CN117304132A - Synthesis method of visible light-promoted selenothiazolin compound - Google Patents
Synthesis method of visible light-promoted selenothiazolin compound Download PDFInfo
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- CN117304132A CN117304132A CN202311193688.5A CN202311193688A CN117304132A CN 117304132 A CN117304132 A CN 117304132A CN 202311193688 A CN202311193688 A CN 202311193688A CN 117304132 A CN117304132 A CN 117304132A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 37
- 238000001308 synthesis method Methods 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 13
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 claims abstract description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 15
- 239000003480 eluent Substances 0.000 claims description 14
- 239000003208 petroleum Substances 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 5
- -1 diaryl diselenide Chemical compound 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000002541 furyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 239000000741 silica gel Substances 0.000 description 20
- 229910002027 silica gel Inorganic materials 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
- 239000011669 selenium Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- QHMUIBVNHLEFQN-UHFFFAOYSA-N n-prop-2-enylbenzenecarbothioamide Chemical compound C=CCNC(=S)C1=CC=CC=C1 QHMUIBVNHLEFQN-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003549 thiazolines Chemical class 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- RSPCKAHMRANGJZ-UHFFFAOYSA-N thiohydroxylamine Chemical compound SN RSPCKAHMRANGJZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D277/10—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of organic synthetic chemistry, in particular to a method for synthesizing a selenothiazolin compound by using visible light to promote. The N-allyl thioamide and diselenide undergo selenocyclic reaction under the irradiation of visible light to obtain selenothiazolin. The invention does not need to additionally add transition metal, oxidant and photocatalyst, and has the advantages of green environmental protection and the like; the invention also has the advantages of mild reaction conditions and simple post-treatment operation, develops a new synthesis method for the selenothiazolin compound, and has good application potential and research value.
Description
Technical Field
The invention relates to the technical field of organic synthetic chemistry, in particular to a method for synthesizing a selenothiazolin compound by using visible light to promote.
Background
Thiazolines compounds are important heterocyclic compounds in nature and are widely applied to the fields of medicine, materials and synthesis. The synthesis method comprises condensation of carboxylic acid and amino mercaptan and derivatives thereof, ring closure of beta-hydroxyamide and a thio reagent, intramolecular cyclization of thiohydroxyamide/beta-amino mercaptan ester/beta-mercapto amide and the like (Chin.J. org.chem.,2008, 1358-1365).
On the other hand, the physiological activity of organic selenium compounds has attracted considerable interest to many scientists. Many selenoethers and selenium-containing heterocyclic drugs are successively developed, and intensive researches on their properties have been conducted. Thus, developing a novel and efficient method for introducing selenium atoms into organic molecules is one of the hot spots of current research in the field of organic synthesis.
In view of the unique structural skeleton of thiazoline and the wide biological activity of selenium-containing compounds, the development of a green and efficient novel method for synthesizing seleno thiazoline compounds has very important significance. The methods reported in the publication include oxidation of diselenide to active selenium species using an oxidizing agent (chemistry select2022,7, e 202200933) or electrochemical (chip. J. Org. Chem.2020,40, 2855-2862) method, which reacts with N-allylthioamides to produce selenothiazolines. However, these methods have significant drawbacks or disadvantages: high cost, complex post-treatment, no compliance with green chemical requirements, and the like.
The visible light catalytic reaction is an emerging green synthesis process, and the method is usually mild in reaction condition, safe and environment-friendly to operate. However, literature studies have shown that methods for synthesizing selenothiazolines based on visible light promotion have not been reported so far. Here, the present application constructs a green and efficient photocatalytic reaction by utilizing the unique advantages of photochemistry in the synthesis field, so as to realize the preparation of selenothiazolines.
Disclosure of Invention
The invention aims to provide a method for synthesizing a selenothiazolin compound by using visible light to promote the synthesis of the selenothiazolin compound, so as to solve the problems in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions: a method for synthesizing a visible light-promoted selenothiazolin compound comprises the following steps:
in an organic solvent, N-allylthioamide with a structure shown in a formula (I) and diselenide with a structure shown in a formula (II) are used as reaction raw materials, the reaction is carried out under the irradiation of visible light under the conditions of opening and room temperature, after the reaction is finished, the solvent is removed from the reaction liquid under reduced pressure to obtain a crude product, and the crude product is purified by column chromatography to obtain the selenothiazolin compound with the structure shown in the formula (III), wherein the reaction equation is shown as follows:
wherein the compound of formula (I) is N-allylthioamide, and the substituent R 1 Straight-chain or branched-chain alkyl of C1-C10, C3-C7 cycloalkyl, benzyl, naphthyl, furyl, thienyl, phenyl and phenyl substituted by one or more substituents, wherein the substituents are alkoxy, alkyl, trifluoromethyl, trifluoromethoxy, nitro, halogen and cyano; the compound of formula (II) is a diaryl diselenide, a dialkyl diselenide.
Preferably, the molar ratio of the N-allylthioamide of the structure of formula (I) to the diselenide of the structure of formula (II) is 1:0.5-1: 1, preferably 1:0.6.
Preferably, the organic solvent is acetonitrile, chloroform, dichloromethane, nitromethane, preferably dichloromethane.
Preferably, the irradiation light source for the reaction is one of sunlight, a fluorescent lamp, a tungsten lamp and an LED lamp, and preferably a fluorescent lamp.
Preferably, the reaction time is 20h-30h.
Preferably, after the reaction is finished, the reaction solution is concentrated under reduced pressure, the concentrate is separated by column chromatography, and the mixed solution of petroleum ether and ethyl acetate is used as an eluent, wherein the petroleum ether is as follows: the volume ratio of the ethyl acetate is (1-50): and 1, collecting eluent, and performing rotary evaporation on the solvent to obtain the seleno oxazoline compound shown in the formula (III).
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention does not need expensive transition metal, chemical oxidant and photocatalyst, and has low cost and little environmental pollution.
(2) The invention can be carried out under the air condition, and has simple operation.
(3) The invention uses visible light as energy source, and has the characteristics of safety and environmental protection.
(4) The invention can be carried out under room temperature, the reaction condition is mild, and the application range of the substrate is wide.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides the following technical scheme: a method for synthesizing a visible light-promoted selenothiazolin compound comprises the following steps:
in an organic solvent, N-allylthioamide with a structure shown in a formula (I) and diselenide with a structure shown in a formula (II) are used as reaction raw materials, the reaction is carried out under the irradiation of visible light under the conditions of opening and room temperature, after the reaction is finished, the solvent is removed from the reaction liquid under reduced pressure to obtain a crude product, and the crude product is purified by column chromatography to obtain the selenothiazolin compound with the structure shown in the formula (III), wherein the reaction equation is shown as follows:
wherein the compound of formula (I) is N-allylthioamide, and the substituent R 1 Straight-chain or branched-chain alkyl of C1-C10, C3-C7 cycloalkyl, benzyl, naphthyl, furyl, thienyl, phenyl and phenyl substituted by one or more substituents, wherein the substituents are alkoxy, alkyl, trifluoromethyl, trifluoromethoxy, nitro, halogen and cyano; the compound of formula (II) is a diaryl diselenide, a dialkyl diselenide.
Example 1
The reaction equation is shown as follows:
filling N-alkene into 20 ml test tube with magnetic stirrerPropylthiobenzamide (0.5 mmol), ph 2 Se 2 (0.3 mmol), CH 2 Cl 2 (3 ml), after the addition, a fluorescent lamp was placed at a distance of 2 cm from the test tube, and reacted at room temperature for 30 hours under open conditions, after the completion of the reaction, the solvent was removed from the organic phase by a rotary evaporator, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent petroleum ether/ethyl acetate=8/1), to give 136 mg of the objective compound in 82% yield.
The nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.92(d,2H),7.55(dd,J＝6.5,3.0Hz,2H),7.50(d,J＝7.3Hz,1H),7.47(t,J＝7.6Hz,2H),7.37–7.30(m,3H),4.62(dd,J＝15.8,3.4Hz,1H),4.36(dd,J＝15.9,8.0Hz,1H),4.10(m,1H),3.15(dd,J＝12.6,6.4Hz,1H),3.10(dd,J＝12.7,9.0Hz,1H)； 13 C NMR(100MHz,CDCl 3 ):δ169.2,133.6,132.3,131.8,129.3,128.6,128.5,128.4,127.5,67.9,50.3,33.1。
example 2
The reaction equation is shown as follows:
into a 20 ml test tube equipped with a magnetic stirrer was charged N-allylthiobenzamide (0.5 mmol), ph 2 Se 2 (0.3 mmol), CH 2 Cl 2 (3 ml), after the addition, a fluorescent lamp was placed at a distance of 2 cm from the test tube, and reacted at room temperature for 30 hours under open conditions, after the completion of the reaction, the solvent was removed from the organic phase by a rotary evaporator, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent petroleum ether/ethyl acetate=4/1), to give 130 mg of the objective compound in a yield of 72%.
The nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.77(d,J＝8.8Hz,2H),7.57–7.53(m,2H),7.33–7.27(m,3H),6.92(d,J＝8.8Hz,2H),4.58(dd,J＝16.0,3.0Hz,1H),4.29(dd,J＝16.0,8.0Hz,1H),4.09(m,1H),3.86(s,3H),3.16(dd,J＝12.5,6.2Hz,1H),3.05(dd,J＝12.6,9.0Hz,1H)； 13 C NMR(100MHz,CDCl 3 ):δ163.7,162.4,133.8,130.2,129.5,129.1,127.9,120.6,114.0,78.9,60.5,55.5,32.3。
example 3
The reaction equation is shown as follows:
into a 20 ml test tube equipped with a magnetic stirrer was charged N-allylthiobenzamide (0.5 mmol), ph 2 Se 2 (0.3 mmol), CH 2 Cl 2 (3 ml), after the addition, a fluorescent lamp was placed at a distance of 2 cm from the test tube, and reacted at room temperature for 30 hours under open conditions, after the completion of the reaction, the organic phase was subjected to removal of the solvent by a rotary evaporator, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent petroleum ether/ethyl acetate=4/1), to give 151 mg of the objective compound in 80% yield.
The nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ8.25(d,J＝8.6Hz,2H),7.94(d,J＝8.6Hz,2H),7.56–7.52(m,2H),7.33–7.29(m,3H),4.62(dd,J＝16.6,3.2Hz,1H),4.34(dd,J＝16.4,8.0Hz,1H),4.11(m,1H),3.12(dd,J＝12.6,6.3Hz,1H),3.05(dd,J＝12.6,9.0Hz,1H)； 13 C NMR(100MHz,CDCl 3 ):δ165.1,149.1,138.2,133.2,129.0,128.9,128.5,127.4,123.4,69.5,51.3,33.1。
example 4
The reaction equation is shown as follows:
into a 20 ml test tube equipped with a magnetic stirrer was charged N-allylthiobenzamide (0.5 mmol), ph 2 Se 2 (0.3 mmol), CH 2 Cl 2 (3 ml) after the addition, the fluorescent lamp was placed at a distance of 2 cm from the test tube, and reacted at room temperature under open conditions for 30 hours, and reversedAfter completion, the solvent was removed from the organic phase by rotary evaporation, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent petroleum ether/ethyl acetate=8/1) to give 141 mg of the objective compound in 77% yield.
The nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.75–7.73(m,2H),7.56(dd,J＝6.5,3.0Hz,2H),7.40–7.27(m,5H),4.58(dd,J＝16.4,3.2Hz,1H),4.30(dd,J＝16.3,8.0Hz,1H),4.10–4.01(m,1H),3.14(dd,J＝12.6,6.2Hz,1H),3.08–3.00(m,1H)； 13 C NMR(100MHz,CDCl 3 ):δ166.1,137.6,133.7,131.8,130.0,129.4,129.0,128.9,127.6,69.6,51.2,33.8。
example 5
The reaction equation is shown as follows:
into a 20 ml test tube equipped with a magnetic stirrer was charged N-allylthiobenzamide (0.5 mmol), ph 2 Se 2 (0.3 mmol), CH 2 Cl 2 (3 ml), after the addition, a fluorescent lamp was placed at a distance of 2 cm from the test tube, and reacted at room temperature for 30 hours under open conditions, after the completion of the reaction, the solvent was removed from the organic phase by a rotary evaporator, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent petroleum ether/ethyl acetate=12/1), to give 144 mg of the objective compound in 72% yield.
The nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.95(d,J＝8.2Hz,2H),7.84(d,J＝8.0Hz,2H),7.52(d,J＝7.8Hz,2H),7.36–7.28(m,3H),4.48(dd,J＝16.6,3.6Hz,1H),4.35(dd,J＝16.5,8.2Hz,1H),4.32–4.24(m,1H),3.24(d,J＝7.4Hz,2H)； 13 C NMR(100MHz,CDCl 3 ):δ164.2,136.5,132.1,131.6,131.2,131.0,129.7,129.6,128.8,127.2,126.0,125.8,124.4,69.6,51.6,32.8。
example 6
The reaction equation is shown as follows:
into a 20 ml test tube equipped with a magnetic stirrer was charged N-allylthiobenzamide (0.5 mmol), ph 2 Se 2 (0.3 mmol), CH 2 Cl 2 (3 ml), after the addition, a fluorescent lamp was placed at a distance of 2 cm from the test tube, and reacted at room temperature for 30 hours under open conditions, after the completion of the reaction, the solvent was removed from the organic phase by a rotary evaporator, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent petroleum ether/ethyl acetate=10/1), to give 130 mg of the objective compound in a yield of 68%.
The nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ8.80(d,J＝7.8Hz,1H),8.10(d,J＝8.2Hz,1H),8.04(d,J＝9.0Hz,1H),7.80(d,J＝6.6Hz,1H),7.66–7.59(m,5H),7.34(dt,J＝12.2,6.8Hz,3H),4.65(dd,J＝16.0,3.5Hz,1H),4.52(dd,J＝16.3,8.1Hz,1H),4.32–4.21(m,1H),3.34(d,J＝7.3Hz,2H)； 13 C NMR(100MHz,CDCl 3 ):δ165.4,134.0,132.2,131.9,130.7,130.4,130.1,129.4,129.0,128.1,127.9,127.2,126.4,126.1,125.6,71.3,51.1,33.4。
example 7
The reaction equation is shown as follows:
into a 20 ml test tube equipped with a magnetic stirrer was charged N-allylthiobenzamide (0.5 mmol), ph 2 Se 2 (0.3 mmol), CH 2 Cl 2 (3 ml), after the addition, a fluorescent lamp was placed at a distance of 2 cm from the test tube, and reacted at room temperature for 30 hours under open conditions, after the completion of the reaction, the organic phase was passed through a rotary evaporator to remove the solvent, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent petroleum ether/ethyl acetate=12/1) to give 110 mg of the objective compound in a yield65%.
The nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.82(d,J＝6.2Hz,1H),7.52(d,J＝8.0Hz,2H),7.41(d,J＝3.6Hz,1H),7.36–7.25(m,3H),7.16–7.11(m,1H),4.39–4.20(m,3H),3.25(d,J＝6.4Hz,2H)； 13 C NMR(100MHz,CDCl 3 ):δ159.0,137.2,132.6,131.7,131.5,130.1,130.0,128.8,127.8,69.3,52.7,33.2。
example 8
The reaction equation is shown as follows:
into a 20 ml test tube equipped with a magnetic stirrer was charged N-allylthiobenzamide (0.5 mmol), ph 2 Se 2 (0.3 mmol), CH 2 Cl 2 (3 ml), after the addition, a fluorescent lamp was placed at a distance of 2 cm from the test tube, and reacted at room temperature for 30 hours under open conditions, after the completion of the reaction, the solvent was removed from the organic phase by a rotary evaporator, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent petroleum ether/ethyl acetate=6/1), to give 118 mg of the objective compound in 73% yield.
The nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.88(s,1H),7.52(d,J＝7.6Hz,2H),7.42–7.38(m,3H),7.02(d,J＝3.4Hz,1H),6.74(d,J＝3.4Hz,1H),4.44(dd,J＝16.2,3.2Hz,1H),4.30–4.20(m,2H),3.23(d,J＝7.6Hz,2H)； 13 C NMR(100MHz,CDCl 3 ):δ155.3,148.1,146.4,132.5,130.2,130.1,127.6,114.2,112.8,69.6,51.1,33.1。
example 9
The reaction equation is shown as follows:
into a 20 ml test tube equipped with a magnetic stirrer was charged N-allylthiobenzamide (0)5 mmol), me 2 Se 2 (0.3 mmol), CH 2 Cl 2 (3 ml), after the addition, a fluorescent lamp was placed at a distance of 2 cm from the test tube, and reacted at room temperature for 30 hours under open conditions, after the completion of the reaction, the organic phase was subjected to removal of the solvent by a rotary evaporator, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent petroleum ether/ethyl acetate=8/1), to give 92 mg of the objective compound in a yield of 68%.
The nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.80–7.76(m,2H),7.54(t,J＝7.2Hz,1H),7.48(t,J＝7.3Hz,2H),4.46–4.32(m,3H),2.84–2.75(m,2H),2.07(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ165.7,133.5,132,0,129.3,128.6,70.1,51.6,31.2,5.1。
example 10
The reaction equation is shown as follows:
into a 20 ml test tube equipped with a magnetic stirrer was charged N-allylthiobenzamide (0.5 mmol), bn 2 Se 2 (0.3 mmol), CH 2 Cl 2 (3 ml), after the addition, a fluorescent lamp was placed at a distance of 2 cm from the test tube, and reacted at room temperature for 30 hours under open conditions, after the completion of the reaction, the solvent was removed from the organic phase by a rotary evaporator, and the residue was purified by a silica gel column (silica gel size: 200 to 300 mesh, eluent petroleum ether/ethyl acetate=10/1), to give 128 mg of the objective compound in 74% yield.
The nuclear magnetic spectrum data of the obtained product are: 1 H NMR(400MHz,CDCl 3 ):δ7.80(d,J＝8.0Hz,2H),7.56(t,J＝7.4Hz,1H),7.50(t,J＝7.4Hz,2H),7.34(q,J＝8.25,7.8Hz,4H),7.24(t,J＝7.2Hz,1H),4.40(dd,J＝15.6,2.8Hz,1H),4.30(dd,J＝16.0,7.8Hz,1H),4.26(dt,J＝7.4,3.6Hz,1H),3.94(s,2H),2.76(d,J＝7.0Hz,2H)； 13 C NMR(100MHz,CDCl 3 ):δ165.6,140.0,133.6,132.0,129.4,129.3,129.0,128.4,127.4,70.2,51.8,29.9,27.3。
in summary, the invention provides a method for synthesizing a selenothiazolin compound by using visible light, wherein under the irradiation of the visible light, an N-allylthioamide derivative and diselenide undergo intramolecular cyclization reaction to obtain the selenothiazolin compound. The method has the advantages of mild reaction conditions, high reaction yield of products, simple operation, energy conservation, environmental protection and the like, and further has good application prospects in organic synthesis and drug synthesis.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A method for synthesizing a visible light promoted selenothiazolin compound is characterized by comprising the following steps: the method comprises the following steps: in an organic solvent, N-allylthioamide with a structure shown in a formula (I) and diselenide with a structure shown in a formula (II) are used as reaction raw materials, the reaction is carried out under the irradiation of visible light under the conditions of opening and room temperature, after the reaction is finished, the solvent is removed from the reaction liquid under reduced pressure to obtain a crude product, and the crude product is purified by column chromatography to obtain the selenothiazolin compound with the structure shown in the formula (III), wherein the reaction equation is shown as follows:
wherein the compound of formula (I) is N-allylthioamide, and the substituent R 1 Straight-chain or branched-chain alkyl of C1-C10, C3-C7 cycloalkyl, benzyl, naphthyl, furyl, thienyl, phenyl and phenyl substituted by one or more substituents, wherein the substituents are alkoxy, alkyl, trifluoromethyl, trifluoromethoxy, nitro, halogen and cyano; the compound of formula (II) is diaryl diselenide, dialkyl diselenide;
the irradiation light source of the reaction is a fluorescent lamp; the organic solvent is dichloromethane.
2. The method for synthesizing the visible light-promoted selenothiazolin compound, according to claim 1, wherein the method comprises the following steps: the molar ratio of the N-allylthioamide with the structure shown in the formula (I) to the diselenide with the structure shown in the formula (II) is 1:0.5-1: 1.
3. the method for synthesizing the visible light-promoted selenothiazolin compound, according to claim 2, wherein the method comprises the following steps: the molar ratio of the N-allylthioamide of the structure of formula (I) to the diselenide of the structure of formula (II) is 1:0.6.
4. The method for synthesizing the visible light-promoted selenothiazolin compound, according to claim 1, wherein the method comprises the following steps: the reaction time is 20-30 h.
5. The method for synthesizing the visible light-promoted selenothiazolin compound, according to claim 1, wherein the method comprises the following steps: after the reaction is finished, the reaction solution is decompressed and concentrated, the concentrate is separated by column chromatography, and the mixed solution of petroleum ether and ethyl acetate is used as eluent, wherein the petroleum ether is as follows: the volume ratio of the ethyl acetate is (1-50): and 1, collecting eluent, and spin-evaporating the solvent to obtain the selenothiazolin compound shown in the formula (III).
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