CN109456237B - Method for synthesizing alkynyl sulfone - Google Patents

Method for synthesizing alkynyl sulfone Download PDF

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CN109456237B
CN109456237B CN201811518349.9A CN201811518349A CN109456237B CN 109456237 B CN109456237 B CN 109456237B CN 201811518349 A CN201811518349 A CN 201811518349A CN 109456237 B CN109456237 B CN 109456237B
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alkynyl
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sulfone
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CN109456237A (en
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赵子剑
罗正红
柯舒婷
连琰
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Huaihua University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Abstract

The invention provides a synthesis method of alkynyl sulfone, which comprises the following steps: mixing the substrate
Figure DDA0001902602300000011
Mixing 2-chloro-1-methyliodized pyridine, an alkaline substance and an organic solvent to form a reaction system, reacting at room temperature, and dehydrating a substrate to generate alkynyl sulfone shown as a formula II; wherein R is1Aryl, polyaryl, alkyl, alkenyl, alkynyl, alkoxy and halogenated hydrocarbon radicals; r2Aryl, polyaryl, alkyl, alkenyl, alkynyl, alkoxy, and halogenated hydrocarbyl. According to the method for synthesizing the alkynyl sulfone, the C-C triple bond is efficiently synthesized under the condition of not using transition metal in the process of synthesizing the alkynyl sulfone, so that the use of a transition metal catalyst is avoided, the synthesis cost is reduced, the synthesis yield is improved, and the generation of byproducts is reduced. Furthermore, the alkynyl sulfone synthesis method adopts a one-pot method, and the one-step synthesis of the C-C triple bond reduces the synthesis operation steps and improves the synthesis efficiency.

Description

Method for synthesizing alkynyl sulfone
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing alkynyl sulfone.
Background
The alkynyl sulfone is a key intermediate which can be converted into other heterocyclic compounds, has various biological activities and photoconductivity, and has important significance in organic synthesis and drug synthesis. Thus, the modification of unsaturated C-C bond containing sulfones to alkynyl sulfones has attracted considerable research interest. A great deal of work has been done on the synthesis of alkynyl sulfones, and a typical synthesis method is to use acetylene, acetylene bromide, aryl propionic acid, 1-dihalo-1-alkene, etc. and a corresponding coupling agent containing S to obtain sp-hybridized C and S coupled compounds under the catalysis of transition metals. However, in the case of using palladium and copper as transition metals as catalysts, the reaction is costly and homogeneous coupling of unstable acetylenic compounds or dibromoolefins inevitably occurs with many by-products. How to avoid using transition metal catalyst, and how to form alkynyl sulfone synthetic method of C-C triple bond with high efficiency is the technical problem that this field needs to solve urgently.
Disclosure of Invention
In view of the above, it is necessary to provide a method for synthesizing an alkynyl sulfone, which is a problem of how to avoid the use of a transition metal catalyst and to form a C — C triple bond with high efficiency.
The invention provides a synthesis method of alkynyl sulfone, which comprises the following steps:
mixing a substrate shown as a formula I, 2-chloro-1-methyl pyridine iodide, an alkaline substance and an organic solvent to form a reaction system, reacting at room temperature, and dehydrating the substrate to generate alkynyl sulfone shown as a formula II;
Figure GDA0002451784090000011
wherein R is1Is aryl, alkyl, alkenyl, alkynyl, alkoxy or halogenated hydrocarbon;
R2is aryl, alkyl, alkenyl, alkynyl, alkoxy or halogenated hydrocarbon.
In one embodiment, the alkaline substance is any one or more of sodium hydroxide, sodium carbonate, potassium acetate, potassium tert-butyl alkoxide, cesium carbonate and triethylamine.
In one embodiment, the basic substance is triethylamine, sodium hydroxide or potassium carbonate.
In one embodiment, the organic solvent is any one or more of dichloromethane, acetonitrile, 1, 2-dichloroethane, and N, N-dimethylformamide.
In one embodiment, the organic solvent is dichloromethane.
In one embodiment, R is characterized in that1Is any one of phenyl, p-methylphenyl, o-methylphenyl, 4-methoxyphenyl, 3, 4-methylenedioxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 3, 4-dichlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-cyanophenyl, 4-biphenyl and 2- (6-methoxynaphthalene) group.
In one embodiment, R2Is any one of phenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 3-chlorophenyl, 4-iodophenyl, 4-trifluoromethylphenyl, 4-nitrophenyl, 2-naphthyl and cyclopropyl.
In one embodiment, the reaction time of the reaction under the room temperature condition is 2h to 4h, and the reaction under the room temperature condition is carried out under the protection of nitrogen.
In one embodiment, the molar ratio of the substrate, the 2-chloro-1-methyliodized pyridine, the basic substance and the organic solvent is (0.8-1.2): (0.8-1.2, (0.8-1.2) and (52-94).
In one embodiment, the molar ratio of the substrate, 2-chloro-1-methyliodized pyridine, basic substance, and organic solvent is 1: 1: 1: 78.
according to the method for synthesizing the alkynyl sulfone, in the process of synthesizing the alkynyl sulfone, the C-C triple bond is efficiently synthesized at room temperature under the condition of not using transition metal, so that the use of a transition metal catalyst is avoided, the synthesis cost is reduced, the synthesis yield is improved, and the generation of byproducts is reduced. Furthermore, the alkynyl sulfone synthesis method adopts a one-pot method, and the one-step synthesis of the C-C triple bond reduces the synthesis operation steps and improves the synthesis efficiency.
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In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for the embodiments will be briefly described below.
Fig. 1 to 21 are nuclear magnetic resonance spectra of the target product prepared in example, respectively.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below by way of embodiments and with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The synthesis method of alkynyl sulfone provided by the invention comprises the following steps:
mixing a substrate shown as a formula I, 2-chloro-1-methyl pyridine iodide, an alkaline substance and an organic solvent to form a reaction system, reacting at room temperature, and dehydrating the substrate to generate alkynyl sulfone shown as a formula II;
Figure GDA0002451784090000031
wherein R is1Is aryl, alkyl, alkenyl, alkynyl, alkoxy or halogenated hydrocarbon;
R2is aryl, alkyl, alkenyl, alkynyl, alkoxy or halogenated hydrocarbon.
According to the method for synthesizing the alkynyl sulfone, in the process of synthesizing the alkynyl sulfone, the C-C triple bond is efficiently synthesized at room temperature under the condition of not using transition metal, so that the use of a transition metal catalyst is avoided, the synthesis cost is reduced, the synthesis yield is improved, and the generation of byproducts is reduced. Furthermore, the alkynyl sulfone synthesis method adopts a one-pot method, and the one-step synthesis of the C-C triple bond reduces the synthesis operation steps and improves the synthesis efficiency.
As an optional embodiment, the basic substance is any one or more of sodium hydroxide, sodium carbonate, potassium acetate, potassium tert-butyl alkoxide, cesium carbonate and triethylamine. Preferably, the basic substance is triethylamine, sodium hydroxide or potassium carbonate.
As an alternative embodiment, the organic solvent is any one or more of dichloromethane, acetonitrile, 1, 2-dichloroethane, and N, N-dimethylformamide. Preferably, the organic solvent is dichloromethane.
As an alternative embodiment, R1Is phenylP-methylphenyl, o-methylphenyl, 4-methoxyphenyl, 3, 4-methylenedioxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 3, 4-dichlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-cyanophenyl, 4-biphenyl, and 2- (6-methoxynaphthalene) groups.
As an alternative embodiment, R2Is any one of phenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 3-chlorophenyl, 4-iodophenyl, 4-trifluoromethylphenyl, 4-nitrophenyl, 2-naphthyl and cyclopropyl.
As an alternative embodiment, the reaction time of the reaction under the room temperature condition is 2h to 4h, and the reaction under the room temperature condition is carried out under the protection of protective gas.
As an alternative embodiment, the molar ratio of the substrate, the 2-chloro-1-methyliodized pyridine, the alkali and the organic solvent is (0.8-1.2): (0.8-1.2, (0.8-1.2) and (52-94).
As an alternative embodiment, the molar ratio of substrate, 2-chloro-1-methyliodized pyridine, base and organic solvent is 1: 1: 1: 78.
the second aspect of the present invention provides an alkynyl sulfone prepared by the above-mentioned alkynyl sulfone synthesis method.
The third aspect of the present invention provides an application of the alkynyl sulfone described above in organic synthesis or pharmaceutical synthesis.
Example 1
Mixing 1.0mmol of 1-phenyl-2-tosylethanone (1a), 1.0mmol of 2-chloro-1-methyliodide pyridine, 1.0mmol of sodium hydroxide and 5.0mL of dichloromethane, stirring for reaction at room temperature for 3.0h under the protection of nitrogen, extracting according to a conventional flow, removing the solvent, separating and purifying by column chromatography, and using petroleum ether/ethyl acetate (10:1) as an eluent to obtain a yellow solid target product 2a with a melting point of 74-75 ℃ and a yield of 52%.
The synthetic reaction formula is shown as follows:
Figure GDA0002451784090000041
referring to fig. 1, the nmr spectrum data of the target product:1H NMR(400MHz,CDCl3)＝8.08(d,J＝7.6Hz,2H),7.69(t,J＝7.3Hz,1H),7.60(t,J＝7.5Hz,2H),7.52(d,J＝7.6Hz,2H),7.47(t,J＝7.4Hz,1H),7.37(t,J＝7.5Hz,2H)ppm。
carbon nuclear magnetic resonance spectrogram data of a target product:13C NMR(101MHz,CDCl3) 141.89,134.32,132.89,131.72,129.52,128.82,127.54,117.97,93.63,85.42,77.48,77.16 and 76.84ppm. Mass spectrum data of the target product: ms (ei): m/z (%) (77.04 (51),89.03(38),125.00(49),178.06(100),241.99(30). Infrared spectrum data of the target product: IR (KBr): nu 2169,1651,1455,1323,1155,1081,866,756,720,688,653,569cm-1. High resolution mass spectrometry data of the target product: HRMS (EI) Calcd for C14H10O2S]+242.0402 and Found 242.0398. Examples 2 to 17 are different from example 1 in that the synthesis reaction was carried out using different kinds of bases or different kinds of solvents, and the results of the synthesis reaction are shown in table 1.
TABLE 1 results of synthetic reactions of examples 1 to 17 with different reaction systems
Figure GDA0002451784090000042
Figure GDA0002451784090000051
As can be seen from Table 1, the base used in example 2 was sodium carbonate (Na)2CO3) Sodium carbonate allows the synthesis reaction to take place, but the yield of the target product alkynyl sulfone (2a) is only 28%. Example 3 the base used was potassium carbonate (K)2CO3) The potassium carbonate can ensure that the synthesis reaction is relatively complete, and the yield of the target product alkynyl sulfone (2a) is as high as 86%. The bases adopted in the examples 4 and 5 are potassium acetate and tert-butyl potassium alcoholate respectively, but the difference rate of the target product alkynyl sulfone (2a) is only 20%. As can be seen, the synthetic reaction of the invention is obviously superior to other potassium salts when potassium carbonate is adopted. Example 6 the base used was cesium carbonate (Cs)2CO3)，This reaction can occur, but the yield of the target product alkynylsulfone (2a) is only 20%. The bases used in examples 7 to 9 are each organic bases ET2HN、ET3N and pyridine, the experimental results show that ET2HN and pyridine were not able to proceed, Et3N, unlike the other organic base reagents tested, gave the desired product, alkynyl sulfone (2a), in excellent yield, 92%. It was further demonstrated by example 10 that the base is very important for the reaction to take place, and example 10 did not detect the target product alkynyl sulfone in the absence of base. Examples 11-16 examine the effect of different solvents on the reaction. The reaction was carried out in example 11 using acetonitrile as solvent, in example 12 using 1, 2-Dichloroethane (DCE) as solvent, and in example 13 using N, N-Dimethylformamide (DMF) as solvent, but the yield was low, up to 85%. The reaction did not proceed when 1, 4-dioxane was used as a solvent in example 14, toluene was used as a solvent in example 15, and ethyl acetate was used as a solvent in example 16, and these solvents were ineffective for conversion, and the objective alkynyl sulfone (2a) was not detected after 3 hours of the reaction. Further, example 17 differs from example 1 in that the reaction was carried out under an argon atmosphere, demonstrating the effect of molecular oxygen, without affecting the yield at room temperature.
TABLE 2 results of different functional group synthesis reactions of examples 18-37 substrates
Figure GDA0002451784090000061
The reaction systems of examples 18 to 37 were different from those of example 1 in that triethylamine (Et3N) was used as a base, methylene chloride (DCM) was used as an organic solvent, and the substrate R was reacted1、R2Having different substituents as shown in Table 2, the substrate R was investigated under mild reaction conditions1、R2Compatibility of different functional groups. EXAMPLE 18R of substrate 1- (p-tolyl) -2-phenylsulfonylethanolidone (1b)1The substituent was p-tolyl, and the substrate (1b) was smoothly subjected to dehydration to give the desired objective sulfonylalkynylsulfone (2b) in a yield of 90%. In example 19, the substrate was the same as that of example 1Is different in that R1The substituent was o-tolyl and after treatment with CMPI, compound 2c was isolated in 89% yield. In examples 20 and 21, the substrate R1The substituents are each an electron-rich aryl group, and the yield of the objective compound 2d of example 20 was 88% and the yield of the objective compound 2e of example 21 was 85%. It has further been found by way of examples 22 to 26 that in general the conversion performance of halo-substituted substrates is lower than that of alkoxy substrates. The yields of the objective compound 2f of example 22, the objective compound 2g of example 23, the objective compound 2h of example 24, the objective compound 2i of example 25 and the objective compound 2j of example 26 were 72%, 79%, 70%, 76% and 70%, respectively, and the yield was only 70% to 79%. In example 27, the substrate R1When the substituent is electron-deficient aryl, the yield of the target compound 2k is only 76%.
In examples 28 and 29, the substrate R1When it is aryl, e.g. R11- (4,4' -biphenyl) -2-phenyl ethanone (1l) and 1- (6-methoxy-naphthalen-2-yl) -2-phenyl ethanone (1m), respectively, undergo a one-pot reaction to give the desired three-carbon bond modified sulfone compound 21 and compound 2m in 80% and 79% yields, respectively. Example 30 also checks R in the reaction2Tolerance of the substituent to the substrate sulfonic acid moiety. It was found that the change of the functional group generally lowers the yield. The 1-phenyl-2-tert-butylphenyl-sulfonylethanone (1n) is smoothly converted into the corresponding compound 2n in a yield of 60%. Example 31 demonstrates that other electron rich aryl groups have a positive effect on the conversion, with a 68% yield of compound 2 o. Examples 32-33 halogen of2The substituent is halide, and the yield of the target product, compound 2p and compound 2q, is 52% and 60%, respectively. In examples 34 to 35, R2Is an electron-deficient aryl substituent, is also observed in the reaction system, as compound 2r and compound 2s, in yields of 48% and 45%, respectively).
In examples 36 to 37, R2For aryl, the yield is 72% as compound 2 t. Notably, a yield of 68% of compound 2u was observed after CMPI treatment at room temperature.
Referring to fig. 1, the structural formula of the target product prepared in example 1 of the present invention is shown in formula 2 a.
Figure GDA0002451784090000071
Extracting according to a conventional flow, removing the solvent, separating and purifying by column chromatography, and taking petroleum ether/ethyl acetate (10:1) as an eluent to obtain a yellow solid target product 2 a. The melting point is 74-75 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) 8.08(d, J ═ 7.6Hz,2H),7.69(t, J ═ 7.3Hz,1H),7.60(t, J ═ 7.5Hz,2H),7.52(d, J ═ 7.6Hz,2H),7.47(t, J ═ 7.4Hz,1H),7.37(t, J ═ 7.5Hz,2H) ppm.13C NMR(101MHz,CDCl3) Mass spectrum data for target product 141.89,134.32,132.89,131.72,129.52,128.82,127.54,117.97,93.63,85.42,77.48,77.16,76.84 ppm: ms (ei) m/z (%) 77.04(51),89.03(38),125.00(49),178.06(100),241.99(30) infrared spectral data of target product: IR (KBr): nu 2169,1651,1455,1323,1155,1081,866,756,720,688,653,569cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C14H10O2S]+:242.0402,Found 242.0398.
Referring to fig. 2, the structural formula of the target product prepared in example 18 of the present invention is shown in fig. 2 b.
Figure GDA0002451784090000072
Extracting according to a conventional flow, removing the solvent, separating and purifying by column chromatography, and taking petroleum ether/ethyl acetate (10:1) as an eluent to obtain a yellow solid target product 2 b. The melting point is 82-83 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) 8.08(d, J ═ 7.8Hz,2H),7.68(t, J ═ 7.3Hz,1H),7.60(t, J ═ 7.3Hz,2H),7.42(d, J ═ 7.4Hz,2H),7.17(d, J ═ 7.6Hz,2H),2.37(s,3H) ppm.13C NMR(101MHz,CDCl3) Mass spectrum data for target product 142.60,142.07,134.20,132.87,129.61,129.48,127.49,114.85,94.37,85.03,21.94 ppm: ms (ei) m/z (%) 77.04(48),103.05(48),125.00(29),165.06(20),192.07(97),256.00(100) infrared spectral data of target product: IR (KBr): nu 2962,2177,1604,1508,1443,1334,1155,1083,1023,857,813,779,720,685,619,569,512cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C15H12O2S]+:256.0558,Found 256.0556.
Referring to fig. 3, the structural formula of the target product prepared in example 19 of the present invention is shown in formula 2 c.
Figure GDA0002451784090000081
Extracting according to a conventional flow, removing the solvent, separating and purifying by column chromatography, and taking petroleum ether/ethyl acetate (10:1) as an eluent to obtain a yellow solid target product 2 c. The melting point is 47-48 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) 8.08(d, J ═ 7.9Hz,2H),7.68(t, J ═ 7.2Hz,1H),7.59(t, J ═ 7.5Hz,2H),7.43(d, J ═ 7.7Hz,1H),7.34(t, J ═ 7.5Hz,1H), 7.23-7.12 (m,2H),2.35(s,3H) ppm. carbon nuclear magnetic resonance spectrum data of target product:13C NMR(101MHz,CDCl3) Mass spectrum data of target product 142.58,142.26,134.22,133.19,131.72,130.06,129.50,127.41,126.05,117.83,93.32,89.13,20.50 ppm: ms (ei) m/z (%) 77.04(93),103.05(57),115.05(100),125.00(37),165.06(31),191.07(91),256.00(66). IR (KBr): nu 3059,2179,1651,1325,1157,1082,850,755,727,688,653,572,541cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C15H12O2S]+:256.0558,Found 256.0561.
Referring to fig. 4, the structural formula of the target product prepared in example 20 of the present invention is shown in formula 2 d.
Figure GDA0002451784090000082
Extracting according to a conventional process, removing the solvent, separating and purifying by column chromatography, and taking petroleum ether/ethyl acetate (10:1) as an eluent to obtain a yellow solid target product 2 d. The melting point is 84-85 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) 8.07(d, J ═ 7.5Hz,2H),7.67(t, J ═ 7.4Hz,1H),7.58(t, J ═ 7.6Hz,2H),7.46(d, J ═ 8.7Hz,2H),6.86(d, J ═ 8.6Hz,2H),3.82(s,3H) ppm.13C NMR(101MHz,CDCl3) Mass spectrum data of target product 162.31,142.20,134.81,134.10,129.43,127.37,114.56,109.55,94.81,84.71,55.58 ppm: ms (ei) m/z (%) 77.04(100),131.05(88),207.23(98),272.32 (21.) infrared spectral data of the target product: IR (KBr): nu 2939,2168,1670,1598,1510,1441,1321,1263,1172,1153,1089,1023,798,739,686,554,521cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C15H12O3S]+:272.3190,Found 272.3195.
Referring to fig. 5, the structural formula of the target product prepared in example 21 of the present invention is shown in formula 2 e.
Figure GDA0002451784090000091
Extracting according to a conventional process, removing the solvent, separating and purifying by column chromatography, and taking petroleum ether/ethyl acetate (10:1) as an eluent to obtain a yellow solid target product 2 e. The melting point was 102-103 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) 8.06(d, J ═ 7.8Hz,2H),7.68(t, J ═ 7.3Hz,1H),7.59(t, J ═ 7.5Hz,2H),7.09(d, J ═ 8.1Hz,1H),6.92(s,1H),6.78(d, J ═ 8.1Hz,1H),6.01(s,2H) ppm.13C NMR(101MHz,CDCl3) Mass spectrum data for target product 150.91,147.87,142.09,134.19,129.48,129.02,127.45,112.15,110.83,109.02,102.09,94.31,84.25 ppm: MS (EI) m/z (%) 77.04(23),133.02(54),163.04(31),222.04(35),285.97(100). infrared spectral data of the target product: IR (KBr): nu 2964,2169,1789,1651,1504,1255,1161,1085,1035,810,667cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C15H10O4S]+:286.0300,Found 286.0294.
Referring to fig. 6, the structural formula of the target product prepared in example 22 of the present invention is shown in formula 2 f.
Figure GDA0002451784090000092
And (3) extracting according to a conventional flow, removing the solvent, separating and purifying by column chromatography, and taking petroleum ether/ethyl acetate (10:1) as an eluent to obtain a yellow solid target product 2 f. The melting point is 54-55 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) Carbon nmr spectrum data of target product 8.07(d, J ═ 7.6Hz,2H),7.70(t, J ═ 7.4Hz,1H),7.60(t, J ═ 7.5Hz,2H), 7.56-7.50 (m,2H),7.07(t, J ═ 8.1Hz,2H) ppm:13C NMR(101MHz,CDCl3)＝164.52(JC-F＝255.4Hz),141.77,135.29(JC-F＝9.1Hz),134.39,129.55,127.56,116.49(JC-F＝22.5Hz),114.13(JC-F3.6Hz),92.50,85.39ppm, data of fluorine nmr spectrum of target product:19F NMR(376MHz,CDCl3) Mass spectrum data of target product-104.33 ppm: ms (ei) m/z (%) 77.04(20),107.02(20),125.00(30),196.04(100),259.98 (36.) infrared spectral data of target product: IR (KBr): nu 2181,1602,1504,1336,1155,1085,839,794,723,684,617,568cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C14H9FO2S]+:260.0307,Found 260.0301.
Referring to FIG. 7, the structural formula of the target product prepared in example 23 of the present invention is shown in formula 2 g.
Figure GDA0002451784090000101
The solvent is removed after extraction according to the conventional flow, and the yellow solid target product 2g is obtained by column chromatography separation and purification with petroleum ether/ethyl acetate (10:1) as eluent. The melting point is 91-92 ℃. Data of hydrogen nuclear magnetic resonance spectrum of target product:1HNMR(400MHz,CDCl3) 8.08(d, J ═ 7.6Hz,2H),7.70(t, J ═ 7.3Hz,1H),7.61(t, J ═ 7.5Hz,2H),7.46(d, J ═ 8.0Hz,2H),7.36(d, J ═ 7.9Hz,2H) ppm.13C NMR(101MHz,CDCl3) Mass spectrum data of target product 141.70,138.28,134.46,134.09,129.58,129.36,127.64,116.48 ppm: ms (ei) m/z (%) 77.04(55),124.99(97),176.04(38),212.01(100),275.94(48) infrared spectral data of target product: IR (KBr): nu 2351,2179,1789,1651,1556,1340,1158,1085,1013,852,802,732,697,587,417cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C14H9ClO2S]+:276.0012,Found 276.0009.
Referring to fig. 8, the structural formula of the target product prepared in example 24 of the present invention is shown in formula 2 h.
Figure GDA0002451784090000102
Extracting according to conventional process, removing solvent, separating and purifying by column chromatography, and eluting with petroleum ether/ethyl acetate (10:1) to obtain yellow solid target product for 2 h. The melting point is 54-55 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) 8.07(d, J ═ 8.0Hz,2H),7.71(t, J ═ 7.3Hz,1H), 7.64-7.58 (m,3H),7.46(d, J ═ 8.3Hz,1H),7.35(d, J ═ 8.3Hz,1H) ppm.13C NMR(101MHz,CDCl3) Mass spectrum data of target product 141.40,136.70,134.63,134.27,133.47,131.75,131.06,129.64,127.70,117.90,90.32,86.94 ppm: ms (ei) m/z (%) 77.04(36),125.00(67),176.05(42),245.95(100),309.92(58) infrared spectral data of target product: IR (KBr): nu 2351,1652,1539,1456,1339,1163,1085,910,744,689,594cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C14H8Cl2O2S]+:309.9622,Found 309.9625.
Referring to fig. 9, the structural formula of the target product prepared in example 25 of the present invention is shown in formula 2 i.
Figure GDA0002451784090000111
And (3) extracting according to a conventional flow, removing the solvent, separating and purifying by column chromatography, and taking petroleum ether/ethyl acetate (10:1) as an eluent to obtain a yellow solid target product 2 i. Melting point 116-.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) 8.07(d, J ═ 8.0Hz,2H),7.70(t, J ═ 7.4Hz,1H),7.61(t, J ═ 7.6Hz,2H),7.52(d, J ═ 8.2Hz,2H),7.38(d, J ═ 8.1Hz,2H) ppm.13C NMR(101MHz,CDCl3) Mass spectrum data for target product 141.68,134.46,134.14,132.29,129.58,127.63,126.72,116.94,92.23,86.42 ppm: ms (ei) m/z (%) 77.04(77),125(100),176.04(55),255.94(64),321.90(35), infrared spectral data of the target product: IR (KBr): nu 2351,1645,1506,1336,1260,1162,1085,1016,800,686,434cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C14H9ClO2S]+:321.9486,Found 321.9480.
Referring to fig. 10, the structural formula of the target product prepared in example 26 of the present invention is shown in formula 2 j.
Figure GDA0002451784090000112
And (3) extracting according to a conventional flow, removing the solvent, separating and purifying by column chromatography, and taking petroleum ether/ethyl acetate (10:1) as an eluent to obtain a yellow solid target product 2 j. The melting point was 134-135 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3)＝8.07(d,J＝7.8Hz,2H),7.73(d, J ═ 8.1Hz,2H),7.69(t, J ═ 7.2Hz,1H),7.60(t, J ═ 7.6Hz,2H),7.22(d, J ═ 8.1Hz,2H) ppm.13C NMR(101MHz,CDCl3) Mass spectrum data of target product 141.61,138.14,134.46,133.93,129.57,127.59,117.40,98.92,92.39,86.56 ppm: ms (ei) m/z (%) 77.04(49),88.03(31),125.00(67),176.04(59),214.91(33),303.93(65),367.87(100) infrared spectral data of target product: IR (KBr): nu 2183,1651,1328,1161,1085,1001,815,692,580cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C14H9IO2S]+:367.9368,Found 367.9365.
Referring to fig. 11, the structural formula of the target product prepared in example 27 of the present invention is shown in formula 2 k.
Figure GDA0002451784090000121
Extracting according to the conventional flow, removing the solvent, separating and purifying by column chromatography, and taking petroleum ether/ethyl acetate (10:1) as an eluent to obtain a yellow solid target product 2 k. The melting point is 107-108 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) C-nmr spectrum data of target product 8.08(d, J ═ 7.9Hz,2H),7.73(t, J ═ 7.4Hz,1H),7.69 to 7.61(m,6H) ppm:13CNMR(101MHz,CDCl3) Mass spectrum data for target product 141.22,134.79,133.31,132.43,129.70,127.81,122.78,117.66,115.11,90.14,88.56 ppm: ms (ei) m/z (%) 77.04(36),125(100),203.05(100),266.98(34) infrared spectral data of the target product: IR (KBr): nu 2230,2185,1681,1499,1449,1338,1159,1081,854,745,682,603,554,431cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C15H9NO2S]+:267.0354,Found 267.0349.
Referring to fig. 12, the structural formula of the target product prepared in example 28 of the present invention is shown in formula 2 l.
Figure GDA0002451784090000122
The solvent is removed after extraction according to the conventional flow, and the product is separated and purified by column chromatography, and petroleum ether/ethyl acetate (10:1) is used as an eluent to obtain 2l of a yellow solid target product. The melting point is 92-93 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) Carbon nmr spectrum data of target product 8.11(d, J ═ 7.7Hz,2H),7.70(t, J ═ 7.2Hz,1H), 7.64-7.56 (m,8H),7.46(t, J ═ 7.3Hz,2H),7.39(t, J ═ 7.2Hz,1H) ppm:13C NMR(101MHz,CDCl3) Mass spectrum data for target product 144.51,141.96,139.56,134.31,133.38,129.53,129.15,128.53,127.55,127.44,127.26,116.59,93.79,85.97 ppm: ms (ei) m/z (%) 77.04(20),165.06(36),254.06(61),318.02 (100.) infrared spectral data of the target product: IR (KBr): nu 3062,2177,1600,1481,1445,1328,1163,1085,1005,856,765,743,718,686,640,576,551cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C20H14O2S]+:318.0715,Found 318.0716.
Referring to fig. 13, the structural formula of the target product prepared in example 29 of the present invention is shown in formula 2 m.
Figure GDA0002451784090000123
Extracting according to conventional process, removing solvent, separating and purifying by column chromatography, and eluting with petroleum ether/ethyl acetate (10:1) to obtain yellow solid target product 2 m. The melting point is 59-60 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) 8.11(d, J ═ 7.7Hz,2H),8.02(s,1H), 7.72-7.67 (m,3H),7.61(t, J ═ 7.5Hz,2H),7.46(d, J ═ 8.5Hz,1H),7.19(d, J ═ 9.0Hz,1H),7.10(s,1H),3.93(s,3H) ppm. carbon nuclear magnetic resonance spectrum data of target product:13C NMR(101MHz,CDCl3)＝159.82,142.15,136.01,134.33,134.20,130.00,129.50,128.39,128.01,127.52,127.45,120.38,112.44,106.03,94.96,85.13,55.59ppm. mass spectrum data of target product: ms (ei) m/z (%) 77.04(35),126.04(37),139.05(31),169.05(55),215.06(44),322.01(100) infrared spectral data of target product: IR (KBr): nu 2964,2167,1867,1651,1622,1327,1241,1157,1085,1027,940,853,773,731,645,584cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C19H14O3S]+:322.0664,Found 322.0669.
Referring to fig. 14, the structural formula of the target product prepared in example 30 of the present invention is shown in formula 2 n.
Figure GDA0002451784090000131
Extracting according to a conventional process, removing the solvent, separating and purifying by column chromatography, and taking petroleum ether/ethyl acetate (10:1) as an eluent to obtain a yellow solid target product 2 n. The melting point is 76-77 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) 7.99(d, J ═ 7.7Hz,2H),7.60(d, J ═ 7.7Hz,2H),7.53(d, J ═ 7.7Hz,2H),7.47(t, J ═ 7.4Hz,1H),7.37(t, J ═ 7.5Hz,2H),1.36(s,9H) ppm.13C NMR(101MHz,CDCl3) Mass spectrum data of target product 158.42,138.91,132.90,131.59,128.80,127.46,126.55,118.20,93.10,85.73,35.52,31.18 ppm: ms (ei) m/z (%) 77.04(31),91.05(32),149.00(52),283.01(100),298.05(25), infrared spectral data of target product: IR (KBr): nu 2964,2181,1593,1489,1332,1161,1111,1082,850,755,669,617,562,547,517cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C18H18O2S]+:298.1028,Found 298.1033.
Referring to fig. 15, the structural formula of the target product prepared in example 31 of the present invention is shown in formula 2 o.
Figure GDA0002451784090000132
Extracting according to a conventional process, removing the solvent, separating and purifying by column chromatography, and taking petroleum ether/ethyl acetate (10:1) as an eluent to obtain a yellow solid target product 2 o. The melting point is 70-71 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) 8.00(d, J ═ 8.0Hz,2H),7.51(d, J ═ 7.6Hz,2H),7.46(t, J ═ 7.4Hz,1H),7.36(t, J ═ 7.5Hz,2H),7.05(d, J ═ 8.0Hz,2H),3.90(s,3H) ppm.13C NMR(101MHz,CDCl3) Mass spectrum data of target product 164.33,133.55,132.82,131.51,129.99,128.78,118.25,114.72,92.64,85.99,55.92 ppm: ms (ei) m/z (%) 77.04(20),165.06(36),193.04(46),208.06(100),272.01(48) infrared spectral data of target product: IR (KBr): nu 2945,2179,1593,1496,1442,1330,1263,1151,1082,1020,848,755,682,642,558cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C15H12O3S]+:272.0507,Found 272.0504.
Referring to fig. 16, the structural formula of the target product prepared in example 32 of the present invention is shown in formula 2 p.
Figure GDA0002451784090000141
Extracting according to a conventional flow, removing the solvent, separating and purifying by column chromatography, and taking petroleum ether/ethyl acetate (10:1) as an eluent to obtain a yellow solid target product 2 p.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) 8.06(s,1H),7.97(d, J ═ 7.8Hz,1H),7.65(d, J ═ 8.0Hz,1H),7.52(m,5H),7.39(t, J ═ 7.5Hz,2H) ppm.13C NMR(101MHz,CDCl3) Mass spectrum data of target product 143.53,135.74,134.46,133.01,131.98,130.86,128.90,127.66,125.69,117.70,94.52,84.96 ppm: ms (ei) m/z (%) 77.04(20),151.05(26),176.05(100),212.03(72),276.03(57), infrared spectral data of the target product: IR (KBr): nu 2179,1681,1575,1338,1165,1118,1078,854,794,754,680,576cm-1High resolution of the target productSpectral data: HRMS (EI) Calcd for C14H9ClO2S]+:276.0012,Found276.0018.
Referring to fig. 17, the target product prepared in example 33 of the present invention has a structural formula shown in formula 2 q.
Figure GDA0002451784090000142
Extracting according to a conventional flow, removing the solvent, separating and purifying by column chromatography, and taking petroleum ether/ethyl acetate (10:1) as an eluent to obtain a yellow solid target product 2 q. The melting point was 106-107 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) 7.96(d, J ═ 7.7Hz,2H),7.78(d, J ═ 7.5Hz,2H),7.50(m,3H),7.38(t, J ═ 7.5Hz,2H) ppm.13C NMR(101MHz,CDCl3) Mass spectrum data for target product 141.65,138.86,132.96,131.90,128.89,128.87,117.81,102.43,94.20,85.18 ppm: ms (ei) m/z (%) 77.04(20),176.04(25),250.85(62),303.92(74),367.86(100) infrared spectral data of the target product: IR (KBr): nu 2179,1867,1681,1506,1338,1157,1085,1005,850,734,659,590,536cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C14H9IO2S]+:837.9368,Found 367.9375.
Referring to fig. 18, the structural formula of the target product prepared in example 34 of the present invention is shown in formula 2 r.
Figure GDA0002451784090000151
Extracting according to conventional process, removing solvent, separating and purifying by column chromatography, and eluting with petroleum ether/ethyl acetate (10:1) to obtain yellow solid target product 2 r. The melting point is 56-57 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) 8.22(d, J ═ 8.1Hz,2H),7.87(d, J ═ 8.1Hz,2H),7.52(m,3H),7.39(t, J ═ 7.6Hz,2H) ppm targetCarbon nuclear magnetic resonance spectroscopy data of the product:13C NMR(101MHz,CDCl3)＝145.36,135.90(JC-F＝33.3Hz),133.03,132.11,128.94,128.16,126.73(JC-F＝3.6Hz),123.22(JC-F271.5Hz),117.59,95.11,84.82ppm, data of fluorine nmr spectrum of target product:19F NMR(376MHz,CDCl3) Mass spectrum data of target product-63.24 ppm: ms (ei) m/z (%) 77.04(46),89.03(41),105.03(99),145.02(100),246.02(83),309.98(40). IR (KBr): nu 2181,1732,1681,1405,1321,1163,1064,852,758,715,663,591,533,431cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C15H9F3O2S]+:310.0275,Found 310.0277.
Referring to fig. 19, the structural formula of the target product prepared in example 35 of the present invention is shown in formula 2 s.
Figure GDA0002451784090000152
Extracting according to conventional process, removing solvent, separating and purifying by column chromatography, and eluting with petroleum ether/ethyl acetate (10:1) to obtain yellow solid target product 2 s. The melting point is 120-121 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) Carbon nmr spectrum data for target product 8.44(d, J ═ 8.3Hz,2H),8.28(d, J ═ 8.3Hz,2H),7.53(m,3H),7.40(t, J ═ 7.5Hz,2H) ppm:13C NMR(101MHz,CDCl3) Mass spectrum data for target product 151.10,147.26,133.10,132.34,129.01,128.99,124.80,117.31,96.01,84.47 ppm: ms (ei) m/z (%) 77.04(33),89.03(100),165.06(20),176.05(38),193.05(21),223.04(29),286.97(70), infrared spectral data of the target product: IR (KBr): nu 2179,1685,1533,1348,1159,1085,848,740,685,598,532,463cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C14H9NO4S]+:287.0252,Found287.0245.
Referring to fig. 20, the structural formula of the target product prepared in example 36 of the present invention is shown in formula 2 t.
Figure GDA0002451784090000161
Extracting according to conventional process, removing solvent, separating and purifying by column chromatography, and eluting with petroleum ether/ethyl acetate (10:1) to obtain yellow solid target product 2 t. The melting point is 90-91 ℃.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) 8.65(s,1H),8.04(d, J ═ 7.4Hz,3H),7.95(d, J ═ 8.0Hz,1H),7.68(m,2H),7.52(d, J ═ 7.6Hz,2H),7.46(t, J ═ 7.4Hz,1H),7.36(t, J ═ 7.5Hz,2H) ppm.13C NMR(101MHz,CDCl3) Mass spectrum data of target product 138.76,135.71,132.91,132.26,131.69,129.96,129.83,129.75,129.39,128.82,128.19,127.99,122.29,118.07,93.88,85.66 ppm: ms (ei) m/z (%) 77.04(20),127.05(30),228.07(100),292.00(27). infrared spectral data of the target product: IR (KBr): nu 2360,2177,1843,1716,1648,1543,1508,1338,1155,1070,860,812,751,680,551,434cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C18H12O2S]+:292.0558,Found 292.0560.
Referring to FIG. 21, the target product prepared in example 37 of the present invention has a structural formula shown in FIG. 2 u.
Figure GDA0002451784090000162
Extracting according to a conventional process, removing the solvent, separating and purifying by column chromatography, and taking petroleum ether/ethyl acetate (10:1) as an eluent to obtain a yellow solid target product 2 u.
Data of hydrogen nuclear magnetic resonance spectrum of target product:1H NMR(400MHz,CDCl3) 7.59(d, J ═ 7.6Hz,1H),7.50(t, J ═ 7.4Hz,1H),7.41(t, J ═ 7.5Hz,1H), 2.89-2.74 (m,1H), 1.52-1.41 (m,1H),1.18(q, J ═ 6.4Hz,1H) ppm.13C NMR(101MHz,CDCl3) Mass spectrum data of target product 132.94,131.65,128.87,118.01,91.30,84.23,35.30,6.53 ppm: ms (ei) m/z (%) 89.05(28),115.06(26),141.07(100),206.03(70) infrared spectral data of target product: IR (KBr): nu 3057,2183,1681,1488,1445,1330,1143,888,850,757,713,652,547,532cm-1High resolution mass spectral data of the target product: HRMS (EI) Calcd for C11H10O2S]+:206.0402,Found206.0399.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The method for synthesizing the alkynyl sulfone is characterized by comprising the following steps of:
mixing a substrate shown as a formula I, 2-chloro-1-methyl pyridine iodide, an alkaline substance and an organic solvent to form a reaction system, reacting at room temperature, and dehydrating the substrate to generate alkynyl sulfone shown as a formula II;
Figure FDA0002599590070000011
wherein R is1Is aryl, alkyl, alkenyl, alkynyl, alkoxy or halogenated hydrocarbon;
R2is aryl, cyclopropyl, alkyl, alkenyl, alkynyl, alkoxy or halogenated hydrocarbon;
the alkaline substance is any one or more of sodium hydroxide, sodium carbonate, potassium acetate, tert-butyl potassium alcoholate, cesium carbonate and triethylamine;
the organic solvent is any one or more of dichloromethane, acetonitrile, 1, 2-dichloroethane and N, N-dimethylformamide.
2. The method for synthesizing alkynyl sulfone according to claim 1, wherein the basic substance is triethylamine, sodium hydroxide or potassium carbonate.
3. The method for synthesizing an alkynyl sulfone according to claim 1, wherein the basic substance is triethylamine.
4. The method for synthesizing alkynyl sulfone according to claim 1, wherein the organic solvent is dichloromethane.
5. The method for synthesizing alkynyl sulfone according to claim 1, wherein R is1Is any one of phenyl, p-methylphenyl, o-methylphenyl, 4-methoxyphenyl, 3, 4-methylenedioxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 3, 4-dichlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-cyanophenyl, 4-biphenyl and 2- (6-methoxynaphthalene) group.
6. The method for synthesizing alkynyl sulfone according to any one of claims 1 to 5, wherein R is2Is any one of phenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 3-chlorophenyl, 4-iodophenyl, 4-trifluoromethylphenyl, 4-nitrophenyl, 2-naphthyl and cyclopropyl.
7. The method for synthesizing alkynyl sulfone according to claim 6, wherein the reaction time under room temperature condition is 2-4 h, and the reaction under room temperature condition is carried out under protection of protective gas.
8. The method for synthesizing alkynyl sulfone according to claim 6, wherein the molar ratio of the substrate, 2-chloro-1-methyliodized pyridine, basic substance and organic solvent is (0.8-1.2): (0.8-1.2): (0.8-1.2): (52-94).
9. The method for the synthesis of alkynyl sulfones of claim 8 wherein the molar ratio of substrate, 2-chloro-1-methyliodized pyridine, base, and organic solvent is 1: 1: 1: 78.
10. the method for the synthesis of alkynyl sulfones of claim 7 wherein the protective gas is nitrogen.
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