18) or aromatic alcohol, and Fatty Alcohol(C12-C14 and C12-C18) is selected from methyl alcohol, ethanol or propyl alcohol; Aromatic alcohol is a benzylalcohol, and its consumption is with 2,3,5 of 1g, and 6-tetrafluoro terephthaldehyde acyl fluorides is that benchmark calculates, and pure consumption is 2mL～40mL; Temperature of reaction is 20 ℃～120 ℃, and the reaction times is 0.1h～10h;
3) the reduction reaction reductive agent is sodium borohydride or POTASSIUM BOROHYDRIDE, and solvent is tetramethylene sulfone or diethylene glycol dimethyl ether, and its consumption is with 2,3,5 of 1g, and 6-tetrafluoro terephthalate is that benchmark calculates, and the reductive agent consumption is 0.2g～2g; Solvent load is 2mL～40mL; Temperature of reaction is-10 ℃～60 ℃, and the reaction times is 5h～50h;
4) bromination reaction adopts HBr acid, bromo-succinimide or Br
2Be bromizating agent, solvent is benzene, toluene or dimethylbenzene; Its consumption is with 2,3,5 of 1mol, and the 6-tetrafluoro is that benchmark calculates to two benzylalcohols, and the bromizating agent consumption is 1mol～5mol; Temperature of reaction is 30 ℃～160 ℃, and the reaction times is 1h～20h;
5) reduction reaction employing magnesium powder or zinc powder are reductive agent, and solvent is methyl alcohol or ethanol; Its consumption is with 2,3,5 of 1g, and the 6-tetrafluoro is that benchmark calculates to brooethyl benzylalcohol, and the reductive agent consumption is 0.2g～20g, and solvent load is 20mL～100mL; Temperature of reaction is-10 ℃～50 ℃, and the reaction times is 5h～50h.
2. described 2,3,5 by claim 1, the 6-tetrafluoro is characterized in that the preparation method of xylyl alcohol: the temperature of fluoridation is 100 ℃～200 ℃, and the catalyst levels of fluorination process is 0.05mol～0.5mol; Esterification reaction temperature is 50 ℃～100 ℃; The bromination reaction temperature is 50 ℃～100 ℃.
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| WO2008099966A1 (en) * | 2007-02-16 | 2008-08-21 | Sumitomo Chemical Company, Limited | Method for producing 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol |
| JP2008222710A (en) * | 2007-02-16 | 2008-09-25 | Sumitomo Chemical Co Ltd | Production method of 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol |
| US8039680B2 (en) | 2007-02-16 | 2011-10-18 | Sumitomo Chemical Company, Limited | Process for producing 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol |
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