CN1117037A - Method for preparing polymethyl substituted tetrahydroindane by selective hydrogenation of polymethyl substituted indane - Google Patents

Method for preparing polymethyl substituted tetrahydroindane by selective hydrogenation of polymethyl substituted indane Download PDF

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Publication number
CN1117037A
CN1117037A CN94112270A CN94112270A CN1117037A CN 1117037 A CN1117037 A CN 1117037A CN 94112270 A CN94112270 A CN 94112270A CN 94112270 A CN94112270 A CN 94112270A CN 1117037 A CN1117037 A CN 1117037A
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CN
China
Prior art keywords
hydrogenation
indane
catalyzer
pentamethyl
tetrahydrochysene
Prior art date
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Pending
Application number
CN94112270A
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Chinese (zh)
Inventor
谷运璀
李步祥
钱莉群
霍月琴
袁慧芳
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PERFUME INDUSTRY SCIENCE INST MINISTRY OF LIGHT INDUSTRY
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PERFUME INDUSTRY SCIENCE INST MINISTRY OF LIGHT INDUSTRY
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Priority to CN94112270A priority Critical patent/CN1117037A/en
Publication of CN1117037A publication Critical patent/CN1117037A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • C07C5/11—Partial hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/18—Carbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/14—All rings being cycloaliphatic
    • C07C2602/24—All rings being cycloaliphatic the ring system containing nine carbon atoms, e.g. perhydroindane

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

In the said prepn process, the catalyst for selective hydrogenation is 5% Pa/C with a hydrogenation pressure of 3-7 MPa, and the hydrogenation temp. of 100-150 deg.C. The merits of the said prepn process include: mild hydrogenation conditions, the selectivity to tetrahydroindane is 1-2 times higher than the available techn, and it greatly increases yield. The present invention makes it possible to greatly reduce the cost for synthesizing precious perfume with the fragrance of musk, banksia root and ambergris.

Description

Many methyl substituted indane selects hydrogenation to prepare the method for many methyl substituted tetrahydrochysene indane
The invention relates to the many methyl substituted indane shown in the following general formula (I) and prepare the many methyl substituted tetrahydrochysene indane shown in the general formula (II) through selecting hydrogenation. In the formula: R 1=CH 3, R 2=H
R 1＝H，R 2＝CH 3
Many methyl substituted four indanes can synthesize many precious spices with Moschus, the banksia rose, Ambergris fragrance, the method of synthetic pentamethyl-indane deutero-spices is disclosed in the United States Patent (USP) 3773836 of Joho.B.Hall application in 1973, this method is from 1,1,2,3,3-pentamethyl-indane (formula I) (R 1=CH 3, R 2=H) hydrogenation preparation 1,1,2,3,3-pentamethyl--4,5,6,7-tetrahydrochysene indane (formula II) (R1=CH 3, R 2=H) method is made catalyzer with Raney-Ni (Raney's nickel) in its example, 150-185 ℃ of temperature, and 1000-1500 pound/inch 2(be converted under 6～9MPa) hydrogen pressures from 1800g1,1,2, divide gold-plating to make 401g1 in 3,3-pentamethyl-indane (content 85%) hydride, 1,2,3,3-pentamethyl--4,5,6,7-tetrahydrochysene indane calculates by theoretical, and its yield only is 25.7%.The shortcoming of this method is the temperature of reaction height, hydrogenation pressure pressure height, and the more important thing is that desirable tetrahydrochysene indane yield is low, causing thus, the synthetic spice product costs an arm and a leg.
Purpose of the present invention is exactly in order to solve the shortcoming that above-mentioned prior art exists, to provide a kind of hydrogenation conditions comparatively gentle, the selectivity height of tetrahydrochysene indane, the preparation method that yield is high.
Method of the present invention is for to prepare the many methyl substituted tetrahydrochysene indane shown in the above-mentioned general formula (II) by the many methyl substituted indane shown in the above-mentioned general formula (I) through highly selective hydrogenation, the used catalyzer of described selection hydrogenation adopts 5% Pa/C (palladium/carbon) catalyzer, hydrogenation pressure is 3～7MPa, and hydrogenation temperature is 100 ℃～150 ℃.
Further specify the present invention with embodiment below.
Embodiment 1.
1,1,2,3,3-pentamethyl-indane is selected hydrogenation preparation 1,1,2,3,3-pentamethyl--4,5,6,7-tetrahydrochysene indane.
Have magnetic stirrer at 1L, thermometer, tensimeter, hydrogen inlet in the stainless steel pressure still of venting port and external application nichrome wire process furnace, adds 300 grams 1,1,2,3,3-pentamethyl-indane (content 85%), 3 gram 5%Pa/C catalyzer.Earlier drain air in the still with hydrogen, under agitation feed hydrogen to hydrogen pressure then and reach 6MPa, slowly heating, still is pressed the nearly 7MPa that boosts automatically, reaches 130 ℃ until temperature in the kettle and begins to inhale hydrogen, and hydrogen pressure slowly descends in the still thereupon, when reducing to 5MPa, feed hydrogen again, make pressure rise to 7MPa again, so operation is until inhaling hydrogen to theoretical amount, and hydrogenation finishes.Be cooled to then below 40 ℃, bleed off remaining hydrogen, take out hydride, remove by filter the Pa/C catalyzer and make next hydrogenation usefulness, obtain 300 gram hydrogenation products from venting port.The gas chromatographic analysis of hydrogenation product, its result contains unconverted raw material 1,1,2,3, and 3-pentamethyl-indane is 7.9%, and transformation efficiency is 90.7%; Contain desirable 1,1,2,3,3-pentamethyl--4,5,6,7-tetrahydrochysene indane 62.8%, selectivity is 73.0%.
Embodiment 2:
1,1,3,3,5-pentamethyl-indane is selected hydrogenation preparation 1,1,3,3,5-pentamethyl--4,5,6,7-tetrahydrochysene indane.
Have mechanical stirrer at 0.1L, thermometer, tensimeter, hydrogen inlet in the stainless steel pressure still of venting port and external application nichrome wire process furnace, adds 30 gram (content 99%) 1,1,3,3,5-pentamethyl-indane 0.5g5%Pa/C catalyzer.With example 1 operation, obtain hydrogenation product 30g, product is through gas chromatographic analysis: contain unreacted raw material 1,1,3,3,5-pentamethyl-indane 32.5%, transformation efficiency 67.5% contains desirable 1,1,3,3,5-pentamethyl--4,5,6,7-tetrahydrochysene indane 38.1%, selectivity is 57.3%.
Embodiment 3: reference examples:
With example 1, except that doing the catalyzer with 7.5gRaney-Ni, all the other are fully by example 1 operation.Gained hydrogenation product is through gas chromatographic analysis: contain unreacting material 1,1, and 2,3,3-pentamethyl-indane 8.6%, transformation efficiency 89.9%, desirable product 1,1,2,3,3-pentamethyl--4,5,6,7-tetrahydrochysene indane 28.9%, selectivity is 37.8%.
From top three embodiment as can be known the inventive method select for use 5%Pa/C to have much higher hydrogenation selectivity than with the Raney-Ni catalyzer as catalyzer, make the selectivity of desirable product tetrahydrochysene indane reach 50～70% than 1～2 times of prior art raising, its yield also improves greatly, synthetic cost with precious spices of Moschus, the banksia rose, Ambergris fragrance is reduced greatly, the used Pa/C catalyzer of present method can be reused 8～12 times, and hydrogenation rate, conversion of raw material and desirable tetrahydrochysene indane selectivity and yield are not had obvious influence.

Claims (3)

1. the many methyl substituted indane shown in the general formula (I) prepares the method for the many methyl substituted tetrahydrochysene indane shown in the general formula (II) through highly selective hydrogenation, Wherein: R 1=CH 3, R 2=H
R 1=H, R 2=CH 3It is characterized in that: selecting Pa/C (palladium, carbon) catalyzer, the hydrogenation pressure of the used catalyzer employing 5% of hydrogenation is 3～7MPa, and hydrogenation temperature is 100 ℃～150 ℃.
2. method according to claim 1 is characterized in that described Pa/C catalyst consumption is 0.5～5% of a raw material charging capacity.
3. according to claim 1,2 described methods, it is characterized in that described Pa/C catalyzer can leach from the hydrogenation product, and reuse 8～12 times.
CN94112270A 1994-08-19 1994-08-19 Method for preparing polymethyl substituted tetrahydroindane by selective hydrogenation of polymethyl substituted indane Pending CN1117037A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN94112270A CN1117037A (en) 1994-08-19 1994-08-19 Method for preparing polymethyl substituted tetrahydroindane by selective hydrogenation of polymethyl substituted indane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN94112270A CN1117037A (en) 1994-08-19 1994-08-19 Method for preparing polymethyl substituted tetrahydroindane by selective hydrogenation of polymethyl substituted indane

Publications (1)

Publication Number Publication Date
CN1117037A true CN1117037A (en) 1996-02-21

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1060147C (en) * 1996-07-08 2001-01-03 中国科学院山西煤炭化学研究所 High concentrative non-flocculant humic acids complexed nutrient liquid and preparation thereof
EP3257831A3 (en) * 2016-06-16 2018-03-21 International Flavors & Fragrances Inc. Circular economy methods of preparing unsaturated compounds
CN108409632A (en) * 2018-05-28 2018-08-17 仪征市海帆化工有限公司 A kind of synthetic method of cis- 1,2,3,6- tetrahydric phthalimides
CN108689910A (en) * 2018-05-18 2018-10-23 仪征市海帆化工有限公司 A kind of synthetic method of 1- cyclohexene -1,2- dicarboximides
CN113929564A (en) * 2021-09-14 2022-01-14 安徽金禾化学材料研究所有限公司 Method for preparing kestone spice
CN115385770A (en) * 2022-10-10 2022-11-25 安徽金禾化学材料研究所有限公司 Method for preparing 1,2, 3-pentamethyl-4, 5,6, 7-tetrahydroindane

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1060147C (en) * 1996-07-08 2001-01-03 中国科学院山西煤炭化学研究所 High concentrative non-flocculant humic acids complexed nutrient liquid and preparation thereof
EP3257831A3 (en) * 2016-06-16 2018-03-21 International Flavors & Fragrances Inc. Circular economy methods of preparing unsaturated compounds
US10435345B2 (en) 2016-06-16 2019-10-08 International Flavors & Fragrances Inc. Circular economy methods of preparing unsaturated compounds
US11753360B2 (en) 2016-06-16 2023-09-12 International Flavors & Fragrances Inc. Circular economy methods of preparing unsaturated compounds
CN108689910A (en) * 2018-05-18 2018-10-23 仪征市海帆化工有限公司 A kind of synthetic method of 1- cyclohexene -1,2- dicarboximides
CN108689910B (en) * 2018-05-18 2022-04-12 仪征市海帆化工有限公司 Synthesis method of 1-cyclohexene-1, 2-dicarboximide
CN108409632A (en) * 2018-05-28 2018-08-17 仪征市海帆化工有限公司 A kind of synthetic method of cis- 1,2,3,6- tetrahydric phthalimides
CN113929564A (en) * 2021-09-14 2022-01-14 安徽金禾化学材料研究所有限公司 Method for preparing kestone spice
CN113929564B (en) * 2021-09-14 2023-10-03 安徽金禾化学材料研究所有限公司 Method for preparing spice kemesdone
CN115385770A (en) * 2022-10-10 2022-11-25 安徽金禾化学材料研究所有限公司 Method for preparing 1,2, 3-pentamethyl-4, 5,6, 7-tetrahydroindane
CN115385770B (en) * 2022-10-10 2023-10-03 安徽金禾化学材料研究所有限公司 Method for preparing 1,2, 3-pentamethyl-4, 5,6, 7-tetrahydroindane

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