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CN-122010731-A - Synthesis method of cis-methyl dihydrojasmonate

CN122010731ACN 122010731 ACN122010731 ACN 122010731ACN-122010731-A

Abstract

The invention belongs to the technical field of perfume raw material synthesis, in particular to a synthesis method of cis-methyl dihydrojasmonate, which comprises the following steps of dissolving 1-heptyne in toluene, discharging into a first reaction tank, adding a cobalt catalyst, and discharging 1-bromo-ethylene and carbon monoxide gas into the first reaction tank; adding triphenylphosphine into a first catalyst recovery tank, discharging catalyst sediment, carrying out fractional distillation to carry out distillation cooling recovery on 1-heptyne, discharging anhydrous methanol into a layering tank, discharging dimethyl malonate into a second reaction tank, slowly adding sodium methoxide, carrying out addition reaction at-5-0 ℃, carrying out decarboxylation reaction by heating, discharging distilled 4-bromo-methyl dihydrojasmonate into a third reaction tank, and discharging methyl jasmonate with alpha, beta-double bonds into a fourth reaction tank for reaction. The invention solves the problems of high cost, low yield, low catalyst recovery rate and the like of the preparation of cis-methyl dihydrojasmonate in the prior art by simplifying steps, improving the recovery rate of the catalyst and realizing continuous production.

Inventors

  • LIU JUN
  • LIU BAOFENG
  • LIU BAOQING
  • LI SHOUWEI
  • LIU ZHENG

Assignees

  • 滕州鑫和生物科技有限公司

Dates

Publication Date
20260512
Application Date
20251231

Claims (10)

  1. 1. A synthesis method of cis-methyl dihydrojasmonate is characterized by comprising the following steps: S1, dissolving 1-heptyne in toluene, discharging into a first reaction tank (1), adding a cobalt catalyst, discharging mixed gas of 1-bromo-ethylene and carbon monoxide into the first reaction tank (1) by using a gas circulation device, stirring and reacting to generate 2-amyl-4-bromo-2-cyclopentenone mixed solution, and discharging into a first catalyst recovery tank (2) after the reaction is completed; s2, adding triphenylphosphine solution into the first catalyst recovery tank (2) to generate catalyst precipitate, discharging and recovering the catalyst precipitate at the bottom of the first catalyst recovery tank (2), performing fractional distillation to perform distillation cooling recovery on 1-heptyne to obtain 2-amyl-4-bromo-2-cyclopentenone solution, and discharging the solution into the layering tank (3); S3, discharging anhydrous methanol into a layering tank (3), dissolving 2-amyl-4-bromo-2-cyclopentenone in the anhydrous methanol to form an upper organic mixed phase, discharging a toluene phase at the bottom layer, and discharging the rest organic mixed phase into a second reaction tank (4); S4, supplementing a proper amount of anhydrous methanol into a second reaction tank (4), then discharging dimethyl malonate, slowly adding sodium methoxide, carrying out reflux addition reaction at the temperature of-5-0 ℃, continuously stirring, heating to carry out decarboxylation reaction after the reaction is finished, discharging the reaction product into a second catalyst recovery tank (5), carrying out fractional reduced pressure distillation to collect 4-bromo-methyl dihydrojasmonate, and discharging sodium methoxide solution from the bottom; S5, discharging the distilled 4-bromo-methyl dihydrojasmonate into a third reaction tank, adding toluene and sodium carbonate, performing debromination reaction to generate methyl jasmonate solution with alpha, beta-double bonds, and purifying methyl jasmonate with alpha, beta-double bonds; s6, discharging methyl jasmonate with alpha, beta-double bonds into a fourth reaction tank, adding a Pt/C catalyst and a halogen curing agent, and introducing hydrogen to generate cis-methyl dihydrojasmonate.
  2. 2. The synthesis method of cis-methyl dihydrojasmonate according to claim 1, wherein the gas circulation device comprises an air pump, a gas diversion cylinder (14) and a plurality of gas supply pipes (15), the top of the gas diversion cylinder (14) is provided with a total gas inlet pipe, the bottom of the gas diversion cylinder is uniformly provided with a circle of gas outlet branch pipes, the gas outlet end of the air pump is connected with the total gas inlet pipe through a first hose, and each gas outlet branch pipe is connected with the bottom end of one gas supply pipe (15) through a second hose; The bottom of the first reaction tank (1) is provided with a detachable arc-shaped base cover (12), a first reaction discharge pipe (121) is arranged at the center of the arc-shaped base cover (12), a circle of air supply pipe (15) is inserted through the arc-shaped base cover (12) around the first reaction discharge pipe (121), an air exhaust head (16) is screwed on the end part of the air supply pipe on the inner side of the arc-shaped base cover (12), and air exhaust holes (161) are uniformly distributed on the air exhaust head (16); The novel reaction kettle is characterized in that a first reaction kettle cover (13) is sealed on a first reaction kettle (1), four first electromagnetic valve pipes are arranged on the first reaction kettle cover (13), a first stirring device (131) with mechanical sealing is arranged at the middle position of the first reaction kettle cover (13), the first stirring device (131) is inserted into the first reaction kettle (1), one of the first electromagnetic valve pipes is used for adding 1-heptyne solution dissolved in toluene, a catalyst discharge branch pipe is connected to a 1-heptyne solution conveying pipeline, the second electromagnetic valve pipe and the third electromagnetic valve pipe are respectively an air inlet pipe and an air outlet pipe, and the fourth electromagnetic valve pipe is connected with the air inlet end of an air pump through a third hose.
  3. 3. The method for synthesizing methyl cis-dihydrojasmonate according to claim 2, wherein a mixed gas of 1-bromo-ethylene and carbon monoxide is discharged from a second one of the first solenoid valve pipes into a first reaction tank (1), the gas is discharged from a third one of the first solenoid valve pipes to ventilate the first reaction tank (1), then a solution of 1-heptyne dissolved in toluene and a mixed cobalt catalyst solution are discharged into the first reaction tank (1), solenoid valves in the first and third one of the first solenoid valve pipes are closed, the second one of the first solenoid valve pipes continues to pressurize the first reaction tank (1) so that the gas pressure in the first reaction tank (1) reaches 2-6 atm, then the solenoid valve in the second one of the first solenoid valve pipes is closed, the first reaction tank (1) is heated to 60-95 ℃, and the reaction is carried out for 18-24 hours; The gas pump circulates and pumps air to circularly discharge the gas in the first reaction tank (1) into the gas diversion cylinder (14), and then the gas is uniformly dispersed and discharged into the bottom of the first reaction tank (1) through the plurality of gas supply pipes (15), so that the gas is fully contacted with the reaction liquid; and monitoring the air pressure in the first reaction tank (1) in real time, and when the air pressure is lower than a preset value, opening a second electromagnetic valve in the first electromagnetic valve pipe, and exhausting air in the first reaction tank (1) to supplement air and boost pressure.
  4. 4. The synthesis method of cis-methyl dihydrojasmonate according to claim 2, wherein a precipitation cylinder (23) is arranged at the bottom of the first catalyst recovery tank (2), a discharge pipe I (231) is arranged at a position, close to the top, of the precipitation cylinder (23), a first recovery tank cover (22) is arranged at the top of the first catalyst recovery tank (2), four second electromagnetic valve pipes are arranged on the first recovery tank cover (22), a second stirring device (221) is arranged at the middle position of the first recovery tank cover (22), the first reaction discharge pipe (121) is connected with the first second electromagnetic valve pipe, the second electromagnetic valve pipe is a distillation pipe, the third electromagnetic valve pipe is a feeding pipe, and the fourth electromagnetic valve pipe is a pressure relief pipe; When the electromagnetic valve in the fourth electromagnetic valve pipe is opened, the first reaction tank (1) discharges the reacted solution into the first catalyst recovery tank (2), after the reaction solution is discharged, the first electromagnetic valve pipe is closed, the triphenylphosphine solution starts to be discharged into the first catalyst recovery tank (2) from the third electromagnetic valve pipe, the electromagnetic valve in the third electromagnetic valve pipe is closed, the electromagnetic valve in the second electromagnetic valve pipe is stirred for 30min at normal temperature, triphenylphosphine and cobalt catalyst react to generate catalyst sediment combined by triphenylphosphine and cobalt catalyst, the catalyst sediment is precipitated into a precipitation cylinder (23), a valve at the bottom of the precipitation cylinder (23) is opened, the solution in the precipitation cylinder (23) is discharged, the electromagnetic valve at the bottom of the precipitation cylinder (23) is closed, the first catalyst recovery tank (2) is started to be slowly heated, distillation is carried out at 3-5 ℃ per minute, the temperature is heated to 90-95 ℃, and the temperature is kept for 10-15min, and toluene and 1-heptyne are recovered.
  5. 5. The synthesis method of cis-methyl dihydrojasmonate according to claim 4, wherein a discharge pipe at the bottom of the layering tank (3) is connected with an inclined 90-degree T-shaped three-way pipe (321), a top interface of the inclined 90-degree T-shaped three-way pipe (321) is connected with the discharge pipe at the bottom of the layering tank (3), a glass pipe (323) is connected with a bottom interface of the inclined 90-degree T-shaped three-way pipe (321), an electromagnetic valve is arranged in a side joint pipe (322) at the middle position of the inclined 90-degree T-shaped three-way pipe (321), an electromagnetic valve is arranged in the bottom end position of the glass pipe (323), the top of the layering tank (3) is covered with a layering tank cover (33), four third electromagnetic valve pipes are arranged on the layering tank cover (33), a third stirring device (34) is arranged at the middle position of the layering tank cover (33), the first electromagnetic valve pipe is connected with the first discharge pipe (231), the second electromagnetic valve pipe is an anhydrous methanol adding pipe, and the third electromagnetic valve pipe is a third air pipe and the third electromagnetic valve is replaced by the third electromagnetic valve; After the first catalyst recovery tank (2) discharges raw materials into the layering tank (3), closing an electromagnetic valve in a first electromagnetic valve pipe, starting to discharge absolute methanol into the layering tank (3) by a second electromagnetic valve pipe, stirring and dissolving for 20-30min, and standing for layering; And when the light transmission detector detects that the glass tube (323) has obvious light transmission difference, the electromagnetic valve in the glass tube (323) is closed, the electromagnetic valve in the upper side pipe (322) of the inclined 90-degree T-shaped tee pipe (321) is opened, and the organic mixed phase is discharged into the second reaction tank (4).
  6. 6. The method for synthesizing cis-methyl dihydrojasmonate according to claim 5, wherein a second reaction tank cover (42) is arranged at the top of the second reaction tank (4), five fourth electromagnetic valve pipes are arranged on the second reaction tank cover (42), a fourth stirring device (43) is arranged in the middle of the second reaction tank cover (42), the first fourth electromagnetic valve pipe is a liquid inlet pipe, the second fourth electromagnetic valve pipe is a methanol adding pipe, the third fourth electromagnetic valve pipe is a sodium methoxide adding pipe, and the fourth and fifth electromagnetic valve pipes are a ventilation air inlet pipe and an air outlet pipe respectively; After the organic mixed phase is discharged into the second reaction tank (4) by the layering tank (3), closing an electromagnetic valve in the first electromagnetic valve pipe, supplementing a proper amount of anhydrous methanol into the second reaction tank (4) by the second electromagnetic valve pipe, slowly discharging sodium methoxide into the second reaction tank (4) through the third electromagnetic valve pipe, continuously stirring and mixing, stirring and reacting for 2-4h, continuously adding a proper amount of anhydrous methanol, then adjusting the temperature of the second reaction tank (4) to 60-70 ℃, carrying out methanol reflux reaction for 20-24h, and discharging all the reaction liquid into the second catalyst recovery tank (5) after the decarboxylation reaction of the second reaction tank (4) is completed.
  7. 7. The method for synthesizing methyl cis-dihydrojasmonate according to claim 6, wherein each second reaction tank (4) has 2-3 bottom side connecting pipes (322) of layered tanks (3) and is connected with the liquid inlet end of the second reaction tank (4) through the connecting pipes, each second catalyst recovery tank (5) is uniformly provided with 4-8 liquid inlet pipes on the tank wall near the top, and each liquid inlet pipe is correspondingly connected with a second liquid outlet pipe at the bottom of one second reaction tank (4).
  8. 8. The synthesis method of cis-methyl dihydrojasmonate according to claim 6, wherein a second catalyst recovery tank cover (52) is covered on the top of the second catalyst recovery tank (5), four fifth electromagnetic valve pipes are arranged on the second catalyst recovery tank cover (52), a fifth stirring device (53) is arranged at the middle position of the second catalyst recovery tank cover (52), the first fifth electromagnetic valve pipe is a nitrogen inlet pipe, the second fifth electromagnetic valve pipe is a methanol evaporation pipe, the third fifth electromagnetic valve pipe is a low-boiling impurity evaporation pipe, and the fourth fifth electromagnetic valve pipe is a 4-bromo-methyl dihydrojasmonate evaporation pipe; heating the second catalyst recovery tank (5) to 60-80 ℃ to evaporate the methanol, and then starting reduced pressure distillation; the decompression distillation step comprises the steps of pumping out the third electromagnetic valve pipe to enable the second catalyst recovery tank to decompress, supplementing a small amount of nitrogen into the first electromagnetic valve pipe, heating to 80-120 ℃, distilling residual low-boiling impurities, closing an electromagnetic valve in the third electromagnetic valve pipe, opening an electromagnetic valve in the fourth electromagnetic valve pipe to pump out, heating to 140-160 ℃, distilling 4-bromo-methyl dihydrojasmonate, and cooling again to discharge sodium methoxide mixture at the bottom of the second catalyst recovery tank (5).
  9. 9. The synthesis method of cis-methyl dihydrojasmonate according to claim 8, wherein a fourth electromagnetic valve pipe is connected with liquid inlet ends in a plurality of third reaction tanks through branch pipes, the third reaction tank has the same structure as the second reaction tank (4), five sixth electromagnetic valve pipes are arranged on a tank cover at the top of the third reaction tank, the first electromagnetic valve pipe is connected with the branch pipes, the second electromagnetic valve pipe and the third electromagnetic valve pipe are respectively an air inlet end and an air outlet end, the fourth electromagnetic valve pipe is a solvent adding pipe, and the fifth electromagnetic valve pipe is a sodium carbonate adding pipe; And (3) discharging toluene solvent into a third reaction tank through a fourth electromagnetic valve pipe to dissolve the methyl 4-bromo-dihydrojasmonate, slowly adding a proper amount of sodium carbonate into the fifth electromagnetic valve pipe to dissolve the methyl 4-bromo-dihydrojasmonate, stirring for reaction at a reaction temperature of 110-115 ℃, and carrying out toluene reflux reaction for 8-12h to obtain methyl jasmonate with alpha, beta-double bonds.
  10. 10. The method for synthesizing cis-methyl dihydrojasmonate according to claim 9, wherein each two third reaction tanks are used for conveying the product into a fourth reaction tank, nano-scale Pt particles are added into the fourth reaction tank to load the catalyst on the surface of the powdery active carbon, then a halogen curing agent is added, and stirring is carried out for 30min at room temperature; Purifying the methyl jasmonate product with alpha, beta-double bonds, discharging the purified methyl jasmonate product into a fourth reaction tank, sealing the fourth reaction tank, replacing air in the fourth reaction tank with hydrogen for 3-5 times, introducing hydrogen to the target pressure of 0.5-1 MPa, heating to 30-40 ℃, controlling the stirring speed to 300-500 r/min, and reacting for 4-6h.

Description

Synthesis method of cis-methyl dihydrojasmonate Technical Field The invention belongs to the technical field of synthesis of perfume raw materials, and particularly relates to a synthesis method of cis-methyl dihydrojasmonate. Background At present, the industrialized production route of methyl dihydrojasmonate mainly starts from cyclopentanone and n-valeraldehyde, a key 2-amyl-2-cyclopentenone intermediate is obtained through aldol condensation and strong acid isomerization, and dimethyl malonate is added to the 2-amyl-2-cyclopentenone intermediate, and then decarboxylation is carried out to obtain the methyl dihydrojasmonate product. The synthesis process is complex, the purification steps in the synthesis process are more, the production cost is high, the continuous preparation process can not be realized, and the recovery rate of the product is low. Because the number of the catalyst used in the preparation steps is correspondingly large, the catalyst is a key raw material for recovering the catalyst and improving the catalytic effect, and the cost for preparing cis-methyl dihydrojasmonate is reduced. The production cost is greatly reduced and the production efficiency is improved by simplifying the preparation steps, improving the yield and improving the recovery rate of the catalyst. Disclosure of Invention The invention aims to provide a synthesis method of cis-methyl dihydrojasmonate, which solves the problems of high cost, low yield, low catalyst recovery rate and the like in the existing preparation method of cis-methyl dihydrojasmonate by simplifying steps, improving the recovery rate of a catalyst and realizing continuous production. In order to solve the technical problems, the invention is realized by the following technical scheme: A synthesis method of cis-methyl dihydrojasmonate comprises the following steps: S1, dissolving 1-heptyne in toluene, discharging into a first reaction tank, adding a cobalt catalyst, discharging mixed gas of 1-bromo-ethylene and carbon monoxide into the first reaction tank by using a gas circulation device, stirring and reacting to generate 2-amyl-4-bromo-2-cyclopentenone mixed solution, and discharging into the first catalyst recovery tank after the reaction is completed; s2, adding triphenylphosphine solution into a first catalyst recovery tank to generate a catalyst precipitate, discharging and recovering the catalyst precipitate at the bottom of the first catalyst recovery tank, performing fractional distillation to perform distillation and cooling recovery on 1-heptyne to obtain a 2-amyl-4-bromo-2-cyclopentenone solution, and discharging the 2-amyl-4-bromo-2-cyclopentenone solution into a layering tank; S3, discharging anhydrous methanol into a layering tank, dissolving 2-amyl-4-bromo-2-cyclopentenone in the anhydrous methanol to form an upper organic mixed phase, discharging a toluene phase at the bottom layer, and discharging the rest organic mixed phase into a second reaction tank; S4, adding a proper amount of anhydrous methanol into a second reaction tank, then discharging dimethyl malonate, slowly adding sodium methoxide, carrying out reflux addition reaction at the temperature of-5-0 ℃, continuously stirring, heating to carry out decarboxylation reaction after the reaction is finished, discharging the reaction product into a second catalyst recovery tank, carrying out fractional reduced pressure distillation to collect 4-bromo-methyl dihydrojasmonate, and discharging sodium methoxide solution from the bottom; S5, discharging the distilled 4-bromo-methyl dihydrojasmonate into a third reaction tank, adding toluene and sodium carbonate, performing debromination reaction to generate methyl jasmonate solution with alpha, beta-double bonds, and purifying methyl jasmonate with alpha, beta-double bonds; s6, discharging methyl jasmonate with alpha, beta-double bonds into a fourth reaction tank, adding a Pt/C catalyst and a halogen curing agent, and introducing hydrogen to generate cis-methyl dihydrojasmonate. Further, the gas circulation device comprises a gas pump, a gas diversion cylinder and a plurality of gas supply pipes, wherein the top of the gas diversion cylinder is provided with a main gas inlet pipe, the bottom of the gas diversion cylinder is uniformly provided with a circle of exhaust branch pipes, the gas outlet end of the gas pump is connected with the main gas inlet pipe through a first hose, and each exhaust branch pipe is connected with the bottom end of one gas supply pipe through a second hose; the bottom of the first reaction tank is provided with a detachable arc-shaped base cover, a first reaction discharge pipe is arranged in the center of the arc-shaped base cover, a circle of air supply pipe penetrates through the arc-shaped base cover on the periphery of the first reaction discharge pipe, an exhaust head is screwed on the end part of the air supply pipe on the inner side of the arc-shaped base cover, and exhaust pores are uniformly di