CN101565363A - Method for preparing 4-[2'-(trans-4'-alkylcyclohexyl)ethyl] cyclohexanone liquid crystal intermediate compound - Google Patents
Method for preparing 4-[2'-(trans-4'-alkylcyclohexyl)ethyl] cyclohexanone liquid crystal intermediate compound Download PDFInfo
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Abstract
The invention discloses a method for preparing a 4-[2'-(trans-4'-alkylcyclohexyl) ethyl] cyclohexanone liquid crystal intermediate compound, which is characterized by comprising the following steps: reacting trans-4-alkylcyclohexylmethylchloride with magnesium chips in an organic solvent to obtain a Grignard reagent, reacting the Grignard reagent with benzyloxy benzonitrile, and subjecting the product of the reaction to acidic hydrolysis to obtain trans-4'-alkylcyclohexylacetyl-4-benzyloxy benzene (B); subjecting the (B) to a step hydrogenation reaction in an organic solvent under the catalysis of a catalyst to obtain 4-[2'-(trans-4'-alkylcyclohexyl)ethyl] cyclohexanol (C), and subjecting the (C) to precise fractional distillation and purification; and using the (C) to prepare a 4-[2'-(trans-4'-alkylcyclohexyl)ethyl] cyclohexanone compound in an organic solvent in the presence of an environmentally-friendly oxidant, and subjecting the 4-[2'-(trans-4'-alkylcyclohexyl)ethyl] cyclohexanone compound to precise fractional distillation, purification and recrystalization to obtain the 4-[2'-(trans-4'-alkylcyclohexyl) ethyl] cyclohexanone liquid crystal intermediate compound. The method can meet the high-purity and high-quality requirements of TFT-LCD on liquid crystal intermediates.
Description
Technical field
The present invention relates to a kind of preparation method of liquid crystal intermediates compound, relate more specifically to 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] preparation method of cyclohexanone analog liquid crystal intermediates compound.
Background technology
Thin Film Transistor-LCD (TFT-LCD) is most important a kind of in the liquid-crystal display (LCD), its output value and influence power have critical role in liquid-crystal display family, be widely used in all respects such as televisor, notebook computer, watch-dog, mobile phone.
Liquid crystal material is one of several big materials that constitute by liquid-crystal display (LCD), and, being accompanied by the difference of display format, required liquid crystal material is also different.Therefore, also be accompanied by the development of liquid-crystal display and grow in strength as the liquid crystal material that shows usefulness, a large amount of novel liquid crystalline cpds have appearred, as: cyclohexyl (connection) benzene class, ethane bridged bond class, end alkene class with contain fluorobenzene class liquid crystalline cpd etc., constantly to satisfy display devices such as TN-LCD, STN-LCD, TFT-LCD to performance demands.
It is generally acknowledged, contain the center bridged bond in the liquid crystal molecule, (liquid crystal molecule CH2CH2-) is referred to as ethane class liquid crystalline cpd, and it is very important one type of liquid crystal compound, wherein, is divided into several hypotype groups again promptly to contain ethylene.The introducing of ethane bridged bond has given liquid crystal molecule many advantageous properties, and as optical anisotropy little (Δ n), viscosity is lower, and response speed is fast, and chemical stability is good, and good light stability, low temperature mutual solubility are good etc.Therefore, ethane class liquid crystalline cpd in high-grade liquid crystal material, as: have among STN, the TFT widely and to use, become wherein indispensable composition.
In order to obtain the required various characteristics of display format, liquid crystal material uses with the form of mixtures of plurality of liquid crystals compound usually, therefore, needs liquid crystalline cpd to have good mutual solubility, particularly at low temperatures.
Open the liquid crystalline cpd that all is mentioned to alkyl-cyclohexyl ethyl cyclohexyl polyfluorobenzene in the patents such as flat 9-71779 and US5728319 disclosed US20030001138, US6682784, spy:
These liquid crystalline cpds constitute the mixed liquid crystal material that STN-LCD and TFT-LCD use with other liquid crystalline cpd, and become wherein very important integral part, have in TFT-LCD widely and use, and become wherein indispensable composition.
And to prepare above-mentioned ethane class monomer liquid crystal compound, and just must use 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] the cyclohexanone analog liquid crystal intermediates.EP0,280,902 patents are thought: 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] the cyclohexanone analog liquid crystal intermediates is a kind of important intermediate of synthetic ethane class liquid crystal, it can with corresponding grignard reagent reaction, go out a series of ethane class liquid crystalline cpds by dehydration, hydrogenation preparing.
At present, about 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] the preparation report of cyclohexanone analog liquid crystal intermediates is few; only have＜fine chemistry industry the 19th the 07th phase of volume in 2002 reported the Zhang Xiaojun of Tsing-Hua University; one piece of article that Tang Hong etc. deliver; with trans-4-amyl group hexahydrobenzoic acid is raw material; pass through lithium aluminium hydride reduction; bromo, grignard reaction, dehydration of alcohols, catalytic hydrogenation, demethylation, 4-[2 '-(trans-4 " amyl group cyclohexyl) ethyl has been synthesized in the reaction of high pressure catalytic hydrogenation and sodium dichromate 99 oxidation etc. 8 step] pimelinketone; 40.9 ℃ of fusing points, its massfraction of gas chromatograph for determination is 99.1%.This kind compound can be used as the important intermediate of preparation ethane class polycyclic system liquid crystal.But, this operational path is not only oversize, processing condition are harsh, but also with sodium dichromate 99 as the oxygenant contaminate environment, very easily produce by product in its preparation process, be difficult for purifying, make the purity of the finished product relatively poor, only be 99.1%, TFT-LCD can not be satisfied to liquid crystal intermediates high purity, high-quality requirement, simultaneously, the theory that current environmental protection is produced can not be satisfied and adapt to.
Summary of the invention
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art, simple, the high yield of a kind of technology, highly purified 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl is provided] novel preparation method of cyclohexanone analog liquid crystal intermediates compound; satisfy TFT-LCD to liquid crystal intermediates high purity, high-quality requirement, adapt to the needs of TFT-LCD with the liquid crystal material fast development.
4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] general formula (I) structure of cyclohexanone analog liquid crystal intermediates compound is as follows:
Wherein:
R is C
1-C
10Alkyl; Further, R is preferably C
1-C
10Straight chained alkyl;
More preferably, R is C
1-C
7Straight chained alkyl;
Most preferably, R is-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11Or-C
7H
15
For realizing that purpose of the present invention provides a kind of 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] novel preparation method of cyclohexanone analog liquid crystal intermediates compound (general formula (I)), its synthetic route is as follows:
4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] preparation method's step of cyclohexanone analog liquid crystal intermediates compound general formula (I) is as follows:
(1) with trans-4-alkyl-cyclohexyl methyl chloride (A) in organic solvent with magnesium chips reaction, obtain grignard reagent, again with to the reaction of benzyloxy benzene cyanogen, then carry out acidic hydrolysis obtain trans accordingly-4 '-alkyl-cyclohexyl ethanoyl-4-benzyloxy benzene (B);
(2) trans-4 '-alkyl-cyclohexyl ethanoyl-4-benzyloxy benzene (B) in organic solvent under the catalysis of catalyzer, carry out highly compressed ladder hydrogenation reaction after the first low pressure, reduce the generation of side reaction, obtain corresponding 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexyl alcohol (C), carry out precision fractional distillation, purification again;
(3) in organic solvent, 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexyl alcohol (C) is in the presence of the environmental protection oxygenant; oxidation makes 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexanone analog compound (I), carry out precision fractional distillation, purification, recrystallization again, obtain target product with high purity.
Organic solvent described in the step of the present invention (1) is at least a in ether, tetrahydrofuran (THF), methyltetrahydrofuran, benzene, toluene and the dimethylbenzene, and it is preferably the mixture of tetrahydrofuran (THF) and toluene.
Acidic hydrolysis described in the step of the present invention (1), be in the presence of acid, to implement, preferred randomly hydrochloric acid, sulfuric acid, the glacial acetic acid of dilute with water, the more preferably hydrochloric acid of dilute with water, sulfuric acid, most preferably be the sulfuric acid of dilute with water, generally speaking, the concentration after the various acid dilutions is 10-50%.
Step of the present invention (1) can be implemented in wide relatively temperature range, and typical temperature is 10 ℃ to 105 ℃, and preferred temperature is 20 ℃ to 105 ℃.Most preferably the reaction of each reactive component further is reflected at 70 ℃ to 85 ℃ and carries out earlier 60 ℃ to 75 ℃ following initiation reactions in the step (1), then, carries out acidic hydrolysis again under 90 ℃ to 105 ℃.
In the enforcement of step of the present invention (1), for trans-4-alkyl-cyclohexyl methyl chloride (A) of 1mol, employed magnesium chips is generally 0.7mol to 1.5mol, is preferably 0.9mol to 1.3mol, more preferably 1.0mol to 1.1mol; Employed benzyloxy benzene cyanogen is generally 0.6mol to 1.4mol, more preferably 0.8mol to 1.2mol most preferably is 0.9mol to 1.0mol.
In the step of the present invention (1), the reaction times is not crucial, can how much selecting in the scope of broad according to production lot.Generally speaking, the time of each reaction combines and reaches 15 hours most in the step poly-(1), and its preferred time is 10 hours, and more preferably the time is 8 hours.
Catalyzer described in the step of the present invention (2) is at least a among Raney's nickel catalyst, active nickel catalyst, Pd/C, the Pt/C, is preferably Raney's nickel catalyst, most preferably is neutral Raney's nickel catalyst.
Organic solvent described in the step of the present invention (2) is at least a in ethyl acetate, ethanol, methyl alcohol, Virahol, toluene, dimethylbenzene and the methylene dichloride, is preferably ethanol and methyl alcohol, most preferably is ethanol.
The ladder hydrogenation reaction described in poly-(2) that the present invention goes on foot is meant highly compressed hydrogenation process after the first low pressure: the first step is that 0.5Mpa, temperature heated hydrogenation reaction 2～3 hours when being 95～100 ℃ at hydrogen pressure earlier; In second step, being warmed up to 125～135 ℃, pressure is under the condition of 3.6～4.0Mpa, repeated hydrogenation reaction 5～6 hours.
Step of the present invention (2) can be implemented in wide relatively temperature and pressure scope.Typical temperature is that 50 ℃ to 200 ℃, pressure are 0.1Mpa to 10.0Mpa.Preferred temperature is that 60 ℃ to 180 ℃, pressure are 0.2Mpa to 8.0Mpa, and more preferably temperature is that 80 ℃ to 150 ℃, pressure are 0.3Mpa to 6.0Mpa.Most preferably in the step (2), the reaction of each reactive component is divided into two stages and carries out: earlier under 85 ℃ to 110 ℃ of temperature, pressure 0.3Mpa to 0.7Mpa reaction 1-3 hour, then, again under 110 ℃ to 150 ℃ of temperature, pressure 2.5Mpa to 5.0Mpa reaction 3-7 hour.
Reaction times in the step of the present invention (2) is not crucial, can how much selecting in the scope of broad according to production lot.Generally speaking, the reaction times that each reactant combines reaches 12 hours most, and the preferred reaction time is 10 hours, and more preferably the reaction times is 8 hours.More concrete is is 1-3 hour in reaction times fs, and the subordinate phase reaction times is 3-7 hour.
Environmental protection oxygenant described in the step of the present invention (3) is at least a in clorox, Losantin, Manganse Dioxide, potassium permanganate, hydrogen peroxide and the additive oxygenants such as (as: ammonium vanadate, potassium bromates), be preferably clorox and Losantin, more preferably clorox.And for the 4-[2 ' of 1mol-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexyl alcohol (C); the molar weight of used oxygenant generally is 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] 40-100% of cyclohexyl alcohol (C), be preferably 40-70%, most preferably be 40-50%.
Organic solvent described in the step of the present invention (3) is at least a in methylene dichloride, chloroform, tetracol phenixin, dithiocarbonic anhydride, tetrachloroethane, 1,4-diox, tetrahydrofuran (THF), ether, methyl tertiary butyl ether, acetone, butanone, glacial acetic acid and the propionic acid, be preferably at least a in chloroform, glacial acetic acid, 1,4-diox, methyl tertiary butyl ether, acetone, the butanone, more preferably at least a in chloroform, glacial acetic acid, 1,4-diox, the acetone.
Step of the present invention (3) can be implemented in wide relatively temperature range.Typical temperature is-10 ℃ to 50 ℃, and preferred temperature is-5 ℃ to 40 ℃, and more preferably temperature is 0 ℃ to 30 ℃, and most preferably temperature is 0 ℃ to 20 ℃.
Step of the present invention (3), the reaction times is not crucial, can how much selecting in the scope of broad according to production lot.Generally speaking, each reactant combines maximum response time and reaches 10 hours, and the preferred reaction time is 8 hours, and most preferably the reaction times is 6 hours.Adopt gas chromatograph to monitor in the reaction process always and follow the tracks of reaction.
In the step of the present invention (3), carry out the used organic solvent of last recrystallization and be at least a in acetone, butanone, pimelinketone, ethyl acetate, ethanol, methyl alcohol, Virahol, toluene and the dimethylbenzene, be preferably at least a in butanone, pimelinketone, ethyl acetate, ethanol, toluene, the Virahol, more preferably butanone, pimelinketone, ethyl acetate, alcoholic acid mixture.
The precision fractional distillation of being carried out in step of the present invention (2) and the step (3) preferably adopts the molecular distillation instrument to carry out precision fractional distillation.
Advantage of the present invention and positively effect are as follows:
(1) at the second step preparation 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] in the process of cyclohexyl alcohol (C); owing to adopted highly compressed ladder hydrogenation process after the first low pressure; the product that obtains carries out precise distillation again; reached the technology of very optimizing, make by product in the product as: 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl alcohol] cyclohexyl alcohol and 4-[2 '-(trans-4 "-alkyl-cyclohexyl) ethyl] amount of hexanaphthene reduces to technology acceptable degree;
(2) in the preparation process in the 3rd step, 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexyl alcohol (C) adopts under the condition of the oxygenant of relative environmental protection; prepare 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexanone analog compound (I), in conjunction with precise distillation and purification, can obtain purity and reach white crystal product more than 99.8%;
(3) the synthetic route uniqueness of the present invention's design, the material and the technological line of environmental protection have been adopted, operational path is shorter, and processing condition are reasonable, and treatment process is suitable, product quality is excellent, the purity height, the yield height is suitable for the quality requirements of TFT-LCD liquid crystal material to intermediate, can satisfy TFT-LCD fully to liquid crystal intermediates high purity, high-quality requirement, to adapt to the needs of TFT-LCD with the liquid crystal material fast development.
Embodiment
Below in conjunction with specific embodiment the present invention is done further detailed description, yet described embodiment should not explain in the mode of restriction.
Embodiment 1:
Present embodiment is 4-[2 '-(trans-4 " amyl group cyclohexyl) ethyl] preparation of pimelinketone, its preparation step is poly-as follows:
Step 1: trans-4 '-amyl group cyclohexyl ethanoyl-4-benzyloxy benzene (B) synthetic.
In there-necked flask, add 4.8g (0.2mol) magnesium chips, 250ml exsiccant tetrahydrofuran (THF) and 100ml toluene, reflux, add two milliliters of trans-4-amyl group cyclohexyl methyl chlorine and two iodine, after the initiation reaction, begin to drip 36.5g (0.18mol) trans-4-amyl group cyclohexyl methyl chlorine, be advisable with little backflow, approximately drip half an hour; Finish heating reflux reaction 3 hours.Drip the solution of 33.5g (0.16mol) to benzyloxy benzene cyanogen and 50ml toluene, approximately dripped 1 hour, after finishing, heating begins to steam solvent, ends for 105 ℃ to temperature, adds 100ml toluene, and back flow reaction is 3 hours again; Be cooled to 20 ℃, drip the solution of the 20ml vitriol oil and 50ml water, finish reheat to 95 ℃ left and right sides back flow reaction 2 hours; Be cooled to 20 ℃, separatory with 100ml * 2 toluene extraction secondary, merges organic layer, uses 200ml * 3 warm water to wash again three times, uses anhydrous MgSO
4Dry; The filtering siccative, evaporated under reduced pressure gets crude product, uses 500mL * 2 dehydrated alcohol recrystallization secondaries again, gets white crystal 49.0g, product gas chromatograph purity assay 〉=99.5%, yield 81%.
Step 2:4-[2 '-(trans-4 " amyl group cyclohexyl) ethyl] cyclohexyl alcohol (C) synthetic.
Add in the autoclave 500g (1.32mol) trans-4 '-amyl group cyclohexyl ethanoyl-4-benzyloxy benzene (B), 1500ml dehydrated alcohol, Raney's nickel catalyst 150g, the lid kettle cover, with nitrogen replacement air three times, use hydrogen exchange nitrogen again three times, hydrogen pressure is decided to be 0.5Mpa, temperature is decided to be 95～100 ℃, begins to heat hydrogenation; Control hydrogenation reaction after 2 hours, being warmed up to 125～135 ℃, pressure is under the condition of 3.6～4.0Mpa, repeated hydrogenation reaction 5 hours～6 hours (gas chromatograph is followed the tracks of reaction to having reacted).Reaction solution is reduced to room temperature, carry out press filtration under the nitrogen protection, with 100mL * 2 alcohol flushing catalyzer secondaries; merge all filtrate, neat solvent is removed in decompression, and excess carries out precise distillation with the molecular distillation instrument; collect the cut of 145 ± 2 ℃/1mmHg, get white solid 351.1g.Products obtained therefrom gas chromatograph analysis, purity 〉=99.2%, yield: 95%.
Step 3:4-[2 '-(trans-4 " amyl group cyclohexyl) ethyl] pimelinketone synthetic.
Adding 80ml methylene dichloride, 100ml glacial acetic acid, 100ml 1,4-diox, 30ml tetrahydrofuran (THF) and 4-[2 ' in the there-necked flask-(trans-4 " the amyl group cyclohexyl) ethyl] cyclohexyl alcohol (C) 50.4g (0.18mol); stirring and dissolving; controlled temperature is at 7～10 ℃; begin to drip an amount of (available chlorine 10%) clorox; gas chromatograph is followed the tracks of reaction while dripping, and approximately drips 2 hours; Finish, again insulation reaction 2～3 hours (gas chromatograph is followed the tracks of the response analysis terminal point); Separatory with 100ml * 2 toluene extraction secondary, merges organic layer, uses 200ml * 3 sodium bicarbonates (10%) solution washing again three times, washes neutrality again, uses anhydrous MgSO
4Dry; The filtering siccative, underpressure distillation gets crude product, and excess carries out precise distillation with the molecular distillation instrument, collects the cut of 140 ± 1 ℃/1mmHg, uses 200mL ethyl acetate and 30mL butanone recrystallization secondary again, gets white crystal 35.5g.Products obtained therefrom gas chromatograph analysis, purity 〉=99.8%, yield 71%, melting point compound: 41.7 ℃.
Embodiment 2:
Present embodiment is 4-[2 '-(trans-4 " propyl group cyclohexyl) ethyl] preparation of pimelinketone.
Preparation process is with embodiment 1, and difference is: the trans-4-amyl group cyclohexyl methyl chlorine raw material in the step 1 is replaced with trans-4-propyl group cyclohexyl methyl chlorine, prepares target product 4-[2 '-(trans-4 " propyl group cyclohexyl) ethyl] pimelinketone.
The result is as follows in preparation: products obtained therefrom gas chromatograph analysis, purity 〉=99.8%, yield are 71%, melting point compound: 45.3 ℃.
Embodiment 3
Present embodiment is 4-[2 '-(trans-4 " heptyl cyclohexyl) ethyl] preparation of pimelinketone.
Preparation process is with embodiment 1, and difference is: the trans-4-amyl group cyclohexyl methyl chlorine raw material in the step 1 is replaced with trans-4-heptyl cyclohexyl methyl chlorine, prepares target product 4-[2 '-(trans-4 " heptyl cyclohexyl) ethyl] pimelinketone.
The result is as follows in preparation: products obtained therefrom gas chromatograph analysis, purity 〉=99.8%, yield 71%, melting point compound: 44.3 ℃.
Embodiment 4
Present embodiment is 4-[2 '-(trans-4 " methylcyclohexyl) ethyl] preparation of pimelinketone.
Preparation process is with embodiment 1, and difference is: the trans-4-amyl group cyclohexyl methyl chlorine raw material in the step 1 is replaced with trans-4-methylcyclohexyl methyl chloride, prepares target product 4-[2 '-(trans-4 " methylcyclohexyl) ethyl] pimelinketone.
The result is as follows in preparation: products obtained therefrom gas chromatograph analysis, purity 〉=99.8%, yield 71%, melting point compound: 57.3 ℃.
With the preparation product 4-[2 ' identical-(trans-4 " amyl group cyclohexyl) ethyl with embodiment 1] pimelinketone is example, and being compared as follows of prior art:
By＜fine chemistry industry〉2002 years the 19th volume the 07th phase reported method, be prepared 4-[2 '-(trans-4 " amyl group cyclohexyl) ethyl] pimelinketone; the target product of preparing---4-[2 '-(trans-4 " the amyl group cyclohexyl) ethyl] pimelinketone, its product gas chromatograph purity assay is 98.5%, and total recovery is: 11.2%.Product has the big impurity of a coupling 1%, and product is yellowish white, and melting point compound is: 38.9 ℃.This shows, the present invention compared with prior art, not only preparation technology is simple, and prepared product purity height, the yield height, the melting point compound height, quality better is compared than prior art and to be had tangible substantive distinguishing features and obvious improvement.
Claims (11)
1, a kind of 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] preparation method of cyclohexanone analog liquid crystal intermediates compound, it is characterized in that following these steps to carry out:
(1) with trans-4-alkyl-cyclohexyl methyl chloride in organic solvent with magnesium chips reaction, obtain grignard reagent, again with to the reaction of benzyloxy benzene cyanogen, carry out then acidic hydrolysis make trans-4 '-alkyl-cyclohexyl ethanoyl-4-benzyloxy benzene;
(2) trans-4 '-alkyl-cyclohexyl ethanoyl-4-benzyloxy benzene in organic solvent under the catalysis of catalyzer, carry out highly compressed ladder hydrogenation reaction after the first low pressure, make 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexyl alcohol, carry out precision fractional distillation, purification again;
(3) in organic solvent, 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] cyclohexyl alcohol is in the presence of the environmental protection oxygenant; oxidation makes 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] the cyclohexanone analog compound, carry out precision fractional distillation, purification, recrystallization again, obtain target product with high purity.
2, according to the described 4-[2 ' of claim 1-(trans-4 " alkyl-cyclohexyl) ethyl] preparation method of cyclohexanone analog liquid crystal intermediates compound, it is characterized in that the organic solvent described in the step (1) is at least a in ether, tetrahydrofuran (THF), methyltetrahydrofuran and benzene, toluene and the dimethylbenzene; Described acidic hydrolysis is to implement in the presence of acid, and described acid is that the concentration of dilute with water is at least a in the hydrochloric acid, sulfuric acid, glacial acetic acid of 10-50%.
3, according to the described 4-[2 ' of claim 1-(trans-4 " alkyl-cyclohexyl) ethyl] preparation method of cyclohexanone analog liquid crystal intermediates compound; it is characterized in that in the step (1) trans-4-alkyl-cyclohexyl methyl chloride; employed magnesium chips is 0.7mol to 1.5mol, and employed is 0.6mol to 1.4mol to benzyloxy benzene cyanogen for 1mol; The temperature of reaction of step (1) is 10 ℃ to 105 ℃.
4, according to the described 4-[2 ' of claim 3-(trans-4 " alkyl-cyclohexyl) ethyl] preparation method of cyclohexanone analog liquid crystal intermediates compound; the reaction that it is characterized in that each reactive component in the step (1) is earlier 60 ℃ to 75 ℃ following initiation reactions; further be reflected at 70 ℃ to 85 ℃ and carry out; then, carry out acidic hydrolysis again under 90 ℃ to 105 ℃.
5, according to the described 4-[2 ' of claim 1-(trans-4 " alkyl-cyclohexyl) ethyl] preparation method of cyclohexanone analog liquid crystal intermediates compound, it is characterized in that the catalyzer described in the step (2) is at least a among Raney's nickel catalyst, active nickel catalyst, Pd/C and the Pt/C; Described organic solvent is at least a in ethyl acetate, ethanol, methyl alcohol, Virahol, toluene, dimethylbenzene and the methylene dichloride.
6, according to the described 4-[2 ' of claim 1-(trans-4 " alkyl-cyclohexyl) ethyl] preparation method of cyclohexanone analog liquid crystal intermediates compound; highly compressed ladder hydrogenation process is after it is characterized in that the first low pressure described in the step poly-(2): the first step is 0.5Mpa at hydrogen pressure, when temperature is 95～100 ℃ hydrogenation reaction 2--3 hour; In second step, being warmed up to 125～135 ℃, pressure is under the condition of 3.6～4.0Mpa, repeated hydrogenation reaction 5 hours～6 hours.
7, according to the described 4-[2 ' of claim 1-(trans-4 " alkyl-cyclohexyl) ethyl] preparation method of cyclohexanone analog liquid crystal intermediates compound, it is characterized in that step (2) is that 50 ℃ to 200 ℃, pressure are to implement under the condition of 0.1Mpa to 10.0Mpa in temperature.
8, according to the described 4-[2 ' of claim 7-(trans-4 " alkyl-cyclohexyl) ethyl] preparation method of cyclohexanone analog liquid crystal intermediates compound; the reaction that it is characterized in that each reactive component of step (2) divides two stages to carry out: the fs, subordinate phase was reaction under 110 ℃ to 150 ℃ of the temperature, under the pressure 2.5Mpa to 5.0Mpa 3-7 hour reaction under 85 ℃ to 110 ℃ of the temperature, under the pressure 0.3Mpa to 0.7Mpa 1-3 hour.
9, according to the described 4-[2 ' of claim 1-(trans-4 " alkyl-cyclohexyl) ethyl] preparation method of cyclohexanone analog liquid crystal intermediates compound, it is characterized in that the environmental protection oxygenant described in the step (3) is at least a in clorox, Losantin, Manganse Dioxide, potassium permanganate, hydrogen peroxide and ammonium vanadate, the potassium bromate additive; Described organic solvent is at least a in methylene dichloride, chloroform, tetracol phenixin, dithiocarbonic anhydride, tetrachloroethane, 1,4-diox, tetrahydrofuran (THF), ether, methyl tertiary butyl ether, acetone, butanone, glacial acetic acid and the propionic acid; Carry out the used organic solvent of last recrystallization and be at least a in acetone, butanone, pimelinketone, ethyl acetate, ethanol, methyl alcohol, Virahol, toluene and the dimethylbenzene.
10, according to the described 4-[2 ' of claim 1-(trans-4 " alkyl-cyclohexyl) ethyl] preparation method of cyclohexanone analog liquid crystal intermediates compound; it is characterized in that in the step (3) 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl for 1mol] cyclohexyl alcohol, and the molar weight of the environmental protection oxygenant that is added is 4-[2 '-(trans-4 " alkyl-cyclohexyl) ethyl] 40-100% of cyclohexyl alcohol.
11, according to the described 4-[2 ' of claim 1-(trans-4 " alkyl-cyclohexyl) ethyl] preparation method of cyclohexanone analog liquid crystal intermediates compound, it is characterized in that the enforcement temperature of step (3) is-10 ℃ to 50 ℃.
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Cited By (2)
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|---|---|---|---|---|
| CN103265417A (en) * | 2013-05-03 | 2013-08-28 | 西安彩晶光电科技股份有限公司 | Method for synthesizing 4-[2-(trans-4-alkyl cyclohexyl )ethyl]cyclohexanone |
| CN112811995A (en) * | 2021-01-14 | 2021-05-18 | 惠泽化学科技(濮阳)有限公司 | Synthesis method of 4-substituent cyclohexanone liquid crystal intermediate |
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| CN101337870B (en) * | 2008-08-08 | 2011-04-06 | 西安瑞联近代电子材料有限责任公司 | Method for synthesizing 4-(4'-n-alkyl cyclohexyl)cyclohexanone |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265417A (en) * | 2013-05-03 | 2013-08-28 | 西安彩晶光电科技股份有限公司 | Method for synthesizing 4-[2-(trans-4-alkyl cyclohexyl )ethyl]cyclohexanone |
| CN103265417B (en) * | 2013-05-03 | 2015-05-13 | 西安彩晶光电科技股份有限公司 | Method for synthesizing 4-[2-(trans-4-alkyl cyclohexyl )ethyl]cyclohexanone |
| CN112811995A (en) * | 2021-01-14 | 2021-05-18 | 惠泽化学科技(濮阳)有限公司 | Synthesis method of 4-substituent cyclohexanone liquid crystal intermediate |
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