CN112961042B - Synthesis method of trans-4- (trans-4' -alkyl cyclohexyl) cyclohexyl formaldehyde - Google Patents

Synthesis method of trans-4- (trans-4' -alkyl cyclohexyl) cyclohexyl formaldehyde Download PDF

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CN112961042B
CN112961042B CN202110147405.8A CN202110147405A CN112961042B CN 112961042 B CN112961042 B CN 112961042B CN 202110147405 A CN202110147405 A CN 202110147405A CN 112961042 B CN112961042 B CN 112961042B
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cyclohexyl
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刘显伟
韩津
马青松
陈芳
王晓莹
马心旺
苏建
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Huize Chemical Technology Puyang Co ltd
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Abstract

The invention discloses a synthesis method of trans-4- (trans-4 ' -alkyl cyclohexyl) cyclohexyl formaldehyde, which comprises the steps of carrying out catalytic oxidation reaction on trans-4- (trans-4 ' -alkyl cyclohexyl) cyclohexyl methanol to obtain trans-4- (trans-4 ' -alkyl cyclohexyl) cyclohexyl formaldehyde, wherein an oxidant is oxygen or air, and a catalytic system comprises a catalyst A, a catalyst B and a catalyst C; the catalyst A is piperidine nitroxide free radical and its derivative, the catalyst B is nitric oxide equivalent, and the catalyst C is bromide, acid or ferric salt. The catalytic system of the synthesis method is efficient and environment-friendly, and the whole reaction process is clean and safe, and has great advantages from the economic or environment-friendly point of view.

Description

Synthesis method of trans-4- (trans-4' -alkyl cyclohexyl) cyclohexyl formaldehyde
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a synthesis method of trans-4- (trans-4' -alkyl cyclohexyl) cyclohexyl formaldehyde.
Background
Compared with the traditional biphenyl liquid crystal monomer, the cyclohexane liquid crystal monomer has the advantages of higher phase transition temperature, wider nematic phase temperature zone, lower viscosity, faster response speed and the like, so the cyclohexane liquid crystal monomer gradually becomes the most used liquid crystal material synthesis intermediate at present. Trans-4- (trans-4 '-alkyl cyclohexyl) cyclohexyl formaldehyde is one of the most widely used intermediates in the synthesis process of dicyclohexyl liquid crystal monomers, so that research on the synthesis of the trans-4- (trans-4' -alkyl cyclohexyl) cyclohexyl formaldehyde has important value and significance.
Patent CN1450040a mentions that trans-4- (trans-4 ' -alkylcyclohexyl) cyclohexyl methanoic acid is used as raw material, firstly reduced into trans-4- (trans-4 ' -alkylcyclohexyl) cyclohexyl methanol by lithium aluminum hydride, and then oxidized by chromic chloride pyridine hydrochloride to obtain trans-4- (trans-4 ' -alkylcyclohexyl) cyclohexyl formaldehyde.
The patents CN101671242A and CN101823943A prepare target products by using 4- (4 '-alkyl cyclohexyl) cyclohexyl methanol through an oxidation catalytic system of piperidine nitroxide free radical and derivatives, bromide and hypochlorite to obtain 4- (4' -alkyl cyclohexyl) cyclohexyl formaldehyde.
Disclosure of Invention
Based on the problems existing in the background technology, the invention provides a synthesis method of trans-4- (trans-4' -alkyl cyclohexyl) cyclohexyl formaldehyde.
The invention is realized by the following technical scheme:
A synthesis method of trans-4- (trans-4' -alkyl cyclohexyl) cyclohexyl formaldehyde comprises the following steps:
carrying out catalytic oxidation reaction on trans-4- (trans-4 '-alkyl cyclohexyl) cyclohexyl methanol to obtain trans-4- (trans-4' -alkyl cyclohexyl) cyclohexyl formaldehyde; the oxidant is oxygen or air; the catalyst system comprises a catalyst A, a catalyst B and a catalyst C; the catalyst A is piperidine nitroxide free radical and its derivative, the catalyst B is nitric oxide equivalent, and the catalyst C is bromide, acid or ferric salt.
Preferably, the alkyl group in the trans-4- (trans-4' -alkylcyclohexyl) cyclohexylmethanol is selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl.
Preferably, the piperidine nitroxide radical and its derivative are one or more combinations of the following compounds:
preferably, the nitric oxide equivalent is one or a combination of more of sodium nitrite, potassium nitrite, methyl nitrite, ethyl nitrite, t-butyl nitrite, isoamyl nitrite.
Preferably, the bromide is one or more of hydrogen bromide, sodium bromide and potassium bromide; the acid is one or a combination of more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid; the ferric salt is one or a combination of more of ferric chloride, ferric bromide, ferric sulfate, ferric nitrate and potassium ferricyanide.
Preferably, the reaction solvent is one or more of dichloromethane, chloroform, 1, 2-dichloroethane, nitromethane, chlorobenzene, trichlorotoluene, benzotrifluoride, acetic acid, acetonitrile, toluene, xylene, water; preferably, the reaction temperature is 0 to 120 ℃.
Preferably, the dosage of the piperidine nitroxide free radical and the derivative thereof is 0.1-10% of the molar quantity of trans-4- (trans-4' -alkyl cyclohexyl) cyclohexyl methanol; preferably, the amount of the nitric oxide equivalent is 0.1 to 10% of the molar amount of trans-4- (trans-4' -alkylcyclohexyl) cyclohexylmethanol; preferably, the bromide is used in an amount of 0.1 to 10% of the molar amount of trans-4- (trans-4' -alkylcyclohexyl) cyclohexylmethanol; preferably, the amount of the hydrochloric acid is 0.1 to 10% of the molar amount of trans-4- (trans-4' -alkylcyclohexyl) cyclohexyl methanol; preferably, the trivalent iron salt is used in an amount of 0.1 to 10% of the molar amount of trans-4- (trans-4' -alkylcyclohexyl) cyclohexylmethanol.
The invention provides a synthesis method of trans-4- (trans-4' -alkyl cyclohexyl) cyclohexyl formaldehyde, which further comprises the following steps: the trans-4- (trans-4 ' -alkyl cyclohexyl) cyclohexyl methanoic acid or trans-4- (trans-4 ' -alkyl cyclohexyl) cyclohexyl methanoic acid ester is subjected to reduction reaction under the conditions of a reducing agent and/or a catalyst and/or a cocatalyst and a solvent to obtain trans-4- (trans-4 ' -alkyl cyclohexyl) cyclohexyl methanoic acid, and the synthetic route is as follows:
wherein R is selected from methyl, ethyl, n-propyl, n-butyl and n-pentyl; r' is selected from hydrogen, methyl, ethyl, propyl, butyl and isopropyl.
Preferably, the reducing agent is a borohydride; the catalyst is zinc chloride, calcium chloride, aluminum trichloride and the like; the cocatalyst is tertiary amine; the solvent is tetrahydrofuran and/or dimethyl tetrahydrofuran; preferably, the borohydride is potassium borohydride and/or sodium borohydride; preferably, the tertiary amine is trimethylamine, triphenylamine and/or N, N-dimethylaniline.
Preferably, the reducing agent is used in an amount of 100% to 200% of the molar amount of trans-4- (trans-4 '-alkylcyclohexyl) cyclohexyl formic acid or trans-4- (trans-4' -alkylcyclohexyl) cyclohexyl formate; the catalyst dosage is 100% -200% of the reducer molar quantity; the usage amount of the cocatalyst is 100% -200% of the mole amount of trans-4- (trans-4 '-alkyl cyclohexyl) cyclohexyl formic acid or trans-4- (trans-4' -alkyl cyclohexyl) cyclohexyl formic acid ester; preferably, the reaction temperature is 20-80 ℃.
The preparation method takes trans-4- (trans-4 ' -alkyl cyclohexyl) cyclohexyl formic acid or trans-4- (trans-4 ' -alkyl cyclohexyl) cyclohexyl formate as a raw material, firstly generates trans-4- (trans-4 ' -alkyl cyclohexyl) cyclohexyl methanol through borohydride reduction, and then takes oxygen or air as an oxidant, and forms a catalytic system by piperidine nitroxide free radicals and derivatives/nitric oxide equivalents/bromides or hydrochloric acid or ferric salt, so as to oxidize the trans-4- (trans-4 ' -alkyl cyclohexyl) cyclohexyl methanol to obtain the trans-4- (trans-4 ' -alkyl cyclohexyl) cyclohexyl formaldehyde. The reaction raw materials in the whole process are green and cheap, the catalytic system is efficient and environment-friendly, and the whole reaction process is clean and safe and has great advantages from the economic or environment-friendly point of view.
Detailed Description
In order to enable those skilled in the art to better understand the technical scheme of the present invention, the technical scheme of the present invention will be further described in detail with reference to specific embodiments.
Example 1
252.4G (1 mol) of trans-4- (trans-4 '-propylcyclohexyl) cyclohexyl formic acid, 37.8g (1 mol) of sodium borohydride, 136.3g (1 mol) of zinc chloride and 59.11g (1 mol) of trimethylamine are dissolved in 500mL of tetrahydrofuran, the mixture is stirred at 65 ℃ under reflux for 2 hours, then the mixture is quenched with 20% ammonium chloride solution and extracted with chloroform, the organic phase is washed with saturated saline solution and dried with anhydrous sodium sulfate overnight, and then the solvent is recovered by reduced pressure distillation to obtain trans-4- (trans-4' -propylcyclohexyl) cyclohexyl methanol;
Adding 0.86g (0.005 mol) of trans-4- (trans-4 '-propylcyclohexyl) cyclohexyl methanol, 4-hydroxy-2, 6-tetramethylpiperidine oxide obtained in the last step, 1.35g (0.005 mol) of ferric trichloride hexahydrate and 0.34g (0.005 mol) of sodium nitrite into a three-necked flask, adding 400mL of 1, 2-dichloroethane, stirring uniformly, introducing oxygen, heating to 80 ℃, refluxing for 2 hours, cooling to room temperature, transferring the reaction solution into a liquid separating funnel, washing twice with a saturated sodium thiosulfate solution, drying the separated organic phase with anhydrous sodium sulfate overnight, distilling under reduced pressure to recover a solvent, and recrystallizing the crude product with a mixed solvent prepared by petroleum ether and ethanol in a mass ratio of 1:3 to obtain trans-4- (trans-4' -propylcyclohexyl) cyclohexyl formaldehyde with the content of 99 percent and the yield of 88 percent.
Nuclear magnetic hydrogen spectrum data ：1H NMR(400MHz,CDCl3δ：0.87～0.93(t,3H),1.06～1.24 (q,2H),1.24～1.33(m,8H),1.38～1.52(m,9H),1.56～1.81(q,4H),2.3～2.5 (m,1H),9.0～9.5(s,1H).
Example 2
Methyl trans-4- (trans-4 '-propylcyclohexyl) cyclohexylformate 266.4g (1 mol), potassium borohydride 53.9g (1 mol), aluminum trichloride 133.3g (1 mol) and triphenylamine 245.3g (1 mol) were dissolved in 500mL tetrahydrofuran, stirred at 65℃under reflux for 2 hours, then quenched with a 20% ammonium chloride solution, extracted with trichloromethane, the organic phase was washed with saturated brine, dried overnight with anhydrous sodium sulfate, and the solvent was recovered by distillation under reduced pressure to give trans-4- (trans-4' -propylcyclohexyl) methanol;
17.1g (0.1 mol) of trans-4- (trans-4 '-propylcyclohexyl) cyclohexyl methanol, 4-amino-2, 6-tetramethylpiperidine oxide, 11.9g (0.1 mol) of potassium bromide and 10.3g (0.1 mol) of tert-butyl nitrite are put into a three-necked flask, 500mL of 1, 2-dichloroethane is added, the mixture is stirred uniformly, oxygen is introduced, the temperature is raised to 80 ℃, the reflux reaction is carried out for 2 hours, the mixture is cooled to room temperature after the completion, the reaction solution is transferred to a separating funnel, the mixture is washed twice with saturated sodium thiosulfate solution, the separated organic phase is dried overnight with anhydrous sodium sulfate, the recovered solvent is distilled under reduced pressure, and the crude product is recrystallized by a mixed solvent prepared by petroleum ether and ethanol in a mass ratio of 1:3 to obtain trans-4- (trans-4' -propylcyclohexyl) formaldehyde, and the content is 99%, and the yield is 90%.
Example 3
280.45G (1 mol) of ethyl trans-4- (trans-4 '-propylcyclohexyl) cyclohexyl formate, 37.8 (1 mol) of sodium borohydride, 136.3g (1 mol) of zinc chloride, and 121.2g (1 mol) of N, N-dimethylaniline are dissolved in 500mL of tetrahydrofuran, and the mixture is stirred at 65 ℃ under reflux for 2 hours, then quenched with 20% ammonium chloride solution, extracted with chloroform, the organic phase is washed with saturated saline, dried over night with anhydrous sodium sulfate, and the solvent is recovered by distillation under reduced pressure to obtain trans-4- (trans-4' -propylcyclohexyl) cyclohexyl methanol;
Adding 5.4g (0.03 mol) of trans-4- (trans-4 '-propylcyclohexyl) cyclohexyl methanol, 2, 6-tetramethylpiperidine oxide, 12g (0.1 mol) of 30% hydrochloric acid and 3.5g (0.05 mol) of sodium nitrite obtained in the last step into a three-neck flask, adding 500mL of 1, 2-dichloroethane, stirring uniformly, introducing oxygen, heating to 80 ℃, carrying out reflux reaction for 2 hours, cooling to room temperature after finishing, transferring the reaction solution into a separating funnel, washing the reaction solution twice with saturated sodium thiosulfate solution, drying the separated organic phase by anhydrous sodium sulfate overnight, distilling under reduced pressure to recover the solvent, and recrystallizing the crude product by using a mixed solvent prepared by petroleum ether and ethanol in a mass ratio of 1:3 to obtain trans-4- (trans-4' -propylcyclohexyl) cyclohexyl formaldehyde, wherein the content is 99 percent and the yield is 86 percent.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art who is skilled in the art should make equivalent substitutions or modifications according to the technical solution of the present invention and the inventive concept thereof within the scope of the present invention.

Claims (5)

1. A synthesis method of trans-4- (trans-4' -alkyl cyclohexyl) cyclohexyl formaldehyde is characterized by comprising the following steps:
carrying out catalytic oxidation reaction on trans-4- (trans-4 '-alkyl cyclohexyl) cyclohexyl methanol to obtain trans-4- (trans-4' -alkyl cyclohexyl) cyclohexyl formaldehyde;
the oxidant is oxygen or air; the catalyst system comprises a catalyst A, a catalyst B and a catalyst C; the catalyst A is piperidine nitroxide free radical and derivative thereof, the catalyst B is nitric oxide equivalent, and the catalyst C is bromide;
The bromide is potassium bromide;
The nitric oxide equivalent is tert-butyl nitrite;
the time of the catalytic oxidation reaction is 2 hours;
the piperidine nitroxide free radical and the derivative thereof are compounds with the following structures:
The dosage of the piperidine nitroxide free radical and the derivative thereof is 0.1-10% of the molar quantity of trans-4- (trans-4' -alkyl cyclohexyl) cyclohexyl methanol; the dosage of the nitric oxide equivalent is 0.1 to 10 percent of the mole amount of trans-4- (trans-4' -alkyl cyclohexyl) cyclohexyl methanol; the dosage of the bromide is 0.1-10% of the mole of trans-4- (trans-4' -alkyl cyclohexyl) cyclohexyl methanol.
2. The method for synthesizing trans-4- (trans-4 '-alkylcyclohexyl) cyclohexylformaldehyde according to claim 1, wherein the alkyl group in the trans-4- (trans-4' -alkylcyclohexyl) cyclohexylmethanol is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl and n-pentyl.
3. The method for synthesizing trans-4- (trans-4' -alkylcyclohexyl) cyclohexyl formaldehyde according to claim 1 or 2, wherein the reaction solvent is one or more of dichloromethane, chloroform, 1, 2-dichloroethane, nitromethane, chlorobenzene, trichlorotoluene, benzotrifluoride, acetic acid, acetonitrile, toluene, xylene, and water; the reaction temperature is 0-120 ℃.
4. The method for synthesizing trans-4- (trans-4' -alkylcyclohexyl) cyclohexylformaldehyde according to claim 1 or 2, further comprising: trans-4- (trans-4 ' -alkyl cyclohexyl) cyclohexyl methanoic acid or trans-4- (trans-4 ' -alkyl cyclohexyl) cyclohexyl methanoic acid ester is subjected to reduction reaction under the condition of taking borohydride as a reducing agent to obtain trans-4- (trans-4 ' -alkyl cyclohexyl) cyclohexyl methanoic acid, and the synthetic route is shown as follows:
Wherein R is selected from methyl, ethyl, n-propyl, n-butyl and n-pentyl; r' is selected from hydrogen, methyl, ethyl, propyl, isopropyl and butyl.
5. The method for synthesizing trans-4- (trans-4' -alkylcyclohexyl) cyclohexylformaldehyde according to claim 4, wherein the reducing agent borohydride is potassium borohydride and/or sodium borohydride.
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