CN107151237A - A kind of 3 sulfuryl cumarins and preparation method thereof - Google Patents
A kind of 3 sulfuryl cumarins and preparation method thereof Download PDFInfo
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- CN107151237A CN107151237A CN201710339751.XA CN201710339751A CN107151237A CN 107151237 A CN107151237 A CN 107151237A CN 201710339751 A CN201710339751 A CN 201710339751A CN 107151237 A CN107151237 A CN 107151237A
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- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
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Abstract
The invention discloses a kind of 3 sulfuryl cumarin and preparation method thereof, the inventive method is that in organic solvent, arylamine, phenylpropiolic acid phenyl ester and sodium formaldehyde sulfoxylate react, and 3 sulfuryl coumarin compounds, the structure warp of such compound are made1H NMR、13The methods such as C NMR, HRMS are characterized and confirmed.The inventive method is reacted in a mild condition, is originated by the use of sodium formaldehyde sulfoxylate as sulfur dioxide, is directly realized sulfonylating reaction, constructs 3 sulfuryl coumarin compounds；This conversion reaction raw material is simple and easy to get, and avoids the use of sulfonic acid chloride in prior synthesizing method, fairly large preparation is applicable to, with extraordinary application prospect.
Description
Technical field
The invention belongs to cumarin technical field, more particularly to a kind of 3- sulfuryls cumarin and preparation method thereof.
Background technology
Coumarin compound is played an important role in fields such as medicine, dyestuff, materials.Coumarin skeleton is common miscellaneous
One of ring structure, is widely present among a variety of natural products with notable biological activity and drug molecule.For example, from plant
The Calanolide A extracted in diversiform-leaved poplar paulownia show extraordinary HIV1-RT inhibitory activity, are a kind of potential anti-
AIDS-treating medicine；Coumarin kind compound warfarin (Wafarin) is a kind of anti-coagulants for being widely used in clinical medicine；Rue
In umbelliferone, the aesculetin in the bark of ash and the angelica lactone in levisticum etc. all have coumarin skeleton；Work
The fluorescent coumarin dye of industry includes disperse yellow 184, disperse yellow 232, solvent red 196 and disperse red 277 etc..Its derivative
It is also used as the fields such as fluorescence probe, semi-conducting material, optical switch material and bio-imaging.Due to Coumarins chemical combination
Thing has these extensive and important effects, develops the new structure and its brand-new synthetic method of coumarin skeleton and has very big
Demand.
Sulfuryl fragment is also widely present in many natural products and drug molecule, these compounds in clinical medicine and
It has been widely used in Chemical Manufacture.The method of traditional synthesis sulfone compound relate generally to sulfur-containing compound such as thiophenol,
The oxidation of mercaptan and thioether；And sulfinate carries out substitution reaction with electrophilic reagent.The method of oxidation needs to use some strong
Oxidant, and sulfur-bearing regent have the smell of stench, are unfavorable for operating with.In addition, sulfinate derives from corresponding sulphur
Acyl chlorides, and some strong chlorination reagents are needed to use in the preparation process of sulfonic acid chloride.In order to overcome these shortcomings, using industrial
Cheap and easily-available, simple and stable, easy to operate sulfur dioxide substitute is originated as sulfur dioxide, and has been applied it to
It will become very valuable in machine synthesis.
Based on this, the present invention is reacted using arylamine, phenylpropiolic acid phenyl ester and sodium formaldehyde sulfoxylate.Reaction experience aryl sulfonyl is free
Base, then carries out addition and intramolecular cyclization to alkynyl in phenylpropiolic acid phenyl ester, further occurs ester group migration and aromatisation,
3- sulfuryl cumarins are made, so that there is provided a kind of new technology for efficiently synthesizing 3- sulfuryl cumarins.
The content of the invention
The technical problems to be solved by the invention are just to provide a kind of 3- sulfuryls cumarin and preparation method thereof.
In order to solve the above technical problems, the present invention is adopted the following technical scheme that：A kind of 3- sulfuryls cumarin, general structure I
A shown class 3- sulfuryl coumarin derivatives：
Wherein, Ar is phenyl, the aromatic substituent containing electron-donating group or electron withdraw group；It is preferred that, it is described to contain power supply
The aromatic substituent of subbase group is p-methylphenyl, p-methoxyphenyl, o-methyl-phenyl, o-methoxyphenyl, a methylbenzene
Base or m-methoxyphenyl；The aromatic substituent containing electron withdraw group is rubigan, p-fluorophenyl, to bromobenzene
Base, p-nitrophenyl, Chloro-O-Phenyl, o-fluorophenyl, o-bromophenyl, a chlorphenyl, a fluorophenyl or m-bromophenyl.
R1 is H, electron-donating group or electron withdraw group；It is preferred that, the electron-donating group be methyl, ethyl, the tert-butyl group,
Normal-butyl or methoxyl group；The electron withdraw group is chlorine, fluorine, bromine, ester group, acetyl group or trifluoromethyl.
R2 is aromatic substituent or alkyl containing electron-donating group or electron withdraw group；It is preferred that, it is described to contain power supply
The aromatic substituent of subbase group is p-methylphenyl, p-methoxyphenyl, o-methyl-phenyl, o-methoxyphenyl, a methylbenzene
Base or m-methoxyphenyl；Aromatic substituent containing electron withdraw group is rubigan, p-fluorophenyl, p-bromophenyl, right
Nitrobenzophenone, p-trifluoromethyl phenyl, to acetylphenyl, Chloro-O-Phenyl, o-fluorophenyl, o-bromophenyl, a chlorphenyl, a fluorine
Phenyl or m-bromophenyl；Alkyl is methyl, ethyl, n-propyl or normal-butyl.
The preparation method for the 3- sulfuryl cumarins that the present invention is provided, is anti-using arylamine, phenylpropiolic acid phenyl ester and sodium formaldehyde sulfoxylate
Should.Reaction experience aryl sulfonyl free radical, then carries out addition and intramolecular cyclization to alkynyl in phenylpropiolic acid phenyl ester, enters
Ester group migration and aromatisation occur for one step, efficiently synthesize 3- sulfuryl cumarins.Specifically, the inventive method is in organic solvent
In, arylamine, phenylpropiolic acid phenyl ester and sodium formaldehyde sulfoxylate react at 70~80 DEG C.Reaction experience aryl sulfonyl free radical, it is then right
Alkynyl carries out addition and intramolecular cyclization in phenylpropiolic acid phenyl ester, further occurs ester group migration and aromatisation, 3- sulfones are made
Butylcoumariii 1, its reaction equation is：
A kind of preparation method of 3- sulfuryls cumarin, comprises the following steps：
Step one：Sequentially added in reaction tube arylamine, boron trifluoride ether solution,tBuONO and organic solvent, in inertia
Under gas nitrogen or argon gas protection, stirred 0.5-1.0 hours in 70~80 DEG C；
Step 2：Phenylpropiolic acid phenyl ester and sodium formaldehyde sulfoxylate are added, is stirred 5.0-6.0 hours at 70~80 DEG C；It is completely anti-to TLC detections
Should；Step 3：After reaction solution washing, ethyl acetate extraction, column chromatography for separation after extract concentration obtains corresponding 3- sulfuryls fragrant
Legumin.
It is preferred that, the organic solvent in the step one is one in 1,2- dichloroethanes, Isosorbide-5-Nitrae-dioxane or toluene
Plant or two or more mixtures.
It is preferred that, using phenylpropiolic acid phenyl ester as 1.0 equivalents, arylamine consumption is 1.2-1.5 equivalents, preferably 1.5 equivalents.Hang
The consumption of white block is 1.5-2.0 equivalents, preferably 1.6 equivalents.tBuONO consumption is 1.6-2.0 equivalents, and preferably 1.8 work as
Amount；The consumption of boron trifluoride ether solution is 1.4-1.6 equivalents, preferably 1.5 equivalents.
Compared with prior art, present invention reaction is used as dioxy under the conditions of as mild as a dove simply by the use of sodium formaldehyde sulfoxylate
Change sulphur source, be directly realized sulfonylating reaction, construct 3- sulfuryl coumarin compounds；This conversion reaction raw material is simply easy
, and the use of sulfonic acid chloride in prior synthesizing method is avoided, fairly large preparation is applicable to, with extraordinary application
Prospect.
Embodiment
The present invention is described in further detail below by way of specific embodiment, but it is not as a limitation of the invention.
Embodiment 1
A kind of 3- sulfuryls cumarin, structural formula is：
Preparation method is：Sequentially added in reaction tube the equivalent of arylamine 1.5,1,2- dichloroethanes 1.5mL, tBuONO1.8 equivalent,
The equivalent of boron trifluoride ether solution 1.5, under inert nitrogen gas or argon gas protection, is stirred 10 minutes in 0 DEG C；It is subsequently added benzene
Propine acid phenenyl ester 0.2mmol, the equivalent of sodium formaldehyde sulfoxylate 1.6 and 1,2- dichloroethanes 2.0mL, are stirred 5.0-6.0 hours at 70~80 DEG C,
To the complete reaction of TLC detections.After reaction solution washing, ethyl acetate extraction, column chromatography for separation after extract concentration obtains corresponding
3- sulfuryl cumarin Ia, reaction yield is 83%.
The structure warp of the compound1H NMR、13The methods such as C NMR, HRMS are characterized and confirmed：1H NMR(400MHz,
CDCl3) δ 7.95 (d, J=8.9Hz, 2H), 7.56-7.58 (m, 3H), 7.32-7.34 (m, 2H), 7.14 (s, 1H), 6.95-
7.00 (m, 3H), 6.88 (d, J=8.3,1H), 3.86 (s, 3H), 2.44 (s, 3H)；13C NMR(100MHz,CDCl3)δ
163.7,158.8,155.9,153.8,146.5,132.9,131.7,131.5,129.5,129.0,128.0,127.3,
126.0,125.1,117.8,116.7,113.7,55.6,21.8；HRMS(ESI)calcd for C22H17O5S:393.0791(M
+H+),found:393.0793。
Embodiment 2
A kind of 3- sulfuryls cumarin, structural formula is
Preparation method is：Arylamine (1.5 equivalent), 1,2- dichloroethanes (1.5mL), tBuONO (1.8 are sequentially added in reaction tube
Equivalent), boron trifluoride ether solution (1.5 equivalent), inert nitrogen gas or argon gas protection under, in 0 DEG C stir 10 minutes；With
Phenylpropiolic acid phenyl ester (0.2mmol), sodium formaldehyde sulfoxylate (1.6 equivalent) and 1,2- dichloroethanes (2.0mL) are added afterwards, are stirred at 70~80 DEG C
Mix 5.0-6.0 hours, to the complete reaction of TLC detections.After reaction solution washing, ethyl acetate extraction, column chromatography after extract concentration
Separation, obtains corresponding 3- sulfuryls cumarin Ib, reaction yield is 84.5%.
The structure warp of the compound1H NMR、13The methods such as C NMR, HRMS are characterized and confirmed：1H NMR(400MHz,
CDCl3) δ 7.94 (d, J=8.6Hz, 2H), 7.58-7.89 (m, 3H), 7.47 (d, J=8.6Hz, 2H), 7.32-7.34 (m,
2H), 7.16 (s, 1H), 7.02 (d, J=8.2Hz, 1H), 6.90-6.92 (d, J=8.1Hz, 1H), 2.46 (s, 3H)；13C NMR
(100MHz,CDCl3)δ159.9,155.8,147.1,140.2,138.7,132.5,130.6,129.6,129.2,128.8,
127.3,126.2,124.2,117.7,116.8,21.8；HRMS(ESI)calcd for C22H16ClO4S:411.0452(M+H+),found:411.0441。
Embodiment 3
A kind of 3- sulfuryls cumarin, structural formula is
Preparation method is：Arylamine (1.5 equivalent), 1,2- dichloroethanes (1.5mL), tBuONO (1.8 are sequentially added in reaction tube
Equivalent), boron trifluoride ether solution (1.5 equivalent), inert nitrogen gas or argon gas protection under, in 0 DEG C stir 10 minutes；With
Phenylpropiolic acid phenyl ester (0.2mmol), sodium formaldehyde sulfoxylate (1.6 equivalent) and 1,2- dichloroethanes (2.0mL) are added afterwards, are stirred at 70~80 DEG C
Mix 5.0-6.0 hours, to the complete reaction of TLC detections.After reaction solution washing, ethyl acetate extraction, column chromatography after extract concentration
Separation, obtains corresponding 3- sulfuryls cumarin Ic, reaction yield is 85%.
The structure warp of the compound1H NMR、13The methods such as C NMR, HRMS are characterized and confirmed：1H NMR(400MHz,
CDCl3) δ 7.87 (d, J=8.7Hz, 2H), 7.64 (d, J=8.7Hz, 2H), 7.58-7.59 (m, 3H), 7.32-7.34 (m,
2H), 7.17 (s, 1H), 7.02 (d, J=8.3Hz, 1H), 6.91 (d, J=8.3Hz, 1H), 2.46 (s, 3H)；13C NMR
(100MHz,CDCl3)δ159.9,155.8,154.0,147.1,139.3,132.5,131.8,130.7,129.6,129.2,
128.9,128.1,127.3,126.2,124.2 117.7,116.9,21.8；HRMS(ESI)calcd for C22H16BrO4S:
454.9947(M+H+),found:454.9943。
Compared with prior art, present invention reaction is used as dioxy under the conditions of as mild as a dove simply by the use of sodium formaldehyde sulfoxylate
Change sulphur source, be directly realized sulfonylating reaction, construct 3- sulfuryl coumarin compounds；This conversion reaction raw material is simply easy
, and the use of sulfonic acid chloride in prior synthesizing method is avoided, fairly large preparation is applicable to, with extraordinary application
Prospect.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (9)
1. a kind of 3- sulfuryls cumarin, it is characterised in that the class 3- sulfuryl coumarin derivatives shown in general structure I：
Wherein, Ar is phenyl, the aromatic substituent containing electron-donating group or electron withdraw group；
R1 is H, electron-donating group or electron withdraw group；
R2 is aromatic substituent or alkyl containing electron-donating group or electron withdraw group.
2. 3- sulfuryls cumarin according to claim 1, it is characterised in that：It is described to contain electron-donating group in Ar selection
Group aromatic substituent be p-methylphenyl, p-methoxyphenyl, o-methyl-phenyl, o-methoxyphenyl, an aminomethyl phenyl or
Person's m-methoxyphenyl；The aromatic substituent containing electron withdraw group is rubigan, p-fluorophenyl, p-bromophenyl, right
Nitrobenzophenone, Chloro-O-Phenyl, o-fluorophenyl, o-bromophenyl, a chlorphenyl, a fluorophenyl or m-bromophenyl.
3. 3- sulfuryls cumarin according to claim 1, it is characterised in that：In R1 selection, the electron-donating group is
Methyl, ethyl, the tert-butyl group, normal-butyl or methoxyl group；The electron withdraw group is chlorine, fluorine, bromine, ester group, acetyl group or trifluoro
Methyl.
4. 3- sulfuryls cumarin according to claim 1, it is characterised in that：It is described to contain electron-donating group in R2 selection
Group aromatic substituent be p-methylphenyl, p-methoxyphenyl, o-methyl-phenyl, o-methoxyphenyl, an aminomethyl phenyl or
Person's m-methoxyphenyl；Aromatic substituent containing electron withdraw group be rubigan, p-fluorophenyl, p-bromophenyl, to nitro
Phenyl, p-trifluoromethyl phenyl, to acetylphenyl, Chloro-O-Phenyl, o-fluorophenyl, o-bromophenyl, a chlorphenyl, a fluorophenyl
Or m-bromophenyl；Alkyl is methyl, ethyl, n-propyl or normal-butyl.
5. a kind of preparation method of 3- sulfuryls cumarin, it is characterised in that comprise the following steps：
Step one：Sequentially added in reaction tube arylamine, boron trifluoride ether solution,tBuONO and organic solvent, in indifferent gas
Under body nitrogen or argon gas protection, stirred 0.5-1.0 hours in 70~80 DEG C；
Step 2：Phenylpropiolic acid phenyl ester and sodium formaldehyde sulfoxylate are added, is stirred 5.0-6.0 hours at 70~80 DEG C；It is completely anti-to TLC detections
Should；
Step 3：After reaction solution washing, ethyl acetate extraction, column chromatography for separation after extract concentration obtains corresponding 3- sulfuryls
Cumarin.
6. the preparation method of 3- sulfuryls cumarin according to claim 5, it is characterised in that：It is organic in the step one
Solvent is 1,2- dichloroethanes, the mixture of Isosorbide-5-Nitrae-one or both of dioxane or toluene above.
7. the preparation method of 3- sulfuryls cumarin according to claim 5, it is characterised in that：Using phenylpropiolic acid phenyl ester as
1.0 equivalents, arylamine consumption is 1.2-1.5 equivalents, preferably 1.5 equivalents；The consumption of sodium formaldehyde sulfoxylate is 1.5-2.0 equivalents, is preferably
1.6 equivalent；tBuONO consumption is 1.6-2.0 equivalents, preferably 1.8 equivalents；The consumption of boron trifluoride ether solution is 1.4-
1.6 equivalents, preferably 1.5 equivalents.
8. the preparation method of 3- sulfuryls cumarin according to claim 7, it is characterised in that：Using phenylpropiolic acid phenyl ester as
1.0 equivalents, arylamine consumption is 1.5 equivalents；The consumption of sodium formaldehyde sulfoxylate is 1.6 equivalents；tBuONO consumption is 1.8 equivalents；It is borontrifluoride
The consumption of borate ether solution is 1.5 equivalents.
9. the 3- sulfuryls coumarin derivative or its physiologically acceptable salt according to claim any one of 1-4 are in anti-Chinese mugwort
Grow medicine, the anti-coagulants of clinical medicine, fluorescent coumarin dye, fluorescence probe, semi-conducting material, optical switch material and life
Application in thing imaging.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107619404A (en) * | 2017-09-28 | 2018-01-23 | 河南工业大学 | A kind of hydroxycoumarin derivatives of 3 sulphur aryl 4 and its synthetic method |
| CN108586406A (en) * | 2018-04-16 | 2018-09-28 | 青岛科技大学 | A kind of preparation method of 3- sulfuryls coumarin compound |
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| CN106045955A (en) * | 2016-07-11 | 2016-10-26 | 复旦大学 | Method for preparing 3-sulfonyl coumarin compound |
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| CN106045955A (en) * | 2016-07-11 | 2016-10-26 | 复旦大学 | Method for preparing 3-sulfonyl coumarin compound |
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| DANQING ZHENG ET AL.: "Generation of Sulfonyl Radicals from Aryldiazonium Tetrafluoroborates and Sulfur Dioxide: The Synthesis of 3-Sulfonated Coumarins", 《ANGEW. CHEM. INT. ED.》 * |
| WEI WEI ET AL.: "Direct and metal-free arylsulfonylation of alkynes with sulfonylhydrazides for the construction of 3-sulfonated coumarins", 《CHEM. COMMUN.》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107619404A (en) * | 2017-09-28 | 2018-01-23 | 河南工业大学 | A kind of hydroxycoumarin derivatives of 3 sulphur aryl 4 and its synthetic method |
| CN108586406A (en) * | 2018-04-16 | 2018-09-28 | 青岛科技大学 | A kind of preparation method of 3- sulfuryls coumarin compound |
| CN108586406B (en) * | 2018-04-16 | 2022-03-15 | 曲阜师范大学 | Preparation method of 3-sulfonyl coumarin compound |
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