CN107652183B - Synthesis method of tert-butyl cyclohexyl ethyl carbonate spice - Google Patents
Synthesis method of tert-butyl cyclohexyl ethyl carbonate spice Download PDFInfo
- Publication number
- CN107652183B CN107652183B CN201710964925.1A CN201710964925A CN107652183B CN 107652183 B CN107652183 B CN 107652183B CN 201710964925 A CN201710964925 A CN 201710964925A CN 107652183 B CN107652183 B CN 107652183B
- Authority
- CN
- China
- Prior art keywords
- tert
- ethanol
- reaction
- oil layer
- ethyl carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
- C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/02—Preparation of esters of carbonic or haloformic acids from phosgene or haloformates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Fats And Perfumes (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of tert-butyl cyclohexyl ethyl carbonate perfume, which relates to the technical field of fine chemical engineering, and is characterized in that phenol and tert-butyl alcohol are used as initial raw materials for alkylation reaction, and then are hydrogenated to be subjected to acetylation reaction with diethyl carbonate to produce tert-butyl cyclohexyl ethyl carbonate, the raw materials are easy to obtain, the yield is high, the ratio of o-tert-butylphenol and p-tert-butylphenol generated by the reaction of phenol and tert-butyl alcohol reaches 7:3, and a byproduct, namely p-tert-butylphenol, can be hydrogenated and esterified to obtain an irigenin product for utilization; and the product has high purity and pure and soft fragrance, and meets the fragrance blending requirements of essences and spices.
Description
The technical field is as follows:
the invention relates to the technical field of fine chemical engineering, in particular to a synthesis method of tert-butyl cyclohexyl ethyl carbonate spice.
Background art:
tert-butyl cyclohexyl ethyl carbonate, chemical name: ethyl- (2-tert-butyl) cyclohexyl carbonate, the presence of tert-butylcyclohexyl ethyl carbonate not being found in nature. Molecular formula C13H24O3CAS number:67801-64-3, the appearance is colorless to light yellow transparent liquid, the boiling point 306 deg.C (73 deg.C/5 Pa), the flash point 102-103 deg.C, the relative density (25 deg.C) 0.9700-0.9750, the refractive index (20 deg.C) 1.4470-1.4530, dissolved in ethanol, ethylene glycol and other organic solvent, insoluble in water. The tert-butyl cyclohexyl ethyl carbonate has stable property, fruit fragrance and costustoot fragrance, is accompanied with flower fragrance, and can be used in various types of essences, particularly in soap and washing powder essences.
The tert-butyl cyclohexyl ethyl carbonate is a mixture of cis-isomer and trans-isomer, has strong flowery odour, costus root and apple aroma and similar jasmine aroma and iris-like aroma, and is a common synthetic spice. The essence is very useful in the whole modern essence, can be widely applied to various essence formulas, is particularly better in fragrance and costustoot fragrance type essence, can be stably used in most essence products, can be almost used in all daily essence products, such as perfume essence, cosmetic essence, soap essence and other daily chemical essence formulas, including perfume, cream, antiperspirant, deodorant, shampoo, soap, washing powder, dish washing agent, fabric softener, deodorant spray, detergent powder and the like, is particularly useful for washing powder, soap, cologne, shampoo, skin cream and face cream, the dosage is about 10 percent, the dosage can be determined according to different purposes, the maximum dosage can reach 30 percent, and the IFRA has no limit regulation.
Tert-butyl cyclohexyl ethyl carbonate, tectoridin, o-tert-butyl cyclohexyl and the like are one of important synthetic perfumes with wider application, and the demand is gradually expanded in recent years. The general production method is characterized in that phenol is used as an initial raw material, solid acid catalyst or Lewis acid is used as a catalyst, isobutene gas is introduced to carry out alkylation to obtain o-tert-butyl phenol, raney nickel is used for catalytic hydrogenation to obtain o-tert-butyl cyclohexanol, and finally tert-butyl cyclohexyl ethyl carbonate is obtained through esterification. However, the method has the disadvantages of various process steps, low product yield, high production cost and difficult control of the process conditions for reacting the isobutene gas and the phenol.
The invention content is as follows:
the invention aims to solve the technical problem of providing a synthesis method of tert-butyl cyclohexyl ethyl carbonate spice which has easily obtained raw materials, high product yield, high final product content of more than 98.5 percent, pure and soft product fragrance and accords with the fragrance blending requirement of essence and spice.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a synthesis method of tert-butyl cyclohexyl ethyl carbonate spice comprises the following steps:
a) firstly, adding ethanol into a three-neck glass flask by weighing and metering, then adding phenol into the glass flask, starting a stirrer and a heat and cold exchange all-in-one machine, reducing the temperature of the glass flask to 10-15 ℃, slowly adding a solid acid catalyst into the glass flask, and continuing stirring for 0.5h after the feeding is finished;
b) continuously maintaining the temperature of the glass flask at 10-15 ℃, dropwise adding tert-butyl alcohol into the glass flask by using a dropwise adding pump, controlling the dropwise adding time to be 2 hours, raising the temperature of the kettle to 100-110 ℃ after dropwise adding, continuously stirring for 2-4 hours, sampling for chromatographic detection, cooling when the content of phenol is less than or equal to 0.5%, and finishing the reaction;
c) transferring the generated mixed reaction liquid of the o-tert-butylphenol and the p-tert-butylphenol into a separating funnel, standing and layering for 0.5h, putting an oil layer into a beaker, adding ethanol into a water layer, stirring for 0.5h, standing and layering, merging the oil layers, putting into the beaker, and concentrating the water layer into a waste liquid collecting barrel; respectively washing the solid-phase solid acid catalyst with ethanol and water for recycling, metering a 5% sodium hydroxide solution into a beaker of an oil layer, starting a stirrer, carrying out alkali washing on the collected oil layer, stirring for 0.5h, standing for layering for 0.5h, and concentrating an alkali solution layer into a waste liquid collecting barrel; adding clear water into the oil layer for washing, stirring for 0.5h, standing for layering for 0.5h, transferring the oil layer into a hydrogenation reaction kettle, and collecting the water layer into a waste liquid collecting barrel;
d) adding a 5% palladium-carbon catalyst into a hydrogenation reaction kettle in a fixed amount, sealing the hydrogenation reaction kettle, replacing the hydrogenation reaction kettle with nitrogen for 4-6 times, then filling the nitrogen to the pressure of 2.0MPa, replacing the hydrogenation reaction kettle with hydrogen for 4-6 times after the system pressure is stable, then filling the hydrogen, and adjusting the pressure of the hydrogenation reaction kettle to 2.0 MPa; closing a hydrogen inlet valve after the system pressure is stable, heating to 80-150 ℃, opening the hydrogen valve after the reaction system pressure is balanced, and keeping the reaction pressure at 2.0MPa for 5-10 h;
e) sampling every 2 hours after 5 hours of reaction, carrying out chromatographic detection, ending the reaction when the content of p-tert-butylphenol is less than or equal to 0.5%, decompressing, filtering the generated mixed reaction liquid of o-tert-butylcyclohexanol and p-tert-butylcyclohexanol, transferring the liquid phase filtrate into a rotary evaporator, washing a solid phase catalyst with ethanol, transferring the washed solid phase catalyst into a hydrogenation reaction kettle, and carrying out the next batch of hydrogenation reaction;
f) starting the rotary evaporator in the step e) to heat, recovering ethanol at the normal pressure and the temperature of 60-90 ℃, concentrating the collected ethanol for reuse, starting a vacuum pump, collecting o-tert-butylcyclohexanol at the temperature of 95-100 ℃ and the pressure of 1000-1333 Pa, transferring the collected o-tert-butylcyclohexanol into a four-neck flask, wherein the bottom liquid of the flask is p-tert-butylcyclohexanol, and the collected o-tert-butylcyclohexanol can be used for producing irisoryl ester;
g) adding ethanol into a three-neck flask in a metering manner, then adding catalysts of sodium methoxide and acid-removing agent triethylamine in a metering manner, starting a stirrer and a cold-heat exchange all-in-one machine, and reducing the temperature of a glass flask to 0-5 ℃; slowly adding ethyl chloroformate into the glass flask in a metered manner, controlling the reaction temperature to be 0-5 ℃, and continuing stirring for 0.5h after the reaction is finished; then metering and adding 30% sodium carbonate solution, stirring for 0.5h, transferring into a centrifuge, separating sodium chloride, washing the reaction solution for three times to obtain diethyl carbonate, distilling and recovering ethanol, and collecting the diethyl carbonate for later use;
h) adding diethyl carbonate and p-toluenesulfonic acid into a four-neck flask in a metered manner, starting a stirrer, starting a heat and heat exchange all-in-one machine for heating, controlling the reaction temperature to be 100-120 ℃, reacting for 3-5 h, transferring the reaction liquid into a rotary evaporator, recovering ethanol at normal pressure, and transferring the bottom liquid into a beaker;
i) adding 5% sodium hydroxide solution into a beaker in a metered manner, starting a stirrer, carrying out alkaline washing on the collected bottom liquid of the bottle, stirring for 0.5h, standing and layering for 0.5h, and collecting an alkaline liquid layer into a waste liquid collecting barrel; and adding clear water into the oil layer for washing, stirring for 0.5h, standing for layering for 0.5h, collecting the water layer into a waste liquid collecting barrel, transferring the oil layer into a rotary evaporator, starting the rotary evaporator to heat, starting a vacuum pump, and collecting tert-butyl cyclohexyl ethyl carbonate.
The mass ratio of the ethanol to the phenol in the step a) is 1.0: 1-5.0: 1, preferably 2.0: 1-2.5: 1. The dosage of the solid acid catalyst is 0.5-5 wt%, preferably 1-2 wt% of the total dosage.
The molar ratio of the tert-butyl alcohol to the phenol in the step b) is 1.0: 1-5.0: 1, preferably 1.0: 1-1.5: 1.
The mass ratio of the ethanol to the water layer in the step c) is 0.5: 1-2: 1, preferably 0.5: 1-1: 1; the mass ratio of the sodium hydroxide solution to the reaction liquid oil layer is 0.2: 1-2: 1, preferably 0.2: 1-1: 1; the mass ratio of the clear water to the reaction liquid oil layer is 0.5: 1-2: 1, and preferably 0.5: 1-1: 1.
The material of the hydrogenation reaction kettle in the step d) is stainless steel, and the design pressure is 0-5 MPa.
The molar ratio of the ethanol to the ethyl chloroformate in the step g) is 1: 1-5: 1, preferably 1.5: 1-2.5: 1; the dosage of the sodium methoxide is 0.5-5 wt% of the total dosage, preferably 1-2 wt%; the dosage of the triethylamine is 1-10 wt%, preferably 1-2.5 wt% of the total dosage.
The molar ratio of diethyl carbonate to tert-butylcyclohexanol in the step h) is 1.0: 1-5.0: 1, preferably 1.5: 1-2.0: 1; the dosage of the p-toluenesulfonic acid is 0.5-5 wt%, preferably 1.0-2.0 wt% of the total dosage.
The mass ratio of the sodium hydroxide solution to the oil layer in the step i) is 0.2: 1-2: 1, preferably 0.2: 1-1: 1; the mass ratio of the clean water to the oil layer is 0.5: 1-2: 1, and preferably 0.5: 1-1: 1.
The synthetic scheme is as follows:
the invention has the beneficial effects that:
(1) phenol and tert-butyl alcohol are used as initial raw materials for alkylation reaction, and then are hydrogenated to be subjected to acetylation reaction with diethyl carbonate to produce tert-butyl cyclohexyl ethyl carbonate, the raw materials are easy to obtain, the yield is high, the ratio of o-tert-butylphenol and p-tert-butylphenol generated by the reaction of phenol and tert-butyl alcohol reaches 7:3, and the byproduct p-tert-butylphenol can be hydrogenated and esterified to obtain an iridate product for utilization;
(2) ethanol is used as a reaction solvent for alkylation reaction and hydrogenation reaction, so that the defects of incomplete hydrogenation reaction and inactivation after the catalyst is used mechanically are overcome, and the distillation process step when dichloroethane is used as the solvent in the common alkylation reaction can be omitted; the use of the ethanol not only avoids the use of toxic organic solvents, but also can recycle the ethanol, thereby improving the production environment and reducing the production cost;
(3) the method is suitable for laboratory production, has good process repeatability, and ensures the product yield while simplifying the operation; and the product has high purity and pure and soft fragrance, and meets the fragrance blending requirements of essences and spices.
The specific implementation mode is as follows:
in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Examples
a) 160g of ethanol is added into a three-neck glass flask, 75g of phenol is added into the glass flask, and a stirrer and a heat and cold exchange all-in-one machine are started to reduce the temperature of the glass flask to 15 ℃. Solid acid catalyst (H) was added to a glass flask3O40PW12/TiO2)5g, and after the feeding is finished, stirring is continuously carried out for 0.5 h.
b) And continuously maintaining the temperature of the glass flask at 15 ℃, dropwise adding 72g of tert-butyl alcohol into the glass flask by using a dropwise adding pump, controlling the dropwise adding time to be 2 hours, after the dropwise adding is finished, raising the temperature of the kettle to 130-140 ℃, and continuously stirring for 2-4 hours. Sampling and detecting, and stopping the reaction when the content of phenol is less than or equal to 0.5%.
c) Transferring the generated p-tert-butylphenol reaction liquid to a separating funnel, and standing and layering for 0.5 h. The oil layer was placed in a beaker. Adding 55g of ethanol into a water layer, stirring for 0.5h, standing for layering, combining oil layers, putting into a beaker, and collecting the water layer into a waste liquid collecting barrel. 90g of 5% sodium hydroxide solution is metered into a beaker of the oil layer, a stirrer is started, the collected oil layer is subjected to alkali cleaning, the mixture is stirred for 0.5h and then is kept stand for layering for 0.5h, and the alkali solution layer is concentrated into a waste liquid collecting barrel. And adding 300g of clean water into the oil layer for washing, stirring for 0.5h, standing for layering for 0.5h, and washing twice. The oil layer is transferred to a hydrogenation reaction kettle, and the water layer is concentrated to a waste liquid collecting barrel.
d) Adding 5% palladium carbon catalyst into a hydrogenation reaction kettle according to a fixed amount, sealing the hydrogenation reaction kettle, replacing for 4-6 times by using nitrogen, then filling the nitrogen to the pressure of 2.0MPa, replacing for 4-6 times by using hydrogen after the system pressure is stable, then filling the hydrogen, and adjusting the pressure of the hydrogenation reaction kettle to 2.0 MPa. And (3) closing the hydrogen inlet valve after the system pressure is stable, heating to 90-100 ℃, opening the hydrogen valve after the reaction system pressure is balanced, and keeping the reaction pressure at 2.0MPa for 5-10 h.
e) Sampling every 2h after 5h of reaction for chromatographic detection, and ending the reaction and relieving pressure when the content of the p-tert-butylphenol is less than or equal to 0.5 percent. Filtering the generated reaction liquid of the tert-butyl cyclohexanol, transferring the liquid phase filtrate into a rotary evaporator, washing the solid phase catalyst with ethanol, transferring the washed solid phase catalyst into a hydrogenation reaction kettle, and carrying out the next batch of hydrogenation reaction.
f) And e) starting the rotary evaporator to heat, recovering ethanol at the normal pressure and the temperature of 60-90 ℃, and concentrating and recycling the collected ethanol. And then starting a vacuum pump, collecting the o-tert-butylcyclohexanol at the kettle temperature of 95-100 ℃ and the pressure of 1000-1333 Pa, and transferring the collected o-tert-butylcyclohexanol into a four-neck flask. The bottle bottom liquid is p-tert-butyl cyclohexanol, and the collected p-tert-butyl cyclohexanol can be used for production of irisone.
g) 95g of ethanol is added into a three-neck flask in a metered manner, then 4g of catalyst sodium methoxide and 5g of acid-removing agent triethylamine are added in a metered manner, a stirrer and a cold-heat exchange all-in-one machine are started, and the temperature of a glass flask is reduced to 0-5 ℃. Slowly adding 110g of ethyl chloroformate into a glass flask, controlling the reaction temperature to be 0-5 ℃, and continuously stirring for 0.5h after the reaction is finished. And then 30g of 30% sodium carbonate solution is metered and added, the mixture is stirred for 0.5h, the mixture is transferred into a centrifugal machine, sodium chloride is separated out, the reaction solution is washed for three times to obtain diethyl carbonate, and the diethyl carbonate is collected for later use after ethanol is distilled and recovered.
h) 120g of diethyl carbonate and 3.5g of p-toluenesulfonic acid are added into a four-neck flask in a metering mode, a stirrer is started, a heat and heat exchange all-in-one machine is started to heat, the reaction temperature is controlled to be 100-110 ℃, the reaction time is 3-5 hours, the reaction liquid is transferred into a rotary evaporator, ethanol is recovered under normal pressure, and the bottom liquid of the flask is transferred into a beaker.
i) 25g of 5% sodium hydroxide solution is added into the beaker in a metered mode, a stirrer is started, the collected bottom liquid of the bottle is subjected to alkali washing, the bottom liquid is stirred for 0.5 hour and then is kept stand for layering for 0.5 hour, and an alkali liquid layer is concentrated into a waste liquid collecting barrel. And adding 60g of clear water into the oil layer for washing, stirring for 0.5h, standing for layering for 0.5h, collecting the water layer into a waste liquid collecting barrel, and washing twice. Transferring the oil layer into a rotary evaporator, starting the rotary evaporator to heat, starting a vacuum pump, and collecting tert-butyl cyclohexyl ethyl carbonate to obtain 120.6g of tert-butyl cyclohexyl ethyl carbonate.
The obtained product is colorless transparent liquid, has fruity and woody aroma, has floral aroma, and has purity of 99.01% (sum of isomers) by gas chromatography, detected refractive index (20 deg.C) of 1.4523, and relative density (25 deg.C) of 0.9718. The total yield is 66.3%.
The GC conditions for product detection are as follows: chromatography column HP-5(30m × 0.32mm × 0.25 um); detector FID, temperature 280 ℃; sample introduction: the sample introduction amount is about 0.2ul, the split ratio is 1:100, and the temperature of a sample introduction port is 250 ℃; carrier gas: n is a radical of2The flow rate is 20L/min, and the front column pressure is 34.47 kPa; temperature of the chromatographic furnace: the linear temperature programming is carried out at the speed of 5 ℃/min from 150 ℃ to 250 ℃ and is kept for 10 min.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A synthesis method of tert-butyl cyclohexyl ethyl carbonate spice is characterized by comprising the following steps: the method comprises the following steps:
a) firstly, adding ethanol into a three-neck glass flask by weighing and metering, then adding phenol into the glass flask, starting a stirrer and a heat and cold exchange all-in-one machine, reducing the temperature of the glass flask to 10-15 ℃, slowly adding a solid acid catalyst into the glass flask, and continuing stirring for 0.5h after the feeding is finished;
b) continuously maintaining the temperature of the glass flask at 10-15 ℃, dropwise adding tert-butyl alcohol into the glass flask by using a dropwise adding pump, controlling the dropwise adding time to be 2 hours, raising the temperature of the kettle to 100-110 ℃ after dropwise adding, continuously stirring for 2-4 hours, sampling for chromatographic detection, cooling when the content of phenol is less than or equal to 0.5%, and finishing the reaction;
c) transferring the generated mixed reaction liquid of the o-tert-butylphenol and the p-tert-butylphenol into a separating funnel, standing and layering for 0.5h, putting an oil layer into a beaker, adding ethanol into a water layer, stirring for 0.5h, standing and layering, merging the oil layers, putting into the beaker, and concentrating the water layer into a waste liquid collecting barrel; respectively washing the solid-phase solid acid catalyst with ethanol and water for recycling, metering a 5% sodium hydroxide solution into a beaker of an oil layer, starting a stirrer, carrying out alkali washing on the collected oil layer, stirring for 0.5h, standing for layering for 0.5h, and concentrating an alkali solution layer into a waste liquid collecting barrel; adding clear water into the oil layer for washing, stirring for 0.5h, standing for layering for 0.5h, transferring the oil layer into a hydrogenation reaction kettle, and collecting the water layer into a waste liquid collecting barrel;
d) adding a 5% palladium-carbon catalyst into a hydrogenation reaction kettle in a fixed amount, sealing the hydrogenation reaction kettle, replacing the hydrogenation reaction kettle with nitrogen for 4-6 times, then filling the nitrogen to the pressure of 2.0MPa, replacing the hydrogenation reaction kettle with hydrogen for 4-6 times after the system pressure is stable, then filling the hydrogen, and adjusting the pressure of the hydrogenation reaction kettle to 2.0 MPa; closing a hydrogen inlet valve after the system pressure is stable, heating to 80-150 ℃, opening the hydrogen valve after the reaction system pressure is balanced, and keeping the reaction pressure at 2.0MPa for 5-10 h;
e) sampling every 2 hours after 5 hours of reaction, carrying out chromatographic detection, ending the reaction when the content of p-tert-butylphenol is less than or equal to 0.5%, decompressing, filtering the generated mixed reaction liquid of o-tert-butylcyclohexanol and p-tert-butylcyclohexanol, transferring the liquid phase filtrate into a rotary evaporator, washing a solid phase catalyst with ethanol, transferring the washed solid phase catalyst into a hydrogenation reaction kettle, and carrying out the next batch of hydrogenation reaction;
f) starting the rotary evaporator in the step e) to heat, recovering ethanol at the normal pressure and the temperature of 60-90 ℃, concentrating the collected ethanol for reuse, starting a vacuum pump, collecting o-tert-butylcyclohexanol at the temperature of 95-100 ℃ and the pressure of 1000-1333 Pa, transferring the collected o-tert-butylcyclohexanol into a four-neck flask, wherein the bottom liquid of the flask is p-tert-butylcyclohexanol, and the collected o-tert-butylcyclohexanol can be used for producing irisoryl ester;
g) adding ethanol into a three-neck flask in a metering manner, then adding catalysts of sodium methoxide and acid-removing agent triethylamine in a metering manner, starting a stirrer and a cold-heat exchange all-in-one machine, and reducing the temperature of a glass flask to 0-5 ℃; slowly adding ethyl chloroformate into the glass flask in a metered manner, controlling the reaction temperature to be 0-5 ℃, and continuously stirring for 0.5h after the reaction is finished; then metering and adding 30% sodium carbonate solution, stirring for 0.5h, transferring into a centrifuge, separating sodium chloride, washing the reaction solution for three times to obtain diethyl carbonate, distilling and recovering ethanol, and collecting the diethyl carbonate for later use;
h) adding diethyl carbonate and p-toluenesulfonic acid into a four-neck flask in a metered manner, starting a stirrer, starting a heat and heat exchange all-in-one machine for heating, controlling the reaction temperature to be 100-120 ℃, reacting for 3-5 h, transferring the reaction liquid into a rotary evaporator, recovering ethanol at normal pressure, and transferring the bottom liquid into a beaker;
i) adding 5% sodium hydroxide solution into a beaker in a metered manner, starting a stirrer, carrying out alkali washing on the collected bottom liquid of the bottle, stirring for 0.5h, standing and layering for 0.5h, collecting an alkali liquid layer into a waste liquid collecting barrel, adding clear water into an oil layer for washing, stirring for 0.5h, standing and layering for 0.5h, collecting a water layer into the waste liquid collecting barrel, transferring the oil layer into a rotary evaporator, starting the rotary evaporator for heating, starting a vacuum pump, and collecting tert-butyl cyclohexyl ethyl carbonate.
2. The process for synthesizing tert-butylcyclohexyl ethyl carbonate flavor according to claim 1, wherein: the mass ratio of the ethanol to the phenol in the step a) is 1.0: 1-5.0: 1, and the ingredient amount of the solid acid catalyst is 0.5-5 wt% of the total feeding amount; the molar ratio of the tert-butyl alcohol to the phenol in the step b) is 1.0: 1-5.0: 1; in the step c), the mass ratio of the ethanol to the water layer is 0.5: 1-2: 1, the mass ratio of the sodium hydroxide solution to the reaction liquid oil layer is 0.2: 1-2: 1, and the mass ratio of the clear water to the reaction liquid oil layer is 0.5: 1-2: 1.
3. The process for synthesizing tert-butylcyclohexyl ethyl carbonate flavor according to claim 1, wherein: the material of the hydrogenation reaction kettle in the step d) is stainless steel, and the design pressure is 0-5 MPa.
4. The process for synthesizing tert-butylcyclohexyl ethyl carbonate flavor according to claim 1, wherein: in the step g), the molar ratio of ethanol to ethyl chloroformate is 1: 1-5: 1, the dosage of sodium methoxide is 0.5-5 wt% of the total dosage, and the dosage of triethylamine is 1-10 wt% of the total dosage.
5. The process for synthesizing tert-butylcyclohexyl ethyl carbonate flavor according to claim 1, wherein: the molar ratio of diethyl carbonate to o-tert-butylcyclohexanol in the step h) is 1.0: 1-5.0: 1, and the amount of p-toluenesulfonic acid is 0.5-5 wt% of the total amount of the ingredients.
6. The process for synthesizing tert-butylcyclohexyl ethyl carbonate flavor according to claim 1, wherein: in the step i), the mass ratio of the sodium hydroxide solution to the oil layer is 0.2: 1-2: 1, and the mass ratio of the clear water to the oil layer is 0.5: 1-2: 1.
7. The process for synthesizing tert-butylcyclohexyl ethyl carbonate flavor according to claim 2, wherein: the mass ratio of ethanol to phenol in the step a) is 2.0: 1-2.5: 1, and the ingredient amount of the solid acid catalyst is 1-2 wt%; the molar ratio of the tert-butyl alcohol to the phenol in the step b) is 1.0: 1-1.5: 1; in the step c), the mass ratio of ethanol to the water layer is 0.5: 1-1: 1, the mass ratio of the sodium hydroxide solution to the reaction liquid oil layer is 0.2: 1-1: 1, and the mass ratio of the clear water to the reaction liquid oil layer is 0.5: 1-1: 1.
8. The process for synthesizing tert-butylcyclohexyl ethyl carbonate flavor according to claim 4, wherein: in the step g), the molar ratio of ethanol to ethyl chloroformate is 1.5: 1-2.5: 1, the ingredient amount of sodium methoxide is 1-2 wt%, and the ingredient amount of triethylamine is 1-2.5 wt%.
9. The process for synthesizing tert-butylcyclohexyl ethyl carbonate flavor according to claim 5, wherein: the molar ratio of diethyl carbonate to tert-butylcyclohexanol in the step h) is 1.5: 1-2.0: 1; the dosage of the p-toluenesulfonic acid is 1.0-2.0 wt%.
10. The process for synthesizing tert-butylcyclohexyl ethyl carbonate flavor according to claim 6, wherein: in the step i), the mass ratio of the sodium hydroxide solution to the oil layer is 0.2: 1-1: 1, and the mass ratio of the clear water to the oil layer is 0.5: 1-1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710964925.1A CN107652183B (en) | 2017-10-17 | 2017-10-17 | Synthesis method of tert-butyl cyclohexyl ethyl carbonate spice |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710964925.1A CN107652183B (en) | 2017-10-17 | 2017-10-17 | Synthesis method of tert-butyl cyclohexyl ethyl carbonate spice |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107652183A CN107652183A (en) | 2018-02-02 |
| CN107652183B true CN107652183B (en) | 2021-01-26 |
Family
ID=61118301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710964925.1A Active CN107652183B (en) | 2017-10-17 | 2017-10-17 | Synthesis method of tert-butyl cyclohexyl ethyl carbonate spice |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107652183B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235873A (en) * | 1998-05-19 | 1999-11-24 | 中国石油化工总公司 | Silicon dioxide carried heteropoly acid catalyst, its preparation and use |
| CN1264361A (en) * | 1997-07-17 | 2000-08-23 | 住友化学工业株式会社 | 4-tert-butylcyclohexyl acetate and perfume composition comprising the same |
| CN103193638A (en) * | 2012-01-06 | 2013-07-10 | 南昌洋浦天然香料香精有限公司 | Synthetic method of perfume o-tert-butylcyclohexyl acetate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58146523A (en) * | 1982-02-25 | 1983-09-01 | Sumitomo Chem Co Ltd | Preparation of alkylphenol |
-
2017
- 2017-10-17 CN CN201710964925.1A patent/CN107652183B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1264361A (en) * | 1997-07-17 | 2000-08-23 | 住友化学工业株式会社 | 4-tert-butylcyclohexyl acetate and perfume composition comprising the same |
| CN1235873A (en) * | 1998-05-19 | 1999-11-24 | 中国石油化工总公司 | Silicon dioxide carried heteropoly acid catalyst, its preparation and use |
| CN103193638A (en) * | 2012-01-06 | 2013-07-10 | 南昌洋浦天然香料香精有限公司 | Synthetic method of perfume o-tert-butylcyclohexyl acetate |
Non-Patent Citations (2)
| Title |
|---|
| ETHYL 2-tert-BUTYLCYCLOHEXYL CARBONATE;C.S.Letizia et al.;《Food and chemical Toxicology》;20001231;第38卷;第S77-S79页 * |
| 酸改性介孔分子筛SBA-15催化合成叔丁基苯酚;袁兴东等;《石油化工》;20031231;第32卷;第223-226页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107652183A (en) | 2018-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101904127B1 (en) | Novel carboxylic acid ester compound and method for producing same, and fragrance composition | |
| JP6695890B2 (en) | Method for producing tetrahydropyranyl ester | |
| JP5479466B2 (en) | Isolongifolanil derivatives suitable as odorants | |
| EP3153492B1 (en) | Novel compound and fragrance composition containing same | |
| SG194518A1 (en) | Terpene alcohols for use in fragrance compositions and perfumed products | |
| KR20070006895A (en) | Alicyclic carboxylic acid oxycarbonylmethyl esters and their use as odorants | |
| CN111018682A (en) | Preparation method of citral | |
| JP2010506861A (en) | 2,2,3-Trimethylcyclopent-3-enecarbaldehyde derivatives useful as odor substances | |
| CN107652183B (en) | Synthesis method of tert-butyl cyclohexyl ethyl carbonate spice | |
| CN107879932B (en) | Synthesis method of o-tert-butylcyclohexyl acetate perfume | |
| CN207567141U (en) | A kind of process units of verdox synthetic perfume | |
| KR20190023466A (en) | High purity 1,3-butanediol and its preparation method | |
| EP0411460B1 (en) | Perfumery composition comprising 2-cyclohexylpropionic acid or its derivative | |
| EP2639218B1 (en) | Novel carboxylic acid ester compound and production therefor, and perfume composition thereof | |
| CN107698450B (en) | Synthetic method of irisone spice | |
| CN109195959A (en) | THP trtrahydropyranyl low-carbon alkyl uses the preparation of ketene compound with it | |
| JP6072797B2 (en) | Fragrance compounds and compositions | |
| US7019181B2 (en) | Method for the preparation of trimethylcyclohexyl-alkan-3-ols containing a high proportion of trans isomers | |
| CN107827712A (en) | A kind of production method of verdox synthetic perfume | |
| CN107840797B (en) | Production method of synthetic iridate spice | |
| EP1668102B1 (en) | 3-isopropyl-1-methylcyclopentyl derivatives and their use in fragrance applications | |
| JP2001031608A (en) | OPTICAL ACTIVE, 1-(p-MENTHA-2'-YL)ETHANOL, PERFUME COMPRISING THE SAME, AS ACTIVE INGREDIENT AND PRODUCTION OF THE COMPOUND | |
| EP0998444B1 (en) | Process for the preparation of 4-tert.-butylcyclohexyl acetate | |
| EP3822250B1 (en) | Carboxylic ester compound, production method therefor, composition, and perfume composition | |
| US20040138092A1 (en) | 2,3, 5, 5-tetramethylhexanal derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |