The purpose of this invention is to provide a kind of production method of new cyfloxylate, is raw material with the p-Fluorobenzenecarboxaldehyde, carries out stepwise synthesis, and the processing condition gentleness is feasible, product yield and content height.
Purpose of the present invention can realize by following technical measures: this production method is raw material with the p-Fluorobenzenecarboxaldehyde, add N-bromosuccinimide and carry out bromination reaction, through distill 3-bromo-4-fluorobenzaldehyde; Carry out condensation reaction by 3-bromo-4-fluorobenzaldehyde and triethyl orthoformate, through distill the di-alcohol 3-bromo-4-fluorobenzaldehyde that contracts; Contract 3-bromo-4-fluorobenzaldehyde and phenol of di-alcohol carries out etherification reaction, through wash, extract, distill the di-alcohol 3-phenoxy group-4-fluorobenzaldehyde that contracts; Di-alcohol contracts 3-phenoxy group-4-fluorobenzaldehyde after hydrolysis, and underpressure distillation gets 3-phenoxy group-4-fluorobenzaldehyde; Add DV chrysanthemum acyl chlorides in 3-phenoxy group-4-fluorobenzaldehyde and the sodium cyanide solution, after esterification, precipitation obtains the cyfloxylate product.Its production process proceed step by step, reaction process is as follows:
(1) synthetic 3-bromo-4-fluorobenzaldehyde
(2) the synthetic di-alcohol 3-bromo-4-fluorobenzaldehyde that contracts
(3) the synthetic di-alcohol 3-phenoxy group-4-fluorobenzaldehyde that contracts
(4) synthetic 3-phenoxy group-4-fluorobenzaldehyde
(5) synthetic cyfloxylate
Production technique of the present invention is provided by the following drawings:
The invention will be further described below with reference to accompanying drawing: this production method gets the cyfloxylate product with the raw material stepwise synthesis through bromination, condensation, etherificate, hydrolysis, esterification.
(1) synthetic 3-bromo-4-fluorobenzaldehyde
Embodiment one: add 124g (1.0mol) p-Fluorobenzenecarboxaldehyde, 500ml anhydrous diethyl ether or the vitriol oil in there-necked flask respectively, stirring is cooled to below 0~20 ℃, add 178g (1.0mol) N-bromosuccinimide, suction filtration gets yellow liquid, steam except that behind the ether, 110~112 ℃/30mmHg fraction 162g, yield 80%, content 98.0% are collected in underpressure distillation.
(2) the synthetic di-alcohol 3-bromo-4-fluorobenzaldehyde that contracts
Embodiment two: add 203g (1.0mol) 3-bromo-4-fluorobenzaldehyde and 222g (1.5mol) triethyl orthoformate, 200ml dehydrated alcohol and 2.5g ammonium chloride in flask, reflux 30 minutes, temperature is a back flow reaction under related solvents, normal pressure steams the lower boiling component, in 150 ℃ of oil baths, heat then, 100~103 ℃/20mmHg fraction is collected in underpressure distillation, and yield is 82~86%.
(3) the synthetic di-alcohol 3-phenoxy group-4-fluorobenzaldehyde that contracts
Embodiment three: add solvent phenol 141.2g (1.5mol) or N in flask, dinethylformamide, sodium hydroxide 60g (1.5mol) and toluene 500ml mix, boiling dewaters, steam solvent under the vacuum, add DMF150ml and Red copper oxide 0.5g, be heated to 140~145 ℃, add the di-alcohol 3-phenoxy group-4-fluorobenzaldehyde 145g (0.5mol) that contracts, stirred 4 hours.Through washing, petroleum ether extraction, 130~132 ℃/50mmHg fraction, yield 81%, content 98.2% are collected in distillation.
(4) synthetic 3-phenoxy group-4-fluorobenzaldehyde
Embodiment four: add 145g (0.5mol) di-alcohol contract 3-phenoxy group-4-fluorobenzaldehyde and 80ml concentrated hydrochloric acid in flask, heating is boiling slowly, distillation earlier removes the methyl alcohol that dereaction is disengaged, slowly distillation again stops heating, dilute with water when temperature arrives 90 ℃, underpressure distillation, collect 122~124 ℃/0.020kPa fraction, yield 91%, content 97.3%.
(5) synthetic cyfloxylate
Embodiment five: add 3-phenoxy group-4-fluorobenzaldehyde (97%) 220g (1mol), 20%NaCN aqueous solution 300g, 1000ml hexanaphthene and phase-transfer catalyst 2g in flask, ice bath is cooled to 0~15 ℃, drip DV chrysanthemum acyl chlorides 245g, drip off continuation 15~20 ℃ of reactions 6~10 hours, reaction finishes, layering, alkali cleaning, be washed to neutrality, last atmospheric and vacuum distillation reclaims solvent, gets cyfloxylate, yield 93.8%, content 90.0%
The present invention is starting raw material stepwise synthesis cyfloxylate with the p-Fluorobenzenecarboxaldehyde, opened up new production route, the processing condition gentleness is feasible, the total yield of products height, content is higher, and raw material easily solves, the production comprehensive cost is low, for agriculture production provides the agricultural chemicals of wide spectrum, efficient, low toxicity, remarkable economic efficiency and social benefit are arranged, vast potential for future development is arranged.