CN1188098A - Processes for preparing 4-tert.-butylcyclohexanol and 4-tert-butylcyclohexyl acetate - Google Patents
Processes for preparing 4-tert.-butylcyclohexanol and 4-tert-butylcyclohexyl acetate Download PDFInfo
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- CN1188098A CN1188098A CN97102071A CN97102071A CN1188098A CN 1188098 A CN1188098 A CN 1188098A CN 97102071 A CN97102071 A CN 97102071A CN 97102071 A CN97102071 A CN 97102071A CN 1188098 A CN1188098 A CN 1188098A
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Abstract
4-tert.-Butylcyclohexanol having a larger content of its cis-isomer is prepared by hydrogenating 4-tert-butylphenol in a solvent in the presence of a rhodium catalyst and a compound selected from the group consisting of hydrogen chloride, perchloric acid and (anhydrous) sulfuric acid. Furthermore, obtained 4-tert-butylcyclo-hexanol is acetylated to give 4-tert-butylcyclohexyl acetate.
Description
The present invention relates to by making 4-tert.-butyl phenol hydrogenation preparation contain the method for the 4-tertiary butyl hexalin of a large amount of cis-isomerides.The invention still further relates to the method for preparing acetate 4-tertiary butyl cyclohexyl by the 4-tertiary butyl hexalin acetylize of using aforesaid method to obtain.
Acetate 4-tertiary butyl cyclohexyl is widely used as the spices of the makeup that comprise perfumed soap, and its cis-isomeride is more fragrant than the smell of trans-isomer(ide).Be the high acetate 4-tertiary butyl cyclohexyl of preparation cis isomerism body burden, people are desirable to provide the method that a kind of preparation contains the 4-tertiary butyl hexalin of a large amount of cis-isomerides, and it can be used as the raw material of preparation acetate 4-tertiary butyl cyclohexyl.
In general, 4-tertiary butyl hexalin is by preparing the hydrogenation of 4-tert.-butyl phenol.JP-B-42-13938 discloses a kind of method of the 4-of preparation tertiary butyl hexalin, is included in the rhodium basic catalyst and has catalytic reduction 4-tert.-butyl phenol down.
(1971) the 77th pages of methods that disclose a kind of 4-of preparation tertiary butyl hexalin of MARUZEN OIL TECHNICAL REVIEW (MARUZEN SEKIYUGIHO), the multiple transition metal that it is included in the 8-10 family of the periodic table of elements exists down the hydrogenation of 4-tert.-butyl phenol.
JP-A-54-122253 discloses a kind of method for preparing the cis alkyl cyclohexanol, is included in ruthenium-aluminium oxide catalyst and exists down alkylphenol hydrogenation.
US-A-2927127 discloses the method that a kind of preparation has the 4-tertiary butyl hexalin of high-cis content of isomer, comprises the hydrogenation of 4-tert.-butyl phenol.
JP-A-3-173842 discloses a kind of method of the 4-of preparation tertiary butyl hexalin, be included in the Ru that is stated from the carrier and the acid of boron fluoride type for example under the existence of the composite catalyst of HBF with the hydrogenation of 4-tert.-butyl phenol.
Yet the cis isomerism body burden of the 4-tertiary butyl hexalin of usefulness JP-B-42-13938, MARUZEN OIL TECHNICAL REVIEW and the preparation of JP-A-54-122253 disclosed method is still not enough.The method of US-A-2927127 is in ethanol, be issued to higher cis isomerism body burden in the existence of rhodium catalyst, but this reaction must be carried out under high hydrogen pressure.Thereby, found a kind of improved method of the 4-of preparation tertiary butyl hexalin.In addition, because the method for JP-A-3-173842 has been used the acid of boron fluoride type, need workload to reclaim fluorine or boron, the acid of generation for example HF can be corroded production unit.
The purpose of this invention is to provide the method for preparing 4-tertiary butyl hexalin that under the condition of gentleness, to carry out and the method for producing 4-tertiary butyl hexalin with high-cis content of isomer.
Another object of the present invention provides the method that preparation has the own ester of the acetate 4-tertiary butyl of high-cis content of isomer.
Content according to a first aspect of the invention, the method for the 4-of preparation tertiary butyl hexalin provided by the invention be included in the solvent, at rhodium catalyst be selected from the presence of hydrogenchloride, perchloric acid and (anhydrous) vitriolic compound with the hydrogenation of 4-tert.-butyl phenol.
Content according to a second aspect of the invention, the method for preparing acetate 4-tertiary butyl cyclohexyl provided by the invention comprise in solvent, at rhodium catalyst and be selected from the presence of hydrogenchloride, perchloric acid and (anhydrous) vitriolic compound 4-tertiary butyl hexalin acetylize with 4-tert.-butyl phenol hydrogenation preparation.
The used rhodium catalyst of hydrogenation of the present invention comprises that the metal rhodium (valency is zero) or the valency of rhodium are at most 6 rhodium compound, for example rhodium chloride, rhodium oxide etc.
Metal rhodium or rhodium compound preferably use with the form of supported catalyst, that is to say, metal rhodium or rhodium compound are stated from the carrier such as gac, silicon-dioxide, aluminium sesquioxide.In supported catalyst, more preferably be stated from the metal rhodium on the carrier.For the situation of supported catalyst, the amount of the metal rhodium of carrying usually between the 1-10% (weight), preferably between 3-5% (weight) (based on the weight meter of carrier).
After the reaction, can from reaction mixture, reclaim rhodium catalyst and it is recycled with for example filtration of ordinary method, decantation, centrifugation method.
The consumption of rhodium catalyst is about 0.01-1% (weight) (in metal rhodium) of 4-tert.-butyl phenol raw material weight in the reaction.For the situation of supported catalyst, catalyst consumption (comprising carrier) depends on the amount of the rhodium metal or the compound of carrying, is about 0.1-50% (weight) (dried forms) of 4-tert.-butyl phenol.Along with the increase of catalyst levels, the cis-isomeride selectivity increases.But from cost with in the angle of the workability of filtering recovering catalyst step, catalyst consumption is preferably between 0.5-10% (weight).
Can use any solvent, just can not as long as it does not have a negative impact for reaction.Preferably be the solvent of liquid down, because its easy handling in room temperature (25 ℃).The example of solvent is alkane, the ether with 4-10 carbon atom with 5-10 carbon atom, has the alcohol of 1-6 carbon atom etc.The specific examples of solvent is non-cyclic hydrocarbon (for example pentane, hexane, heptane etc.), cyclic hydrocarbon (for example hexanaphthene etc.), non-annularity ether (for example ether etc.), cyclic ether (for example tetrahydrofuran (THF), dioxane etc.) and alcohol (for example methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, hexanol, 4-methyl-2-amylalcohol, hexalin etc.).Wherein, preferred hexanaphthene and Virahol.Preferred especially Virahol.
The consumption of solvent is generally about 0.2-20 times of 4-tert.-butyl phenol weight, and preferred 0.4-5 doubly.
In the method for the invention, be reflected in the solvent, in the presence of rhodium catalyst and hydrogenchloride, perchloric acid or (anhydrous) vitriolic, carry out.
Can be in any form the mode by hydrogen chloride gas being fed reaction system or hydrogenchloride is added in the reaction system for example by the mode that hydrochloric acid is added in the reaction system.Perhaps generate hydrochloric acid by the mode that in reaction system, drops into water and aluminum chloride or titanium tetrachloride.In addition, also can use the catalyzer rhodium chloride for example that can in reaction system, produce hydrogenchloride.
And, can be in any form the mode by sulfur trioxide gas being fed reaction system or aqueous sulfuric acid is added to mode supplies to (anhydrous) sulfuric acid in the reaction system in the reaction system for example.Perchloric acid is added in the reaction system with the form of the aqueous solution usually.
Adding raw material, rhodium catalyst, solvent and hydrogenchloride, perchloric acid or (anhydrous) vitriolic order can be arbitrarily.
Hydrogenchloride, perchloric acid or (anhydrous) vitriolic consumption are generally every mole of about 0.01-100 mole of the rhodium atom in rhodium catalyst, preferably approximately 0.05-10 mole, more preferably 0.1-10 mole.
Method of the present invention can be carried out in hydrogen stream or pressurized hydrogen atmosphere.Other reaction conditions is not crucial.From the angle of speed of reaction, react in the nitrogen atmosphere that is preferably in pressurization and carry out.In this case, applying pressure reactor.
When carrying out in the nitrogen atmosphere that is reflected at pressurization, the dividing potential drop of hydrogen is at least 1.5 * 10
5Pa.Consider that from the angle of the resistance to pressure of the selectivity of speed of reaction cis-isomeride and device the dividing potential drop of hydrogen is preferably 3 * 10
5To 2 * 10
6Between the Pa, more preferably 5 * 10
5To 1.5 * 10
6Between the Pa.
From the optionally angle of speed of reaction and cis-isomeride, temperature of reaction is at least about 20 ℃, considers the selectivity of cis-isomeride, then preferred 100 ℃ or lower.Consider the selectivity of speed of reaction and cis-isomeride, temperature of reaction is more preferably between 40-80 ℃.
Method of the present invention can be carried out continuously or in batches.
The terminal point of reaction can confirm by ordinary method.Analyze reaction mixture for example, with the transformation efficiency of 4-tertiary butyl hexalin be 100% the time be reaction end, be reaction end when observing that hydrogen pressure no longer reduces perhaps.
In addition, the 4-tertiary butyl hexalin acetylize that is obtained by above-mentioned reaction can be obtained acetate 4-tertiary butyl cyclohexyl.
Acetylize can be carried out continuously by the hydrogenation of above-mentioned 4-tert.-butyl phenol.Perhaps, can from the reaction mixture of above-mentioned reaction, isolate the 4-tertiary butyl hexalin of acquisition, then with step acetylize separately.
With regard to acetylize, can use the acetylation reagent of any routine, for example diacetyl oxide, acetate, Acetyl Chloride 98Min. etc.
The consumption of acetylation reagent is generally per 1 mole of 4-tertiary butyl hexalin 1-5 mole, preferred 1-1.5 mole.
Acetylizad temperature of reaction is usually in room temperature (about 25 ℃) with between 150 ℃, preferably in room temperature (about 25 ℃) with between 130 ℃.
When being 100%, can stop acetylizing by the transformation efficiency of the analysis of reaction mixture being learnt 4-tertiary butyl hexalin.
Appearing in the acetylation of solvent is unimportant, is difficult for acetylizad solvent but can use.From the angle of easy handling, preferably using at room temperature is liquid solvent.The example of this kind solvent has acyclic alkanes (for example pentane, hexane, heptane etc.), cyclic alkane (for example hexanaphthene etc.), unsaturated hydrocarbons (for example toluene etc.), non-annularity ether (for example ether etc.), cyclic ether (for example tetrahydrofuran (THF) etc.) etc.Wherein preferred toluene and hexanaphthene.
Except using acetylation reagent, can also use catalyzer at acetylization reaction.The kind of catalyzer depends on the kind of used acetylation reagent.For example when making acetylation reagent, can use sulfuric acid, hydrochloric acid, tosic acid, zinc chloride, sodium acetate, pyridine etc. with diacetyl oxide.Perhaps, when making acetylation reagent, can use sulfuric acid or boron trifluoride with acetate.Wherein, consider preferably sulfuric acid from the angle of cost.
Catalyst consumption is generally the 0.01-5% (mole) of 4-tertiary butyl hexalin, preferred 0.1-2% (mole).When catalyst levels too hour, speed of reaction is too low, when consumption was too big, 4-tertiary butyl hexalin was easy to hydrolysis.
When making acetylation reagent, consider that from the angle of speed of reaction the acetylizad while is preferably removed water byproduct with acetate.Can by with can with water under refluxad solvent and the water azeotropic vaporization of azeotropic vaporization remove and anhydrate, perhaps by add siccative for example in reaction system the method for interpolation silica gel except that anhydrating.
When making acetylation reagent, consider that from the angle of safety the acetylizad while is preferably removed byproduct hydrogen chloride with Acetyl Chloride 98Min..Can for example mineral alkali (for example salt of wormwood, 10% sodium hydroxide etc.) or organic bases (for example pyridine etc.) remove de-chlorine hydride with alkali.
In acetylation reagent, the angle of conversion of raw material from acetylization reaction, preferred diacetyl oxide.
Be difficult to gained acetate 4-tertiary butyl cyclohexyl is separated from 4-tertiary butyl hexalin by distillation, because their boiling point is close.Therefore, the transformation efficiency of 4-tertiary butyl hexalin preferably equals or approaches 100%.For this reason, for example use acetate or Acetyl Chloride 98Min. to make acetylation reagent, carry out acetylization reaction and reach about 90% or higher, use then with the diacetyl oxide of residual starting material same molar and finish acetylizing, make the raw material completely consumed until transformation efficiency.
The inventive method can be easily from the 4-tertiary butyl hexalin with high-cis content of isomer of 4-tert.-butyl phenol preparation as spices.That is to say that can obtain 4-tertiary butyl hexalin to be not less than 90% yield, the content of cis-isomeride reaches about 80% or higher in the product.
By will obtaining the high acetate 4-tertiary butyl cyclohexyl of cis isomerism body burden with the 4-tertiary butyl hexalin acetylize of the inventive method preparation.
Following embodiment is used for illustrating the present invention, but it does not constitute any restriction to the present invention.Embodiment 1
With 4-tert.-butyl phenol (90 grams, 0.60 mole), in 5%Rh/C (promptly being stated from 5% on the absorbent charcoal carrier (weight) rhodium metal) (counting 1.35 grams), Virahol (180 gram) and 36% hydrochloric acid (0.18 gram) the input autoclave, feed 5 * 10 then based on dry material
5The nitrogen of Pa makes the inside of autoclave be replaced by nitrogen, vacuumizes three times.Injecting 5 * 10
5The hydrogen of Pa replaces with hydrogen with autoclave inside and vacuumizes after three times, injects hydrogen to 1.1 * 10
6Pa rises to 60 ℃ with internal temperature, then stirs 1.75 hours.
With autoclave cooling and resemble replace with nitrogen above-mentioned inner, analyze reaction mixture.The yield of 4-tertiary butyl hexalin is 934%, and cis-isomeride is 89.9: 10.1 with the ratio of trans-isomer(ide).Embodiment 2-10
Prepare 4-tertiary butyl hexalin according to the method identical, but change reaction conditions as shown in Table with embodiment 1.In embodiment 10, use 98% sulfuric acid.
The results are shown in the table.
In embodiment 1-10, the transformation efficiency of 4-tertiary butyl hexalin is 100%.Comparative example 1-3
Prepare 4-tertiary butyl hexalin according to the method identical, but do not use acid (comparative example 1), use phosphoric acid (85%) (comparative example 2) or use nitric acid (61%) (comparative example 3) with embodiment 1.
The results are shown in the table.Comparative example 4 and 5
Prepare 4-tertiary butyl hexalin according to the method identical, but use Ru catalyzer (5%Ru/C) (comparative example 4 and 5) and do not use hydrochloric acid (comparative example 5) with embodiment 1.
The results are shown in the table.
In comparative example 4, the transformation efficiency of 4-tert.-butyl phenol is 42.2%, and in other comparative examples, the transformation efficiency of 4-tert.-butyl phenol is 100%.Table
Table (continuing)
Annotate: IPA: Virahol
| Embodiment number | Catalyzer | Acid | Solvent | Hydrogen partial pressure * 10 5Pa | Temperature (℃) | Time (hr.) | ????BCHL | ||||
| Kind | Quantity (g) | Kind | Quantity (g) | Kind | Quantity (g) | Yield (%) | Cis/trans compares ratio | ||||
| ????1 | ????Rh | ????1.35 | Hydrochloric acid | ????0.18 | ??IPA | ????180 | ????11 | ????60 | ??1.75 | ?93.4 | ?89.9/10.1 |
| ????2 | ????↑ | ????0.90?? | ????↑ | ????0.12 | ????↑ | ????↑ | ????↑ | ????↑ | ??3.0 | ?93.4 | ?87.8/12.2 |
| ????3 | ????↑ | ????2.25 | ????↑ | ????0.30 | ????↑ | ????74 | ????21 | ????40 | ??5.0 | ?93.0 | ?86.3/13.7 |
| ????4 | ????↑ | ????1.45 | ????↑ | ????0.18 | ??CHX | ????180 | ????11 | ????60 | ??1.2 | ?96.3 | ?86.3/13.7 |
| ????5 | ????↑ | ????2.25 | ????↑ | ????0.30 | ????↑ | ????360 | ????6 | ????40 | ??0.6 | ?96.0 | ?87.6/12.4 |
| ????6 | ????↑ | ????↑ | ????↑ | ????↑ | ????↑ | ????74 | ????41 | ????↑ | ??0.3 | ?96.1 | ?86.6/13.4 |
| ????7 | ????↑ | ????↑ | ????↑ | ????↑ | ????↑ | ????↑ | ????21 | ????80 | ??0.5 | ?96.6 | ?84.1/15.9 |
| ????8 | ????↑ | ????↑ | ????↑ | ????0.60 | ????↑ | ????↑ | ????↑ | ????40 | ??1.0 | ?94.6 | ?89.8/10.2 |
| ????9 | ????↑ | ????4.50 | ????↑ | ????↑ | ????↑ | ????↑ | ????↑ | ????↑ | ??0.5 | ?95.9 | ?91.2/8.8 |
| ????10 | ????↑ | ????2.19 | Sulfuric acid | ????0.15 | ????↑ | ????↑ | ????↑ | ????↑ | ??↑ | ?97.0 | ?78.9/20.1 |
| Embodiment number | Catalyzer | Acid | Solvent | Hydrogen partial pressure * 10 5Pa | Temperature (℃) | Time (hr) | ????BCHL | ||||
| Kind | Quantity (g) | Kind | Quantity (g) | Kind | Quantity (g) | Yield (%) | The cis/trans ratio | ||||
| ?C.1 | ????Rh | ??4.50 | Do not have | ????--- | ????CHX | ????74 | ????21 | ????40 | ????0.3 | ?96.6 | ?68.5/31.5 |
| ?C.2 | ????↑ | ??2.25 | Phosphoric acid | ????0.23 | ????↑ | ????↑ | ????↑ | ????↑ | ????0.7 | ?97.0 | ?68.6/31.4 |
| ?C.3 | ????↑ | ??2.19 | Nitric acid | ????0.31 | ????↑ | ????↑ | ????↑ | ????↑ | ????7.0 | ?69.9 | ?60.7/39.3 |
| ?C.4 | ????Ru | ??4.50 | Hydrochloric acid | ????0.30 | ????↑ | ????↑ | ????↑ | ????↑ | ????10.0 | ?39.8 | ?68.3/31.7 |
| ?C.5 | ????↑ | ??↑ | Do not have | ????--- | ????↑ | ????↑ | ????↑ | ????↑ | ????1.5 | ?97.8 | ?63.2/36.8 |
CHX: hexanaphthene
BCHL:4-tertiary butyl hexalin embodiment 11
(1) 4-tert.-butyl phenol (90 grams, 0.60 mole), 5%Rh/C (counting 0.9 gram based on siccative), Virahol (180 gram) and 60% high chloro acid solution (0.10 gram) are dropped in the autoclave, feed 5 * 10 then
5The nitrogen of Pa makes the inside of autoclave be replaced by nitrogen, vacuumizes three times.Inject hydrogen to 1.1 * 10
6Pa rises to 60 ℃ with internal temperature, then stirs 5 hours.
With autoclave cooling and resemble replace with nitrogen above-mentioned inner, analyze reaction mixture.The yield of 4-tertiary butyl hexalin is 95.5%, and cis-isomeride is 82.1: 17.9 with the ratio of trans-isomer(ide).
Reaction mixture is removed by filter catalyzer, and evaporation concentration obtains 4-tertiary butyl hexalin crude product (91 grams, 0.57 mole, purity 98.4%, cis-isomeride is 82.1: 17.9 with the ratio of trans-isomer(ide)).
(2) sulfuric acid (0.17 gram, 1.8 moles) is added in the above-mentioned spissated mixture, mixture is remained on 90 ℃ simultaneously, with 3 hours time dropping diacetyl oxide (76.06 grams, 0.75 mole), then be incubated 1 hour then.
To the analysis revealed of reaction mixture, the yield of acetate 4-tertiary butyl cyclohexyl is 99% (based on 4-tertiary butyl hexalin meter), and cis-isomeride is 82.1: 17.9 with the ratio of trans-isomer(ide).
With reaction mixture washing three times (each 120 grams), use ion-exchange water washing once (120 gram) with 5% sodium bicarbonate aqueous solution.With oil reservoir rectifying, obtain highly purified acetate 4-tertiary butyl cyclohexyl with high yield.Embodiment 12
(1) 4-tert.-butyl phenol (180 grams, 1.20 moles), 5%Rh/C (counting 1.8 grams based on siccative), Virahol (360 gram) and 36% hydrochloric acid (0.12 gram) are dropped in the autoclave, feed 5 * 10 then
5The nitrogen of Pa makes the inside of autoclave be replaced by nitrogen, vacuumizes three times.Injecting 5 * 10
5The hydrogen of Pa replaces with hydrogen with autoclave inside and vacuumizes after three times, injects hydrogen to 1.1 * 10
6Pa rises to 60 ℃ with internal temperature, then stirs 4 hours.
With autoclave cooling and resemble replace inside with nitrogen above-mentioned after, analyze reaction mixture.The yield of 4-tertiary butyl hexalin is 93.2%, and cis-isomeride is 88.6: 11.4 with the ratio of trans-isomer(ide).
Repeat above-mentioned reaction, two kinds of reaction mixtures are merged.
The reaction mixture that merges is removed by filter catalyzer, and evaporation concentration obtains 4-tertiary butyl hexalin crude product (350 grams, 2.20 moles, purity 98.4%, cis-isomeride is 88.6: 11.4 with the ratio of trans-isomer(ide)).
(2) mixture is being remained in 90 ℃, sulfuric acid (0.81 gram, 8.1 mmoles) is being added in the above-mentioned enriched mixture, using 3 hours time that diacetyl oxide (312.4g, 2.94 moles) is added drop-wise in the mixture then, then under this temperature, be incubated 1 hour.
The analysis revealed of reaction mixture, the yield of acetate 4-tertiary butyl cyclohexyl are 99% (based on 4-tertiary butyl hexalin meter), and cis-isomeride is 88.6: 11.4 with the ratio of trans-isomer(ide).
With reaction mixture washing three times (each 450 grams), use ion-exchange water washing once (450 gram) with 5% sodium bicarbonate aqueous solution.With oil reservoir rectifying, obtain highly purified acetate 4-tertiary butyl cyclohexyl with high yield.
Claims (9)
1. the method for preparing 4-tertiary butyl hexalin is included in the solvent, at rhodium catalyst be selected from the presence of hydrogenchloride, perchloric acid and (anhydrous) vitriolic compound the hydrogenation of 4-tert.-butyl phenol.
2. according to the rhodium atom that the process of claim 1 wherein in every mole of rhodium catalyst, hydrogenchloride, perchloric acid or (anhydrous) vitriolic consumption are the 0.05-10 mole.
3. according to the process of claim 1 wherein that described rhodium catalyst comprises the metal rhodium that is stated from the carrier.
4. according to the method for claim 3, wherein the consumption of rhodium catalyst (in dry substance) is the 0.5-10% (weight) of 4-tert.-butyl phenol weight.
5. according to the process of claim 1 wherein that described solvent is to be selected from alkane with 5-10 carbon atom, to have the ether of 4-10 carbon atom and to have the alcohol of 1-6 carbon atom.
6. according to the method for claim 5, wherein said solvent is an ethanol.
7. according to the method for claim 6, wherein said solvent is a Virahol.
8. according to the process of claim 1 wherein that temperature of reaction is 20-100 ℃.
9. the method for preparing acetate 4-tertiary butyl cyclohexyl; comprise that with the acetylize of 4-tertiary butyl hexalin described 4-tertiary butyl hexalin is by in solvent, at rhodium catalyst and be selected from the presence of hydrogenchloride, perchloric acid and (anhydrous) vitriolic compound hydrogenation of 4-tert.-butyl phenol is prepared.
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- 1997-01-17 CN CN97102071A patent/CN1092627C/en not_active Expired - Fee Related
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| CN101511805B (en) * | 2006-06-22 | 2013-10-30 | 生物计划公司 | Carbonylated (aza) cyclohexanes as dopamine D3 receptor ligands |
| CN102448450B (en) * | 2009-04-09 | 2013-11-20 | 西姆莱斯有限公司 | Compositions comprising trans-tert-butyl cyclohexanol as skin irritation-reducing agent |
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| CN101830798A (en) * | 2010-05-26 | 2010-09-15 | 杭州友邦香料香精有限公司 | Preparation method of high-cis vertenex |
| CN109704932A (en) * | 2017-10-25 | 2019-05-03 | 中国石油化工股份有限公司 | Catalytic hydrogenation prepares 2,6- di-t-butyl -4 methyl cyclohexanol method |
| CN109704932B (en) * | 2017-10-25 | 2022-07-26 | 中国石油化工股份有限公司 | Method for preparing 2, 6-di-tert-butyl-4-methylcyclohexanol by catalytic hydrogenation |
| CN110743546A (en) * | 2019-10-31 | 2020-02-04 | 西安凯立新材料股份有限公司 | Catalyst for continuously preparing cis-p-tert-butylcyclohexanol, preparation method and application thereof |
| CN110743546B (en) * | 2019-10-31 | 2022-11-18 | 西安凯立新材料股份有限公司 | Catalyst for continuously preparing cis-p-tert-butylcyclohexanol, preparation method and application thereof |
| CN113372191A (en) * | 2021-05-17 | 2021-09-10 | 江苏馨瑞香料有限公司 | Preparation method of tert-butyl cyclohexanol |
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