CN111808003A - Preparation method of thioether - Google Patents

Preparation method of thioether Download PDF

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CN111808003A
CN111808003A CN202010765894.9A CN202010765894A CN111808003A CN 111808003 A CN111808003 A CN 111808003A CN 202010765894 A CN202010765894 A CN 202010765894A CN 111808003 A CN111808003 A CN 111808003A
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alpha
mixture
thiophenol
diazoacetic acid
ester
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周红艳
杨靖亚
陈淑雯
马奔
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Gansu Agricultural University
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Gansu Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/38—One sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/70—Sulfur atoms
    • C07D277/74—Sulfur atoms substituted by carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/34—Sulfur atoms

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Abstract

The invention relates to a thioether preparation method, which comprises the steps of adding mercaptan/phenol and alpha-diazoacetic ester into an acetonitrile-water mixed solvent, and stirring at room temperature under the irradiation of visible light until the reaction is complete to obtain a mixture; quenching and extracting the mixture to obtain an organic phase, drying, filtering, distilling under reduced pressure to remove the solvent, and performing silica gel column chromatography to obtain the thioether. The invention adopts the S ‒ H insertion reaction of the diazo compound promoted by visible light and mercaptan (phenol) to prepare a large amount of thioether compounds for the first time, which not only avoids using any catalyst, ligand and additive, but also has mild reaction conditions, high yield, economic atoms and steps, no pollution and capability of meeting the requirements of green chemistry.

Description

Preparation method of thioether
Technical Field
The invention relates to the technical field of organic chemistry, in particular to a preparation method of thioether.
Background
Sulfur-containing compounds are not only present in natural products, pharmaceuticals and agrochemicals, but also are widely used as catalysts, ligands and important synthetic intermediates in organic synthesis. Thioethers are a very important class of sulfur-containing compounds, and have wide applications in pharmaceutical, materials, and organic synthesis. Thus, the preparation of thioethers is of great interest and scientists have developed a number of methods for synthesizing such compounds.
At present, S ‒ H insertion reaction of diazo compound as carbene precursor and mercaptan (phenol) is one of the most direct and economic methods in thioether preparation methods, and there are mainly four reported strategies for S ‒ H insertion reaction of diazo compound and mercaptan (phenol). The first is the most common transition metal catalysis, using rhodium, ruthenium, rhenium, iridium, iron and copper as metal catalysts, which effect the reaction by forming metal carbene intermediates. The second is organocatalysis, and urea and phosphate catalyzed reactions have been reported (e.d. Couch, t.j. Auvil and a.e. Mattson,Chem. Eur. J., 2014, 20, 8283;B. Bernardim, E. D. Couch, A. M. Hardman-Baldwin, A. C. B. Burtoloso and A.E. Mattson,Synthesis, 2016, 48, 677). The third is heterogeneously catalyzed, reported by the reaction catalyzed by zeolite-supported Cu (I) and TFMSA @ SBA-15 (P. Saha, H. Jeon, P.K. Mishra, H. -W. Rhee and J.H. Kwak,J. Mol. Catal. A: Chem., 2016, 417, 10; X. Yi, J. Feng, F. Huangand J. B. Baell,Chem. Commun., 2020, 56, 1243). The fourth is biocatalytic, and the reaction catalyzed by myoglobin and cytochrome P450 has been reported (v. Tyagi, r.b. Bonn and r. Fasan,Chem. Sci., 2015, 6, 2488; K. Chen, S.-Q. Zhang, O. F. Brandenberg, X. Hong and F.H. Arnold,J. Am. Chem. Soc., 2018, 140, 16402）。
although the above four methods have been used for the S ‒ H insertion reaction of diazo compounds and thiols (phenols) to prepare thioethers, these methods all require the use of carefully selected catalysts, and usually require the addition of ligands and additives, and have the problems of high cost, severe reaction conditions, poor economy, metal residue, generation of a large amount of harmful waste, environmental hazard, and the like. Therefore, from the perspective of green and sustainable chemistry, the development of a method for the insertion reaction of diazo compounds and thiols (phenols) with S ‒ H under mild conditions without using catalysts, ligands and additives will have a great practical value and a good prospect for industrial production.
Visible light is a clean, inexpensive and sustainable energy source, and in recent years visible light-promoted reactions have evolved into a powerful and practical synthetic strategy in organic synthesis. However, the preparation of thioethers by the S ‒ H insertion reaction of diazo compounds promoted by visible light with thiols (phenols) has not been reported.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing thioether, which is green, efficient, simple to operate, mild in condition, wide in application range and easy to industrialize.
In order to solve the above problems, the present invention provides a method for preparing thioether, which is characterized in that: adding mercaptan/phenol and alpha-diazoacetic ester into an acetonitrile-water mixed solvent, and stirring at room temperature under the irradiation of visible light until the reaction is complete to obtain a mixture; quenching and extracting the mixture to obtain an organic phase, drying, filtering, distilling under reduced pressure to remove the solvent, and performing silica gel column chromatography to obtain thioether; the molar ratio of the thiol/phenol to the alpha-diazoacetic acid ester is 0.3: 0.6.
the resulting thioethers have the following structural formula:
Figure DEST_PATH_IMAGE001
(ii) a In the formula R1Refers to aryl or heteroaryl; r2Refers to hydrogen or aryl; r3Refers to an alkyl group.
The preparation method of the invention can be represented by the following typical reaction formula:
Figure 953869DEST_PATH_IMAGE002
the mercaptan/phenol is one of p-methyl thiophenol, p-isopropyl thiophenol, p-tert-butyl thiophenol, p-methoxy thiophenol, p-fluoro thiophenol, p-trifluoromethyl thiophenol, m-methyl thiophenol, m-methoxy thiophenol, m-bromo thiophenol, m-fluoro thiophenol, o-chloro thiophenol, o-bromo thiophenol, 3, 4-dimethyl thiophenol, 2, 4-dichloro thiophenol, pyridine-2-thiol, 5-nitropyridine-2-thiol, pyrimidine-2-thiol, 4, 6-dimethyl pyrimidine-2-thiol, benzoxazole-2-thiol, benzothiazole-2-thiol and thiophene-2-thiol.
The alpha-diazoacetic acid ester refers to ethyl diazoacetate, alpha-phenyl diazoacetic acid methyl ester, alpha-phenyl diazoacetic acid isopropyl ester, alpha-p-methyl phenyl diazoacetic acid isopropyl ester, alpha-p-methoxyphenyl diazoacetic acid isopropyl ester, alpha-p-fluorophenyl diazoacetic acid isopropyl ester, alpha-p-chlorophenyl diazoacetic acid isopropyl ester, alpha-p-bromophenyl diazoacetic acid isopropyl ester, alpha-p-trifluoromethyl phenyl diazoacetic acid isopropyl ester, alpha-o-methylphenyl diazoacetic acid isopropyl ester, alpha-o-bromophenyl diazoacetic acid isopropyl ester, alpha-m-fluorophenyl diazoacetic acid isopropyl ester, alpha-m-chlorophenyl diazoacetic acid isopropyl ester, alpha-2, 5-difluorophenyl diazoacetic acid isopropyl ester, alpha-phenyl diazoacetic acid cyclopentyl ester, alpha-phenyl diazoacetic acid cyclohexyl ester, alpha-phenyl diazoacetic acid isopropyl ester, One kind of alpha-phenyl diazoacetic acid-2-methyl allyl ester.
The acetonitrile-water mixed solvent is prepared by mixing acetonitrile and deionized water according to the weight ratio of 10: 1 volume ratio of the mixture.
The visible light is 23W Compact Fluorescent Lamp (CFL).
The volume ratio of the chromatographic solution in the silica gel column chromatography is 20: 1 petroleum ether-ethyl acetate.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts the S ‒ H insertion reaction of the diazo compound promoted by visible light and mercaptan (phenol) to prepare a large amount of thioether compounds for the first time, which not only avoids using any catalyst, ligand and additive, but also has mild reaction conditions, high yield, economic atoms and steps, no pollution and capability of meeting the requirements of green chemistry.
2. The present inventors have optimized the respective visible lights and found that the separation yield was 89% when the visible light was a 23W Compact Fluorescent Lamp (CFL) (see table 1).
TABLE 1
Figure DEST_PATH_IMAGE003
Figure 63820DEST_PATH_IMAGE004
Note: 1a (0.3 mmol), 2a (0.6 mmol, 2 equiv), solvent (3 mL), room temperature, 18 h.
3. The method has the advantages of convenient and safe operation, simple and easy method, easy product separation, wide substrate application range and easy realization of structural diversity synthesis and industrial production.
Detailed Description
The process routes of the following examples 1 to 24 are as follows:
Figure DEST_PATH_IMAGE005
example 1A thioether preparation process, which comprises adding 0.3mmol of p-methylthiophenol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 18 h (monitoring the completion of the reaction by TLC), was carried out to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally performing silica gel column chromatography to obtain the 2-p-toluenesulfonyl ethyl acetate 3 aa.
Figure 968190DEST_PATH_IMAGE006
Colorless liquid, yield 89%.1H NMR (600 MHz, CDCl3): = 7.41 (dd,J= 8.4, 1.2Hz, 2H), 7.30-7.28 (m, 2H), 7.23-7.20 (m, 1H), 4.15 (q,J= 7.2 Hz, 2H), 3.63(s, 2H), 1.21 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz, CDCl3): = 169.6, 135.0,133.3, 130.0, 129.0, 126.9, 61.5, 36.7, 14.0.
Example 2A method for preparing thioether, which comprises adding 0.3mmol of thiophenol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, and stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 20 h (monitoring the completion of the reaction by TLC), to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove solvent, and performing silica gel column chromatography to obtain 2-phenylthio ethyl acetate 3 ba.
Figure DEST_PATH_IMAGE007
Colorless liquid, yield 84%.1H NMR (600 MHz, CDCl3): = 7.41-7.40 (m, 2H), 7.30-7.28 (m, 2H), 7.23-7.20 (m, 1H), 4.15 (q,J= 7.2 Hz, 2H), 3.63 (s, 2H), 1.21(t,J= 7.2 Hz, 3H).13C NMR (150 MHz, CDCl3): = 169.7, 137.2, 131.1, 130.9,129.7, 61.3, 37.3, 21.0, 14.0.
Example 3A thioether preparation process, which comprises adding 0.3mmol of p-isopropylthiophenol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, and reacting while stirring at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 15 h (completion of reaction monitored by TLC), gives a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove solvent, and performing silica gel column chromatography to obtain 2-isopropylphenylthioacetate ethyl 3 ca.
Figure 301083DEST_PATH_IMAGE008
Colorless liquid, yield 81%.1H NMR (600 MHz, CDCl3): = 7.35 (d,J= 8.4 Hz,2H), 7.16 (d,J= 8.4 Hz, 2H), 4.15 (q,J= 7.2 Hz, 2H), 3.58 (s, 2H), 2.89-2.85 (m, 1H), 1.23 (s, 3H), 1.22 (s, 3H), 1.21 (t,J= 7.2 Hz, 3H).13C NMR(150 MHz, CDCl3): = 169.8, 148.2, 131.5, 130.9, 127.2, 61.4, 37.3, 33.7,23.8, 14.0.
Example 4A thioether production process, which comprises adding 0.3mmol of p-tert-butylphenol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, and reacting while stirring at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 15 hours (completion of reaction was monitored by TLC), gave a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally performing silica gel column chromatography to obtain the 2-p-tert-butyl benzene sulfenyl ethyl acetate 3 da.
Figure DEST_PATH_IMAGE009
Colorless liquid, yield 75%.1H NMR (600 MHz, CDCl3): = 7.35 (dd,J= 7.8, 1.8Hz, 2H), 7.32 (dd,J= 7.8, 1.8 Hz, 2H), 4.15 (q,J= 7.2 Hz, 2H), 3.59 (s,2H), 1.29 (s, 9H), 1.21 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz, CDCl3): =169.8, 150.4, 131.3, 130.4, 126.0, 61.4, 37.1, 34.5, 31.2, 14.0.
Example 5A thioether preparation process, which comprises adding 0.3mmol of p-methoxythiophenol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 6 h (monitoring the completion of the reaction by TLC), was carried out to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally performing silica gel column chromatography to obtain 2-p-methoxyphenylthioacetate 3 ea.
Figure 302406DEST_PATH_IMAGE010
Colorless liquid, yield 95%.1H NMR (600 MHz, CDCl3): = 7.40 (dd,J= 6.6, 2.4Hz, 2H), 6.83 (dd,J= 6.6, 2.4 Hz, 2H), 4.12 (q,J= 7.2 Hz, 2H), 3.77 (s,3H), 3.49 (s, 2H), 1.20 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz, CDCl3): =169.8, 159.6, 134.1, 124.9, 114.6, 61.3, 55.2, 38.6, 14.0.
Example 6A thioether preparation method, which comprises adding 0.3mmol of p-fluorobenzenethiol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 12 h (monitoring the completion of the reaction by TLC), obtaining a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove solvent, and performing silica gel column chromatography to obtain 2-p-fluorophenyl ethyl thioglycolate 3 fa.
Figure DEST_PATH_IMAGE011
Colorless liquid, yield 85%.1H NMR (600 MHz, CDCl3): = 7.42 (dd,J= 9.0, 5.4Hz, 2H), 6.99 (t,J= 9.0 Hz, 2H), 4.13 (q,J= 7.2 Hz, 2H), 3.54(s, 2H),1.20 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz, CDCl3): = 169.8, 162.4 (d,J=246.15 Hz), 133.4 (d,J= 8.1 Hz), 129.7 (d,J= 3.3 Hz), 116.1 (d,J= 2.75Hz), 61.5, 37.8, 14.1.
Example 7A thioether production process, in which p-trifluoromethylthiophenol 0.3mmol and ethyl diazoacetate 0.6 mmol (2 equiv) were added to an acetonitrile-water mixed solvent, and the mixture was stirred at room temperature under irradiation of a 23W Compact Fluorescent Lamp (CFL) for 15 hours (completion of the reaction was monitored by TLC), was obtained. Mixture ofQuenching with saturated brine (2 mL), and extracting with ethyl acetate (3X 5 mL) to give an organic phase which is then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove solvent, and performing silica gel column chromatography to obtain 2-p-trifluoromethylphenylthioacetate 3 ga.
Figure 62551DEST_PATH_IMAGE012
Colorless liquid, yield 60%.1H NMR (600 MHz, CDCl3): = 7.42 (dd,J= 9.0, 5.4Hz, 2H), 6.99 (t,J= 9.0 Hz, 2H), 4.13 (q,J= 7.2 Hz, 2H), 3.54 (s, 2H),1.20 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz, CDCl3): = 169.1, 140.5, 134.9,128.4 (q,J= 32.4 Hz), 128.1, 125.8 (q,J= 3.9 Hz), 124.0 (q,J= 240.3Hz), 61.8, 35.4, 14.0.
Example 8A thioether preparation process, which comprises adding 0.3mmol of m-methylthiophenol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 18 h (monitoring the completion of the reaction by TLC), was carried out to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally performing silica gel column chromatography to obtain the 2-m-tolylthio ethyl acetate 3 ha.
Figure DEST_PATH_IMAGE013
Colorless liquid, yield 88%.1H NMR (600 MHz, CDCl3): = 7.22 (m, 3H), 7.02 (d,J= 7.2 Hz, 1H), 4.16 (q,J= 7.2 Hz, 2H), 3.61 (s, 2H), 2.31 (s, 3H), 1.22(t,J= 7.2 Hz, 3H).13C NMR (150 MHz, CDCl3): = 169.7, 138.7, 134.7, 130.5,128.8, 127.7, 126.9, 61.4, 36.6, 21.2, 14.0.
Example 9A thioetherThe preparation method of (1) is that 0.3mmol of m-methoxythiophenol and 0.6 mmol (2 equiv) of ethyl diazoacetate are added into a mixed solvent of acetonitrile and water, and the mixture is stirred and reacted for 15 h (the reaction is monitored to be complete by TLC) under the irradiation of a 23W Compact Fluorescent Lamp (CFL) at room temperature to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove solvent, and performing silica gel column chromatography to obtain 2-m-methoxyphenylthioacetate 3 ia.
Figure 516535DEST_PATH_IMAGE014
Colorless liquid, yield 83%.1H NMR (600 MHz, CDCl3): = 7.19 (t,J= 8.4 Hz,1H), 6.97-6.95 (m, 2H), 6.75 (dd,J= 8.4, 2.4 Hz, 1H), 4.16 (q,J= 7.2 Hz,2H), 3.78 (s, 3H), 3.63 (s, 2H), 1.22 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz,CDCl3): = 169.6, 159.8, 136.3, 129.8, 121.7, 114.8, 112.7, 61.5, 55.2,36.5, 14.1.
Example 10A thioether was prepared by adding 0.3mmol of m-bromophenylthiol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, and stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 20 hours (completion of the reaction was monitored by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally performing silica gel column chromatography to obtain the 2-m-bromophenylthioacetic acid ethyl ester 3 ja.
Figure DEST_PATH_IMAGE015
Colorless liquid, yield 77%.1H NMR (600 MHz, CDCl3): = 7.54 (t,J= 1.8 Hz,1H), 7.34-7.30 (m, 2H), 7.15 (t,J= 8.4 Hz, 1H), 4.17 (q,J= 7.2 Hz, 2H),3.63 (s, 2H), 1.23 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz, CDCl3): = 169.2,137.4, 132.0, 130.3, 129.8, 128.0, 122.8, 61.7, 36.3, 14.1.
Example 11 a thioether preparation process, which comprises adding m-fluoro thiophenol 0.3mmol, ethyl diazoacetate 0.6 mmol (2 equiv) to a mixed solvent of acetonitrile and water, and stirring the reaction for 15 h (reaction completion monitored by TLC) under the irradiation of 23W Compact Fluorescent Lamp (CFL) at room temperature to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering and distilling under reduced pressure to remove the solvent, and finally carrying out silica gel column chromatography to obtain the 2-m-fluorophenylsulfanylacetic acid ethyl ester 3 ka.
Figure 653119DEST_PATH_IMAGE016
Colorless liquid, yield 76%.1H NMR (400 MHz, CDCl3): = 7.44 (dd,J= 8.8, 5.2Hz, 2H), 7.00 (t,J= 8.8 Hz, 2H), 4.22 (q,J= 7.2 Hz, 2H), 3.56 (s, 2H),1.22 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz, CDCl3): = 169.2, 137.4, 132.0,130.3, 129.8, 128.0, 122.8, 61.7, 36.3, 14.1.
Example 12A thioether was prepared by adding 0.3mmol of o-fluorobenzenethiol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, and stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 12 h (completion of the reaction was monitored by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally performing silica gel column chromatography to obtain the 2-o-fluorophenylsulfanylacetic acid ethyl ester 3 la.
Figure DEST_PATH_IMAGE017
Colorless liquid, yield 92%.1H NMR (600 MHz, CDCl3): = 7.47-7.44 (m, 1H),7.28-7.24 (m, 1H), 7.10-7.05 (m, 2H), 4.12 (q,J= 7.2 Hz, 2H), 3.60 (s, 2H),1.18 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz, CDCl3): = 169.3, 161.8 (d,J=245.1 Hz), 133.4 (d,J= 1.35 Hz), 129.6 (d,J= 7.8 Hz), 124.5 (d,J= 3.75Hz), 121.4 (d,J= 17.55 Hz), 115.8 (d,J= 22.35 Hz), 61.5, 36.0, 14.0.
Example 13A thioether production process, which comprises adding 0.3mmol of o-chlorothiophenol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, reacting while stirring at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 12 hours (completion of reaction monitored by TLC), gives a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove solvent, and performing silica gel column chromatography to obtain 2-o-chlorophenylethyl acetate 3 ma.
Figure 508948DEST_PATH_IMAGE018
Colorless liquid, yield 82%.1H NMR (600 MHz, CDCl3): = 7.41-7.36 (m, 2H),7.23-7.20 (m, 1H), 7.17-7.14 (m, 1H), 4.16 (q,J= 7.2 Hz, 2H), 3.67 (s, 2H),1.22 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz, CDCl3): = 169.1, 134.2, 134.1,130.0, 129.8, 127.7, 127.2, 61.7, 35.2, 14.0.
Example 14A thioether was prepared by adding 0.3mmol of o-bromophenylthiol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, and stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 15 h (completion of the reaction was monitored by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then separatedAnhydrous Na for second pass2SO4Drying, filtering and distilling under reduced pressure to remove the solvent, and finally carrying out silica gel column chromatography to obtain the 2-o-bromophenylthioacetic acid ethyl ester 3 na.
Figure DEST_PATH_IMAGE019
Colorless liquid, yield 72%.1H NMR (600 MHz, CDCl3): = 7.55 (dd,J= 7.8, 1.2Hz, 1H), 7.38 (dd,J= 7.8, 1.8 Hz, 1H), 7.27 (dd,J= 7.2, 1.2 Hz, 1H),7.08-7.05 (m, 1H), 4.17 (q,J= 7.2 Hz, 2H), 3.67 (s, 2H), 1.23 (t,J= 7.2Hz, 3H).13C NMR (150 MHz, CDCl3): = 169.1, 134.3, 133.1, 129.5, 127.9,127.7, 124.2, 61.7, 35.6, 14.1.
Example 15A thioether production process, which comprises adding 0.3mmol of 3, 4-dimethylthiophenol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, reacting while stirring at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 9 hours (completion of reaction was monitored by TLC), gives a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally performing silica gel column chromatography to obtain the 2- (3, 4-dimethylphenylthio) ethyl acetate 3 oa.
Figure 626946DEST_PATH_IMAGE020
Colorless liquid, yield 86%.1H NMR (600 MHz, CDCl3): = 7.21 (br, 1H), 7.17-7.16 (m, 1H), 7.06 (d,J= 7.8 Hz, 1H), 4.15 (q,J= 7.2 Hz, 2H), 3.57 (s,2H), 2.23 (s, 3H), 2.22 (s, 3H), 1.22 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz,CDCl3): = 169.9, 137.4, 136.0, 132.1, 131.3, 130.3, 128.3, 61.4, 37.4,19.7, 19.4, 14.1.
EXAMPLE 16A method for producing a thioether in which an acetonitrile-water mixed solvent is added0.3mmol of 2, 4-dimethylthiophenol and 0.6 mmol (2 equiv) of ethyl diazoacetate were added, and the reaction was stirred at room temperature under irradiation of a 23W Compact Fluorescent Lamp (CFL) for 9 h (completion of the reaction was monitored by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove solvent, and performing silica gel column chromatography to obtain 2- (2, 4-dimethylphenylthio) ethyl acetate 3 pa.
Figure DEST_PATH_IMAGE021
Colorless liquid, yield 92%.1H NMR (600 MHz, CDCl3): = 7.29 (d,J= 8.4 Hz,1H), 7.01 (s, 1H), 6.96 (d,J= 7.8 Hz, 1H), 4.13 (q,J= 7.2 Hz, 2H), 3.54(s, 2H), 2.40 (s, 3H), 2.28 (s, 3H), 1.21 (t,J= 7.2 Hz, 3H).13C NMR (150MHz, CDCl3): = 169.7, 139.0, 137.3, 131.2, 131.1, 130.2, 127.3, 61.4, 36.6,20.9, 20.3, 14.0.
Example 17A thioether was prepared by adding 0.3mmol of 2, 4-dichlorothiophenol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, and reacting while stirring at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 20 h (completion of reaction was monitored by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally performing silica gel column chromatography to obtain the 2- (2, 4-dichlorophenylthio) ethyl acetate 3 qa.
Figure 318958DEST_PATH_IMAGE022
Colorless liquid, yield 88%.1H NMR (600 MHz, CDCl3): = 7.40 (d,J= 8.4 Hz,1H), 7.35 (d,J= 8.4 Hz, 1H), 7.20 (dd,J= 8.4, 2.4 Hz, 1H), 4.16 (q,J=7.2 Hz, 2H), 3.64 (s, 2H), 1.23 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz, CDCl3):= 168.9, 135.2, 133.2, 132.8, 131.1, 129.6, 127.5, 61.8, 35.3, 14.1.
Example 18A thioether was prepared by adding 0.3mmol of pyridine-2-thiol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, and stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 11 h (completion of the reaction was monitored by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove solvent, and performing silica gel column chromatography to obtain 2- (pyridine-2-sulfenyl) ethyl acetate 3 ra.
Figure DEST_PATH_IMAGE023
Colorless liquid, yield 82%.1H NMR (600 MHz, CDCl3): = 8.37 (dd, J = 4.8, 1.2Hz, 1H), 7.48-7.45 (m, 1H), 7.21 (d,J= 8.4 Hz, 1H), 6.98-6.96 (m, 1H), 4.18(q,J= 7.2 Hz, 2H), 3.96 (s, 2H), 1.24 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz,CDCl3): = 169.7, 156.9, 149.3, 136.0, 121.9, 119.7, 61.5, 32.3, 14.1.
Example 19A thioether was prepared by adding 0.3mmol of 5-nitropyridine-2-thiol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, and reacting the mixture at room temperature under irradiation of a 23W Compact Fluorescent Lamp (CFL) with stirring for 6 hours (completion of the reaction was monitored by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove solvent, and performing silica gel column chromatography to obtain 2- (5-nitropyridine-2-sulfenyl) ethyl acetate 3 sa.
Figure 242921DEST_PATH_IMAGE024
Colorless liquid, yield 87%.1H NMR (600 MHz, CDCl3): = 9.19 (d,J= 2.4 Hz,1H), 8.25 (dd,J= 9.0, 3.0 Hz, 1H), 7.36 (d,J= 9.0 Hz, 1H), 4.21 (q,J=7.2 Hz, 2H), 4.03 (s, 2H), 1.27 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz, CDCl3):= 168.5, 165.4, 114.9, 130.6, 121.3, 61.9, 32.7, 14.1.
Example 20A thioether was prepared by adding 0.3mmol of pyrimidine-2-thiol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, and stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 9 h (completion of the reaction was monitored by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove solvent, and performing silica gel column chromatography to obtain 2- (pyrimidine-2-sulfenyl) ethyl acetate 3 ta.
Figure DEST_PATH_IMAGE025
Colorless liquid, yield 90%.1H NMR (600 MHz, CDCl3): = 8.49 (d,J= 4.8 Hz,2H), 6.96 (t,J= 4.8 Hz, 1H), 4.19 (q,J= 7.2 Hz, 2H), 3.91 (s, 2H), 1.24(t,J= 7.2 Hz, 3H).13C NMR (150 MHz, CDCl3): = 170.8, 169.1, 157.2, 116.8,61.6, 33.4, 14.1.
Example 21A thioether was prepared by adding 0.3mmol 4, 6-dimethylpyrimidine-2-thiol and 0.6 mmol ethyl diazoacetate (2 equiv) to a mixed solvent of acetonitrile and water, and stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 6 hours (monitoring the completion of the reaction by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove solvent, and passingPerforming silica gel column chromatography to obtain 3ua of 2- (4, 6-dimethylpyrimidine-2-sulfenyl) ethyl acetate.
Figure 703989DEST_PATH_IMAGE026
Colorless liquid, yield 93%.1H NMR (600 MHz, CDCl3): = 6.96 (s, 1H), 4.19 (q,J= 7.2 Hz, 2H), 3.90 (s, 2H), 2.37 (s, 6H), 1.26 (t,J= 7.2 Hz, 3H).13C NMR(150 MHz, CDCl3): = 169.5, 169.4, 167.0, 115.9, 61.4, 33.5, 23.7, 14.2.
Example 22A thioether was prepared by adding 0.3mmol of benzoxazole-2-thiol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, and reacting the mixture at room temperature under irradiation of a 23W Compact Fluorescent Lamp (CFL) with stirring for 24 hours (completion of the reaction was monitored by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove solvent, and performing silica gel column chromatography to obtain 2- (benzoxazole-2-sulfenyl) ethyl acetate 3 va.
Figure DEST_PATH_IMAGE027
Colorless liquid, yield 48%.1H NMR (600 MHz, CDCl3): = 7.59-7.58 (m, 1H),7.44-7.43 (m, 1H), 7.29-7.26 (m, 1H), 7.24-7.23 (m, 1H), 4.25 (q,J= 7.2 Hz,2H), 4.11 (s, 2H), 1.28 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz, CDCl3): =167.9, 163.3, 152.1, 141.7, 124.4, 124.1, 118.6, 110.0, 62.2, 34.2, 14.1.
Example 23A thioether preparation process, which comprises adding 0.3mmol of benzothiazole-2-thiol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, reacting at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) with stirring for 24 h (reaction completion monitored by TLC), gives a mixture. The mixture is saturated with foodQuenching with brine (2 mL), extraction with ethyl acetate (3X 5 mL) gave an organic phase which was then purified over anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally performing silica gel column chromatography to obtain the 2- (benzothiazole-2-sulfenyl) ethyl acetate 3 wa.
Figure 320784DEST_PATH_IMAGE028
Colorless liquid, yield 63%.1H NMR (600 MHz, CDCl3): = 7.84 (d,J= 7.8 Hz,1H), 7.74 (d,J= 7.8 Hz, 1H), 7.41-7.39 (m, 1H), 7.30-7.28 (m, 1H), 4.24 (q,J= 7.2 Hz, 2H), 4.16 (s, 2H), 1.28 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz,CDCl3): = 168.2, 164.7, 152.9, 135.5, 126.0, 124.4, 121.7, 121.0, 62.0,35.1, 14.1.
Example 24A thioether was prepared by adding 0.3mmol of thiophene-2-thiol and 0.6 mmol (2 equiv) of ethyl diazoacetate to a mixed solvent of acetonitrile and water, and reacting while stirring at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 7 h (completion of reaction was monitored by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering and distilling under reduced pressure to remove the solvent, and finally carrying out silica gel column chromatography to obtain the 2- (thiophene-2-sulfenyl) ethyl acetate 3 xa.
Figure DEST_PATH_IMAGE029
Colorless liquid, yield 80%.1H NMR (600 MHz, CDCl3): = 7.37 (dd,J= 5.4, 1.2Hz, 1H), 7.20 (dd,J= 3.6, 1.2 Hz, 1H), 6.97 (dd,J= 5.4, 3.6 Hz, 1H), 4.16(q,J= 7.2 Hz, 2H), 3.49 (s, 2H), 1.24 (t,J= 7.2 Hz, 3H).13C NMR (150 MHz,CDCl3): = 169.3, 135.0, 132.4, 130.5, 127.6, 61.5, 41.0, 14.1.
The process route of the following examples 25 to 40 is as follows:
Figure 500093DEST_PATH_IMAGE030
example 25A thioether production process, which comprises adding 0.3mmol of p-methoxythiophenol and 0.6 mmol (2 equiv) of methyl α -phenyldiazoacetate to a mixed solvent of acetonitrile and water, reacting while stirring at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 20 hours (completion of reaction was monitored by TLC), gives a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally performing silica gel column chromatography to obtain 2-p-methoxyphenylthio-2-phenylacetic acid methyl ester 3 eb.
Figure DEST_PATH_IMAGE031
Colorless liquid, yield 71%.1H NMR (600 MHz, CDCl3): = 7.39-7.38 (m, 2H),7.32-7.28 (m, 5H), 6.80-6.77 (m, 2H), 4.76 (s, 1H), 3.78 (s, 3H), 3.66 (s,3H).13C NMR (150 MHz, CDCl3): = 171.0, 160.2, 136.2, 135.8, 128.5, 128.1,123.6, 114.5, 110.0, 57.4, 55.3, 52.5.
Example 26A thioether preparation process, which comprises adding 0.3mmol of p-methoxythiophenol and 0.6 mmol (2 equiv) of isopropyl α -phenyldiazoacetate to a mixed solvent of acetonitrile and water, reacting while stirring at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 24 h (completion of reaction monitored by TLC), gives a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally performing silica gel column chromatography to obtain the isopropyl 2-p-methoxyphenylthio-2-phenylacetate 3 ec.
Figure 956307DEST_PATH_IMAGE032
Colorless liquid, yield 78%.1H NMR (600 MHz, CDCl3): = 7.40 (d,J= 7.2 Hz,2H), 7.33-7.27 (m, 5H), 6.78 (d,J= 8.4 Hz, 2H), 4.98-4.94 (m, 1H), 4.72 (s,1H), 3.78 (s, 3H), 1.14 (t,J= 7.2 Hz, 6H).13C NMR (150 MHz, CDCl3): =170.0, 160.1, 136.1, 136.0, 128.6, 128.5, 128.0, 123.9, 114.4, 69.2, 57.5,55.3, 21.6, 21.5.
Example 27A thioether was prepared by adding 0.3mmol of p-methoxythiophenol and 0.6 mmol (2 equiv) of isopropyl α -p-methylphenyldiazoacetate to a mixed solvent of acetonitrile and water, and stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 24 h (monitoring the completion of the reaction by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally performing silica gel column chromatography to obtain the isopropyl 2-p-methoxyphenylthio-2-p-tolylacetate 3 ed.
Figure DEST_PATH_IMAGE033
Colorless liquid, yield 76%.1H NMR (600 MHz, CDCl3): = 7.35 (d,J= 8.4 Hz,2H), 7.31 (d,J= 7.8 Hz, 2H), 7.11 (d,J= 8.4 Hz, 2H), 6.79 (d,J= 8.4 Hz,2H), 4.98-4.94 (m, 1H), 4.71 (s, 1H), 3.77 (s, 3H), 2.32 (s, 3H), 1.15 (d,J= 6.6 Hz, 3H), 1.14 (d,J= 6.0 Hz, 3H).13C NMR (150 MHz, CDCl3): = 170.1,160.0, 137.8, 135.8, 132.9, 129.1, 128.4, 124.3, 114.4, 69.0, 57.2, 55.2,21.6, 21.5, 21.1.
EXAMPLE 28A method for producing a thioether by adding 0.3mmol of p-methoxythiophenol and 0.6 mmol (2 equiv) of isopropyl α -p-methoxyphenyldiazoacetate to a mixed solvent of acetonitrile and water and reacting them with stirring at room temperature under irradiation of a 23W Compact Fluorescent Lamp (CFL) for 28 hoursTLC monitored reaction complete) to give a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove solvent, and performing silica gel column chromatography to obtain 2-p-methoxyphenylthio-2-p-methoxyphenylacetic acid isopropyl ester 3 ee.
Figure 537461DEST_PATH_IMAGE034
Colorless liquid, yield 86%.1H NMR (600 MHz, CDCl3): = 7.33 (d,J= 7.8 Hz,4H), 6.82 (d,J= 8.4 Hz, 2H), 6.78 (d,J= 9.0 Hz, 2H), 4.97-4.92 (m, 1H),4.69 (s, 1H), 3.78 (s, 3H), 3.76 (s, 3H), 1.15 (d,J= 6.0 Hz, 3H), 1.13 (d,J= 6.0 Hz, 3H).13C NMR (150 MHz, CDCl3): = 170.2, 160.1, 159.4, 135.9,129.7, 128.0, 124.2, 114.4, 113.9, 69.0, 56.8, 55.3, 55.2, 21.7, 21.5.
Example 29A thioether was prepared by adding 0.3mmol of p-methoxythiophenol and 0.6 mmol (2 equiv) of isopropyl α -p-fluorophenyldiazoacetate to a mixed solvent of acetonitrile and water, and stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 20 hours (completion of the reaction was monitored by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally performing silica gel column chromatography to obtain the 2-p-methoxyphenylthio-2-p-fluorophenylacetic acid isopropyl ester 3 ef.
Figure DEST_PATH_IMAGE035
Colorless liquid, yield 68%.1H NMR (600 MHz, CDCl3): = 7.37-7.35 (m, 2H),7.31-7.29 (m, 2H), 6.97 (t,J= 9.0 Hz, 2H), 6.78 (d,J= 9.0 Hz, 2H), 4.98-4.94 (m, 1H), 4.69 (s, 1H), 3.77 (s, 3H), 1.15 (d,J= 7.2 Hz, 6H).13C NMR(150 MHz, CDCl3): = 169.8, 162.5 (d,J= 245.7 Hz), 160.3, 136.2, 131.9 (d,J= 3.15 Hz), 130.3 (d,J= 33.0 Hz), 123.6, 115.3 (d,J= 21.45 Hz), 114.5,69.3, 56.7, 55.3, 21.5.
Example 30A thioether was prepared by adding 0.3mmol of p-methoxythiophenol and 0.6 mmol (2 equiv) of isopropyl α -p-chlorophenyldiazoacetate to a mixed solvent of acetonitrile and water, and stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 18 h (monitoring the completion of the reaction by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally performing silica gel column chromatography to obtain the isopropyl 2-p-methoxyphenylthio-2-p-chlorophenylacetate 3 eg.
Figure 59579DEST_PATH_IMAGE036
Colorless liquid, yield 70%.1H NMR (600 MHz, CDCl3): = 7.33-7.29 (m, 4H), 7.25(d,J= 8.4 Hz, 2H), 6.78 (d,J= 8.4 Hz, 2H), 5.00-4.93 (m, 1H), 4.67 (s,1H), 3.77 (s, 3H), 1.15 (d,J= 6.0 Hz, 6H).13C NMR (150 MHz, CDCl3): =169.6, 160.3, 136.2, 134.7, 133.9, 129.9, 128.6, 123.4, 114.5, 69.3, 56.8,55.3, 21.5.
Example 31A thioether was prepared by adding 0.3mmol of p-methoxythiophenol and 0.6 mmol (2 equiv) of isopropyl α -bromophenyldiazoacetate to a mixed solvent of acetonitrile and water, and stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 26 h (monitoring completion of the reaction by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove solvent, and performing silica gel column chromatography to obtain 2-p-methoxyphenylthio3eh of isopropyl-2-p-bromophenylacetate.
Figure DEST_PATH_IMAGE037
Colorless liquid, yield 65%.1H NMR (600 MHz, CDCl3): = 7.32-7.29 (m, 4H), 7.26(d,J= 9.0 Hz, 2H), 6.78 (d,J= 8.4 Hz, 2H), 4.98-4.94 (m, 1H), 4.67 (s,1H), 3.77 (s, 3H), 1.15 (d,J= 6.0 Hz, 6H).13C NMR (150 MHz, CDCl3): =169.6, 160.3, 136.3, 134.6, 133.9, 129.9, 128.6, 123.4, 114.5, 69.4, 56.7,55.3, 21.5.
Example 32A thioether was prepared by adding 0.3mmol of p-methoxythiophenol and 0.6 mmol (2 equiv) of isopropyl α -p-trifluoromethylphenyldiazoacetate to a mixed solvent of acetonitrile and water, and stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 28 hours (monitoring the completion of the reaction by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove solvent, and performing silica gel column chromatography to obtain isopropyl 2-p-methoxyphenylthio-2-p-trifluoromethylphenyl acetate 3 ei.
Figure 913134DEST_PATH_IMAGE038
Colorless liquid, yield 60%.1H NMR (600 MHz, CDCl3): = 7.55 (d,J= 7.8 Hz,2H), 7.49 (d,J= 8.4 Hz, 2H), 7.31-7.28 (m, 2H), 6.78 (dd,J= 7.2, 2.4 Hz,2H), 5.00-4.95 (m, 1H), 4.72 (m, 1H), 3.78 (s, 3H), 1.16 (d,J= 3.6 Hz, 3H),1.15 (d, J = 3.0 Hz, 3H).
EXAMPLE 33A method for preparing thioether, which comprises adding 0.3mmol of p-methoxythiophenol and 0.6 mmol (2 equiv) of isopropyl α -methylbenzene diazoacetate to a mixed solvent of acetonitrile and water, stirring and reacting for 20 h under the irradiation of a 23W Compact Fluorescent Lamp (CFL) at room temperatureReaction completion was monitored by TLC), a mixture was obtained. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally carrying out silica gel column chromatography to obtain the isopropyl 2-p-methoxyphenylthio-2-o-methylphenylacetate 3 ej.
Figure DEST_PATH_IMAGE039
Colorless liquid, yield 75%.1H NMR (600 MHz, CDCl3): = 7.53 (dd,J= 5.4, 3.6Hz, 1H), 7.36-7.33 (m, 2H), 7.17-7.12 (m, 3H), 6.79-6.77 (m, 2H), 5.00-4.95(m, 1H), 4.96 (s, 1H), 3.77 (s, 3H), 2.33 (s, 3H), 1.14 (d,J= 3.0 Hz, 3H),1.13 (d,J= 2.4 Hz, 3H).13C NMR (150 MHz, CDCl3): = 170.3, 160.1, 136.1,136.0, 134.2, 130.4, 128.2, 127.9, 126.3, 124.2, 114.4, 69.1, 55.3, 53.8,21.6, 21.5, 19.5.
Example 34A thioether was prepared by adding 0.3mmol of p-methoxythiophenol and 0.6 mmol (2 equiv) of isopropyl α -bromobenzenediazoacetate to a mixed solvent of acetonitrile and water, and stirring the mixture at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 30 h (monitoring completion of the reaction by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally carrying out silica gel column chromatography to obtain the 2-p-methoxyphenylthio-2-o-bromophenyl isopropyl acetate 3 ek.
Figure 929631DEST_PATH_IMAGE040
Colorless liquid, yield 72%.1H NMR (600 MHz, CDCl3): = 7.63 (dd,J= 8.4, 1.8Hz, 1H), 7.53 (dd,J= 7.8, 1.2 Hz, 2H), 7.38-7.36 (m, 2H), 7.28-7.25 (m,1H), 7.13-7.10 (m, 1H), 6.80-6.77 (m, 2H), 5.27 (s, 1H), 5.00-4.96 (m, 1H),3.77 (s, 3H), 1.16 (s, 3H), 1.15 (s, 3H).13C NMR (150 MHz, CDCl3): = 169.6,160.2, 136.3, 135.5, 132.8, 130.2, 129.3, 127.6, 124.5, 123.9, 114.4, 69.4,55.9, 55.3, 21.6, 21.5.
EXAMPLE 35A method for producing a thioether, which comprises adding 0.3mmol of p-methoxythiophenol and 0.6 mmol (2 equiv) of isopropyl α -m-fluorophenyldiazoacetate to an acetonitrile-water mixed solvent, and reacting the mixture at room temperature under irradiation of a 23W Compact Fluorescent Lamp (CFL) with stirring for 28 hours (completion of the reaction was monitored by TLC), was provided. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally performing silica gel column chromatography to obtain 2-p-methoxyphenylthio-2-m-fluorophenylacetic acid isopropyl ester 3 el.
Figure DEST_PATH_IMAGE041
Colorless liquid, yield 66%.1H NMR (600 MHz, CDCl3): = 7.32-7.30 (m, 2H),7.25-7.22 (m, 1H), 7.17-7.12 (m, 2H), 6.98-6.95 (m, 1H), 6.80-6.77 (m, 2H),4.99-4.95 (m, 1H), 4.68 (s, 1H), 3.77 (s, 3H), 1.16 (d,J= 6.0 Hz, 3H), 1.15(d,J= 6.0 Hz, 3H).13C NMR (150 MHz, CDCl3): = 169.5, 162.6 (d,J= 244.95Hz), 160.3, 138.4 (d, J = 7.5 Hz), 136.2, 129.8 (d, J = 8.25 Hz), 124.3 (d, J= 2.7 Hz), 123.3, 115.6 (d, J = 22.8 Hz), 115.0 (d, J = 21.0 Hz), 114.5,69.4, 57.0, 56.9, 55.3, 21.5.
Example 36A thioether was prepared by adding 0.3mmol of p-methoxythiophenol and 0.6 mmol (2 equiv) of isopropyl α -chlorophenyldiazoacetate to a mixed solvent of acetonitrile and water, and reacting the mixture at room temperature under irradiation of a 23W Compact Fluorescent Lamp (CFL) with stirring for 25 h (completion of reaction was monitored by TLC) to obtain a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase, which wasThe organic phase is sequentially passed through anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally carrying out silica gel column chromatography to obtain the isopropyl 2-p-methoxyphenylthio-2-m-chlorophenylacetate 3 em.
Figure 614560DEST_PATH_IMAGE042
Colorless liquid, yield 78%.1H NMR (600 MHz, CDCl3): = 7.40-7.39 (m, 1H),7.32-7.30 (m, 2H), 7.26-7.20 (m, 3H), 6.79 (dd,J= 6.6, 2.4 Hz, 1H), 5.00-4.94 (m, 1H), 4.65 (s, 1H), 3.77 (s, 3H), 1.16 (d,J= 6.0 Hz, 3H), 1.15 (d,J= 6.6 Hz, 3H).13C NMR (150 MHz, CDCl3): = 169.5, 160.3, 138.0, 136.3,134.2, 129.6, 128.7, 128.2, 126.8, 123.2, 114.5, 69.4, 56.9, 55.3, 21.6,21.5.
Example 37A thioether preparation process, which comprises adding 0.3mmol of p-methoxyphenylphenol and 0.6 mmol (2 equiv) of isopropyl α -2, 5-difluorophenyldiazoacetate to a mixed solvent of acetonitrile and water, reacting while stirring at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 20 h (monitoring the completion of the reaction by TLC), gives a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally performing silica gel column chromatography to obtain the isopropyl 2-p-methoxyphenylthio-2- (2, 5-difluorophenyl) acetate 3 en.
Figure DEST_PATH_IMAGE043
Colorless liquid, yield 67%.1H NMR (600 MHz, CDCl3): = 7.34-7.28 (m, 3H),6.97-6.91 (m, 2H), 6.79 (d,J= 9.0 Hz, 2H), 5.01 (s, 1H), 5.00-4.96 (m, 2H),3.77 (s, 3H), 1.18 (d,J= 2.4 Hz, 3H), 1.17 (d,J= 3.0 Hz, 3H).13C NMR (150MHz, CDCl3): = 169.0, 160.5, 158.4 (dd,J= 241.05, 2.4 Hz), 155.0 (dd,J=242.4, 2.55 Hz), 136.5, 125.2 (q,J= 6.6 Hz), 122.7, 116.7 (dd,J= 25.5,3.15 Hz), 116.1 (dd,J= 51.45, 8.55 Hz), 116.0 (dd,J= 8.55, 2.1 Hz),114.5, 69.6, 55.3, 48.8, 21.5.
Example 38A thioether preparation process, in which p-methoxythiophenol 0.3mmol and α -phenyldiazoacetic acid cyclopentyl ester 0.6 mmol (2 equiv) are added to an acetonitrile-water mixed solvent, and the mixture is stirred at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 28h (completion of the reaction is monitored by TLC). The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally carrying out silica gel column chromatography to obtain the 2-p-methoxyphenylthio-2-phenylacetic acid cyclopentyl ester 3 eo.
Figure 323890DEST_PATH_IMAGE044
Colorless liquid, yield 66%.1H NMR (600 MHz, CDCl3): = 7.41-7.39 (m, 2H),7.33-7.25 (m, 5H), 6.80-6.77 (m, 2H), 5.13-5.10 (m, 1H), 4.71 (s, 1H), 3.78(s, 3H), 1.77-1.73 (m, 2H), 1.60-1.51 (m, 6H).13C NMR (150 MHz, CDCl3): =170.2, 160.1, 136.0, 135.9, 128.6, 128.5, 128.0, 123.9, 114.4, 76.8, 57.4,55.3, 32.5, 32.4, 23.6.
Example 39A thioether preparation process, which comprises adding 0.3mmol of p-methoxythiophenol and 0.6 mmol (2 equiv) of cyclohexyl α -phenyldiazoacetate to a mixed solvent of acetonitrile and water, reacting while stirring at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 20 h (monitoring the completion of the reaction by TLC), was carried out to give a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally carrying out silica gel column chromatography to obtain the 2-p-methoxyphenylthio-2-phenylacetic acid cyclohexyl ester 3 ep.
Figure DEST_PATH_IMAGE045
Colorless liquid, yield 81%.1H NMR (600 MHz, CDCl3): = 7.41-7.39 (m, 2H),7.33-7.25 (m, 5H), 6.80-6.77(m, 2H), 5.13-5.10 (m, 1H), 4.71 (s, 1H), 3.78(s, 3H), 1.77-1.73 (m, 2H), 1.60-1.51 (m, 6H).13C NMR (150 MHz, CDCl3): =170.2, 160.1, 136.0, 135.9, 128.6, 128.5, 128.0, 123.9, 114.4, 76.8, 57.4,55.3, 32.5, 32.4, 23.6.
Example 40A thioether production process, which comprises adding 0.3mmol of p-methoxythiophenol and 0.6 mmol (2 equiv) of 2-methylallyl α -phenyldiazoacetate to a mixed solvent of acetonitrile and water, reacting while stirring at room temperature under the irradiation of a 23W Compact Fluorescent Lamp (CFL) for 32 hours (monitoring the completion of the reaction by TLC), gave a mixture. The mixture was quenched with saturated brine (2 mL) and extracted with ethyl acetate (3X 5 mL) to give an organic phase which was then extracted with anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and finally carrying out silica gel column chromatography to obtain 3eq of 2-p-methoxyphenylthio-2-phenylacetic acid-2-methallyl ester.
Figure 461479DEST_PATH_IMAGE046
Colorless liquid, yield 66%.1H NMR (600 MHz, CDCl3): = 7.44-7.41 (m, 2H),7.35-7.30 (m, 5H), 6.80 (dd,J= 10.2, 3.0 Hz, 2H), 4.86 (s, 2H), 4.80 (s,1H), 4.49 (s, 2H), 3.79 (s, 3H), 1.63 (s, 3H).13C NMR (150 MHz, CDCl3): =170.2, 160.2, 139.4, 136.1, 135.8, 128.6, 128.5, 128.2, 123.7, 114.5, 113.3,68.7, 57.5, 55.3, 19.3.
In the above embodiments 1 to 40, the acetonitrile-water mixed solvent is a mixture of acetonitrile and deionized water in a ratio of 10: 1 (mL/mL) was added to the resulting mixture.
The volume ratio (mL/mL) of the chromatographic solution in the silica gel column chromatography is 20: 1 petroleum ether-ethyl acetate.

Claims (6)

1. A method for preparing thioether, which is characterized in that: adding mercaptan/phenol and alpha-diazoacetic ester into an acetonitrile-water mixed solvent, and stirring at room temperature under the irradiation of visible light until the reaction is complete to obtain a mixture; quenching and extracting the mixture to obtain an organic phase, drying, filtering, distilling under reduced pressure to remove the solvent, and performing silica gel column chromatography to obtain thioether; the molar ratio of the thiol/phenol to the alpha-diazoacetic acid ester is 0.3: 0.6.
2. the process according to claim 1, wherein: the mercaptan/phenol is one of p-methyl thiophenol, p-isopropyl thiophenol, p-tert-butyl thiophenol, p-methoxy thiophenol, p-fluoro thiophenol, p-trifluoromethyl thiophenol, m-methyl thiophenol, m-methoxy thiophenol, m-bromo thiophenol, m-fluoro thiophenol, o-chloro thiophenol, o-bromo thiophenol, 3, 4-dimethyl thiophenol, 2, 4-dichloro thiophenol, pyridine-2-thiol, 5-nitropyridine-2-thiol, pyrimidine-2-thiol, 4, 6-dimethyl pyrimidine-2-thiol, benzoxazole-2-thiol, benzothiazole-2-thiol and thiophene-2-thiol.
3. The process according to claim 1, wherein: the alpha-diazoacetic acid ester refers to ethyl diazoacetate, alpha-phenyl diazoacetic acid methyl ester, alpha-phenyl diazoacetic acid isopropyl ester, alpha-p-methyl phenyl diazoacetic acid isopropyl ester, alpha-p-methoxyphenyl diazoacetic acid isopropyl ester, alpha-p-fluorophenyl diazoacetic acid isopropyl ester, alpha-p-chlorophenyl diazoacetic acid isopropyl ester, alpha-p-bromophenyl diazoacetic acid isopropyl ester, alpha-p-trifluoromethyl phenyl diazoacetic acid isopropyl ester, alpha-o-methylphenyl diazoacetic acid isopropyl ester, alpha-o-bromophenyl diazoacetic acid isopropyl ester, alpha-m-fluorophenyl diazoacetic acid isopropyl ester, alpha-m-chlorophenyl diazoacetic acid isopropyl ester, alpha-2, 5-difluorophenyl diazoacetic acid isopropyl ester, alpha-phenyl diazoacetic acid cyclopentyl ester, alpha-phenyl diazoacetic acid cyclohexyl ester, alpha-phenyl diazoacetic acid isopropyl ester, One kind of alpha-phenyl diazoacetic acid-2-methyl allyl ester.
4. The process according to claim 1, wherein: the acetonitrile-water mixed solvent is prepared by mixing acetonitrile and deionized water according to the weight ratio of 10: 1 volume ratio of the mixture.
5. The process according to claim 1, wherein: the visible light is 23W compact fluorescent lamp.
6. The process according to claim 1, wherein: the volume ratio of the chromatographic solution in the silica gel column chromatography is 20: 1 petroleum ether-ethyl acetate.
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Publication number Priority date Publication date Assignee Title
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Title
HIDEO TOMIOKA，等: "Neighboring Group Participation in Carbene Chemistry. Effect of Neighboring Carboxylate Group on Carbene Reactivities", 《J. AM. CHEM. SOC.》 *
HODA KEIPOUR,等: "Copper-Catalyzed Carbenoid Insertion Reactions of α‑Diazoesters and α‑Diazoketones into Si−H and S−H Bonds", 《J. ORG. CHEM.》 *
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