CN104803895A - Method for preparing sulfinic acid ester from phenylsulfonyl methyl isocyanide - Google Patents
Method for preparing sulfinic acid ester from phenylsulfonyl methyl isocyanide Download PDFInfo
- Publication number
- CN104803895A CN104803895A CN201510163821.1A CN201510163821A CN104803895A CN 104803895 A CN104803895 A CN 104803895A CN 201510163821 A CN201510163821 A CN 201510163821A CN 104803895 A CN104803895 A CN 104803895A
- Authority
- CN
- China
- Prior art keywords
- acid ester
- sulfinic acid
- equivalent
- compounds
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing sulfinic acid ester from phenylsulfonyl methyl isocyanide. According to a preliminary biological activity test, the sulfinic acid ester has potential anti-leukemia activity. The structural formula of the prepared sulfinic acid ester compound is as shown in the Specification, wherein Ar1 and Ar2 refer to aryl groups and the like; R1 refers to hydrogen atoms, alkyl groups and the like. The preparation method comprises the following steps: benzyl alcohol compounds, phenylsulfonyl methyl isocyanide compounds, catalysts and additives are stirred for one day in nitromethane solvent at the room temperature. After the reaction, water and ethyl acetate are added in a reaction system; extraction, solvent drying, concentration and column chromatography purification are performed to obtain the sulfinic acid ester compounds; the productive rate is 42-71%; the catalysts comprise bismuth tribromide and the like; the additives comprise acetic acid and the like.
Description
Technical field
The present invention relates to a kind of with benzenesulfonylmethyl isonitrile for the method for-sulfinic acid ester prepared by raw material.
Background technology
-sulfinic acid ester compound is crucial organic synthesis intermediate, synthetic chemistry and medicinal chemistry art have important use (
j. Org. Chem.
1987,
52, 2598;
tetrahedron Lett.
1991,
47, 9167;
tetrahedron 1999,
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).Such as,-sulfinic acid ester compound is a kind of important Medicinal molecular fragment, its representative compound propargite be favourable incoming road company of the U.S. 1964 exploitation a kind of low toxicity, without interior absorption, low residue organosulfur acaricide (
can. J. Plant Sci.
1966,
46, 521;
j. Agr. Food Chem.
1971,
19, 894;
pesticides 1981,
15, 22).The synthesis of-sulfinic acid ester compound mainly contains three kinds of methods: 1) alcohol compound and-sulfinic acid compounds dewater under dewatering agent DCC effect generate-sulfinic acid ester compound (
tetrahedron Lett.
2006,
47, 2717); 2) alcohol compound and SULPHURYL CHLORIDE compounds generate under alkalescence/reductive condition-sulfinic acid ester compound (
j. Org. Chem.
1987,
52, 2598); 3) alcohol compound and sulfinyl nitrile compounds generate in the basic conditions-sulfinic acid ester compound (
tetrahedron Lett.
1991,
47, 9167).The present invention for raw material, prepares-sulfinic acid ester compound with benzenesulfonylmethyl isonitrile compounds and alcohol compound under mildly acidic conditions.
Summary of the invention
The object of the invention be to provide a kind of with benzenesulfonylmethyl isonitrile for the method for-sulfinic acid ester prepared by raw material.
For achieving the above object,-sulfinic acid ester compound structure provided by the invention is as Fig. 1:
Fig. 1 is the general structure figure of target compound-sulfinic acid ester compound
Wherein: Ar
1and Ar
2for aryl etc.; R
1for hydrogen atom, alkyl etc.
Preparation method provided by the invention, key step is: benzalcohol derivatives, benzenesulfonylmethyl isonitrile compounds, and catalyzer and additive stir 1 day under room temperature condition in Nitromethane 99Min. solvent.After reaction terminates, add water and ethyl acetate to reaction system.By extraction, solvent seasoning, concentrated, column chromatography is purified, and obtain-sulfinic acid ester compound, productive rate is 42 ~ 71%.Gained compound through nmr spectrum (
1h-NMR and
13c-NMR) and infrared spectra confirm, high resolution is determined, structure is errorless.
The present invention adopts substituted or unsubstituted benzalcohol derivatives and benzenesulfonylmethyl isonitrile compounds can directly commercially.
The catalyzer that the present invention adopts is bismuth tribromide etc., and catalyst levels is 0.1 equivalent;
The additive that the present invention adopts is acetic acid etc., and consumption is 1 equivalent;
The organic solvent that the present invention adopts is Nitromethane 99Min. etc.;
Column chromatography of the present invention eluent used is sherwood oil or alkane etc.
Accompanying drawing explanation
Fig. 1 is the general structure figure of target compound-sulfinic acid ester compound; Fig. 2 is for the reaction expression figure of-sulfinic acid ester compound prepared by raw material with Benzenesulfonylmethyl isonitrile.
Embodiment
Its reaction process is as Fig. 2:
Fig. 2 is for the reaction expression figure of-sulfinic acid ester compound prepared by raw material with Benzenesulfonylmethyl isonitrile
Wherein: Ar
1and Ar
2for aryl etc.; R
1for hydrogen atom, alkyl etc.
Concrete preparation method's citing: 0.2 mmole 3,5-difluoro-benzyl alcohol, 0.3 mmole is to Methyl benzenesulfonyl methyl isocyanide, 0.02 mmole bismuth tribromide (catalyzer), 0.2 mmole acetic acid (additive) and 1 milliliter of Nitromethane 99Min. mix, at ambient temperature abundant stirring reaction 24 hours.Reaction terminates backward reaction system and adds 5 ml waters and 10 milliliters of ethyl acetate, and concussion, organic phase is separated with inorganic phase.Aqueous phase is extracted with ethyl acetate three times (3 × 10 mL).Merge organic phase, anhydrous sodium sulfate drying, concentrated, column chromatography is purified, and obtain 3,5-difluorobenzyl to toluenesulfinic acid ester 40 milligrams, yield is 70%.Colourless liquid; Proton nmr spectra
1h NMR (400 MHz, CDCl
3) 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 spectra
13c NMR (100 MHz, CDCl
3) 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 spectra FTIR (film): 1629,1599,1464,1368,1323,1137,1119,946,854,813,759,673 cm
-1. high resolution mass spectrum HRMS (ESI) m/z:Calcd for C
14h
12f
2naO
2s [M+Na]
+: 305.0418. Found:305.0416.
Claims (2)
1. prepare the method for compound claims, key step is:
A) 1 equivalent benzalcohol derivatives and 1.5 equivalent benzenesulfonylmethyl isonitrile compounds are joined in reaction tubes, add catalyzer (as bismuth tribromide) and 1 equivalent additive (as acetic acid) of 0.1 equivalent again, then add a little solvent (as Nitromethane 99Min.), react 1 day under ambient temperature;
B) reaction terminates backward, and reaction system adds water and ethyl acetate, extraction into ethyl acetate, anhydrous sodium sulfate drying, filters, concentrated;
C) column chromatography for separation, eluent is sherwood oil or alkane etc., obtains-sulfinic acid ester compound.
2. the catalyzer that the present invention adopts usually is bismuth tribromide, and catalyst levels is 0.1 equivalent; The additive of usual employing is acetic acid, and consumption is 1 equivalent; The organic solvent of usual employing is Nitromethane 99Min..
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510163821.1A CN104803895B (en) | 2015-04-09 | 2015-04-09 | A kind of method for preparing sulfinic acid ester as raw material with benzenesulfonylmethyl isonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510163821.1A CN104803895B (en) | 2015-04-09 | 2015-04-09 | A kind of method for preparing sulfinic acid ester as raw material with benzenesulfonylmethyl isonitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104803895A true CN104803895A (en) | 2015-07-29 |
| CN104803895B CN104803895B (en) | 2017-06-13 |
Family
ID=53689138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510163821.1A Active CN104803895B (en) | 2015-04-09 | 2015-04-09 | A kind of method for preparing sulfinic acid ester as raw material with benzenesulfonylmethyl isonitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104803895B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286542A (en) * | 2022-07-27 | 2022-11-04 | 浙江工业大学 | Preparation method of sulfinate compound |
-
2015
- 2015-04-09 CN CN201510163821.1A patent/CN104803895B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| GARIMA ET AL.: "Direct sulfonylation of Baylis-Hillman alcohol and diarylmethanols with TosMIC in ionic liquid-[Hmim]HSO4: an unexpected reaction", 《TETRAHEDRON LETTERS》 * |
| JOSEPH SISKO ET AL.: "An Efficient Method For The Synthesis Of Substituted TosMIC Precursors", 《TETRAHEDRON LETTERS》 * |
| PALAKODETY RADHA KRISHNA ET AL.: "InCl3 catalyzed C–C coupling of aryl alcohols and TosMIC", 《TETRAHEDRON LETTERS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286542A (en) * | 2022-07-27 | 2022-11-04 | 浙江工业大学 | Preparation method of sulfinate compound |
| CN115286542B (en) * | 2022-07-27 | 2023-08-15 | 浙江工业大学 | Preparation method of sulfinate compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104803895B (en) | 2017-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104356109B (en) | A kind of preparation method of 2-((4R, 6S)-6-bromomethyl-2,2-dimethyl-1,3-dioxane-4-base) acetic acid esters | |
| CN103694204B (en) | 1,2,4-trisubstituent furan compound and preparation method thereof | |
| CN108409602B (en) | Method for preparing α -aryl nitrile compound | |
| CN105906537A (en) | One-pot synthesis method of (Z)-type sulfonyl olefine acid ester compound | |
| CN104803895A (en) | Method for preparing sulfinic acid ester from phenylsulfonyl methyl isocyanide | |
| CN103087033B (en) | Synthesis method of poly-substituted oxacycloheptatriene-3(2H) ketone compounds | |
| CN115093372B (en) | Synthesis method of imidazole derivative | |
| CN105820174A (en) | Polysubstituted thienoindole derivative and preparation method thereof | |
| Tu et al. | Green Synthesis of aryl thioethers through Cu-catalysed CS coupling of thiols and aryl boronic acids in water | |
| CN108727323B (en) | Method for catalytically synthesizing trifluoromethyl substituted homoisoflavone compound by using N-heterocyclic carbene | |
| CN112341417A (en) | Method for synthesizing polysubstituted furan through photo/copper co-catalysis | |
| CN106995428B (en) | A kind of synthetic method of 6H- benzo [C] benzopyrans compounds | |
| CN106008434A (en) | Synthetic method for 3-benzoyl coumarin compound | |
| Chen et al. | A Novel Method for One‐pot Synthesis of Furo [3, 2‐c] coumarin Derivatives from 4‐Hydroxycoumarin and Arylglyoxal under Microwave Irradiation | |
| CN107721917B (en) | Green synthesis method of polysubstituted nicotinate compound | |
| CN110372718B (en) | Difluoromethane thiochromanonthiophene compound and preparation method thereof | |
| CN105085460B (en) | A kind of preparation method of 4 phenyl coumarin class compound | |
| CN104610127B (en) | A kind of synthetic method of 2 (hetero) aryl indole of N alkyl, 3 aldehyde | |
| CN110642818B (en) | Method for preparing benzofuran-2-carboxamide compound | |
| CN110305083B (en) | Process for preparing 5-chloromethyl furfural from fructose | |
| CN104761600B (en) | Synthesis and uses of beta-1-imidazole-2,3,4,6-tetrahydroxy-D-glucopyranose bromide | |
| CN103130702A (en) | Method for synthesizing 3-substituted indole and 2,3-disubstituted indole | |
| RU2755123C1 (en) | (6r,8r,10s,12r,13ar)-5-methyl-3,6,7,8,9,10,11,12,13,13а-decahydro-1н-2,6: 6а,10:8,12-trimethanocyclonone[c]-azocine production method | |
| CN110577483B (en) | Green synthesis method of 3, 3-disubstituted-2-indolone | |
| CN109020922B (en) | Preparation method of cyclic sulfonamide compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
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) |
|
| TR01 | Transfer of patent right |