CN1291966C - Synthesis of 5(6) caproleic acid - Google Patents
Synthesis of 5(6) caproleic acid Download PDFInfo
- Publication number
- CN1291966C CN1291966C CN 200410021510 CN200410021510A CN1291966C CN 1291966 C CN1291966 C CN 1291966C CN 200410021510 CN200410021510 CN 200410021510 CN 200410021510 A CN200410021510 A CN 200410021510A CN 1291966 C CN1291966 C CN 1291966C
- Authority
- CN
- China
- Prior art keywords
- decenoic acid
- alkyl ketone
- synthetic
- butyl alkyl
- essence
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 5
- KHAVLLBUVKBTBG-UHFFFAOYSA-N dec-9-enoic acid Chemical compound OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 title 2
- 239000002253 acid Substances 0.000 claims abstract description 20
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 230000000694 effects Effects 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 150000007513 acids Chemical class 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 5
- POYYYXPQBFPUKS-UHFFFAOYSA-N 2-butylcyclohexan-1-one Chemical compound CCCCC1CCCCC1=O POYYYXPQBFPUKS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- -1 butyl alkyl ketone Chemical class 0.000 abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 6
- 150000002596 lactones Chemical class 0.000 abstract description 5
- 235000013336 milk Nutrition 0.000 abstract description 5
- 239000008267 milk Substances 0.000 abstract description 5
- 210000004080 milk Anatomy 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000006071 cream Substances 0.000 abstract description 3
- 238000006049 ring expansion reaction Methods 0.000 abstract description 3
- 235000016623 Fragaria vesca Nutrition 0.000 abstract description 2
- 240000009088 Fragaria x ananassa Species 0.000 abstract description 2
- 235000011363 Fragaria x ananassa Nutrition 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000001577 simple distillation Methods 0.000 abstract description 2
- WXBXVVIUZANZAU-CMDGGOBGSA-N trans-2-decenoic acid Chemical compound CCCCCCC\C=C\C(O)=O WXBXVVIUZANZAU-CMDGGOBGSA-N 0.000 abstract 6
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 229910003445 palladium oxide Inorganic materials 0.000 abstract 1
- 238000007142 ring opening reaction Methods 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 235000013618 yogurt Nutrition 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YKVIWISPFDZYOW-UHFFFAOYSA-N 6-Decanolide Chemical compound CCCCC1CCCCC(=O)O1 YKVIWISPFDZYOW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 208000030208 low-grade fever Diseases 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 235000021262 sour milk Nutrition 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a synthetic method for 5(6)-decenoic acid, which belongs to the technical field of 5(6)-decenoic acid preparation. The present invention provides a new method for preparing the 5(6)-decenoic acid. The method is characterized by the synthesis of butyl alkyl ketone as a key intermediate in the synthesis of 5(6)-decenoic acid. The present invention synthesizes the butyl alkyl ketone without using any solvent, and cyclohexanone is condensed, dewatered and hydrogenated with butanal under the action of a bifunctional catalyst of palladium / aluminium oxide, and the preparation of the butyl alkyl ketone is realized by a one-step method. The present invention has the effects and benefits of little by-product, little pollution and high product purity, the purity of the butyl alkyl ketone obtained by simple distillation is 99.5%, and the reaction selection is 95%. The butyl alkyl ketone becomes lactone by the ring expansion of hydrogen peroxide, and finally, 5(6)-decenoic acid is obtained by ring opening under an acid condition. The 5(6)-decenoic acid is suitable for preparing cream essence, milk essence, yoghurt essence, strawberry essence, etc.
Description
Technical field
The invention belongs to food and beverage preparation technical field.5 (6)-decylenic acids (milk lactone), trade name is the milk lactone, is the safe edible spices (registration number: 3742), also meet GB 2760-1996 " foodstuff additive use hygienic standard " simultaneously of U.S. flavouring agent producer association approval.It has strong milk fragrance, and lasting fragrance, is the important source material of milk, cream, cheese essence.
Background technology
Because range of application is extremely extensive, consumption is big, the study on the synthesis of relevant 5 (6)-decylenic acids road that appears in the newspapers more.In existent method, patent " 5 (6)-decylenic acids synthetic " (CN 1266841) is arranged, and its operational path is to be raw material with pimelinketone and butyraldehyde, through parlkaline condensation, selective hydrogenation, the hydrogen peroxide ring expansion is a lactone, and open loop obtains 5 (6)-decylenic acids under acidic conditions at last; Patent " a kind of novel process (CN1426992) for preparing decylenic acid; this invention provides a kind of technology for preparing decylenic acid; be to be that the product that raw material carries out after the alkaline condensation carries out selective hydrogenation with palladium carbon as catalyzer with aldehydes and cyclic ketones; the product of selective hydrogenation is after 20% Peracetic Acid oxidation, and the carclazyte open loop through handling with phosphoric acid obtains decylenic acid is arranged.Two kinds of methods have all that synthetic route is long, yield is low, and owing to use the alkali condensation to pollute shortcomings such as bigger, have limited mass production.
Summary of the invention
The novel method that the purpose of this invention is to provide a kind of preparation 5 (6)-decylenic acids.
Technical scheme of the present invention is be synthetic 5 (6)-decylenic acid key intermediate butyl alkyl ketone synthetic.Need not any solvent during synthetic butyl alkyl ketone, with pimelinketone under heterogeneous dual-function catalyst palladium/aluminium sesquioxide effect with butyraldehyde condensation, dehydration, hydrogenation, single stage method has realized the preparation of butyl alkyl ketone.Owing to be reflected under no any solvent and carry out, thereby simplified production process greatly, and eliminated pollution from beginning of production.Temperature of reaction 80-280 of the present invention ℃, be preferably in 100-200 ℃; Dropping into the raw material pimelinketone of reaction and the mol ratio of butyraldehyde is 10: 1 to 100: 10, and reaction catalyst system therefor amount is 3～8% of a material total amount, is preferably 5～6%; This reacts required hydrogen pressure is 0.1～10.0, preferably 4.0～5.0MPa; Catalyzer used herein all can be obtained by the traditional preparation process mode.
Effect of the present invention and benefit are that by product is few, and the product purity height is through simple distillation gained butyl alkyl ketone purity 99.5%, reaction preference 95%.This product is widely used in food and beverage, is applicable to type essence such as preparation cream, dairy products, sour milk and strawberry.
The butyl alkyl ketone of above-mentioned gained is a lactone through the hydrogen peroxide ring expansion again, and open loop obtains 5 (6)-decylenic acids under acidic conditions at last.
Embodiment
Be described in detail the specific embodiment of the present invention below in conjunction with technical scheme.
Synthesizing of embodiment 1:2-butyl cyclohexanone
In autoclave, add 1090 gram (11 moles) pimelinketone, 270 gram (3.7 moles) butyraldehyde-ns and 70 gram 0.5%Pa/Al
2O
3Catalyzer.Charge into 1.0MPa hydrogen with behind the hydrogen exchange three times, be warming up to 110 ℃ (hydrogen pressure 3.5MPa) reaction 3 hours, be warming up to 160 ℃ (hydrogen pressure 5.0MPa) reaction then, need 10 hours approximately altogether to not inhaling till the hydrogen.Leach the catalyzer straight run distillation after the reactant cooling.Reclaim pimelinketone 705 grams, get 2-butyl cyclohexanone 462 grams (purity 99.5%).
Synthesizing of embodiment 2:5 (6)-decylenic acid
(1), the hydrogen peroxide complex compound is synthetic:
The 450g30% hydrogen peroxide adds 180g urea, and low-grade fever to 30 ℃ stirring and dissolving is cooled to 0 ℃ and folds complex compound, filter 264g.
(2), oxidation makes ε-decalactone
810ml formic acid (86%) adds the 162g complex compound, after the stirring and dissolving, adds 81g 2-butyl cyclohexanone, is warming up to 30 ℃ of stirring reactions (needing cooling) 1 hour.After having reacted, add 486ml water, extract extracting, be washed to neutrality with toluene, 126～130/4mmHg fraction 51.7g ε-decalactone (99% purity) is collected in underpressure distillation behind the piptonychia benzene.
(3), 5 (6)-decylenic acids is synthetic
54g ε-decalactone adds 49.5g sodium hydroxide in the 87g aqueous solution, 110 ℃ of following saponification 3 hours.The cooling back adds the mixing solutions acidifying of 60g sulfuric acid and 60g water, branch vibration layer.The mixing solutions that adds 50g sulfuric acid and 50g water again, back flow reaction 2 hours.Add the 100ml hexanaphthene, branch vibration layer, oil-reservoir water are washed till water layer PH=6, add the mixture of 0.5g carclazyte and 0.5g gac, reflux and stir decolouring in 15 minutes, filter, and the decylization hexane gets product 48g.
Claims (6)
1, a kind of 5 (6)-decylenic acids is synthetic, it is characterized in that with pimelinketone under heterogeneous dual-function catalyst palladium/alchlor effect with butyraldehyde condensation, dehydration, hydrogenation one-step synthesis 2-butyl cyclohexanone.
2, a kind of 5 (6)-decylenic acids according to claim 1 is synthetic, it is characterized in that reaction need not any solvent.
3, a kind of 5 (6)-decylenic acids according to claim 1 is synthetic, it is characterized in that dropping into the raw material pimelinketone of reaction and the mol ratio of butyraldehyde is 10: 1 to 100: 10.
4, a kind of 5 (6)-decylenic acids according to claim 1 and 2 is synthetic, it is characterized in that wherein said reaction is to carry out under 80-280 ℃ temperature.
5, a kind of 5 (6)-decylenic acids according to claim 1 is synthetic, it is characterized in that wherein catalyst levels is 3～8% of a material total amount.
6, a kind of 5 (6)-decylenic acids according to claim 1 is synthetic, it is characterized in that hydrogen pressure is 0.1～10.0MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410021510 CN1291966C (en) | 2004-07-19 | 2004-07-19 | Synthesis of 5(6) caproleic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410021510 CN1291966C (en) | 2004-07-19 | 2004-07-19 | Synthesis of 5(6) caproleic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1597655A CN1597655A (en) | 2005-03-23 |
| CN1291966C true CN1291966C (en) | 2006-12-27 |
Family
ID=34663335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410021510 Expired - Lifetime CN1291966C (en) | 2004-07-19 | 2004-07-19 | Synthesis of 5(6) caproleic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1291966C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588633B (en) * | 2013-11-22 | 2015-08-05 | 浙江安赛生物科技有限公司 | The preparation technology of 5 (6)-decylenic acids |
| CN110128259A (en) * | 2019-06-12 | 2019-08-16 | 广东广益科技实业有限公司 | 5 (6)-decene acid production process |
| CN110143866A (en) * | 2019-06-12 | 2019-08-20 | 广东广益科技实业有限公司 | 5 (6)-decylenic acid synthetic method |
| CN110922324A (en) * | 2019-10-24 | 2020-03-27 | 上海大学 | Preparation method of 5(6) -decenoic acid |
| CN114075101A (en) * | 2020-08-20 | 2022-02-22 | 中国科学院大连化学物理研究所 | Preparation method of 2-alkyl cyclohexanone compound |
| CN114507123B (en) * | 2020-11-17 | 2023-10-10 | 中国科学院大连化学物理研究所 | Preparation method of 2-alkyl cyclohexanone homolog |
-
2004
- 2004-07-19 CN CN 200410021510 patent/CN1291966C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1597655A (en) | 2005-03-23 |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: DALIAN LUCK FINE CHEMICAL CO.,LTD. Assignor: DALIAN JINJU CHEMICAL FACTORY Contract fulfillment period: 2007.2.10 to 2017.2.10 Contract record no.: 2008210000068 Denomination of invention: Synthesis of 5 (6) - sebacic acid Granted publication date: 20061227 License type: Exclusive license Record date: 20081112 |
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| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.2.10 TO 2017.2.10; CHANGE OF CONTRACT Name of requester: DALIAN LAIKE REFINEMENT CO., LTD. Effective date: 20081112 |
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Assignee: DALIAN LUCK FINE CHEMICAL CO.,LTD. Assignor: DALIAN JINJU CHEMICAL FACTORY Contract record no.: 2008210000068 Date of cancellation: 20180105 |
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Application publication date: 20050323 Assignee: DALIAN LUCK FINE CHEMICAL CO.,LTD. Assignor: DALIAN JINJU CHEMICAL FACTORY Contract record no.: 2018210000002 Denomination of invention: Synthesis of 5 (6) - sebacic acid Granted publication date: 20061227 License type: Exclusive License Record date: 20180108 |
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