CN103772170A - Catalytic hydrolysis method of enamine - Google Patents
Catalytic hydrolysis method of enamine Download PDFInfo
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- CN103772170A CN103772170A CN201310596157.0A CN201310596157A CN103772170A CN 103772170 A CN103772170 A CN 103772170A CN 201310596157 A CN201310596157 A CN 201310596157A CN 103772170 A CN103772170 A CN 103772170A
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- Prior art keywords
- enamine
- hydrolysis method
- catalytic hydrolysis
- organic
- formula
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- 150000002081 enamines Chemical class 0.000 title claims abstract description 26
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 12
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- 238000010025 steaming Methods 0.000 description 5
- ZOFWBOFWZMFYCB-GCZGRYASSA-N (1e,3r)-n,n-diethyl-3,7-dimethylocta-1,6-dien-1-amine Chemical compound CCN(CC)\C=C\[C@H](C)CCC=C(C)C ZOFWBOFWZMFYCB-GCZGRYASSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalytic hydrolysis method of enamine, and belongs to the field of chemical engineering technology. According to the invention, enamine used as the raw material is hydrolyzed under the catalysis of organic nickle with a specific structure and an ammonium chloride aqueous solution with specific concentration, and corresponding aldehyde can be prepared with relative high yield and low cost. The catalytic hydrolysis method disclosed by the invention is high in yield, low in cost, simple in operation, and suitable for industrial production, and has a certain industrialization prospect.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, be specifically related to a kind of catalytic hydrolysis method of enamine.
Background technology
Enamine is a kind of very active organic chemical industry's intermediate, under certain acid catalysis, is easily hydrolyzed to corresponding aldehyde.Principle is the lone-pair electron coordination on proton and the enamine nitrogen in the aqueous solution, causes the fracture of carbon nitrogen singly-bound, and diethylamine fragment departs from, and the other side fragment becomes enol, and enol tautomerizes to rapidly more stable aldehyde.This is a kind of important synthesis step of the aldehyde that obtains various forms and function, and aldehyde can be used as further chemical intermediate or sells as the product with standalone feature.
Because enamine is very active, under sour catalysis, Intermediates activity is too high is easy to occur side reaction.If with strong acid, acid meeting is higher, causes more by product.There is foreign literature report weak acid, as acetic acid catalysis a kind of enamine (N wherein for the reports such as Kazuhide Tani, N-diethyl-(R)-3,7-dimethyl-(E)-1,6-octadiene-1-amine), obtain corresponding aldehyde (the Kazuhide Tani of 91.4% yield; Tsuneaki Yamagata; Sei Otsuka; Hidenori Kumobayashi; Susumu Akutagawa; Org.Synth.Coll.Vol.8, p.183 (1993) .).But yield or on the low side, and acetic acid price is also relatively expensive.Therefore, we are in the urgent need to finding a kind of method that has suitable acidity and can reduce Intermediates activity, to implement the production of heavy industrialization.We researchist finds through a large amount of theoretical investigationes and experiment combination, find a kind of organic nickel of ad hoc structure, first use organic nickel nitrogen-atoms on complexing enamine in organic phase, due to the sterically hindered effect of organic group, make proton attack rate reduction, along with leaving away of nickel, thereby proton slowly starts hydrolysis in conjunction with the nitrogen-atoms on enamine.Due to the reduction of Intermediates activity, reaction preference is improved greatly.It is acid that the aqueous ammonium chloride solution that our choice for use is cheap provides, due to its acidity relatively a little less than, further improved selectivity.And reaction finishes rear organic nickel and be dissolved in organic phase, by steaming after solvent and product, organic nickel can also recovery, has further reduced cost, is applicable to suitability for industrialized production.This organic nickel preparation is simple, and bibliographical information is generally used for catalysis cross-coupling reaction, existing shiploads of merchandiseization supply on open market.
Summary of the invention
The object of the present invention is to provide the catalytic hydrolysis method of the enamine that a kind of yield is high, cost is low, simple to operate.
For achieving the above object, the technical solution used in the present invention is as follows:
A catalytic hydrolysis method for enamine, is characterized in that, the method, take the enamine shown in formula I as raw material, under the organic nickel of the ad hoc structure shown in formula II and the catalysis of certain concentration aqueous ammonium chloride solution, makes the aldehyde shown in formula III with higher yield;
Hydrolysis reaction formula of the present invention is as follows:
In formula, what R represented is the alkyl of C1-16, and organic nickel is suc as formula shown in II:
In formula, X represents halogen Cl or Br.
This catalyzed reaction is first together with the organic nickel of enamine and ad hoc structure, to be dissolved in organic solvent, and described organic solvent is the mixture of toluene, benzene or the above solvent.Temperature of reaction is 0-10 ℃, and the reaction times is 1-10h.The mol ratio of described middle enamine, organic nickel, ammonium chloride, water is 1:0.5-1.5:1-5:76-100.After reaction finishes, the organic phase that layering obtains is by vacuum distillation recovered solvent and obtain product, steamed the organic nickel that rear container bottom stays and reused.
Beneficial effect of the present invention:
The catalytic hydrolysis method of enamine disclosed in this invention, due to the organic nickel complexing enamine of ad hoc structure, has reduced the activity of Intermediates by sterically hindered effect, reaction preference is improved greatly; And the aqueous ammonium chloride solution acidity under certain concentration a little less than, further improved selectivity.Yield of the present invention is high, cost is low, simple to operate, be applicable to suitability for industrialized production.
Embodiment
Contribute to understand the present invention by following examples, but be not limited to content of the present invention.
Embodiment 1:
In a 500ml reaction flask, add 60g suc as formula the organic nickel shown in II, wherein X represents halogen Cl.Then add 21g N, N-diethyl-(R)-3,7-dimethyl-(E)-1,6-octadiene-1-amine, then add 100ml toluene to stir 0.5h dissolving, system temperature is dropped to 3 ℃, drip the solution being made up of 20g ammonium chloride and 160g water, about 0.5h drips off, and continues to stir 3.5h, leave standstill 2h, layering.50ml toluene extraction for water, merges organic phase, and pressure reducing and steaming solvent, obtains colourless liquid 15.26g, and the content of the corresponding aldehyde of detection display is 99.78%, and yield is 98.6%.
Embodiment 2:
In a 500ml reaction flask, add 66g suc as formula the organic nickel shown in II, wherein X represents halogen Cl.Then add 21g N, N-diethyl-(R)-3,7-dimethyl-(E)-1,6-octadiene-1-amine, then add 100ml toluene to stir 0.5h dissolving, system temperature is dropped to 3 ℃, drip the solution being made up of 20g ammonium chloride and 160g water, about 0.5h drips off, and continues to stir 3.5h, leave standstill 2h, layering.50ml toluene extraction for water, merges organic phase, and pressure reducing and steaming solvent, obtains colourless liquid 15.35g, and the content of the corresponding aldehyde of detection display is 99.84%, and yield is 99.2%.
Embodiment 3:
By boiling off the organic nickel that container bottom stays after solvent and product in embodiment 2, add 21g N, N-diethyl-(R)-3,7-dimethyl-(E)-1,6-octadiene-1-amine, stirs 0.5h with 100ml toluene and dissolves, and joins in a 500ml reaction flask, system temperature is dropped to 3 ℃, drip the solution being made up of 20g ammonium chloride and 160g water, about 0.5h drips off, and continues to stir 3.5h, leave standstill 2h, layering.50ml toluene extraction for water, merges organic phase, and pressure reducing and steaming solvent, obtains colourless liquid 15.32g, and the content of the corresponding aldehyde of detection display is 99.79%, and yield is 99.0%.
Embodiment 4:
In a 500ml reaction flask, add 75g suc as formula the organic nickel shown in II, wherein X represents halogen Br.Then add 21g N, N-diethyl-(R)-3,7-dimethyl-(E)-1,6-octadiene-1-amine, then add 100ml toluene to stir 0.5h dissolving, system temperature is dropped to 3 ℃, drip the solution being made up of 20g ammonium chloride and 160g water, about 0.5h drips off, and continues to stir 3.5h, leave standstill 2h, layering.50ml toluene extraction for water, merges organic phase, and pressure reducing and steaming solvent, obtains colourless liquid 15.28g, and the content of the corresponding aldehyde of detection display is 99.77%, and yield is 98.8%.
Claims (5)
1. a catalytic hydrolysis method for enamine, is characterized in that, the method, take the enamine shown in formula I as raw material, under the organic nickel of the ad hoc structure shown in formula II and the catalysis of certain concentration aqueous ammonium chloride solution, makes the aldehyde shown in formula III with higher yield;
Wherein, R representative is the alkyl of C1-16; X represents halogen Cl or Br.
2. the catalytic hydrolysis method of enamine according to claim 1, is characterized in that, described enamine needs first and together with the organic nickel of ad hoc structure to be dissolved in organic solvent; Described organic solvent is the mixture of toluene, benzene or the above solvent.
3. the catalytic hydrolysis method of enamine according to claim 1, is characterized in that, described hydrolysising reacting temperature is 0-10 ℃, and hydrolysis time is 1-10h.
4. the catalytic hydrolysis method of enamine according to claim 1, is characterized in that, the mol ratio of described enamine, organic nickel, ammonium chloride, water is 1:0.5-1.5:1-5:76-100.
5. the catalytic hydrolysis method of enamine according to claim 1, is characterized in that, the organic phase that after described hydrolysis reaction completes, layering obtains is by vacuum distillation recovered solvent and obtain product, has steamed the organic nickel that rear container bottom stays and has reused.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310596157.0A CN103772170B (en) | 2013-11-21 | 2013-11-21 | A kind of catalyzed hydrolytic methods of enamine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310596157.0A CN103772170B (en) | 2013-11-21 | 2013-11-21 | A kind of catalyzed hydrolytic methods of enamine |
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| Publication Number | Publication Date |
|---|---|
| CN103772170A true CN103772170A (en) | 2014-05-07 |
| CN103772170B CN103772170B (en) | 2015-10-14 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4695631A (en) * | 1981-06-30 | 1987-09-22 | Takasago Perfumery Co., Ltd. | Process for the preparation of enamines or imines |
| CN101602651A (en) * | 2008-06-13 | 2009-12-16 | 上海万香日化有限公司 | The synthetic method of L-menthol |
| CN103254047A (en) * | 2013-05-29 | 2013-08-21 | 上海灏翔生物科技有限公司 | Method for preparing L-menthol intermediate d-citronellal |
-
2013
- 2013-11-21 CN CN201310596157.0A patent/CN103772170B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4695631A (en) * | 1981-06-30 | 1987-09-22 | Takasago Perfumery Co., Ltd. | Process for the preparation of enamines or imines |
| CN101602651A (en) * | 2008-06-13 | 2009-12-16 | 上海万香日化有限公司 | The synthetic method of L-menthol |
| CN103254047A (en) * | 2013-05-29 | 2013-08-21 | 上海灏翔生物科技有限公司 | Method for preparing L-menthol intermediate d-citronellal |
Non-Patent Citations (1)
| Title |
|---|
| RUDOLF SCHMID，ET AL: "35. Axially Dissymmetric Diphosphines in the Biphenyl Series: Synthesis of (6,6"-Dimethoxybiphenyl-2,2"-diyl)bis(diphenylphosphine) (‘MeO-BIPHEP’) and Analogues via an ortho-Lithiation/Iodination Ullmann-Reaction Approach", 《HELVETICA CHIMICA ACTA》, vol. 74, 31 December 1991 (1991-12-31), pages 370 - 389, XP002097708, DOI: doi:10.1002/hlca.19910740215 * |
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| CN103772170B (en) | 2015-10-14 |
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Owner name: HUANGSHAN TIANXIANG TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: HEFEI HEWEI FOOD CO., LTD. Effective date: 20140917 |
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Free format text: CORRECT: ADDRESS; FROM: 230051 HEFEI, ANHUI PROVINCE TO: 245200 HUANGSHAN, ANHUI PROVINCE |
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Effective date of registration: 20140917 Address after: 245200 Shexian Circular Economy Park, Anhui, Huangshan City Applicant after: HUANGSHAN TIANXIANG TECHNOLOGY CO., LTD. Address before: Yanan Lu, Baohe Industrial District of Hefei City, Anhui Province, No. 7 230051 Applicant before: HEFEI HIWELL FOOD CO., LTD. |
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