SU447883A1 - Method of producing fluoroalkyl esters of chloropropionic acid - Google Patents

Description

(54) METHOD FOR OBTAINING FLUORALCYL ETHERS

p-chloropropionic acid

A ditch with properties similar to pure ether.

Example 1. To 22.5 wt. including CiFgCHzCHaOH at 50 ° C for 12 min., 12 wt. including ClCHsCHaCOCl. Then for 1 hour at 80 ° C. The mixture is stirred under a weak stream of nitrogen, cooled and washed with 70 wt. h of water. After separating the upper aqueous phase, the organic layer is dried with calcium chloride and distilled. Get 26 weight. including (86% of theoretical) С4Р9СН2СН2ОСОСН2СН2С1, t. bale. 104 ° C / 114 mm Hg Art., chlorine content of 9.85% (10.0% according to theory).

Example 2. To 180 weight. h. CeFiaCHaCHaOH at 50 ° C is added dropwise over 50 minutes to 69 weight. including the acid chloride of p-chloropropionic acid. Then for 1 hour, the reaction mixture was stirred at 80 ° C and after cooling, washed with 235 wt. h of water. The liquid phases are separated, the lower phase is dried by heating at 50 ° C under vacuum and distilled. Receive 217 weight. h. (96.5% of theoretical) SbP1zSN2CHNOSOCHN2CHNS1, t. bales. 78 ° C / 14 mmHg Art., chlorine content (7.82% according to theory).

Example 3. To 221 wt. including C8P17CH2SP2OP poured dropwise at 50 ° C for 1 hour 66 weight. h. С1СН2СН2СОС1. Then come, as indicated in example 2. Output 259 weight. including (98% of theoretical) С8РпСН2СН20ССН2СН2С1, t. Kin. 94 ° C / 14 mmHg Art., chlorine content 6.4% (6.4% according to theory), pour point 23 ° C.

Example 4. K 138 wt. including CioF2iCH2CH2OH is added dropwise at 110 ° C to 34 weight. including the acid chloride of p-chloropropionic acid for 1 hour. The mixture is then stirred for 1 hour at 90 ° C, distilled off under a vacuum of a water-jet pump and distilled at a pressure of 0.4 Torr. Get 152 weight. including (95% of theoretical) ClCH2CH2COOCH2CH2CioF2b so kip. 116- 118 ° C / 14 mm Hg. Art., the temperature of fluidity 71-73 ° C, chlorine content of 5.43% (5.4% according to theory).

Example 5. To 46 wt. Part C12P25CH2CH2OH at 110 ° C is added dropwise over 30 minutes to 9.7 wt. including C1SI2CH2COC1. Then the reaction mixture for 1 hour, stirred at 100 ° C in a stream of nitrogen and distilled under vacuum. Get 47 weight. including (90.5% of theoretical) ClCH2CH2COOCn2CH2Ci2P25, t. bales. 129 ° С, flow temperature 104–106 ° С, chlorine content 4.58% (4.7% according to theory).

Example 6. K 36 wt. including C7Pi5CH2OH and 0.15 weight. including concentrated sulfuric acid at 50 ° C is poured dropwise to 12.5 wt. h. C1CH2 CH2COC1. The reaction mixture is stirred for 1 hour at 80 ° C, washed with an excess of water, the phases are separated, dried and distilled. Output 42 wt. including (95% of theoretical) C7Pi5CH2OCOCH2CH2Cl, t. Kip.

72 ° C / 14 mmHg Art., chlorine content of 7.22% (7.2% according to theory).

Example 7. To 59.5 wt. h. SbPl3z (SP) 2ON at 50 ° C is added dropwise during

30 min 22.5 wt. including the acid chloride of p-chloropropionic acid. After processing the reaction mass with water, it is distilled, get 66 weight. h. (90% of theoretical) С1СП2СН2СООСП2СН2СбР1з, t. bale. 96-100 ° C /

14 mmHg Art., chlorine content of 7.2% (7.38% according to theory).

Example 8. In 64 wt. including C8P17 (SP2) 4OH is added dropwise over 45 minutes at 55-60 ° C. 19 weight. including the acid chloride of p-chloropropionic acid. Then mass over. 1 hour at 80 ° C is stirred in a stream of nitrogen and washed with 150 wt. h of water. The ether phase is separated, dried and distilled. Get 73 g (96.5% of theoretical)

С8Р17 (СН2) 40 СОСП 2 СН2 С1, t. Bale. 121-125С / 14 mm Hg Art., chlorine content 5,91% (6,19% according to theory).

Example 9. K 72 wt. CioP2i (CH2) 4OH at 100 ° C is added dropwise over a period of

1 hour 17.5 weight. including the acid chloride p-chloropropionic acid. Stir the reaction mixture for 1 hour at 90-100 ° C and then distill. Receive 80.5 weight. h. (97% of theoretical)

CioP2i (CH2) 40COCH2Cn2Cl, t. Kip. 133-137 ° C / 114 mm Hg Art., pour point 60-62 ° C, chlorine content of 4.98% (5.2% according to theory).

Example 10. A mixture of 30.76 wt. h

SbR1zSP2SP20P, 28.13 weight. including C8Fi7CH2CH2OH, 18.57 wt. including CioP2iCH2CH2OH and 11.96 wt. including Ci2P25Cn2CH2OH and at 50 ° C 28 weight is added dropwise to it within 1 hour. including the acid chloride of p-chloropropionic acid. After

stirring for 1 hour at 80 ° C under a stream of nitrogen pour 0.4 weight. including water prc room temperature. After 0.5 hour of stirring, drop by drop in a stream of nitrogen for 30 min. 28 wt. including triethylamine, while the temperature rises to 60 ° C. The mass is then stirred for 2 hours at 80 ° C, cooled to 50 ° C and the solution is poured 0.384 weight. including concentrated sulfuric acid in 40 weight. h of water. The liquid phases are separated, the lower ether phase is dried. Get 96 weight. including mixtures of acrylates. According to gas chromatographic analysis, it was established that the mixture contains various fluorine-containing acrylates in the initial ratio. Residual alcohol content below 0.1%.

Example 11. To 100 weight. including 7-trifluoromethyl-1, 1 -dihydroperfluorooctanol, and 0.17 wt. including concentrated sulfuric acid. At 50 ° C and stirring, 31 wt. including the acid chloride p-chloropropionic acid and continue to stir for 3 hours at 85 ° C. The excess p-chloropropionic acid chloride is distilled off under vacuum, and the residue is distilled.

116 g of a compound of the formula

CPPDC (CPP) (CP2) 5CH2 - OCOCHaCHsCl, kip. 70-76 ° C / 14 mm Hg. Art.

Subject invention

Method for preparing fluoroalkyl esters of p-chloropropionic acid of general formula

С „Р2" +1 (CH, LOCOCH, CH, C1

where n 4-12, t 1-4,

characterized in that p-chloropropionic acid chloride is reacted with polyfluorinated alcohol of the general formula

5С „Р2 +1 (СН,)„ ОН

where p and t have the indicated meanings, or with a mixture of these alcohols at 20-140 ° C with isolation of the target product by 10 known techniques.