CN116874348A - Green synthesis method of 2-campholenic butanol - Google Patents
Green synthesis method of 2-campholenic butanol Download PDFInfo
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- CN116874348A CN116874348A CN202310680605.9A CN202310680605A CN116874348A CN 116874348 A CN116874348 A CN 116874348A CN 202310680605 A CN202310680605 A CN 202310680605A CN 116874348 A CN116874348 A CN 116874348A
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- China
- Prior art keywords
- campholenic
- butanol
- catalyst
- synthesis method
- reaction
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000006722 reduction reaction Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical group [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000002537 cosmetic Substances 0.000 abstract 1
- 239000003599 detergent Substances 0.000 abstract 1
- 239000000344 soap Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 3
- OGCGGWYLHSJRFY-SECBINFHSA-N (+)-alpha-Campholenal Natural products CC1=CC[C@H](CC=O)C1(C)C OGCGGWYLHSJRFY-SECBINFHSA-N 0.000 description 2
- 241000221035 Santalaceae Species 0.000 description 2
- 235000008632 Santalum album Nutrition 0.000 description 2
- OGCGGWYLHSJRFY-UHFFFAOYSA-N alpha-campholenaldehyde Chemical compound CC1=CCC(CC=O)C1(C)C OGCGGWYLHSJRFY-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and discloses a green synthesis method of 2-campholenic butanol, which specifically comprises the following steps: mixing 2-campholenic butyraldehyde with a catalyst in a solvent, heating and pressurizing in a hydrogen atmosphere to perform a reduction reaction, filtering a reaction solution after the reaction is finished, and then removing reduced pressure for rectification to obtain a 2-campholenic butanol finished product. The invention does not need washing step, can not generate waste water, has no environmental protection pressure, has low-cost metal catalyst, can be used mechanically, has low cost, and the obtained finished product has high transparency and pure fragrance, and can be widely applied to cosmetic essence, soap essence, detergent essence and household essence.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, relates to synthesis of a spice compound, and in particular relates to a green synthesis method of 2-campholenic butanol.
Background
2-campholenic butanol, CAS 28219-61-6, molecular formula C 14 H 24 O, commonly known as sandalwood 208, is an important component in sandalwood-series fragrances, and should have strong sandalwood fragrance and weak rosesFloral fragrance, and can be widely applied to various essences.
The method for synthesizing 2-campholenic butanol at home and abroad mainly takes campholenic aldehyde as a raw material, and under the catalysis of inorganic base, aldol condensation and dehydration are carried out on the campholenic aldehyde and n-butyraldehyde to obtain an intermediate 2-campholenic butyraldehyde, and then the 2-campholenic butanol is obtained through different reduction methods. CN16607037 and CN101492347 are selected from potassium borohydride and sodium borohydride as reducing agents, and the method has the advantages that the products can be obtained without high temperature and high pressure, but a large amount of water is needed for washing materials, a large amount of wastewater is generated, a large amount of salt is generated, and environmental protection pressure is high. The hydrogen is selected as the reducing agent in US4619781 and US4666629, and the copper-chromium is used as the catalyst, so that the catalyst is stable in industrial production for decades, but the metal chromium in the catalyst has high toxicity and is environment-friendly and difficult to treat.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a green synthesis method of 2-campholenic butanol, which adopts 2-campholenic butyraldehyde as a raw material to synthesize 2-campholenic butanol under the action of a cheap metal catalyst.
The invention is realized by the following technical scheme:
a green synthesis method of 2-campholenic butanol comprises the following steps:
mixing 2-campholenic butyraldehyde with a catalyst in a solvent, heating and pressurizing in a hydrogen atmosphere to perform a reduction reaction, filtering a reaction solution after the reaction is finished, and then removing reduced pressure for rectification to obtain a 2-campholenic butanol finished product.
The reaction equation is shown below:
the invention further improves the scheme as follows:
the mass ratio of the 2-campholenic butyraldehyde to the catalyst to the solvent is 1:0.005-0.01:0.5-2.
Further, the solvent is a C1-C4 polar solvent.
Preferably, the solvent is one or more of methanol, ethanol, isopropanol, n-butanol or sec-butanol.
Further, the catalyst is a copper-silicon type catalyst.
Further, the temperature of the reduction reaction is 140-160 ℃, the hydrogen pressure is 20-30 bar, and the reaction time is 2-3h.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method has mild reaction conditions and simple equipment, and the obtained finished product has high transparency and pure fragrance.
(2) The method does not need a washing step, does not generate waste water and has no environmental protection pressure.
(3) The catalyst used in the method is cheap metal, and can be used mechanically, so that the production cost is greatly reduced.
Description of the embodiments
The present invention will be described in detail with reference to specific examples.
The copper-silicon catalyst used in the invention is a commercial catalyst, and the catalyst of three families of China petrochemical catalyst, namely Kaili New Material Co., ltd, beijing trimerization environmental protection New Material Co., ltd, and Siam Kaili New Material Co., ltd, has excellent performance in the system.
Example 1
2-campholenic butyraldehyde is put into a 1L hydrogenation kettle: 200g, methanol: 200g of copper-silicon catalyst: 2.0g, stirring was started, nitrogen was replaced 3 times, then the temperature was raised to 160℃and the hydrogen pressure was maintained at about 30bar, after which the reaction was completed for 3 hours. After filtration, methanol was recovered at normal pressure to 85 ℃, followed by high vacuum distillation and collection of 124-130 ℃ (1.9 mmHg) fractions: 192g GC 91.3%
Example 2
2-campholenic butyraldehyde is put into a 1L hydrogenation kettle: 200g, isopropanol: 200g of copper-silicon catalyst: 2.0g, stirring was started, nitrogen was replaced 3 times, then the temperature was raised to 160℃and the hydrogen pressure was maintained at about 30bar, after which the reaction was completed for 2 hours. After filtration, methanol was recovered at normal pressure to 85 ℃, followed by high vacuum distillation and collection of 124-130 ℃ (1.9 mmHg) fractions: 189g GC:92.0%
Example 3
2-campholenic butyraldehyde is put into a 1L hydrogenation kettle: 200g, sec-butanol: 200g of copper-silicon catalyst: 2.0g, stirring was started, nitrogen was replaced 3 times, then the temperature was raised to 140℃and the hydrogen pressure was maintained at about 20bar, after which the reaction was completed for 3 hours. After filtration, methanol was recovered at normal pressure to 85 ℃, followed by high vacuum distillation and collection of 124-130 ℃ (1.9 mmHg) fractions: 193g GC:90.3%
Example 4
2-campholenic butyraldehyde is put into a 1L hydrogenation kettle: 200g, ethanol: 200g of copper-silicon catalyst: 2.0g, stirring was started, nitrogen was replaced 3 times, then the temperature was raised to 160℃and the hydrogen pressure was maintained at about 30bar, after which the reaction was completed for 2 hours. Filtering, recovering methanol at normal pressure to 85deg.C, rectifying with high vacuum, and collecting 124-130deg.C (1.9 mmHg) fraction
Example 5: verification of catalyst application
Specifically as shown in table 1:
table 1 catalyst sleeve
| Number of hydrogenations | Reaction time (h) | Reaction temperature (. Degree. C.) | Reaction pressure (bar) | Catalyst amount (%) | Yield (%) | GC(%) |
| First time | 2 | 160 | 30 | 0.5 | 92.5 | 91.5 |
| Second time | 2 | 160 | 30 | / | 92.9 | 90.9 |
| Third time | 3 | 160 | 30 | / | 94.6 | 92.3 |
As can be seen from Table 1, the catalyst of the present invention can be used as a catalyst. When the catalyst is used in a sleeve, the activity tends to decrease, but the selectivity of the reaction increases.
The foregoing embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (6)
1. The green synthesis method of the 2-campholenic butanol is characterized by comprising the following steps of: mixing 2-campholenic butyraldehyde with a catalyst in a solvent, heating and pressurizing in a hydrogen atmosphere to perform a reduction reaction, filtering a reaction solution after the reaction is finished, and then removing reduced pressure for rectification to obtain a 2-campholenic butanol finished product.
2. The green synthesis method of 2-campholenic butanol according to claim 1, wherein: the mass ratio of the 2-campholenic butyraldehyde to the catalyst to the solvent is 1:0.005-0.01:0.5-2.
3. The green synthesis method of 2-campholenic butanol according to claim 1 or 2, wherein: the solvent is a polar solvent of C1-C4.
4. A green synthesis method of 2-campholenic butanol according to claim 3, wherein: the solvent is one or more of methanol, ethanol, isopropanol, n-butanol or sec-butanol.
5. The green synthesis method of 2-campholenic butanol according to claim 1 or 2, wherein: the catalyst is a copper-silicon type catalyst.
6. The green synthesis method of 2-campholenic butanol according to claim 1, wherein: the temperature of the reduction reaction is 140-160 ℃, the hydrogen pressure is 20-30 bar, and the reaction time is 2-3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310680605.9A CN116874348A (en) | 2023-06-09 | 2023-06-09 | Green synthesis method of 2-campholenic butanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310680605.9A CN116874348A (en) | 2023-06-09 | 2023-06-09 | Green synthesis method of 2-campholenic butanol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116874348A true CN116874348A (en) | 2023-10-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310680605.9A Pending CN116874348A (en) | 2023-06-09 | 2023-06-09 | Green synthesis method of 2-campholenic butanol |
Country Status (1)
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| CN (1) | CN116874348A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117942998A (en) * | 2023-12-06 | 2024-04-30 | 江苏宏邦化工科技有限公司 | Cu/SiO2Preparation method of catalyst and application of catalyst in preparation of sandalwood 196 by catalytic hydrogenation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4619781A (en) * | 1985-09-20 | 1986-10-28 | International Flavors & Fragrances Inc. | Process for preparing mixture containing 2-campholenylidenbutanol, product produced thereby and perfumery uses thereof |
| CN1660737A (en) * | 2004-12-21 | 2005-08-31 | 建德市新化化工有限责任公司 | Method for synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol |
| CN102688726A (en) * | 2012-05-30 | 2012-09-26 | 山东一诺生化科技有限公司 | Equipment and technology for preparing furfuryl alcohol by liquid phase hydrogenation of furfural |
| CN116003352A (en) * | 2023-02-10 | 2023-04-25 | 成都中科凯特科技有限公司 | Method for selectively reducing unsaturated compounds by utilizing hydrogen transfer |
-
2023
- 2023-06-09 CN CN202310680605.9A patent/CN116874348A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4619781A (en) * | 1985-09-20 | 1986-10-28 | International Flavors & Fragrances Inc. | Process for preparing mixture containing 2-campholenylidenbutanol, product produced thereby and perfumery uses thereof |
| CN1660737A (en) * | 2004-12-21 | 2005-08-31 | 建德市新化化工有限责任公司 | Method for synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol |
| CN102688726A (en) * | 2012-05-30 | 2012-09-26 | 山东一诺生化科技有限公司 | Equipment and technology for preparing furfuryl alcohol by liquid phase hydrogenation of furfural |
| CN116003352A (en) * | 2023-02-10 | 2023-04-25 | 成都中科凯特科技有限公司 | Method for selectively reducing unsaturated compounds by utilizing hydrogen transfer |
Non-Patent Citations (3)
| Title |
|---|
| MICHELE GARGANO ET AL.: "Selective Preparation of Unsaturated Alcohols via Catalytic Meerwem-Ponudorf Reduction of Unsaturated Carbonyl Compounds over Metal Oxides", 《JOURNAL OF MOLECULAR CATALYSIS》, 31 December 1990 (1990-12-31), pages 5 - 8 * |
| NICOLETTA RAVASIO ET AL.: "Cu/SiO2-catalyzed hydrogenation of cyclohexanones under very mild conditions", 《TETRAHEDRON LETTERS》, 31 December 2002 (2002-12-31), pages 3943 * |
| SABINE VALANGE ET AL.: "One-step generation of highly selective hydrogenation catalysts involving sub-nanometric Cu2O supported on mesoporous alumina: strategies to control their size and dispersion", 《JOURNAL OF MOLECULAR CATALYSIS》, 5 November 2005 (2005-11-05), pages 255 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117942998A (en) * | 2023-12-06 | 2024-04-30 | 江苏宏邦化工科技有限公司 | Cu/SiO2Preparation method of catalyst and application of catalyst in preparation of sandalwood 196 by catalytic hydrogenation |
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