CN104803895B - A kind of method for preparing sulfinic acid ester as raw material with benzenesulfonylmethyl isonitrile - Google Patents
A kind of method for preparing sulfinic acid ester as raw material with benzenesulfonylmethyl isonitrile Download PDFInfo
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- CN104803895B CN104803895B CN201510163821.1A CN201510163821A CN104803895B CN 104803895 B CN104803895 B CN 104803895B CN 201510163821 A CN201510163821 A CN 201510163821A CN 104803895 B CN104803895 B CN 104803895B
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- acid ester
- sulfinic acid
- benzenesulfonylmethyl
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Abstract
The present invention relates to a kind of method for preparing sulfinic acid ester as raw material with benzenesulfonylmethyl isonitrile, preliminary biological activity test such compound has potential anti-leukocythemia liveness.Prepared sulfinic acid ester type compound structural formula such as figure, wherein Ar1And Ar2It is aryl etc.；R1It is hydrogen atom, alkyl etc..Preparation method：Benzalcohol derivatives, the different nitrile compounds of benzenesulfonylmethyl, catalyst and additive are stirred 1 day under room temperature condition in nitromethane solvent.After reaction terminates, water and ethyl acetate are added to reaction system.By extraction, solvent seasoning, concentration, column chromatography purification obtains sulfinic acid ester type compound, and yield is 42~71%.Wherein catalyst is bismuth tribromide etc.；Additive is acetic acid etc..
Description
Technical field
The present invention relates to a kind of method for preparing sulfinic acid ester as raw material with benzenesulfonylmethyl isonitrile.
Background technology
Sulfinic acid ester type compound is crucial organic synthesis intermediate, is had emphatically in synthesis chemistry and medicinal chemistry art
Want purposes（J. Org. Chem. 1987, 52, 2598; Tetrahedron Lett. 1991, 47, 9167;Tetrahedron1999, 55, 2311; Mol. Cryst. Liq. Cryst. 2001, 356, 371;Tetrahedron Lett. 2006, 47, 2717; Chem. Eur. J. 2011, 17, 10417; Tetrahedron Lett. 2012, 53, 1045; Angew. Chem. Int. Ed.2014, 53, 9851; Angew. Chem. Int. Ed.2014, 53, 4404; Nat. Protoc. 2013, 8, 1042; Org. Biomol. Chem. 2014, 12,
3499; RSC Adv.2014, 4, 4286; Chem. Commun. 2014, 50, 11533）.For example, sulfinic acid esters
Compound is a kind of important Medicinal molecular fragment, and its representative compound propargite is that favourable incoming road company of the U.S. develops for 1964
A kind of low toxicity, the organosulfur acaricide without absorbability, low-residual（Can. J. Plant Sci. 1966, 46, 521; J. Agr. Food Chem. 1971, 19, 894; Pesticides1981, 15, 22）.The synthesis of sulfinic acid ester type compound
Mainly there are three kinds of methods：1) alcohol compound is dehydrated generation sulfinic acid ester with sulfinic acid class compound under dehydrating agent DCC effects
Class compound（Tetrahedron Lett. 2006, 47, 2717）；2) alcohol compound and sulfonic acid chloride class compound are in alkali
Property/reductive condition under generate sulfinic acid ester type compound（J. Org. Chem. 1987, 52, 2598）；3) alcohols chemical combination
Thing generates sulfinic acid ester type compound in the basic conditions with sulfenyl nitrile compounds（Tetrahedron Lett. 1991,47, 9167）.The present invention with the different nitrile compounds of benzenesulfonylmethyl and alcohol compound as raw material, under mildly acidic conditions
Prepare sulfinic acid ester type compound.
The content of the invention
Present invention aim at a kind of method for preparing sulfinic acid ester as raw material with benzenesulfonylmethyl isonitrile of offer.
To achieve the above object, sulfinic acid ester type compound structure such as Fig. 1 that the present invention is provided：
Fig. 1 is the general structure figure of target compound sulfinic acid ester type compound
Wherein：Ar1And Ar2It is aryl etc.；R1It is hydrogen atom, alkyl etc..
The preparation method that the present invention is provided, has main steps that：Benzalcohol derivatives, the different nitrile compounds of benzenesulfonylmethyl,
Catalyst and additive are stirred 1 day under room temperature condition in nitromethane solvent.Reaction terminate after, to reaction system add water and
Ethyl acetate.By extraction, solvent seasoning, concentration, column chromatography purification obtains sulfinic acid ester type compound, yield 42~
71%.Gained compound is through nmr spectrum（1H-NMR and13C-NMR）With infrared spectrum confirm, high-resolution determine, structure without
By mistake.
The present invention can be direct using substituted or unsubstituted benzalcohol derivatives and the different nitrile compounds of benzenesulfonylmethyl
Commercially.
The catalyst that the present invention is used is bismuth tribromide etc., and catalyst amount is 0.1 equivalent；
The additive that the present invention is used is acetic acid etc., and consumption is 1 equivalent；
The organic solvent that the present invention is used is nitromethane etc.；
Eluant, eluent used by column chromatography of the invention is petroleum ether or alkane etc..
Brief description of the drawings
Fig. 1 is the general structure figure of target compound sulfinic acid ester type compound；Fig. 2 is to be with Benzenesulfonylmethyl isonitrile
Raw material prepares the reaction expression figure of sulfinic acid ester type compound.
Specific embodiment
Its course of reaction such as Fig. 2：
Fig. 2 is the reaction expression figure for preparing sulfinic acid ester type compound as raw material with Benzenesulfonylmethyl isonitrile
Wherein：Ar1And Ar2It is aryl etc.；R1It is hydrogen atom, alkyl etc..
Specific preparation method citing：0.2 mM of 3,5- difluoro-benzyl alcohol, 0.3 mM different to Methyl benzenesulfonyl methyl
Nitrile, 0.02 mM of bismuth tribromide（Catalyst）, 0.2 mM of acetic acid（Additive）Mixed with 1 milliliter of nitromethane,
Reaction 24 hours is sufficiently stirred at ambient temperature.Reaction terminates backward reaction system and adds 5 milliliters of water and 10 milliliters of acetic acid second
Ester, concussion, organic phase and inorganic phase separation.Water is mutually extracted with ethyl acetate three times（3 × 10 mL）.Merge organic phase, it is anhydrous
Sodium sulphate is dried, concentration, column chromatography purification obtains 3,5- difluorobenzyls to 40 milligrams of toluenesulfinic acid ester, and yield is 70%.Nothing
Color liquid；Proton nmr spectra1H NMR (400 MHz, CDCl3) delta 7.63 (d, J = 8.0 Hz, 2H),
7.35 (d, J = 8.0 Hz, 2H), 6.78–6.70 (m, 3H), 4.95 (d, J = 12.3 Hz, 1H), 4.49
(d, J= 12.3 Hz, 1H), 2.44 (s, 3H);Carbon-13 nmr spectra13C NMR (100 MHz, CDCl3) delta
162.9 (dd, J C-F = 330.2, 16.7 Hz, 1C), 143.3, 141.2, 139.6 (t, J C-F = 12.2 Hz,
1C), 129.8, 125.3, 110.8 (dd, J C-F = 23.0, 10.8 Hz, 1C), 103.6 (t, J C-F = 33.4
Hz, 1C), 63.6, 21.5;Infrared spectrum FTIR (film): 1629, 1599, 1464, 1368, 1323, 1137,
1119, 946, 854, 813, 759, 673 cm-1High resolution mass spectrum HRMS (ESI) m/z: Calcd for
C14H12F2NaO2S[M+Na]+: 305.0418. Found: 305.0416.
Claims (1)
1. a kind of preparation method of sulfinic acid ester type compound shown in formula I, has main steps that：
A) 1 equivalent benzalcohol derivatives and 1.5 different nitrile compounds of equivalent benzenesulfonylmethyl are added to reaction tube
In, 0.1 the catalyst bismuth tribromide and 1 equivalent additive acetic acid of equivalent are added, it is subsequently adding a little solvent nitro first
Alkane, reacts 1 day under ambient temperature；
I
Wherein Ar1And Ar2It is aryl；R is hydrogen atom, alkyl；
B) after reaction terminates, water and ethyl acetate, ethyl acetate extraction, anhydrous sodium sulfate drying, mistake are added to reaction system
Filter, concentration；
C) column chromatography for separation, eluant, eluent is petroleum ether or alkane, obtains sulfinic acid ester type compound.
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Non-Patent Citations (3)
| Title |
|---|
| An Efficient Method For The Synthesis Of Substituted TosMIC Precursors;Joseph Sisko et al.;《Tetrahedron Letters》;19961231;第37卷(第45期);第8113—8116页 * |
| Direct sulfonylation of Baylis-Hillman alcohol and diarylmethanols with TosMIC in ionic liquid-[Hmim]HSO4: an unexpected reaction;Garima et al.;《Tetrahedron Letters》;20110702;第52卷;第4622—4626页 * |
| InCl3 catalyzed C–C coupling of aryl alcohols and TosMIC;Palakodety Radha Krishna et al.;《Tetrahedron Letters》;20070929;第48卷;第9048—9050页 * |
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Effective date of registration: 20200827 Address after: Room 431, block B, 205 Zhuhai Road, Wendeng Economic Development Zone, Weihai City, Shandong Province Patentee after: Weihai marine biological medicine industry technology Research Institute Co., Ltd Address before: High culture in Weihai City West Shandong province 264209 No. 2 Patentee before: HARBIN INSTITUTE OF TECHNOLOGY (WEIHAI) |
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