CN109020848A - (E)-alkenyl sulfone compound synthetic method - Google Patents
(E)-alkenyl sulfone compound synthetic method Download PDFInfo
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- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
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Abstract
The invention discloses (EThe synthetic method of)-alkenyl sulfone compound: using acetonitrile as solvent, in SbCl3Under catalysis, 30%H2O21,2- alkylene oxides compound (IV) is aoxidized into situ generate simultaneouslyβKI is aoxidized generation I in situ by peroxide alcohol compound (V)2.In the presence of Cu (II) salt, I2With reacting for compound (V) catalysis cinnamic acid compound (II) and sulfonyl hydrazines compound (III), synthesize through decarboxylation denitrogenation (E)-alkenyl sulfone compound (I).The invention has the beneficial effects that raw material is easy to get, peroxidic reagentsβPeroxide alcohol compound and iodine generate in situ, and safety economy is Ke Xunhuanliyong containing iodine compound.
Description
Technical field
The present invention relates to organic chemical synthesis fields, specifically (EThe synthetic method of)-alkenyl sulfone compound.
Background technique
(E)-alkenyl sulfone compound has many good bioactivity, is commonly used for the potent inhibitor of enzyme process, example
Such as agent of VCAM-1 expression inhibiting, cystatin, HIV-1 integrase inhibitor.In addition, (E)-alkenyl sulfone
Object is closed as a kind of important organic structure building block, is also had a wide range of applications in Synthetic Organic Chemistry, such as alkenyl sulfone class
Compound can be used as the receptor of Michael addition reaction, also can be used as the important source material of D-A reaction.Li group reports with CuI
Or Cu/Fe collaboration di-tert-butyl peroxide (DTBP) is that catalyst, aromatic alkyne or fragrant alkynyl acid and sulfohydrazide are anti-at 100 DEG C
Should prepare (EThe method of)-alkenyl sulfone compound, yield are medium (J. Org. Chem. 2015,4697).Singh group report
Road is using DBU as alkali, in 40mol%I2In the presence of tert-butyl hydroperoxide (TBHP), cinnamic acid compound and sulfohydrazide exist
Room temperature reaction prepare (EThe method of)-alkenyl sulfone compound, yield are medium above (Org. Lett. 2015,2652).This
The peroxide that a little methods have used operational hazards is raw material, is not suitable for large-scale production.
Summary of the invention
The object of the present invention is to provide (EThe synthetic method of)-alkenyl sulfone compound, which is characterized in that the method is such as
Under: using acetonitrile as solvent, in SbCl3Under catalysis, 30%H2O21,2- alkylene oxides compound (IV) is aoxidized into situ generate simultaneouslyβKI is aoxidized generation I in situ by peroxide alcohol compound (V)2.Again in the presence of Cu (II) salt, I2Meat is catalyzed with compound (V)
Osmanthus acid compounds (II) are reacted with sulfonyl hydrazines compound (III's), through decarboxylation denitrogenation synthesis (E)-alkenyl sulfone compound
(I).Reaction equation is shown below:
In formula, R1It is independently selected from H, CH3, CN, OR, CF3, alkyl, aryl is one or several in fragrance in halogen group
Ortho position, contraposition or the meta position of ring replace；R2It is independently selected from alkyl, naphthenic base, phenyl, various substituted phenyl, aryl is various to take
The aryl in generation；R3It is independently selected from alkyl, replaces alkyl, naphthenic base, phenyl, various substituted phenyl, aryl, various substituted virtues
Base.
Of the invention (EThe synthetic method of)-alkenyl sulfone compound, which is characterized in that Cu (II) salt is CuSO4,
Cu(OAc)2,CuCl2,CuBr2, Cu(NO3)2,Cu(CF3SO2)2,Cu(CF3CO2)2。
Of the invention (EThe synthetic method of)-alkenyl sulfone compound, which is characterized in that the Formula II, formula III, KI,
H2O2, formula IV, Cu (II) salt and SbCl3The ratio between amount of substance be 1:1:0.4-0.5:6-7:2.5-3:0.5-0.6:0.1.
Of the invention (EThe synthetic method of)-alkenyl sulfone compound, which is characterized in that the peroxidic reagents areβIt crosses
Oxygen alcohol compound (V), by 30%H2O2In SbCl3In the presence of aoxidize 1,2- alkylene oxides compound (IV) in-situ preparation, it is described
I2By 30%H2O2Aoxidize KI in-situ preparation, safety economy.
Of the invention (EThe synthetic method of)-alkenyl sulfone compound, which is characterized in that the Formula II and formula III preparation formula
The reaction of I, by generated in-situβPeroxide alcohol compound (V) and I2Catalysis is completed through decarboxylation denitrogenation.
Of the present invention (EThe synthetic method of)-alkenyl sulfone compound, which is characterized in that it is described containing iodine compound can
It recycles.
Specific embodiment
Embodiment below is that the present invention will be described in detail, is not intended to limit the present invention.
Embodiment 1
In the reactor, 148mg (1mmol) cinnamic acid, 206mg (1.2mmol) benzene sulfonyl hydrazide, 66.4mg is added
(0.4mmol) KI, 22.6mg (0.1mmol) SbCl3, 35.4mg (0.6mmol) CuSO4, 300mg (2.5mmol) Oxybenzene
Then the H of 689mg (6mmol) 30% is added in ethylene and 7mLMeCN, stirring2O2, 1h is reacted at room temperature, 15mL saturation is added
NaHSO3Solution stirs 20min, removes MeCN under reduced pressure, add 10mL ethyl acetate and 10mLH2O, layering, ethyl acetate extraction
It taking, dries, filters, filtrate concentration, silica gel column chromatography purifies (petrol ether/ethyl acetate 20:1), obtain (E)-(benzenesulfonyl) second
Alkenyl benzene, yield 63.2%.mp 69-71℃；1H NMR (400MHz, CDCl3) δ 7.95(d, J=15.2Hz, 1H),
7.69(d, J=15.2Hz, 1H), 7.62(t, J=7.2Hz, 1H), 7.55(t, J=7.6Hz, 2H), 7.50-7.47
(m, 2H), 7.42-7.37 (m, 3H), 6.87(d, J=15.2Hz, 1H)。
Embodiment 2
In the reactor, addition 178mg (1mmol) 4- methoxy cinnamic acid, 242mg (1.2mmol) 4- methoxybenzene sulfohydrazide,
66.4mg (0.4mmol) KI, 22.6mg (0.1mmol) SbCl3, 73.2mg (0.55mmol) CuCl2, 216mg (3mmol) 1,2-
Then the H of 804mg (7mmol) 30% is added in epoxy butane and 7mLMeCN, stirring2O2, 1h is reacted at room temperature, 15mL saturation is added
NaHSO3Solution stirs 20min, removes MeCN under reduced pressure, add 10mL ethyl acetate and 10mLH2O, layering, ethyl acetate extraction
It taking, dries, filters, filtrate concentration, silica gel column chromatography purifies (petrol ether/ethyl acetate 20:1), obtain (E) -1- methoxyl group -4-
(2-((4- methoxyphenyl) sulfonyl) alkenyl) benzene, yield 74.7%.1H NMR (400MHz, CDCl3) δ 7.88(d, J=
8.7Hz, 2H), 7.60(d, J=15.3Hz, 1H), 7.42(t, J=8.7Hz, 2H), 7.01(d, J=9.0Hz,
2H), 6.90(d, J=8.7Hz, 2H), 6.72(d, J=15.6Hz,1H), 3.86(s, 3H), 3.83(s, 3H)。
Embodiment 3
In the reactor, 162mg (1mmol) 4- methyl cinnamic acid, 233mg (1.2mmol) n- octyl sulfohydrazide, 66.4mg is added
(0.4mmol) KI, 22.6mg (0.1mmol) SbCl3, 108.6mg (0.6mmol) Cu (OAc)2, 174mg (3mmol) 1,2- ring
Then the H of 804mg (7mmol) 30% is added in Ethylene Oxide and 7mLMeCN, stirring2O2, 1h is reacted at room temperature, 15mL saturation is added
NaHSO3Solution stirs 20min, removes MeCN under reduced pressure, add 10mL ethyl acetate and 10mLH2O, layering, ethyl acetate extraction
It taking, dries, filters, filtrate concentration, silica gel column chromatography purifies (petrol ether/ethyl acetate 20:1), obtain (E) -1- methyl -4-(2-
(octyl sulfonyl) alkenyl) benzene, yield 73.9%.1H NMR (400MHz, CDCl3) δ 7.60(d, J=15.0Hz, 1H),
7.43(d, J=7.8Hz, 2H), 7.24(d, J=7.8Hz, 2H), 6.79(d, J=15.6Hz, 1H), 3.06-2.91
(m, 2H), 2.39(s, 3H), 1.84-1.75(m, 2H), 1.27-1.22(m, 8H), 8.07(t, J=6.9Hz,
3H)。
Embodiment 4
In the reactor, 182mg (1mmol) 3- chloro-cinnamic acid, 223mg (1.2mmol) 4- tolylsulfonyl- hydrazine, 66.4mg is added
(0.4mmol) KI, 22.6mg (0.1mmol) SbCl3, 93.5mg (0.5mmol) Cu (NO3)2, 385mg (2.5mmol) 4- chlorine oxygen
Change styrene and 7mLMeCN, then the H of 689mg (6mmol) 30% is added in stirring2O2, 1h is reacted at room temperature, 15mL saturation is added
NaHSO3Solution stirs 20min, removes MeCN under reduced pressure, add 10mL ethyl acetate and 10mLH2O, layering, ethyl acetate extraction
It taking, dries, filters, filtrate concentration, silica gel column chromatography purifies (petrol ether/ethyl acetate 20:1), obtain (E) chloro- 3-(2-(pairs of -1-
Tosyl) alkenyl) benzene, yield 67.4%.1H NMR (400MHz, CDCl3) δ 7.83(d, J=8.1Hz, 2H),
7.60(d, J=15.0Hz, 1H), 7.43-7.34(m,6H), 6.89(d, J=15.3Hz, 1H), 2.44(s, 3H)。
Embodiment 5
In the reactor, addition 162mg (1mmol) 4- methyl cinnamic acid, 209mg (1.1mmol) 4- fluorophenyl sulfohydrazide,
66.4mg (0.4mmol) KI, 22.6mg (0.1mmol) SbCl3, 159mg (0.55mmol) Cu (CF3CO2)2, 245mg
Then the H of 689mg (6mmol) 30% is added in (2.5mmol) 1,2- epoxy and hexamethylene and 7mLMeCN, stirring2O2, room temperature is anti-
1h is answered, 15mL is added and is saturated NaHSO3Solution, stir 20min, remove MeCN under reduced pressure, add 10mL ethyl acetate with
10mLH2O, layering, ethyl acetate extraction dry, filter, and filtrate concentration, silica gel column chromatography purifies (petrol ether/ethyl acetate
20:1), obtain (E) the fluoro- 4-((4- tolyl of -1-) sulfonyl) alkenyl) benzene, yield 62.6%.1H NMR (400MHz, CDCl3)
δ 7.98(m,2H),7.65(d, J=15.2Hz, 1H), 7.38(d, J=8.0Hz, 2H),7.24-7.19(m,4H),
6.79(d, J=15.2Hz, 1H), 2.37(s, 3H)。
Claims (6)
1.(EThe synthetic method of)-alkenyl sulfone compound, which comprises the steps of:
Using acetonitrile as solvent, in SbCl3Under catalysis, 30%H2O21,2- alkylene oxides compound (IV) is aoxidized into situ generate simultaneouslyβKI is aoxidized generation I in situ by peroxide alcohol compound (V)2；
Again in the presence of Cu (II) salt, I2With compound (V) catalysis cinnamic acid compound (II) and sulfonyl hydrazines compound
(III) reaction, through decarboxylation denitrogenation synthesis (E)-alkenyl sulfone compound (I)；
Reaction equation is shown below:
In formula, R1It is independently selected from H, CH3, CN, OR, CF3, alkyl, aryl is one or several in fragrance in halogen group
Ortho position, contraposition or the meta position of ring replace；R2It is independently selected from alkyl, naphthenic base, phenyl, various substituted phenyl, aryl is various to take
The aryl in generation；R3It is independently selected from alkyl, replaces alkyl, naphthenic base, phenyl, various substituted phenyl, aryl, various substituted virtues
Base.
2. according to claim 1 (EThe synthetic method of)-alkenyl sulfone compound, which is characterized in that Cu (II) salt
For CuSO4,Cu(OAc)2,CuCl2,CuBr2, Cu(NO3)2,Cu(CF3SO2)2,Cu(CF3CO2)2。
3. according to claim 1 (EThe synthetic method of)-alkenyl sulfone compound, which is characterized in that the Formula II, formula
III, KI, H2O2, formula IV, Cu (II) salt and SbCl3The ratio between amount of substance be 1:1:0.4-0.5:6-7:2.5-3:0.5:0.1.
4. according to claim 1 (EThe synthetic method of)-alkenyl sulfone compound, which is characterized in that the peroxidating examination
Agent isβPeroxide alcohol compound (V), by 30%H2O2In SbCl3In the presence of oxidation 1,2- alkylene oxides compound (IV) it is raw in situ
At the I2By 30%H2O2Aoxidize KI in-situ preparation, safety economy.
5. according to claim 1 (EThe synthetic method of)-alkenyl sulfone compound, which is characterized in that the Formula II and formula
The reaction of III preparation formula I, by generated in-situ (V) and I2Catalysis is completed through decarboxylation denitrogenation.
6. according to claim 1 (EThe synthetic method of)-alkenyl sulfone compound, which is characterized in that described to be closed containing iodate
Object can recycle.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961664A (en) * | 2015-07-21 | 2015-10-07 | 安徽理工大学 | Method for synthesizing E-alkenyl sulfone compound |
| CN107162943A (en) * | 2017-06-05 | 2017-09-15 | 同济大学 | A kind of (E) alkenyl sulfone compound and preparation method thereof |
| CN107417582A (en) * | 2017-05-25 | 2017-12-01 | 曲阜师范大学 | A kind of preparation method of E alkenyl sulfone compounds |
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2018
- 2018-09-28 CN CN201811141166.XA patent/CN109020848B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961664A (en) * | 2015-07-21 | 2015-10-07 | 安徽理工大学 | Method for synthesizing E-alkenyl sulfone compound |
| CN107417582A (en) * | 2017-05-25 | 2017-12-01 | 曲阜师范大学 | A kind of preparation method of E alkenyl sulfone compounds |
| CN107162943A (en) * | 2017-06-05 | 2017-09-15 | 同济大学 | A kind of (E) alkenyl sulfone compound and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| RAHUL SINGH 等: "A Direct Metal-Free Decarboxylative Sulfono Functionalization (DSF) of Cinnamic Acids to α,β-Unsaturated Phenyl Sulfones", 《ORGANIC LETTERS》 * |
| YU ZHAO 等: "Electrochemical Decarboxylative Sulfonylation of Cinnamic Acids with Aromatic Sulfonylhydrazides to Vinyl Sulfones", 《J.ORG.CHEM.》 * |
| 胡飞 等: "碘促进的砜基化反应研究进展", 《有机化学》 * |
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