CN1239460C - Synthesis of trans-4-alkyl cyclohexyl formic acid - Google Patents
Synthesis of trans-4-alkyl cyclohexyl formic acid Download PDFInfo
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- CN1239460C CN1239460C CN 03134328 CN03134328A CN1239460C CN 1239460 C CN1239460 C CN 1239460C CN 03134328 CN03134328 CN 03134328 CN 03134328 A CN03134328 A CN 03134328A CN 1239460 C CN1239460 C CN 1239460C
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- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 28
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 claims abstract description 23
- 239000003513 alkali Substances 0.000 claims abstract description 13
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000010189 synthetic method Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 12
- 239000011707 mineral Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 239000000543 intermediate Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000012429 reaction media Substances 0.000 abstract description 2
- 239000005711 Benzoic acid Substances 0.000 abstract 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- KAWUBNUJMFOOOE-UHFFFAOYSA-N 3-amino-3-(3,5-dibromo-4-hydroxyphenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC(Br)=C(O)C(Br)=C1 KAWUBNUJMFOOOE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- CCMGSHLZTIQYKA-UHFFFAOYSA-N formic acid pentylbenzene Chemical compound C(=O)O.C(CCCC)C1=CC=CC=C1 CCMGSHLZTIQYKA-UHFFFAOYSA-N 0.000 description 1
- -1 hydrogen potassium oxide Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a synthetic method for important liquid crystal intermediates (trans-4-alkyl cyclohexyl formic acid). The present invention uses supported ruthenium/carbon as catalysts and uses inorganic aqueous alkali as a reaction medium, and the mixture of cis-trans-4-alkyl cyclohexyl formic acid is generated by hydrogenating 4-alkyl-benzoic acid. Inorganic hydroxide and products in a reaction solution are not separated and carry out isomerization reaction under the condition of no solvent after dewatered by directly distilling, the cis/trans isomer ratio is 4/96 to 1/99 after reaction is finished, the yield is as high as 90%, and cost is obviously lowered. The method has the advantages of simple operation, easy control and easy industrialization production.
Description
Technical field
The present invention relates to a kind of important liquid crystal intermediates anti--synthetic method of 4-alkyl-cyclohexyl formic acid, its structural formula is shown in (I):
R is that carbonatoms is 1～15 straight chain, branched-chain alkyl in the formula, or the substituted cyclohexyl with following structure:
R ' is 1～9 straight chained alkyl for carbonatoms in the formula.
Background technology
The cyclohexanes liquid crystal has higher transformation temperature and lower viscosity, has overcome that at present still widely used biphenyls liquid crystal transformation temperature is low, viscosity big, the slower shortcoming of response speed, and therefore this class liquid crystal development is very fast in recent years.Instead-4-alkyl-cyclohexyl formic acid is the synthetic requisite important intermediate of this class liquid crystal material, and also often is applied to the synthetic of fine chemicals such as medicine, agricultural chemicals, so it synthetic has significant application value.Instead-the synthetic need of 4-alkyl-cyclohexyl formic acid are through the reaction of two steps: hydrogenation and isomerization reaction.Hydrogenation reaction is to be raw material with the 4-alkylbenzoic acid, and in the presence of catalyzer, hydrogenation generates the mixture along anti--4-alkyl-cyclohexyl formic acid, trans-isomer content is very low, usually be less than 40%, must carry out isomerization reaction, make cis-isomeride change trans-isomer(ide) into.Instead-two substituting group alkyl of 4-alkyl-cyclohexyl formic acid and carboxyl all be in the equatorial position on the hexanaphthene with chair form structure, and two substituting groups are in calm and axial position respectively in the cis-isomeride, from thermodynamics, the conformation free energy of trans-isomer(ide) is less than the conformational energy of cis-isomeride, thereby the former is more stable than the latter.Under certain condition, isomerization reaction can take place in cis-isomeride, changes trans-isomer(ide) into, but prior art all can't make isomerization reaction carry out fully, thereby influences reaction yield, below is the isomerization method of prior art.(Yun Kuihong etc. write Advanced Organic Chemistry, P63) introduce in August, 1988, and cis or anti-suitable-4-alkyl-cyclohexyl formic acid are heated to 180 ℃ and carry out isomerization reaction in hydrochloric acid soln, carry out owing to be reflected in the acidic medium, easily equipment are caused corrosion.European patent EP 196222 report cis or anti-suitable-4-alkyl-cyclohexyl methyl-formiate are in the presence of sodium hydride, and isomerization reaction is carried out in heating.This method needs to have increased operation easier through polystep reactions such as over-churning, isomerization, hydrolysis.The clear 60-258141 of Japanese Patent report cis or along anti--4-alkyl-cyclohexyl formic acid is medium with the aqueous sodium hydroxide solution, carries out isomerization reaction under high temperature, condition of high voltage, this method need be used pressure-resistant equipment, has increased cost.And the most key is, uses above-mentioned three kinds of isomerization methods, and the suitable/trans isomer that obtains is than all between 25/75～15/85, needs just can obtain instead-4-alkyl-cyclohexyl formic acid through recrystallization repeatedly, and productive rate is lower than 70%.
Summary of the invention
The invention provides a kind of synthetic method of anti--4-alkyl-cyclohexyl formic acid (I) newly, the reaction yield height significantly reduces cost.
Building-up reactions formula of the present invention is as follows:
R is propyl group or amyl group in the formula, or has the substituted cyclohexyl of following structure:
R ' is propyl group or amyl group in the formula, with the 4-alkylbenzoic acid is raw material, its molecular structure is shown in (II), wherein R is identical with R in the compound (I), be dissolved in the aqueous solution that mineral alkali is potassium hydroxide or sodium hydroxide, in the presence of the loading type ruthenium/carbon catalyst, feed hydrogen, temperature of reaction is 50～150 ℃, reaction pressure is 1～10MPa, and reaction continued to keep 1～2 hour after no longer inhaling hydrogen, generates the mixture along anti--4-alkyl-cyclohexyl formic acid, above-mentioned reaction solution need not separate mineral alkali and product, filter, distillation dewaters and obtains solid particulate, is heated to 100～300 ℃ and carries out the solid phase isomerization reaction in nitrogen atmosphere, after reaction finishes, continue logical nitrogen and reduce to room temperature to temperature of charge, product is soluble in water, add aqueous hydrochloric acid and transfer to acidity, extraction, the extraction liquid distillation removes desolvates, and the suitable/trans isomer ratio that obtains 4-alkyl-cyclohexyl formic acid is 4/96～1/99, and recrystallization obtains product (I).
The mol ratio of mineral alkali and raw material (II) is 10: 1～2: 1.
The isomerization reaction time is 2～8 hours.
The hydrogenation reaction temperature is 80～130 ℃, and reaction pressure is 2～7MPa, and the isomerization reaction temperature is 120～250 ℃, and the mol ratio of mineral alkali and raw material (II) is 5: 1～2: 1.
After hydrogenation reaction of the present invention was finished, the mineral alkali in the reaction solution did not need to separate with product, can be directly as the catalyzer of solid phase isomerization reaction, and operation steps is simple.And the suitable/trans isomer ratio after the isomerization reaction is 4/96～1/99, need not make with extra care or only need recrystallization can obtain pure anti--4-alkyl-cyclohexyl formic acid (I), productive rate has significantly reduced cost up to more than 90%.Easy control of reaction conditions of the present invention, simple to operate, carry out suitability for industrialized production easily.
Embodiment
The present invention is a raw material with 4-alkylbenzoic acid (II), with supported ruthenium/carbon is catalyzer, and hydrogenation generates the mixture (III) along anti--4-alkyl-cyclohexyl formic acid, because reactant is water insoluble, and be dissolved in inorganic base aqueous solution, therefore selecting inorganic base aqueous solution is reaction medium.Mineral alkali is alkali-metal basic cpd, preferably potassium hydroxide or sodium hydroxide.The mol ratio of mineral alkali and reactant is 10: 1-2: 1, preferably 5: 1-2: 1, and temperature of reaction is 50～150 ℃, preferably 80～130 ℃, temperature of reaction surpasses 150 ℃, easily generates by product.Temperature is lower than 50 ℃, can prolong the reaction times, and reaction pressure is 1～10MPa, is preferably 2～7MPa, and reaction continued to keep termination reaction 1-2 hour after no longer inhaling hydrogen.After cooling; reaction solution is extracted out; remove by filter ruthenium/carbon catalyst; record suitable/trans isomer than for 80/20-60/40 through gas chromatographic analysis, do not need in the reaction solution mineral alkali is separated with product, after directly its distillation being concentrated; remove moisture; the solid that obtains is added in the tubular heater, and under nitrogen protection, the solid phase isomerization reaction is carried out in heating.Temperature of reaction is 100～300 ℃, and preferably 120～250 ℃, temperature of reaction surpasses 300 ℃, and pyrolysis can take place, and reduces productive rate, and temperature is lower than 100 ℃, can prolong the reaction times.Reaction times is 2～8 hours.After reaction finishes, continue logical nitrogen to temperature of charge and reduce to room temperature.Be added to the water then, it is dissolved fully, add 30% hydrochloric acid soln while stirring, until solution PH=2, add toluene extraction three times, merge organic phase, distillation removes and desolvates, and obtains product.Through gas chromatographic analysis, suitable/trans isomer ratio is 1/99～4/96, and trans-isomer content is very high, do not need or only need recrystallization can obtain pure anti--4-alkyl-cyclohexyl formic acid (I).Overall yield of reaction is up to 90%.
Embodiment 1 (synthesizing of anti--4-propyl group hexahydrobenzoic acid)
In the 500ml autoclave, add 16.4g (0.1mol) 4-propylbenzoic acid, 100ml water, 11.2g (0.2mol) potassium hydroxide, the commercially available 5% loading type ruthenium/carbon catalyst of 1.64g (moisture 50%).Build kettle cover, logical hydrogen, emptying gas, three times repeatedly.Start stirring, heat temperature raising to 120 ℃, keeping the still internal pressure is 5MPa, and logical repeatedly hydrogen continued to keep termination reaction 2 hours after no longer inhaling hydrogen.After cooling, extract still internal reaction liquid out, remove by filter catalyzer.Through gas chromatographic analysis, reaction conversion ratio 100%, hydrogenation products is suitable/and trans isomer is than being 66.5/33.5, do not need separation of hydrogen potassium oxide and 4-alkyl-cyclohexyl formic acid, straight run distillation is removed moisture, generates solid particulate, it is packed into can lead in the tubular heater of nitrogen, heat temperature raising to 180 ℃ in nitrogen atmosphere, temperature rise rate is 100 ℃/h, kept 2 hours down at 180 ℃, and be cooled to room temperature in nitrogen atmosphere, pour into then in the 100ml water, after treating to dissolve fully, add 30% hydrochloric acid soln while stirring, adjust PH=2, each with 50ml toluene extraction three times, extraction liquid merges the back with 50ml washing three times, distills then to remove and desolvates, and obtains white solid, through gas chromatographic analysis, isomerization reaction product is suitable/inverse ratio is 3.7/96.3, with the sherwood oil recrystallization of this crude product with 20ml, obtain 15.3g pure anti--4-propyl group hexahydrobenzoic acid, mp=95.2～96.7 ℃, productive rate 90.2%.
IR(KBr)v/cm
-1?2500～3350，2962，29?36，2857，1700，1452，1?206，944
Embodiment 2. (synthesizing of anti--4-amyl group hexahydrobenzoic acid)
In the 500ml autoclave, add 19.2g (0.1mol) 4-amylbenzene formic acid, the commercially available 5% loading type ruthenium/carbon catalyst of 1.92g (moisture 50%).Other condition is with embodiment 1, and hydrogenation reaction product is suitable/trans isomer is than being 62.3/37.7, and isomerization reaction product is suitable/trans isomer is than being 2.9/97.1, obtain 17.9g pure anti--4-amyl group hexahydrobenzoic acid, mp=53.2～53.9 ℃, productive rate 90.5%.
IR(KBr)v/cm
-1?2500～3350，2963，2936，2859，1702，1452，1209，946
Embodiment 3. (synthesizing of anti--4-(anti--4 '-propyl group cyclohexyl) hexahydrobenzoic acid)
In the 500ml autoclave, add 24.6 gram 4-(anti--4 '-propyl group cyclohexyl) phenylformic acid, the commercially available 5% loading type ruthenium/carbon catalyst of 2.46g (moisture 50%).Other condition is with embodiment 1, hydrogenation reaction product is suitable/trans isomer is than being 58.2/41.8, isomerization reaction product is suitable/trans isomer is than being 1.6/98.4, obtain 23.0g pure anti--4-(anti--4 '-propyl group cyclohexyl) hexahydrobenzoic acid, mp=196.5～199.3 ℃, productive rate 91.4%.
IR(KBr)v/cm
-1?2500～3350，2911，2852，1699，1441，1419，1261，923
Embodiment 4. (synthesizing of anti--4-(anti--4 '-amyl group cyclohexyl) hexahydrobenzoic acid)
In the 500ml autoclave, add 27.4 gram 4-(anti--4 '-amyl group cyclohexyl) phenylformic acid, the commercially available 5% loading type ruthenium/carbon catalyst of 2.74g (moisture 50%).Other condition is with embodiment 1, hydrogenation products is suitable/inverse ratio is 59.3/40.7, isomerization reaction product is suitable/trans isomer is than being 1.8/98.2, obtain 25.5g pure anti--4-(anti--4 '-amyl group cyclohexyl) hexahydrobenzoic acid, mp=186.3～190.2 ℃, productive rate 91.0%.
IR(KBr)v/cm
-1?2500～3350，2914，2853，1701，1443，1420，1261，926
Embodiment 5
In the 500ml autoclave, add 8g (0.2mol) sodium hydroxide, other condition is with embodiment 1, hydrogenation products is suitable/and trans isomer is than being 65.1/34.9, isomerization reaction product is suitable/and trans isomer is than being 4.0/96.0, obtain 15.2g pure anti--4-propyl group hexahydrobenzoic acid, mp=95.2～96.7 ℃, productive rate 90.0%.
Embodiment 6
In the 500ml autoclave, add 22.4g (0.4mol) potassium hydroxide, other condition is with embodiment 1, hydrogenation products is suitable/and trans isomer is than being 60.1/39.9, isomerization reaction product is suitable/and trans isomer is than being 4.0/96.0, obtain 15.4g pure anti--4-propyl group hexahydrobenzoic acid, mp=95.2～96.7 ℃, productive rate 90.5%.
Embodiment 7
160 ℃ of isomerization reaction temperature, in 4 hours reaction times, other condition is with embodiment 1, isomerization reaction product is suitable/trans isomer is than being 4.5/95.5, obtain 14.8g pure anti--4-propyl group hexahydrobenzoic acid, mp=95.2～96.7 ℃, productive rate 87.6%.
Claims (4)
1, the synthetic method of anti--4-alkyl-cyclohexyl formic acid, its molecular structural formula is shown in (I):
R is propyl group or amyl group in the formula, or has the substituted cyclohexyl of following structure:
R ' is propyl group or amyl group in the formula, with the 4-alkylbenzoic acid is raw material, its molecular structure is shown in (II), wherein R is identical with R in the compound (I), be dissolved in the aqueous solution that mineral alkali is potassium hydroxide or sodium hydroxide, in the presence of the loading type ruthenium/carbon catalyst, feed hydrogen, temperature of reaction is 50～150 ℃, reaction pressure is 1～10MPa, and reaction continued to keep 1～2 hour after no longer inhaling hydrogen, generates the mixture along anti--4-alkyl-cyclohexyl formic acid, it is characterized in that: above-mentioned reaction solution need not separate mineral alkali and product, filter, distillation dewaters and obtains solid particulate, is heated to 100～300 ℃ and carries out the solid phase isomerization reaction in nitrogen atmosphere, after reaction finishes, continue logical nitrogen and reduce to room temperature to temperature of charge, product is soluble in water, add aqueous hydrochloric acid and transfer to acidity, extraction, the extraction liquid distillation removes desolvates, and the suitable/trans isomer ratio that obtains 4-alkyl-cyclohexyl formic acid is 4/96～1/99, and recrystallization obtains product (I).
2, according to claim 1 anti--synthetic method of 4-alkyl-cyclohexyl formic acid, the mol ratio that it is characterized in that mineral alkali and raw material (II) is 10: 1～2: 1.
3, according to claim 1 anti--synthetic method of 4-alkyl-cyclohexyl formic acid, it is characterized in that the isomerization reaction time is 2～8 hours.
4, according to one of in the claim 1～3 described anti--synthetic method of 4-alkyl-cyclohexyl formic acid, it is characterized in that: the hydrogenation reaction temperature is 80～130 ℃, reaction pressure is 2～7MPa, and the isomerization reaction temperature is 120～250 ℃, and the mol ratio of mineral alkali and raw material (II) is 5: 1～2: 1.
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| CN1319931C (en) * | 2005-08-05 | 2007-06-06 | 中国科学院广州化学研究所 | Method for preparing 4-isopropyl-naphthenic acid |
| JP2010083807A (en) * | 2008-09-30 | 2010-04-15 | Fujifilm Corp | Method for producing dicyclohexane derivative |
| CN114276230B (en) * | 2021-12-27 | 2024-05-24 | 江苏康恒化工有限公司 | Cis-trans separation method for 1, 4-cyclohexanedicarboxylic acid |
| CN116410082A (en) * | 2023-03-13 | 2023-07-11 | 苏州敬业医药化工有限公司 | A kind of preparation method of trans-p-methylcyclohexylcarboxylic acid |
| CN117800875B (en) * | 2023-12-21 | 2024-10-22 | 泰州精英化成医药科技有限公司 | Preparation method of trans- (N-Boc-4-aminocyclohexyl) acetic acid |
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