CN110078611A - A kind of α, the preparation method of beta-unsaturated carbonyl compound - Google Patents
A kind of α, the preparation method of beta-unsaturated carbonyl compound Download PDFInfo
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- CN110078611A CN110078611A CN201910359034.2A CN201910359034A CN110078611A CN 110078611 A CN110078611 A CN 110078611A CN 201910359034 A CN201910359034 A CN 201910359034A CN 110078611 A CN110078611 A CN 110078611A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/228—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing six-membered aromatic rings, e.g. phenylacetaldehyde
- C07C47/232—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing six-membered aromatic rings, e.g. phenylacetaldehyde having unsaturation outside the aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/213—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings
- C07C49/217—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the aromatic rings
- C07C49/223—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the aromatic rings polycyclic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/794—Ketones containing a keto group bound to a six-membered aromatic ring having unsaturation outside an aromatic ring
- C07C49/796—Ketones containing a keto group bound to a six-membered aromatic ring having unsaturation outside an aromatic ring polycyclic
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Abstract
The invention discloses a kind of α, the preparation method of beta-unsaturated carbonyl compound, its main feature is that replace propargyl alcohol and water as substrate, Meyer-Schuster rearrangement is carried out under the catalysis of MCM-41, SBA-15, USY, Beta or ZSM-5 acidic molecular sieve, it is described that the mass ratio of propargyl alcohol and deionized water and catalyst is replaced to be 100:10 ~ 150:10 ~ 50, filter off catalyst after reaction, purify product be α, beta-unsaturated carbonyl compound.The present invention has a wide application range of substrates compared with prior art, catalyst system organic solvent-free, and catalyst is cheap, easily system, stabilizations, no pollution to the environment, recyclable reuse, and reaction yield height.
Description
Technical field
The present invention relates to molecular sieve catalyst technical fields, especially a kind of to be reset using Meyer-Schuster by replacing
Propargyl alcohol prepares α, the preparation method of beta-unsaturated carbonyl compound.
Background technique
α, beta-unsaturated carbonyl compound are a kind of important organic synthesis building blocks, it contains carbonyl and alkenyl simultaneously, tool
There is the property of ketone, alkene and conjugated diene, is synthesis precursor or key intermediate important in organic synthesis, and
The good receptor of Michael addition reaction and Diels-Alder reaction, can be widely applied to medicine, pesticide, fine chemicals etc.
Industrial circle.Such as there is the α of pharmacophoric group, alpha, beta-unsaturated ketone can be used for the synthesis of antitumor inhibitor, have dulcet natural
Alpha, beta-unsaturated ketone can be used for the synthesis of fine chemicals.The common method for synthesizing this kind of compound has Aldol condensation, Wittig
Reaction, Horner-Wadsworth-Emmons reaction, Peterson are at alkene, Meyer-Schuster rearrangement etc..Wherein,
Meyer-Schuster is reset due to having the characteristics that reaction raw materials are easy that preparation, Atom economy is high is increasingly subject to chemist
Attention and favor, all used in the synthesis of a variety of natural products such as hydroxyanthecotulide, prostaglandin
Key Strategy of the reaction as building compound scaffold.
There are the deficiencies of following several respects for traditional Meyer-Schuster rearrangement reaction: 1) reaction need in strong acid and
It is carried out under conditions of heating, condition violent in this way be resistant to many functional groups can not, and lead to the region of reaction
Selectivity and stereoselectivity are poor；2) strong acidic condition be easy to cause equipment to corrode, so that Meyer-Schuster is reset very
Hardly possible is applied to large-scale production；3) it when H is contained in β-position of propargyl alcohol class compound, has side reaction Rupe and resets generation.For
Overcome deficiency existing for traditional Meyer-Schuster rearrangement reaction, multiple research groups carry out the reaction in recent years
A large amount of in-depth studies, a variety of mild efficient catalyst systems are established and are reported in succession, including use organic acid catalysis, " soft "
Louis acid catalysis, transition metal oxide catalysis etc..It is excellent that these methods have that reaction condition is mild, stereoselectivity is higher etc.
Point, but needed in reaction process expensive, the cumbersome catalyst preparation process of a large amount of organic solvent and catalyst price with
And catalyst the deficiencies of can not reusing, still constrains further applying for Meyer-Schuster rearrangement reaction.Solid
Acid catalyst is a kind of important catalyst in acid base catalysator, and catalysis, which derives from, has catalysis present on the surface of solids
Active acid sites claims acid site.Their most oxides or mixed oxide for non-transition element, catalytic performance is not
It is same as the oxide catalyst containing transition elements, this kind of catalyst is widely used in the catalysis reaction of ionic mechanism.
Molecular sieve is as a kind of emerging solid acid catalyst, since clear with aperture, internal surface area is high, thermal stability
Good and acid site can be expected to become environmental friendly catalysis material of new generation the advantages that modulation, it be provided simultaneously with Bronsted acid and
The center Lewis and micro- mesopore orbit structure.Compared with traditional organic micromolecule catalyst, molecular sieve have it is environmentally protective,
High financial profit, it is reusable the features such as, increasingly by the attention of scientists, however urged as organic solvent-free
Change and be used for α, the preparation of beta-unsaturated carbonyl compound does not have document report also.
Summary of the invention
The purpose of the present invention is in view of the deficiencies of the prior art and provide a kind of α, the system of beta-unsaturated carbonyl compound
Preparation Method uses and replaces propargyl alcohol for substrate, resets preparation α, beta-unsaturated carbonyl compound, bottom using Meyer-Schuster
Object is applied widely, catalyst system organic solvent-free, catalyst is cheap, easily system, stabilizations, no pollution to the environment, repetition can be recycled
It uses, synthesis can be carried out efficiently in a mild condition, and reduce the use of organic solvent, and product separating-purifying is easy, and be met
The theory of Green Chemistry and the requirement of sustainable development are suitble to industrializing implementation.
Realizing the specific technical solution of the object of the invention is: a kind of α, the preparation method of beta-unsaturated carbonyl compound,
Feature is that the substitution propargyl alcohol of following I formulas is used to mix for substrate with deionized water, MCM-41,., carried out for catalyst
Meyer-Schuster rearrangement reaction 0.5~for 24 hours, reaction temperature is 30~100 DEG C, the substitution propargyl alcohol and deionized water
Be 100:10~150:10~50 with the mass ratio of catalyst, filter off catalyst after reaction, purify product is following II
α shown in formula, beta-unsaturated carbonyl compound:
Wherein: the R in I formula, II formula1For aromatic substituents；R2For the substitution of hydrogen, aromatic substituents or aliphatic；R3For
Hydrogen, aromatic substituents, aliphatic substitution or alkoxy.
The aromatic substituents be phenyl, 2- aminomethyl phenyl, 3- aminomethyl phenyl, 4- aminomethyl phenyl, 2- methoxyphenyl,
3- methoxyphenyl, 4- methoxyphenyl, 2- chlorphenyl, 3- chlorphenyl, 4- chlorphenyl, 2- bromophenyl, 3- bromophenyl, 4- bromobenzene
Base, 2- fluorophenyl, 3- fluorophenyl, 4- fluorophenyl, 2- cyanophenyl, 3- cyanophenyl, 4- cyanophenyl or naphthalene.
The aliphatic substitution is the alkyl comprising 1~4 carbon.
The alkoxy is the alkoxy comprising 1~2 carbon.
The present invention has a wide application range of substrates compared with prior art, catalyst system organic solvent-free, catalyst is cheap,
Easy system, stabilization, no pollution to the environment, recyclable reuse, and reaction yield is high, and selectivity is good, synthetic method step letter
It is single, it can efficiently carry out in a mild condition, greatly reduce the use of organic solvent, product separating-purifying is easy, and meets green
The theory of chemistry and the requirement of sustainable development, are suitble to industrializing implementation.
Specific embodiment
By following specific embodiments, the present invention is described in further detail.
Embodiment 1
Weigh be added after 100mg 1,1,3- triphenyl -2- propine -1- alcohol dissolves by heating at a temperature of 85 DEG C 100 μ L without from
Sub- water is stirred and is slowly added to 30mg MCM-41 type molecular sieve (adding in 5 minutes) after ten minutes, at a temperature of 85 DEG C into
The Meyer-Schuster rearrangement reaction of the following reaction equations of row:
5ml chemistry pure ethyl acetate dissolved organic matter is added after reaction 9 hours, molecular sieve is then filtered out, by ethyl acetate
Solution removes a small amount of water with anhydrous sodium sulfate, and through column chromatography for separation after filtering, being spin-dried for, the product for obtaining 91.3mg is 1,3,3-
Triphenyl propenone, yield 91.3%.
It is 1,3,3- triphenyl propenone that above-mentioned product, which is analyzed to identify, and test data is as follows:
1H NMR (400MHz, CDCl3): δ 7.91 (d, J=10.0Hz, 2H), 7.48 (t, J=9.2Hz, 1H), 7.38-
7.34(m,7H),7.27-7.23(m,3H),7.18(m,2H),1.74-1.66(m,2H),7.11(s,1H)。
Embodiment 2
100mg 1,1 is weighed, 90 μ L are added without ion in-diphenyl -2- heptyne -1- alcohol after dissolving by heating at a temperature of 90 DEG C
Water is stirred and is slowly added to 30mg MCM-41 type molecular sieve (adding in 5 minutes) after ten minutes, carries out at a temperature of 90 DEG C
The Meyer-Schuster rearrangement reaction of following reaction equations:
5ml chemistry pure ethyl acetate dissolved organic matter is added after reaction 6 hours, molecular sieve is then filtered out, by ethyl acetate
Solution removes a small amount of water with anhydrous sodium sulfate, and through column chromatography for separation after filtering, being spin-dried for, the product for obtaining 88.7mg is 1,1 ,-
Diphenyl -1- teracrylic acid -one, yield 88.7%.
It is 1,1 that above-mentioned product, which is analyzed to identify,-diphenyl -1- teracrylic acid -one, and test data is as follows:
1H NMR(600MHz,CDCl3):δ7.39(m,3H),7.31-7.28(m,2H),7.20(m,2H),6.58(s,
1H), 2.23 (t, J=2Hz, 2H), 1.51-1.45 (m, 2H), 1.21-1.16 (m, 2H), 0.80 (t, J=7.2Hz, 3H).
Embodiment 3
Weigh 100mg 1,1,-diphenyl -2- propine -1- alcohol be added after being dissolved by heating at a temperature of 100 DEG C 80 μ L without from
Sub- water is stirred and is slowly added to 8mg SBA-15 type molecular sieve (adding in 5 minutes) after ten minutes, at a temperature of 100 DEG C into
The Meyer-Schuster rearrangement reaction of the following reaction equations of row:
5ml chemistry pure ethyl acetate dissolved organic matter is added after reaction 3 hours, molecular sieve is then filtered out, by ethyl acetate
Solution removes a small amount of water with anhydrous sodium sulfate, and through column chromatography for separation after filtering, being spin-dried for, the product for obtaining 84.5mg is 3,3- bis-
Phenylacrolein, yield 84.5%.
Above-mentioned product is analyzed to identify as 3,3- diphenylpropenal, and test data is as follows:
1H NMR (600MHz, CDCl3): δ 9.55 (d, J=7.8Hz, 2H), 7.50-7.41 (m, 4H), 7.38-7.35
(m, 4H), 7.27 (d, J=7.2Hz, 2H), 6.60 (d, J=7.8Hz, 1H)；
Embodiment 4
Weigh be added after 100mg 1- methyl-1-phenyl-2- propine-1- alcohol dissolves by heating at a temperature of 90 DEG C 60 μ L without from
Sub- water is stirred and is slowly added to 10mg USY type molecular sieve (adding in 5 minutes) after ten minutes, under carrying out at a temperature of 90 DEG C
State the Meyer-Schuster rearrangement reaction of reaction equation:
5ml chemistry pure ethyl acetate dissolved organic matter is added after reaction 7 hours, molecular sieve is then filtered out, by ethyl acetate
Solution removes a small amount of water with anhydrous sodium sulfate, and through column chromatography for separation after filtering, being spin-dried for, the product for obtaining 81.7mg is 3- first
Base -3- phenylacrolein, yield 81.7%.
Above-mentioned product is analyzed to identify as 3- methyl -3- phenylacrolein, and test data is as follows:
1H NMR (600MHz, CDCl3): δ 10.20 (d, J=7.8Hz, 1H), 7.55 (m, 2H), 7.42 (m, 3H), 6.40
(d, J=7.8Hz, 1H), 2.59-2.57 (s, 3H).
Only the present invention will be further described for the above various embodiments, is not intended to limit the invention patent, all is this hair
Bright equivalence enforcement, is intended to be limited solely by within the scope of the claims of the invention patent.
Claims (1)
1. a kind of α, the preparation method of beta-unsaturated carbonyl compound, it is characterised in that use the substitution propargyl alcohol of following I formulas for
Substrate is mixed with deionized water, is catalyst progress in MCM-41, SBA-15, USY, Beta or ZSM-5 acidic molecular sieve
Meyer-Schuster rearrangement reaction 0.5~for 24 hours, reaction temperature is 30~100 DEG C, the substitution propargyl alcohol and deionized water
Be 100:10~150:10~50 with the mass ratio of catalyst, filter off catalyst after reaction, purify product is following II
α shown in formula, beta-unsaturated carbonyl compound:
Wherein: the R in I formula, II formula1For aromatic substituents；R2For the substitution of hydrogen, aromatic substituents or aliphatic；R3For hydrogen,
Aromatic substituents, aliphatic substitution or alkoxy；The aromatic substituents are phenyl, 2- aminomethyl phenyl, 3- methylbenzene
Base, 4- aminomethyl phenyl, 2- methoxyphenyl, 3- methoxyphenyl, 4- methoxyphenyl, 2- chlorphenyl, 3- chlorphenyl, 4- chlorobenzene
Base, 2- bromophenyl, 3- bromophenyl, 4- bromophenyl, 2- fluorophenyl, 3- fluorophenyl, 4- fluorophenyl, 2- cyanophenyl, 3- itrile group benzene
Base, 4- cyanophenyl or naphthalene；The aliphatic substitution is the alkyl comprising 1~4 carbon；The alkoxy is to include 1~2
The alkoxy of a carbon.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009061353A (en) * | 2007-09-04 | 2009-03-26 | Shizuokaken Koritsu Daigaku Hojin | Composite metal catalyst |
| CN104909970A (en) * | 2015-04-14 | 2015-09-16 | 沈阳药科大学 | Novel catalytic method for Meyer-Schuster rearrangement |
| CN105503553A (en) * | 2016-01-27 | 2016-04-20 | 陕西师范大学 | Preparation method of alpha-beta-unsaturated carbonyl compound |
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2019
- 2019-04-30 CN CN201910359034.2A patent/CN110078611A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009061353A (en) * | 2007-09-04 | 2009-03-26 | Shizuokaken Koritsu Daigaku Hojin | Composite metal catalyst |
| CN104909970A (en) * | 2015-04-14 | 2015-09-16 | 沈阳药科大学 | Novel catalytic method for Meyer-Schuster rearrangement |
| CN105503553A (en) * | 2016-01-27 | 2016-04-20 | 陕西师范大学 | Preparation method of alpha-beta-unsaturated carbonyl compound |
Non-Patent Citations (1)
| Title |
|---|
| NARESH MAMEDA等: "Solvent-free hydration of alkynes over Hβ zeolite", 《APPLIED CATALYSIS A: GENERAL》 * |
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