CN107759499B - The method for synthesizing alpha, beta-unsaturated ketone compound is modified by acetophenone derivs α-H is Bifunctionalized - Google Patents
The method for synthesizing alpha, beta-unsaturated ketone compound is modified by acetophenone derivs α-H is Bifunctionalized Download PDFInfo
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Abstract
The invention discloses one kind to synthesize α by the Bifunctionalized modification of acetophenone derivs α-H; the method of beta-unsaturated ketone compound; this method is under protective atmosphere; dimethyl sulfoxide and acetophenone derivs; one pot reaction under the conditions of existing for the alkoxide and ammonium persulfate; generate α, beta-unsaturated ketone compound；This method carries out difunctional modification, high yield, high selectivity α to the α-H of acetophenone derivs using dimethyl sulfoxide simultaneously as methylenation reagents and methylating reagent, beta-unsaturated ketone compound, this method is easy to operate, at low cost, it is environmentally protective, be conducive to industrialized production.
Description
Technical field
Alpha, beta-unsaturated ketone compound is synthesized by the Bifunctionalized modification of acetophenone derivs α-H the present invention relates to a kind of
Under the conditions of nonmetal catalyzed, dimethyl sulfoxide is used as methylenation reagents and methylation examination simultaneously for method, in particular to one kind
Agent carries out the Bifunctionalized reaction of α-H of acetophenone derivs, directly reaction synthesis α, the method for beta-unsaturated ketone compound,
Belong to pharmaceutical intermediate synthesis technical field.
Background technique
α-reaction kinetic of ketone compounds has important meaning in organic synthesis, has become for many years
The focus of research.Especially α, beta-unsaturated ketone compound, due to containing double bond can be modified, being that pharmaceutical synthesis is a kind of in the process
Highly important organic intermediate.At present, it was recently reported that many different preparation α, the method for beta-unsaturated ketone compound, such as text
It offers (Eur.J.Org.Chem.2015,3044-3047) and discloses the chlorination using n,N-dimethylacetamide as methylenation reagents
Iron is catalyst, α, beta-unsaturated ketone compound (such as reaction 1) is generated under potassium persulfate oxidation agent effect, but this method needs
It uses transition metal salt and makees catalyst, and yield is relatively low, effect on environment is big, at high cost.For another example document
(Chem.Commun.2010,46,1715-1717) and document (Tetrahedron Lett.1978,19,2955-2958) are public
It has opened using metaformaldehyde as methylenation reagents, using trifluoroacetic acid secondary amine salt as catalyst, has obtained the α of higher yields,
Beta-unsaturated ketone compound (such as reaction 2 and 3).But these methods have to use paraformaldehyde raw material and special trifluoro
Acetic acid secondary amine salt catalyst, Safety and Environmental Protection is low, at high cost, complicated for operation, is unfavorable for being mass produced.
Reaction 1:
Reaction 2:
Reaction 3:
Currently, there is document (Tetrahedron.2012,68,1560-1565) report with dimethyl sulfoxide for methylation examination
Agent, copper salt catalyst effect under, the substituent methyl sulfidomethyl on heterocycle alkene, in addition have document (Org.Lett.2015,17,
6186-6189) report uses acetylene compound for raw material, using dimethyl sulfoxide as methylating reagent, with diphenyl phosphate azide
For cyclization reagent, the triazole class compounds containing methylthiomethyl are formed.The yield of both methods product is higher, but in reaction
Mantoquita is required as catalyst, higher cost, effect on environment is big.
Reaction 4:
Reaction 5:
Summary of the invention
For existing α, defect existing for the synthetic method of beta-unsaturated ketone compound, the purpose of the present invention is be
A kind of α-H progress using dimethyl sulfoxide while as methylenation reagents and methylating reagent, to acetophenone derivs is provided
Difunctional modification, high yield, high selectivity α, the method for beta-unsaturated ketone compound, this method is easy to operate, at
This is low, environmentally protective, is conducive to industrialized production.
In order to achieve the above technical purposes, the present invention provides one kind is closed by the Bifunctionalized modification of acetophenone derivs α-H
At α, the method for beta-unsaturated ketone compound, this method is under protective atmosphere, and dimethyl sulfoxide and 1 acetophenone of formula are derivative
Object, one pot reaction under the conditions of existing for the alkoxide and ammonium persulfate, 2 α of production, beta-unsaturated ketone compound；
Wherein,
R1And R2It is independently selected from alkyl, alkoxy, halogen, phenyl, nitro, cyano or hydrogen.
More preferably scheme, R1And R2It is independently selected from hydrogen, methoxyl group, methyl, ethyoxyl, isopropyl, fluorine, chlorine, nitro, benzene
Base or cyano.
Most preferred acetophenone derivs are a kind of in following structural formula:
Most preferred alpha, beta-unsaturated ketone compound has the following structure a kind of in formula:
Preferred scheme, the condition of the reaction are as follows: temperature is 110~130 DEG C, and the reaction time is 20~28h.
Preferred scheme, alkoxide include sodium methoxide.
In technical solution of the present invention, dimethyl sulfoxide is used as methylenation reagents and methylating reagent simultaneously, and also makees
For organic solvent.The dosage of dimethyl sulfoxide be it is excessive, this belong to it will be appreciated by those skilled in the art that scope.
In technical solution of the present invention, a molecule acetophenone derivs are reacted with two molecule dimethyl sulfoxides, a molecule two
α-H the methylenation of acetophenone derivs is formed double bond by methyl sulfoxide, and a molecule dimethyl sulfoxide is converted to methylthiomethyl
Remaining α-the H of substituted acetophenone derivative, three α-H realize functionalization on the methyl of final acetophenone derivs.
In technical solution of the present invention, the usual mole dosage of alkoxide and persulfate is the 2 of acetophenone derivs
Times or so.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
1) technical solution of the present invention carries out difunctional modification to the α methyl of acetophenone derivs for the first time, in acetophenone
The α position methyl of derivative introduces double bond and methylthiomethyl simultaneously, obtains a kind of organic centre with modifiable difunctionality
Body provides new raw material for organic synthesis and novel drugs synthesis.
2) technical solution of the present invention is led to for the first time using dimethyl sulfoxide simultaneously as methylenation reagents and methylating reagent
Crossing on the position α of acetophenone derivs while can modify double bond and methylthiomethyl in single step reaction, and yield is high, selectivity
It is good.
3) technical solution of the present invention is without transition metal or trifluoroacetic acid secondary amine salt as catalyst, safety collar
Protect, it is at low cost, overcome the prior art must using non-green environmental protection transition metal or safety in utilization it is poor, be difficult to obtain
The trifluoroacetic acid secondary amine salt obtained is as defect existing for catalyst.
4) technical solution of the present invention generates α, beta-unsaturated ketone compound, step letter by one kettle way single step reaction
Single, process is short, at low cost, is conducive to industrialized production.
Detailed description of the invention
[Fig. 1] is the nucleus magnetic hydrogen spectrum figure of alpha, beta-unsaturated ketone compound prepared by embodiment 1；
[Fig. 2] is the nuclear-magnetism carbon spectrogram of alpha, beta-unsaturated ketone compound prepared by embodiment 1.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits the protection model of the claims in the present invention
It encloses.
Various raw materials and chemical reagent etc. involved in following embodiment are commercial product.
1H NMR (400MHz), 13C NMR (100MHz), with CDCl3For solvent, using TMS as internal standard.
Multiplicity is defined as follows: s (unimodal)；D (doublet)；T (triplet)；Q (quartet) and m (multiplet)；Coupling
Constant(hertz).
Mass spectrum is obtained by the source mass spectrograph EI.
Following example 1~13 are carried out according to following formulas:
By acetophenone derivs (0.5mmol), sodium methoxide (1mmol), (NH4)2S2O8(1mmol) and dimethyl sulfoxide
(3mL) is added in reactor, is filled with nitrogen protection, is reacted for 24 hours at a temperature of 120 DEG C, after reaction, is distilled to recover excessive
Dimethyl sulfoxide, mixture obtain α, beta-unsaturated ketone compound by chromatography post separation.
Embodiment 1
Raw material: acetophenone；
Product:Yield 65%；
1H NMR(400MHz,CDCl3) δ 7.78 (d, J=7.5Hz, 2H), 7.56 (t, J=7.4Hz, 1H), 7.45 (t, J
=7.5Hz, 2H), 5.92 (s, 1H), 5.68 (s, 1H), 3.54 (s, 2H), 2.13 (s, 3H)
13C NMR(101MHz,CDCl3)δ197.0,143.7,137.5,132.5,129.5,128.3,126.0,35.3,
15.5.
Embodiment 2
Raw material: acetanisole；
Product:Yield 62%；
1H NMR(400MHz,CDCl3) δ 7.83 (d, J=7.7Hz, 2H), 6.94 (d, J=7.7Hz, 2H), 5.82 (s,
1H),5.60(s,1H),3.87(s,3H),3.54(s,2H),2.13(s,3H).
13C NMR(101MHz,CDCl3)δ195.7,163.3,143.9,132.0,130.0,123.9,113.6,55.5,
35.8,15.5.
Embodiment 3
Raw material: melilotal；
Product:Yield 69%；
1H NMR(400MHz,CDCl3) δ 7.70 (d, J=7.7Hz, 2H), 7.25 (d, J=8.1Hz, 2H), 5.87 (s,
1H),5.64(s,1H),3.53(s,2H),2.42(s,3H),2.12(s,3H).
13C NMR(101MHz,CDCl3)δ196.7,143.9,143.3,134.8,129.7,129.0,125.1,100.0,
35.5,21.6,15.5.
Embodiment 4
Raw material: to fluoro acetophenone；
Product:Yield 74%；
1H NMR(400MHz,CDCl3)δ7.86-7.79(m,2H),7.16-7.12(m,2H),5.90(s,1H),5.63
(s,1H),3.53(s,2H),2.13(s,3H).
13C NMR(101MHz,CDCl3) δ 195.5,165.4 (d, J=254.4Hz), 143.7,133.6 (d, J=
3.1Hz), 132.1 (d, J=9.2Hz), 125.3,115.5 (d, J=21.9Hz), 35.4,15.5.
Embodiment 5
Raw material: parachloroacetophenone；
Product:Yield 70%；
1H NMR(400MHz,CDCl3) δ 7.73 (d, J=7.9Hz, 2H), 7.43 (d, J=8.0Hz, 2H), 5.92 (s,
1H),5.64(s,1H),3.52(s,2H),2.12(s,3H).
13C NMR(101MHz,CDCl3)δ195.7,143.7,138.9,135.7,130.9,128.6,125.8,35.3,
15.6.
Embodiment 6
Raw material: p-nitroacetophenone；
Product:Yield 69%；
1H NMR(400MHz,CDCl3) δ 8.31 (d, J=8.0Hz, 2H), 7.89 (d, J=8.2Hz, 2H), 6.05 (s,
1H),5.69(s,1H),3.54(s,2H),2.15(s,3H).
13C NMR(101MHz,CDCl3)δ195.1,149.8,143.6,142.8,130.2,127.6,123.5,34.8,
15.6.
Embodiment 7
Raw material: methyl acetophenone；
Product:Yield 69%；
1H NMR(400MHz,CDCl3) δ 7.58 (s, 1H), 7.55 (d, J=7.3Hz, 1H), 7.39-7.3 (m, 2H),
5.91(s,1H),5.67(s,1H),3.53(s,2H),2.41(s,3H),2.13(s,3H).
13C NMR(101MHz,CDCl3)δ197.2,143.9,138.1,137.5,133.2,129.9,128.1,126.8,
125.8,35.3,21.3,15.5.
Embodiment 8
Raw material: m chloroacetophenone；
Product:Yield 69%；
1H NMR(400MHz,CDCl3) δ 7.73 (s, 1H), 7.63 (d, J=7.7Hz, 1H), 7.53 (d, J=7.9Hz,
1H), 7.40 (t, J=7.8Hz, 1H), 5.95 (s, 1H), 5.68 (s, 1H), 3.52 (s, 2H), 2.13 (s, 3H)
13C NMR(101MHz,CDCl3)δ195.4,143.5,139.1,134.5,132.4,129.6,129.4,127.5,
126.5,35.1,15.5.
Embodiment 9
Raw material: m-nitroacetophenone；
Product:Yield 69%；
1H NMR(400MHz,CDCl3) δ 8.58 (s, 1H), 8.42 (d, J=8.1Hz, 1H), 8.10 (d, J=7.6Hz,
1H), 7.68 (t, J=7.9Hz, 1H), 6.03 (s, 1H), 5.70 (s, 1H), 3.55 (s, 2H), 2.16 (s, 3H)
13C NMR(101MHz,CDCl3)δ194.5,148.1,143.4,138.9,134.9,129.6,126.9,126.8,
124.3,35.1,15.6.
Embodiment 10
Raw material: p-phenylacetophenone；
Product:Yield 70%；
1H NMR(400MHz,CDCl3) δ 7.87 (d, J=7.6Hz, 2H), 7.67 (d, J=7.7Hz, 2H), 7.63 (d, J
=7.9Hz, 2H), 7.47 (t, J=7.5Hz, 2H), 7.40 (t, J=7.3Hz, 1H), 5.93 (s, 1H), 5.72 (s, 1H),
3.57(s,2H),2.15(s,3H).
13C NMR(101MHz,CDCl3)δ196.6,145.3,143.9,139.9,136.1,130.2,129.0,128.2,
127.3,127.0,125.5,35.4,15.5.
Embodiment 11
Raw material: 4-Acetylbenzonitrile；
Product:Yield 69%；
1H NMR(400MHz,CDCl3) δ 7.83 (d, J=8.0Hz, 2H), 7.77 (d, J=8.0Hz, 2H), 6.01 (s,
1H),5.67(s,1H),3.53(s,2H),2.13(s,3H).
13C NMR(101MHz,CDCl3)δ195.3,143.5,141.1,132.2,129.7,127.3,117.9,115.7,
34.9,15.6.
Embodiment 12
Raw material: P-isopropyl acetophenone；
Product:Yield 69%；
1H NMR(400MHz,CDCl3) δ 7.74 (d, J=8.0Hz, 2H), 7.30 (d, J=8.0Hz, 2H), 5.87 (s,
1H), 5.66 (s, 1H), 3.53 (s, 2H), 2.97 (dt, J=13.8,6.9Hz, 1H), 2.12 (s, 3H), 1.28 (s, 3H),
1.27(s,3H).
13C NMR(101MHz,CDCl3)δ196.7,154.1,143.9,135.1,129.9,126.4,125.0,35.5,
34.2,23.7,15.5.
Embodiment 13
Raw material: 3,4- dimethoxy-acetophenone；
Product:Yield 70%；
1H NMR(400MHz,CDCl3) δ 7.48-7.43 (m, 2H), 6.89 (d, J=8.2Hz, 1H), 5.82 (s, 1H),
5.61(s,1H),3.95(s,3H),3.94(s,3H),3.54(s,2H),2.12(s,3H).
13C NMR(101MHz,CDCl3)δ195.7,153.2,149.0,143.8,130.0,124.7,123.6,111.6,
109.7,56.0,55.9,35.9,15.5.
Control experiment group 1~11
Acetophenone (0.5mmol), catalyst (1mmol), oxidant (1mmol) and dimethyl sulfoxide (3mL) are added to
In reactor, it is filled with nitrogen protection, is reacted at a certain temperature for 24 hours, after reaction, is distilled to recover excess dimethyl sulfoxide,
Mixture obtains α, beta-unsaturated ketone compound by chromatography post separation.
1 reaction condition of table and yield
| Experimental group | Catalyst | Oxidant | Solvent | Temperature (DEG C) | Yield (%) |
| 1 | CH3COONa | K2S2O8 | DMSO | 120 | trace |
| 2 | CH3COONa | (NH4)2S2O8 | DMSO | 120 | 56 |
| 3 | K2CO3 | (NH4)2S2O8 | DMSO | 120 | 30 |
| 4 | NaOH | (NH4)2S2O8 | DMSO | 120 | 10 |
| 5 | CH3ONa | (NH4)2S2O8 | DMSO | 120 | 65 |
| 6 | CH3ONa | Na2S2O8 | DMSO | 120 | trace |
| 7 | CH3ONa | KHSO5 | DMSO | 120 | trace |
| 8 | CH3ONa | H2O2 | DMSO | 120 | trace |
| 9 | CH3ONa | TBHP | DMSO | 120 | trace |
| 10 | CH3ONa | (NH4)2S2O8 | DMF | 120 | 0 |
| 11 | CH3ONa | (NH4)2S2O8 | DMSO | 110 | 60 |
As can be seen from Table 1: using propiophenone as raw material, being tried by methylenation reagents and methylation of dimethyl sulfoxide
Agent is reacted in ammonium persulfate and sodium methoxide or sodium acetate solution system, and reaction make good progress, and obtained target product yield reaches
To 56% or more (experimental group 1 and 2), when selecting sodium methoxide as catalyst, target product yield reaches 65%.
As can be seen that other inorganic bases (such as potassium carbonate and sodium hydroxide) replace carboxylate or alcohol from experimental group 2~5
Salt, although can be reacted, product yield is lower, no industrial production value.
The selection of oxidant, preferably ammonium persulfate, and use potassium peroxydisulfate, sodium peroxydisulfate, organic peroxide, dioxygen
Water etc. is all hardly obtained product (experimental group 6~9).
If when using DMF as solvent, target product (experimental group 10) is unable to get under experiment condition of the invention.
In order to further verify technical solution of the present invention, the present invention has made following reality by the experiment condition of check experiment group
It tests:
Claims (4)
1. synthesizing α, the method for beta-unsaturated ketone compound by the Bifunctionalized modification of acetophenone derivs α-H, it is characterised in that:
Under protective atmosphere, 1 acetophenone derivs of dimethyl sulfoxide and formula, under the conditions of existing for the alkoxide and ammonium persulfate one pot it is anti-
It answers, α shown in production 2, beta-unsaturated ketone compound；
Wherein,
R1And R2It is independently selected from alkyl, alkoxy, halogen, phenyl, nitro, cyano or hydrogen.
2. according to claim 1 synthesize alpha, beta-unsaturated ketone chemical combination by the Bifunctionalized modification of acetophenone derivs α-H
The method of object, it is characterised in that: R1And R2It is independently selected from hydrogen, methoxyl group, methyl, ethyoxyl, isopropyl, fluorine, chlorine, nitro, phenyl
Or cyano.
3. according to claim 1 or 2 synthesize alpha, beta-unsaturated ketone by the Bifunctionalized modification of acetophenone derivs α-H
The method for closing object, it is characterised in that: the condition of the reaction are as follows: temperature is 110~130 DEG C, and the reaction time is 20~28h.
4. according to claim 1 synthesize alpha, beta-unsaturated ketone chemical combination by the Bifunctionalized modification of acetophenone derivs α-H
The method of object, it is characterised in that: the alkoxide includes sodium methoxide.
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