CN1296364C - Process for phase-transfer catalytic synthesis of alpha, beta-epoxy ketone compound - Google Patents
Process for phase-transfer catalytic synthesis of alpha, beta-epoxy ketone compound Download PDFInfo
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- CN1296364C CN1296364C CNB200310119153XA CN200310119153A CN1296364C CN 1296364 C CN1296364 C CN 1296364C CN B200310119153X A CNB200310119153X A CN B200310119153XA CN 200310119153 A CN200310119153 A CN 200310119153A CN 1296364 C CN1296364 C CN 1296364C
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Abstract
The present invention relates to the synthesis of an alpha, beta-epoxy group ketone compound, particularly to a method for the phase transfer catalytic synthesis of the alpha, beta-epoxy group ketone compound. In the existence of a phase transfer catalyst, trichloroisocyanuric acid (TCCA) as an oxidizing agent, alkali metal hydroxide as an alkaline regulating agent and alpha, beta-unsaturated ketone as a raw material react in pure organic solvent, or organic solvent and water or water, and a reaction formula is disclosed above, wherein substituents R1 and R2 can be alkyl base groups or aryl base groups; when the R1 and/or the R2 are/is the substituent(s) of the aryl base groups, the R1 and/or the R2 can be provided with one or more electron-giving groups and/or electron-absorbing groups, and the product of the present invention is obtained in a conventional method after reaction is completed. The present invention has the advantages of simple operation, mild condition, easy obtainment of the raw material, high selectivity and good yield; the solvent for the reaction can be selected according to the dissolving property of the raw material.
Description
Technical field
The present invention relates to α, beta epoxide base ketone compound synthetic, specifically a kind of phase-transfer catalysis is synthesized α, the method for beta epoxide base ketone compound.
Background technology
α, beta epoxide base ketone compound are the widest class intermediates of purposes in the organic synthesis, and carbonyl and propylene oxide group can carry out functionalization [document: Tetrahedron:Asymmetry, 2001,12,2359-2383 etc.].Wherein the carbonyl functionalization comprises and is reduced into α, beta epoxide base alcohol, reductive amination process, Bayer-Villiger reaction, Meerwein-Ponndorf-Wei Lai reaction etc.And propylene oxide group is subjected to nucleophilic reagent attack open loops such as sulfur-bearing, oxygen, halogen can synthesize miscellaneous compound.
α, the building block of beta epoxide base ketone structure can be used for the synthesis of biologically active compound, as LTRA SK﹠amp; F104353[document: J.Org.Chem.1993,58,6247-6254 etc.], Odizem and taxol Taxol side chain [document: J.Chem.Soc., Perkin Trans.11997,3501-3507 etc.], galacturonic acid derivative [document: J.Chem.Soc., Perkin Trans.12001,149-153. etc.], protein kinase C agonist [document: Tetrahedron Lett.2000,41,9569-9574 etc.].
Conventional at present synthetic α, the method for beta epoxide base ketone compound comprises the alpha, beta-unsaturated ketone epoxidation reaction, dyne reaction [document: Tetrahedron Lett.1998,39,2145-2148 between α halogenated ketone and the aldehyde, Tetrahedron 1999,55,6375-6386 etc.].The alpha, beta-unsaturated ketone epoxidation reaction is synthetic α, the most direct method of beta epoxide base ketone.The oxygenant that is usually used in the alpha, beta-unsaturated ketone epoxidation reaction has hydrogen peroxide [document: Tetrahedron Lett.1998,39,7563-7566 etc.], clorox [document: Tetrahedron Lett.1998,39,1599-1602, etc.], tertbutyl peroxide
[document: J.Am.Chem.Soc.1997,119,2329-2330 etc.] etc., oxygen [document: Angew.Chem., Int.Ed.Engl.1996,35,1725-1728 etc.].Though these oxygenants can be successfully used to α, alpha, beta-unsaturated ketone epoxy reaction, but oxygenant ubiquity poor stabilities such as hydrogen peroxide, clorox, potassium hypochlorite and tertbutyl peroxide, shortcomings such as easy decomposition, and oxygen is made oxygen source, needs to use stoichiometric zinc ethyl auxiliary agent.
Summary of the invention
The object of the present invention is to provide the synthetic α of the low phase-transfer catalysis alpha, beta-unsaturated ketone epoxidation reaction of a kind of reaction conditions gentleness, cost, beta epoxide base ketone compound.
For achieving the above object, the technical solution used in the present invention is: in the presence of phase-transfer catalyst, with α, alpha, beta-unsaturated ketone is a raw material, and trichloroisocyanuric acid is an oxygenant, and the alkali metal hydroxide mineral alkali is made additive, at pure organic solvent, organic solvent-water, or react in the water; Reaction formula is as follows:
Wherein: substituent R
1Can be a kind of alkyl group or aromatic yl group; Substituent R
2Can be a kind of alkyl group or aromatic yl group; Aryl substituent R
1And/or R
2Can be with one or more electronics and/or electron-withdrawing groups given; Aryl substituent R
1And/or R
2One or more different the position of substitution of can being positioned at aromatic ring for electronics and/or electron-withdrawing group; The consumption of oxygenant generally gets final product with the stoichiometric ratio that contained available chlorine content is equal to or greater than itself and raw material, usually the consumption of trichloroisocyanuric acid is 50～500%mol of raw material, the consumption of alkali metal hydroxide also is so, is generally 200～1000%mol of raw material; Catalyzer be generally quaternary ammonium salt or season phosphonium salt or polyoxyethylene glycol or their mixture, their consumption can be 0.1～20%mol of raw material; Solvent gets final product so that raw material is dissolved fully, and the mol ratio of raw material and solvent is generally: 1: 1 to 1: 50; Reaction can be finished at 0.5～72 hour usually; Temperature of reaction is to get final product more than the zero pour of reaction system, usually between-50～30 ℃; Organic solvent is the mixture of one or more polarity or nonpolar inert solvent or polar solvent and non-polar solvent, wherein polar solvent often is toluene, dimethylbenzene, tetrahydrofuran (THF), N, N '-dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), methylene dichloride, chloroform or water etc., non-polar solvent often is hexane or benzene etc., mixed solvent is for example: toluene, dimethylbenzene/water, methylene dichloride/water, trichloromethane/water.Product separates can adopt extraction or separation methods such as recrystallization or column chromatography or simple filtration.
The consumption of described oxygenant trichloroisocyanuric acid is 50～100%mol of raw material; The consumption of phase-transfer catalyst is 0.1～10%mol of raw material; The consumption of alkali metal hydroxide is 200～600%mol of raw material; Temperature of reaction is-20～20 ℃; Described aryl substituent R
1And/or R
2Be with one or more electron substituent groups of giving, wherein substituting group is methyl, methoxyl group, phenyl, halogen or trifluoromethyl; Described reaction product is when separation and purification, and the solvent that is used to extract is selected ether, sherwood oil, Skellysolve A, normal hexane or normal heptane for use; The solvent that is used for recrystallization is selected the aqueous solution, dehydrated alcohol, trichloromethane or the N of 60% dehydrated alcohol, dinethylformamide for use; Using unmodified packed column during column chromatography, is elutriant with n-hexane/ethyl acetate or petrol ether/ethyl acetate.
The present invention has following advantage:
1. solid oxidizing agent trichloroisocyanuric acid stable in properties is cheap and easy to get, is a kind of widely used swimming pool sterilizing agent; With other oxygenant, as aqueous sodium hypochlorite solution, the Losantin solid, hydrogen peroxide etc. are compared, and have that stability is high, the transportation storage is convenient, safe and reliable, and oxidation capacity is strong, good selective; Under phase-transfer catalyst and alkaline conditioner effect, alpha, beta-unsaturated ketone is shown good epoxidation ability.
2. reaction conditions gentleness.In the presence of phase-transfer catalyst, at polarity, non-polar organic solvent, organic solvent/water, or alpha, beta-unsaturated ketone can be changed into α under the pure water medium, beta epoxide base ketone compound.Can react according to reactant (raw material) dissolving properties selective reaction medium (solvent); This is the advantage that other oxygenant hardly matches.
3. reaction preference and transformation efficiency height.The present invention is under specified criteria, and alpha, beta-unsaturated ketone can be with high yield, even Quantitative yield becomes α, and beta epoxide base ketone compound does not have by product, the selectivity height, and productive rate is good.
4. easy and simple to handle, reaction product is easy to separate.Can be by separation methods such as extraction, recrystallization, column chromatography or simple filtration purifying in addition; Organic solvent can be recycled.
In a word, the present invention has easy and simple to handle, mild condition, and raw material is easy to get, the selectivity height, productive rate is good, can be according to advantages such as material dissolution character selective reaction solvents.
Embodiment
Below by embodiment in detail the present invention is described in detail; But the present invention is not limited to following embodiment.
Embodiment 1 solid-liquid two-phase phase-transfer catalysis synthesis of trans-2,3-epoxy-1,3-diphenylprop-1-ketone
In the 100ml round-bottomed flask, add cinnamophenone (2.08g, 10mmol), Tetrabutyl amonium bromide (322mg 1mmol) and 30ml toluene, is cooled to 10 ℃, add the solid trichloroisocyanuric acid (2.32g, 10mmol), add solid KOH (3.36,60mmol).Dropwising back 10 ℃ continues down to stir TLC detection reaction terminal point 4 hours.Be warming up to room temperature, in reaction solution, add the 15ml ether, filter, filtrate water washing, anhydrous MgSO
4Dry.Distillation removes and desolvates, and (silica gel, elutriant are petrol ether/ethyl acetate: 50/1), distillation removes and desolvates, and obtains white crystal, and yield is 92% in the column chromatography separation.
Embodiment 2 solid-liquid two-phase phase-transfer catalysis synthesis of trans-2,3-epoxy-1,3-diphenylprop-1-ketone
Embodiment under the different phase-transfer catalysts existence is summarized as follows with tabulated form: (reaction conditions and step are with embodiment 1)
Table 1. different phase-transfer catalysts and consumption are to the influence of epoxidation reaction
| Sequence number | Catalyzer | Catalyst levels [%] | Alkali | Reaction times [hour] | Yield [%] |
| 1 2 3 4 5 6 7 8 9 10 | PEG-4600 PEG-400 TBPB TBPC CTMAB TBABS TBAB TBAB TBAB TBAB | 10 10 10 10 10 10 10 5 1 0.1 | KOH KOH KOH KOH KOH KOH KOH KOH KOH KOH | 24 24 24 24 24 3 4 4 24 48 | 37 71 71 48 70 91 92 91 42 40 |
Catalyzer:
PEG-4600: polyoxyethylene glycol-4600 (polyethylene glycol-4600),
PEG-400: polyoxyethylene glycol-400 (polyethylene glycol-400),
TBPB: tetrabutyl phosphonium bromide phosphine (tetrabutyl phosphonium bromide),
TBPC: tetrabutylphosphonium chloride (tetrabutyl phosphonium chloride),
CTMAB: cetyl trimethylammonium bromide (Cetyl trimethyl ammonium bromide),
TBABS: 4-butyl ammonium hydrogen sulfate (tetrabutyl ammonium bisulfate),
TBAB: Tetrabutyl amonium bromide (tetrabutyl ammonium bromide).
Embodiment 3 solid-liquid two-phase phase-transfer catalysis synthesis of trans-2,3-epoxy-1,3-diphenylprop-1-ketone
Embodiment under the kind of differential responses solvent, alkali and consumption, the temperature condition is summarized as follows with tabulated form: (reaction conditions and step are with embodiment 1)
The kind of Table 2. reaction solvents, alkali and consumption, TCCA consumption, temperature are to the shadow of epoxidation reaction
Ring
| Sequence number | Solvent | Alkali/[%] | TCCA[％] | Temperature [℃] | Reaction times [hour] | Yield [%] |
| 11 12 13 14 15 16 17 18 19 20 21 22 23 | Carrene dimethylamino benzophenone benzene toluene toluene toluene toluene toluene toluene toluene toluene toluene toluene | KOH/600 KOH/500 KOH/600 KOH/200 LiOH/600 NaOH/600 CsOH/600 KOH/600 KOH/500 KOH/600 KOH/200 KOH/600 KOH/600 | 100 90 100 50 90 90 90 67 100 100 100 100 100 | 0 0 0 0 0 0 0 20 10 10 -10 -10 -20 | 24 5 4 24 24 24 24 24 4 4 8 6 8 | 73 78 91 63 38 53 45 67 92 91 73 87 85 |
Embodiment 4 solid-liquid two-phase phase-transfer catalysis synthesis of trans replace-2,3-epoxy-1,3-diphenylprop-1-ketone
The embodiment of differential responses substrate is summarized as follows with tabulated form: (reaction conditions and step are with embodiment 1)
Table 3.TBAB catalytic epoxidation
| Sequence number | α, beta-unsaturated carbonyl compound | Reaction times [hour] | Yield [%] | |
| R 1 | R 2 | |||
| 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 | C 6H 5 C 6H 5 4-ClC 6H 4 C 6H 5 4-NO 2C 6H 4 C 6H 5 4-ClC 6H 4 2-ClC 6H 4 4-ClC 6H 4 4-ClC 6H 4 3-ClC 6H 5 3-ClC 6H 5 4-ClC 6H 5 3-ClC 6H 4 4-CH 3OC 6H 4 2-CH 3OC 6H 4 | C 6H 5 4-CH 3OC 6H 4 4-FC 6H 4 4-FC 6H 4 C 6H 5 4-ClC 6H 4 C 6H 5 C 6H 5 4-ClC 6H 4 4-CH 3OC 6H 4 4-PhC 6H 4 4-CF 3C 6H 4 4-MeC 6H 4 3-MeC 6H 4 C 6H 5 C 6H 5 | 4 4 3 5 4 4 4 4 2 3 4 4 4 4 5 5 | 88 85 94 81 77 91 93 93 80 72 88 91 93 89 0 0 |
Embodiment 5 solid-liquid two-phase phase-transfer catalysis synthesis of trans-2,3-epoxy-3-phenyl-1-(4-p-methoxy-phenyl)-third-1-ketone
In the 100ml round-bottomed flask, and the adding Tetrabutyl amonium bromide (322mg, 1mmol), 30ml toluene is cooled to 10 ℃, adding solid trichloroisocyanuric acid (2.32g, 10mmol), the adding solid KOH (3.36,60mmol), stirred 15 minutes.(2.38g 10mmol), continues to stir TLC detection reaction terminal point 5 hours to add trans 3-phenyl-1-(4-p-methoxy-phenyl)-acrylketone.Be warming up to room temperature, in reaction solution, add the 15ml ether, filter, filtrate water washing, anhydrous MgSO
4Dry.Distillation removes and desolvates, and (silica gel, elutriant are petrol ether/ethyl acetate: 50/1), obtain white crystal, yield is 79% in the column chromatography separation.
Embodiment 6 solid-liquid two-phase phase-transfer catalysis synthesis of trans-2,3-epoxy-3-phenyl-1-(2-p-methoxy-phenyl)-third-1-ketone
Trans 3-phenyl-1-(2-p-methoxy-phenyl)-acrylketone (2.38g, 10mmol), experimental technique and step are with embodiment 5, and yield is 76%.
Embodiment 7 liquid liquid two-phase phase-transfer catalysis synthesis of trans-2,3-epoxy-1,3-diphenylprop-1-ketone
In the 100ml round-bottomed flask, and the adding cinnamophenone (2.08g, 10mmol), Tetrabutyl amonium bromide (322mg, 1mmol) and 30ml toluene, be cooled to 0 ℃, add solid trichloroisocyanuric acid (2.32g, 10mmol), and the Dropwise 5 0%KOH aqueous solution (6.68g, 60mmol).Dropwising back 0 ℃ continues down to stir TLC detection reaction terminal point 9 hours.Be warming up to room temperature, add 15ml water in reaction solution, two are separated, the anhydrous MgSO of organic phase
4Dry.Distillation removes and desolvates, and obtains faint yellow solid, and the normal hexane recrystallization obtains white crystal, and yield is 75%.
Embodiment 8 organic solvent-free phase-transfer catalysis synthesis of trans-2,3-epoxy-1,3-diphenylprop-1-ketone
Under 20 ℃, in the 100ml round-bottomed flask, the adding cetyl trimethylammonium bromide (0.18g, 0.5mmol), 50ml water, the solid trichloroisocyanuric acid (2.32g, 10mmol), the Dropwise 5 0%KOH aqueous solution (6.68g, 60mmol).(2.08g 10mmol), continues to stir TLC detection reaction terminal point 24 hours to add cinnamophenone.Add the 30ml ether in reaction solution, two are separated, the anhydrous MgSO of organic phase
4Dry.Distillation removes and desolvates, and obtains faint yellow solid, and the normal hexane recrystallization obtains white crystal, and yield is 98%.
Embodiment 9 organic solvent-free phase-transfer catalysis synthesis of trans replace-2,3-epoxy-1,3-diphenylprop-1-ketone
The embodiment of differential responses substrate is summarized as follows with tabulated form: (reaction conditions and step are with embodiment 8)
Table 4.CTMAB catalytic epoxidation
| Sequence number | α, beta-unsaturated carbonyl compound | Reaction times [hour] | Yield [%] | |
| R 1 | R 2 | |||
| 40 41 42 43 44 45 46 47 48 49 50 51 | C 6H 5 4-ClC 6H 4 C 6H 5 4-NO 2C 6H 4 C 6H 5 4-ClC 6H 4 2-ClC 6H 4 4-ClC 6H 4 4-ClC 6H 4 4-CH 3OC 6H 4 4-CH 3OC 6H 4 2-CH 3OC 6H 4 | 4-CH 3OC 6H 4 4-FC 6H 4 4-FC 6H 4 C 6H 5 4-ClC 6H 4 C 6H 5 C 6H 5 4-ClC 6H 4 4-CH 3OC 6H 4 C 6H 4 4-ClC 6H 4 C 6H 4 | 24 24 24 24 24 24 24 24 24 24 24 24 | 86 94 95 86 90 96 95 93 89 90 87 86 |
Claims (8)
1. a phase-transfer catalysis is synthesized α, the method of beta epoxide base ketone compound, it is characterized in that: in the presence of phase-transfer catalyst, with trichloroisocyanuric acid (TCCA) is oxygenant, alkali metal hydroxide is an alkaline conditioner, alpha, beta-unsaturated ketone is a raw material, reacts in pure organic solvent, organic solvent-water or water; Reaction formula is as follows:
Wherein: substituent R
1, R
2Be alkyl group or aromatic yl group; Work as R
1And/or R
2During for aryl substituent, it is with one or more electronics and/or electron-withdrawing groups given; Separate according to a conventional method after reaction is finished and promptly get product.
2. according to the synthetic α of the described phase-transfer catalysis of claim 1, the method for beta epoxide base ketone compound is characterized in that: described phase-transfer catalyst be quaternary ammonium salt, season phosphonium salt, polyoxyethylene glycol or their mixture.
3. according to the synthetic α of the described phase-transfer catalysis of claim 1, the method of beta epoxide base ketone compound, it is characterized in that: the consumption of described oxygenant trichloroisocyanuric acid is 50～500%mol of raw material, and the consumption of alkali metal hydroxide is 200～1000%mol of raw material; Phase-transfer catalyst is 0.1～20%mol of raw material; The mol ratio of raw material and solvent is: 1: 1～1: 50; Temperature of reaction is-50～30 ℃; Being reflected at 0.5～72 hour can finish.
4. according to the synthetic α of the described phase-transfer catalysis of claim 3, the method for beta epoxide base ketone compound is characterized in that: the consumption of described oxygenant trichloroisocyanuric acid is 50～100%mol of raw material; The consumption of phase-transfer catalyst is 0.1～10%mol of raw material; The consumption of alkali metal hydroxide is 200～600%mol of raw material; Temperature of reaction is-20～20 ℃.
5. according to the synthetic α of the described phase-transfer catalysis of claim 1, the method of beta epoxide base ketone compound, it is characterized in that: described organic solvent is toluene, dimethylbenzene, tetrahydrofuran (THF), N, N '-dimethyl formamide, dimethyl sulfoxide (DMSO), methylene dichloride, chloroform, water, hexane, benzene or their mixture.
6. according to the synthetic α of the described phase-transfer catalysis of claim 1, the method for beta epoxide base ketone compound is characterized in that: described aryl substituent R
1And/or R
2Be with one or more electron substituent groups of giving, wherein substituting group is methyl, methoxyl group, phenyl, halogen or trifluoromethyl.
7. according to the synthetic α of the described phase-transfer catalysis of claim 1, the method for beta epoxide base ketone compound is characterized in that: described product separates and adopts extraction, recrystallization, column chromatography or filter in addition purifying.
8. according to the synthetic α of the described phase-transfer catalysis of claim 7, the method for beta epoxide base ketone compound is characterized in that: described reaction product is when separation and purification, and the solvent that is used to extract is selected ether, sherwood oil, Skellysolve A, normal hexane or normal heptane for use; The solvent that is used for recrystallization is selected the aqueous solution, dehydrated alcohol, trichloromethane or the N of 60% dehydrated alcohol, dinethylformamide for use; Using unmodified packed column during column chromatography, is elutriant with n-hexane/ethyl acetate or petrol ether/ethyl acetate.
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