WO2022261992A1 - Method for preparing n-sulfimide - Google Patents

Method for preparing n-sulfimide Download PDF

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Publication number
WO2022261992A1
WO2022261992A1 PCT/CN2021/101095 CN2021101095W WO2022261992A1 WO 2022261992 A1 WO2022261992 A1 WO 2022261992A1 CN 2021101095 W CN2021101095 W CN 2021101095W WO 2022261992 A1 WO2022261992 A1 WO 2022261992A1
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Prior art keywords
reaction
mmol
amide
preparing
sulfonimide
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PCT/CN2021/101095
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French (fr)
Chinese (zh)
Inventor
万小兵
李晶晶
赵彦伟
杨金炜
李如一
曹志宇
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苏州大学
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Priority to PCT/CN2021/101095 priority Critical patent/WO2022261992A1/en
Publication of WO2022261992A1 publication Critical patent/WO2022261992A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/51—Y being a hydrogen or a carbon atom

Definitions

  • the invention relates to a method for preparing N -sulfonimide, which belongs to the technical field of organic synthesis.
  • N -sulfonylimide is widely present in drug molecules, natural products and pesticides, the core skeleton of functional materials, and is also widely used as a ligand molecule for transition metals.
  • N -sulfonylimides they all have obvious disadvantages, such as: the preparation of dangerous azide compounds is required, and the preparation of raw materials is cumbersome; toxic and harmful transition metals are required.
  • Chang’s group reported the preparation of N -sulfonimides from azides, alkynes and alcohols under the catalysis of cuprous iodide, but the reaction must use dangerous azides and toxic copper catalyst. Not suitable for large-scale industrial reactions and synthesis of drug molecules (see: Org.
  • the purpose of the present invention is to provide a method for preparing N-sulfonylimide, which has rich sources of raw materials, wide applicability of reaction substrates, easy operation, and no need to use toxic copper catalysts, which is beneficial for further use in the synthesis of drug molecules. Synthesizing.
  • the technical scheme adopted in the present invention is: a kind of method for preparing N -sulfonimide, with amide, ethyl diazoacetate and sulfonamide as reaction substrate, under catalyst and auxiliary agent effect, Reaction in an organic solvent gives N -sulfonimide.
  • the invention discloses the application of catalyst and/or auxiliary agent in the preparation of N-sulfonimide by using amide, ethyl diazoacetate and sulfonamide as reaction substrates.
  • the chemical structure general formula of described amide is: ;
  • R 1 , R 2 , and R 3 are independently selected from alkyl, heteroaromatic, and substituted aryl, and the substituted aryl is , R Selected from hydrogen, alkyl, fluorine, chlorine, bromine, alkoxy, trifluoromethyl, sulfone;
  • the ethyl diazoacetate is:
  • the general chemical structure formula of described sulfonamide is: , R 5 is selected from alkyl, heteroaromatic hydrocarbon, naphthalene ring, substituted aryl, and substituted aryl is , R 6 is selected from hydrogen, alkyl, alkoxy, trifluoromethoxy.
  • the amount of the catalyst is 5-30% of the molar weight of the amide, preferably 20%; the amount of ethyl diazoacetate is 6 times the molar weight of the amide; the amount of sulfonamide is 1.5 times the molar weight of the amide ; The amount of the auxiliary agent is 1 to 3 times the molar weight of the amide, preferably 2 times.
  • reaction is carried out in air.
  • the present invention discloses the N-sulfonimide prepared according to the above-mentioned method for preparing N - sulfonimide, whose chemical structural formula is: .
  • the reaction temperature of the reaction is 25-100°C, and the time is 12-48 hours; the preferred reaction temperature is 90°C; the reaction time is 24 hours.
  • the catalyst is ferric sulfate, cobalt sulfate, cobalt acetylacetonate, iron acetylacetonate, ferrous sulfate, ferric oxide, ferric chloride;
  • the auxiliary agent is potassium hydrogen sulfate, sodium dihydrogen phosphate, phosphoric acid Potassium dihydrogen;
  • the organic solvent is cyclohexane, hexane, acetonitrile, nitromethane, 1,2-dichloroethane, 1,4-dioxane.
  • the catalyst is iron sulfate
  • the auxiliary agent is potassium hydrogen sulfate
  • the organic solvent is cyclohexane.
  • the reaction of the present invention is carried out in air. After the reaction is completed, it is quenched with saturated sodium chloride solution, extracted with ethyl acetate, the solvent is removed by a rotary evaporator, adsorbed on silica gel, and finally the product is obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether N-sulfonimide.
  • the present invention has the following advantages compared with the prior art.
  • the present invention uses iron sulfate as a catalyst to realize the three-component reaction of amide, sulfonamide and ethyl diazoacetate to prepare N-sulfonimide, which is different from the difficult pre-preparation of raw materials, dangerous operation and use of toxic catalysts in the prior art. Compared with the reaction, it is more green, economical, safe, and the raw materials are easy to get. In particular, the present invention also discloses that the product can still be obtained in a good yield only in the presence of an auxiliary agent without a catalyst, which completely avoids the problem of the need for a catalyst in the prior art.
  • reaction of the method disclosed by the invention can be carried out in the air, and the aftertreatment is simple and convenient, which is beneficial to the application in the synthesis of drug molecules and large-scale industrialization.
  • the reactants, catalysts and other raw materials used in the present invention are cheap and easy to obtain, the reaction composition is reasonable, no ligand is needed, the atom economy is high, the reaction steps are few, and a higher yield can be obtained with only one step reaction, which is in line with contemporary green chemistry and medicine Chemistry requirements and orientation.
  • Amide of the present invention sulfonamide, ethyl diazoacetate, catalyst and solvent are all commercial goods or can be prepared with easy and convenient method.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 90%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • Ferric sulfate was replaced by cobalt acetylacetonate, yield: 32%.
  • Ferric sulfate was replaced by iron acetylacetonate, yield: 67%.
  • Ferric sulfate was replaced by iron oxide, yield: 65%.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 66%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 51%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 62%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 54%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 63%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 42%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 53%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 49%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 62%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 34%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 48%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 48%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 52%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 64%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 66%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 53%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 55%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • Embodiment 20 is a diagrammatic representation of Embodiment 20.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 74%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 90%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • Embodiment twenty-two are identical to Embodiment twenty-two.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 39%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • Embodiment twenty-three Embodiment twenty-three.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 47%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 48%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • Embodiment twenty-five Embodiment twenty-five.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 47%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
  • Embodiment twenty-six Embodiment twenty-six.
  • the product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 71%.
  • the main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Disclosed in the present invention is a method for preparing N-sulfimide, the method comprising: using ferric sulfate as a catalyst or using no catalyst and potassium hydrogen sulfate as an auxiliary agent to achieve a reaction of three components, i.e. an amide, sulfanilamide and ethyl diazoacetate, to prepare the N-sulfimide. The method has the following advantages: the catalyst is cheap and green, the reaction is more economical, the universality of the substrate is broad, the raw materials are readily available, and the method can be carried out in air, has a simple and convenient post-treatment, and is beneficial for application in pharmaceutical molecule synthesis and large-scale industrialization. In addition, the reactants, catalyst, auxiliary agent, etc. used in the present invention are cheap and readily available, the reaction composition is rational, no ligand or toxic metal catalyst is required, the atomic economy is high, there are few reaction steps, a relatively high yield can be obtained simply by means of a one-step reaction, and the requirement and direction of the contemporary green chemistry and pharmaceutical chemistry are met.

Description

一种制备N-磺酰亚胺的方法A kind of method for preparing N-sulfonylimide 技术领域technical field
本发明涉及一种制备 N-磺酰亚胺的方法，属于有机合成技术领域。 The invention relates to a method for preparing N -sulfonimide, which belongs to the technical field of organic synthesis.
背景技术Background technique
N-磺酰亚胺是广泛存在于药物分子、天然产物以及农药，功能材料的核心骨架，也被广泛用为过渡金属的配体分子。目前，制备 N-磺酰亚胺的方法尽管有很多，但均有明显的缺点，比如：需要制备危险的叠氮化合物，原料制备繁琐；需要有毒有害的过渡金属等。例如：（1）Chang课题组报道了从叠氮，炔烃和醇出发，在碘化亚铜催化下制备 N-磺酰亚胺的工作，但是反应必须使用危险的叠氮化合物和有毒的铜催化剂。不适合大规模工业化反应以及药物分子的合成（参见： Org. Lett., 2006 , 8, 1347）；（2）2018年，Poisson课题组报道了微波条件下磺胺与原酸三甲酯制备 N-磺酰亚胺的反应。但反应中需要用到特殊的微波装置，而且反应温度高达180℃。显然不适合工业化以及复杂产物的合成（参见 ： ACS Sustainable Chem. Eng. 2018 , 6, 8563 ）。 N -sulfonylimide is widely present in drug molecules, natural products and pesticides, the core skeleton of functional materials, and is also widely used as a ligand molecule for transition metals. At present, although there are many methods for preparing N -sulfonylimides, they all have obvious disadvantages, such as: the preparation of dangerous azide compounds is required, and the preparation of raw materials is cumbersome; toxic and harmful transition metals are required. For example: (1) Chang’s group reported the preparation of N -sulfonimides from azides, alkynes and alcohols under the catalysis of cuprous iodide, but the reaction must use dangerous azides and toxic copper catalyst. Not suitable for large-scale industrial reactions and synthesis of drug molecules (see: Org. Lett., 2006 , 8, 1347); (2) In 2018, Poisson's research group reported the preparation of N - The reaction of sulfonylimides. However, special microwave equipment is required for the reaction, and the reaction temperature is as high as 180°C. Obviously not suitable for industrialization and synthesis of complex products (see : ACS Sustainable Chem. Eng. 2018 , 6, 8563 ) .
综上，很有必要开发一种原料来源丰富、成本低廉、安全、操作简便的方法来高效率的合成 N-磺酰亚胺类化合物。 In summary, it is necessary to develop a method with abundant raw materials, low cost, safety and easy operation to efficiently synthesize N -sulfonylimides.
技术问题technical problem
本发明的目的是提供一种制备N-磺酰亚胺的方法，该反应原料来源丰富、反应底物普适性广，操作简便，无需使用有毒的铜催化剂，有利于进一步用于药物分子的合成中。The purpose of the present invention is to provide a method for preparing N-sulfonylimide, which has rich sources of raw materials, wide applicability of reaction substrates, easy operation, and no need to use toxic copper catalysts, which is beneficial for further use in the synthesis of drug molecules. Synthesizing.
技术解决方案technical solution
为达到上述发明目的，本发明采用的技术方案是：一种制备 N-磺酰亚胺的方法，以酰胺、重氮乙酸乙酯和磺酰胺为反应底物，在催化剂与助剂作用下，在有机溶剂中反应得到 N-磺酰亚胺。 In order to achieve the above-mentioned purpose of the invention, the technical scheme adopted in the present invention is: a kind of method for preparing N -sulfonimide, with amide, ethyl diazoacetate and sulfonamide as reaction substrate, under catalyst and auxiliary agent effect, Reaction in an organic solvent gives N -sulfonimide.
本发明公开了催化剂和/或助剂在以酰胺、重氮乙酸乙酯、和磺酰胺为反应底物制备N-磺酰亚胺中的应用。The invention discloses the application of catalyst and/or auxiliary agent in the preparation of N-sulfonimide by using amide, ethyl diazoacetate and sulfonamide as reaction substrates.
本发明中，所述酰胺的化学结构通式为：
Figure 367491dest_path_image001
；式中，R 1、R 2、R 3独立的选自烷基、杂芳香烃、取代芳基，取代芳基为
Figure 158861dest_path_image002
，R 4选自氢、烷基、氟、氯、溴、烷氧基、三氟甲基、砜基；所述重氮乙酸乙酯为：
Figure 82954dest_path_image003
；所述磺酰胺的化学结构通式为：
Figure 717198dest_path_image004
，R 5选自烷基、杂芳香烃、萘环、取代芳基，取代芳基为
Figure 17729dest_path_image005
，R 6选自氢、烷基、烷氧基、三氟甲氧基。 In the present invention, the chemical structure general formula of described amide is:
Figure 367491dest_path_image001
; In the formula, R 1 , R 2 , and R 3 are independently selected from alkyl, heteroaromatic, and substituted aryl, and the substituted aryl is
Figure 158861dest_path_image002
, R Selected from hydrogen, alkyl, fluorine, chlorine, bromine, alkoxy, trifluoromethyl, sulfone; The ethyl diazoacetate is:
Figure 82954dest_path_image003
The general chemical structure formula of described sulfonamide is:
Figure 717198dest_path_image004
, R 5 is selected from alkyl, heteroaromatic hydrocarbon, naphthalene ring, substituted aryl, and substituted aryl is
Figure 17729dest_path_image005
, R 6 is selected from hydrogen, alkyl, alkoxy, trifluoromethoxy.
本发明中，所述催化剂的用量为酰胺摩尔量的5～30%，优选20%；所述重氮乙酸乙酯的用量为酰胺摩尔量的6倍；磺胺的用量为酰胺摩尔量的1.5倍；所述助剂的用量为酰胺摩尔量的1～3倍，优选2倍。In the present invention, the amount of the catalyst is 5-30% of the molar weight of the amide, preferably 20%; the amount of ethyl diazoacetate is 6 times the molar weight of the amide; the amount of sulfonamide is 1.5 times the molar weight of the amide ; The amount of the auxiliary agent is 1 to 3 times the molar weight of the amide, preferably 2 times.
本发明中，所述反应在空气中进行。In the present invention, the reaction is carried out in air.
本发明公开了根据上述制备 N-磺酰亚胺的方法制备的 N-磺酰亚胺，其化学结构式为：
Figure 178452dest_path_image006
。 The present invention discloses the N-sulfonimide prepared according to the above-mentioned method for preparing N - sulfonimide, whose chemical structural formula is:
Figure 178452dest_path_image006
.
 上述技术方案中，所述反应的反应温度为25～100℃，时间为12～48小时；优选的反应温度为90℃；反应时间为24小时。In the above technical scheme, the reaction temperature of the reaction is 25-100°C, and the time is 12-48 hours; the preferred reaction temperature is 90°C; the reaction time is 24 hours.
本发明中，所述催化剂为硫酸铁、硫酸钴、乙酰丙酮钴、乙酰丙酮铁、硫酸亚铁、三氧化铁、三氯化铁；所述助剂为硫酸氢钾、磷酸二氢钠、磷酸二氢钾；所述有机溶剂为环己烷、己烷、乙腈、硝基甲烷、1,2-二氯乙烷、1,4-二氧六环。优选的，所述催化剂为硫酸铁，助剂为硫酸氢钾，有机溶剂为环己烷。In the present invention, the catalyst is ferric sulfate, cobalt sulfate, cobalt acetylacetonate, iron acetylacetonate, ferrous sulfate, ferric oxide, ferric chloride; the auxiliary agent is potassium hydrogen sulfate, sodium dihydrogen phosphate, phosphoric acid Potassium dihydrogen; the organic solvent is cyclohexane, hexane, acetonitrile, nitromethane, 1,2-dichloroethane, 1,4-dioxane. Preferably, the catalyst is iron sulfate, the auxiliary agent is potassium hydrogen sulfate, and the organic solvent is cyclohexane.
本发明的反应在空气中进行。反应结束后，用饱和氯化钠溶液淬灭，再用乙酸乙酯萃取后，利用旋转蒸发仪除去溶剂、硅胶吸附，最后用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物N-磺酰亚胺。The reaction of the present invention is carried out in air. After the reaction is completed, it is quenched with saturated sodium chloride solution, extracted with ethyl acetate, the solvent is removed by a rotary evaporator, adsorbed on silica gel, and finally the product is obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether N-sulfonimide.
有益效果Beneficial effect
由于上述技术方案的运用，本发明与现有技术相比具有下列优点。Due to the application of the above technical solutions, the present invention has the following advantages compared with the prior art.
1．本发明使用硫酸铁为催化剂实现了酰胺、磺胺和重氮乙酸乙酯的三组分反应来制备N-磺酰亚胺，与现有技术中的原料预制备难、操作危险和使用有毒催化剂相比，反应更绿色经济、安全、原料易得。尤其是，本发明还公开了仅在助剂存在下，无需催化剂，依然能够较好收率的获得产物，完全避免了现有技术需要催化剂的问题。1. The present invention uses iron sulfate as a catalyst to realize the three-component reaction of amide, sulfonamide and ethyl diazoacetate to prepare N-sulfonimide, which is different from the difficult pre-preparation of raw materials, dangerous operation and use of toxic catalysts in the prior art. Compared with the reaction, it is more green, economical, safe, and the raw materials are easy to get. In particular, the present invention also discloses that the product can still be obtained in a good yield only in the presence of an auxiliary agent without a catalyst, which completely avoids the problem of the need for a catalyst in the prior art.
2．本发明公开的方法反应在空气中即可进行，后处理简便，有利于在药物分子合成和大规模工业化中的应用。2. The reaction of the method disclosed by the invention can be carried out in the air, and the aftertreatment is simple and convenient, which is beneficial to the application in the synthesis of drug molecules and large-scale industrialization.
3．本发明使用的反应物、催化剂等原料廉价易得，反应组成合理，无需配体，原子经济性高，反应步骤少，仅需一步反应即可取得较高的产率，符合当代绿色化学和药物化学的要求和方向。3. The reactants, catalysts and other raw materials used in the present invention are cheap and easy to obtain, the reaction composition is reasonable, no ligand is needed, the atom economy is high, the reaction steps are few, and a higher yield can be obtained with only one step reaction, which is in line with contemporary green chemistry and medicine Chemistry requirements and orientation.
本发明的实施方式Embodiments of the present invention
下面结合实施例对本发明作进一步描述：本发明的酰胺、磺胺、重氮乙酸乙酯、催化剂和溶剂皆为市场化商品或可以用简便方法制备。The present invention will be further described below in conjunction with embodiment: Amide of the present invention, sulfonamide, ethyl diazoacetate, catalyst and solvent are all commercial goods or can be prepared with easy and convenient method.
实施例一。Embodiment one.
Figure 273447dest_path_image007
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Figure 273447dest_path_image007
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   向试管中加入酰胺（0.5 mmol）、对甲氧基苯磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率90%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), p-methoxybenzenesulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally Ethyl diazoacetate EDA (3.0 mmol), and the mixture was reacted in an oil bath at 90°C for 24 hours under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 90%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 7.80–7.75 (m, 2H), 6.96–6.89 (m, 2H), 4.58 (s, 2H), 4.05 (q, J = 7.1 Hz, 2H), 3.81 (s, 3H), 2.51 (s, 3H), 1.13 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 172.3, 166.5, 162.8, 132.9, 128.7, 113.8, 63.8, 61.3, 55.5, 19.6, 13.8; HRMS (ESI-TOF): Anal. Calcd. For C 13H 17NO 6S+Na +: 338.0669, Found: 338.0670; IR (neat, cm -1): υ 2983, 2844, 1743, 1617, 1595, 1442, 1380, 1151, 1022, 835, 803。 1 H NMR (400 MHz, CDCl 3 ) δ 7.80–7.75 (m, 2H), 6.96–6.89 (m, 2H), 4.58 (s, 2H), 4.05 (q, J = 7.1 Hz, 2H), 3.81 ( s, 3H), 2.51 (s, 3H), 1.13 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.3, 166.5, 162.8, 132.9, 128.7, 113.8, 63.8, 61.3 , 55.5, 19.6, 13.8; HRMS (ESI-TOF): Anal. Calcd. For C 13 H 17 NO 6 S+Na + : 338.0669, Found: 338.0670; IR (neat, cm -1 ): υ 2983, 2844, 1743, 1617, 1595, 1442, 1380, 1151, 1022, 835, 803.
实施例二。Embodiment two.
在实施例一的基础上，反应条件做单因素变化。On the basis of Example 1, the reaction conditions were changed in a single factor.
不加硫酸铁，产率：68%。Without adding ferric sulfate, the yield: 68%.
不加硫酸氢钾，产率：35%。Without adding potassium bisulfate, yield: 35%.
将硫酸铁更换为硫酸钴，产率：67%。Ferric sulfate was replaced by cobalt sulfate, yield: 67%.
将硫酸铁更换为乙酰丙酮钴，产率：32%。Ferric sulfate was replaced by cobalt acetylacetonate, yield: 32%.
将硫酸铁更换为乙酰丙酮铁，产率：67%。Ferric sulfate was replaced by iron acetylacetonate, yield: 67%.
将硫酸铁更换为硫酸亚铁，产率：70%。Replace ferric sulfate with ferrous sulfate, yield: 70%.
将硫酸铁更换为氧化铁，产率：65%。Ferric sulfate was replaced by iron oxide, yield: 65%.
将硫酸铁更换为醋酸铜，产率：35%。Ferric sulfate was replaced by copper acetate, yield: 35%.
将硫酸氢钾更换为磷酸二氢钾，产率：33%。Potassium hydrogen sulfate was replaced by potassium dihydrogen phosphate, yield: 33%.
将硫酸氢钾更换为磷酸二氢钠，产率：23%。Potassium hydrogen sulfate was replaced by sodium dihydrogen phosphate, yield: 23%.
将环己烷更换为正己烷，产率：22%。Cyclohexane was replaced by n-hexane, yield: 22%.
将环己烷更换为1,4-二氧六环，产率：32%。Cyclohexane was replaced by 1,4-dioxane, yield: 32%.
将环己烷更换为乙腈，产率：38%。Cyclohexane was exchanged for acetonitrile, yield: 38%.
将环己烷更换为1,2-二氯乙烷，产率：62%。Cyclohexane was replaced by 1,2-dichloroethane, yield: 62%.
将环己烷更换为硝基甲烷，产率：60%。Cyclohexane was replaced by nitromethane, yield: 60%.
将酰胺替换为N-甲基酰胺，产率：45%。Amide was replaced by N-methylamide, yield: 45%.
实施例三。Embodiment three.
Figure 394987dest_path_image008
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Figure 394987dest_path_image008
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向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率66%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 66%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 7.82 (d, J = 8.1 Hz, 2H), 7.76 (d, J = 8.9 Hz, 2H), 7.25 (d, J = 8.1 Hz, 2H), 6.89 (d, J = 8.9 Hz, 2H), 4.70 (s, 2H), 4.01 (q, J = 7.1 Hz, 2H), 3.82 (s, 3H), 2.39 (s, 3H), 1.14 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 168.3, 166.8, 162.6, 143.7, 133.8, 128.7, 128.7, 127.4, 113.7, 64.2, 61.4, 55.5, 21.7, 13.9; HRMS (ESI-TOF): Anal. Calcd. For C 19H 21NO 6S+Na +: 414.0982, Found: 414.0966; IR (neat, cm -1): υ 2986, 2848, 1748, 1595, 1307, 1259, 1210, 1143, 834, 805。 1 H NMR (400 MHz, CDCl 3 ) δ 7.82 (d, J = 8.1 Hz, 2H), 7.76 (d, J = 8.9 Hz, 2H), 7.25 (d, J = 8.1 Hz, 2H), 6.89 (d , J = 8.9 Hz, 2H), 4.70 (s, 2H), 4.01 (q, J = 7.1 Hz, 2H), 3.82 (s, 3H), 2.39 (s, 3H), 1.14 (t, J = 7.1 Hz , 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 168.3, 166.8, 162.6, 143.7, 133.8, 128.7, 128.7, 127.4, 113.7, 64.2, 61.4, 55.5, 21.7, 13.9; TOES) ( Anal. Calcd. For C 19 H 21 NO 6 S+Na + : 414.0982, Found: 414.0966; IR (neat, cm -1 ): υ 2986, 2848, 1748, 1595, 1307, 1259, 1210, 1143, 834, 805.
实施例四。Embodiment four.
Figure 499209dest_path_image009
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Figure 499209dest_path_image009
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向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率51%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 51%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 8.03 (s, 4H), 7.73 (d, J = 8.9 Hz, 2H), 6.92 (d, J = 8.9 Hz, 2H), 4.78 (s, 2H), 4.07 (q, J = 7.1 Hz, 2H), 3.84 (s, 3H), 3.09 (s, 3H), 1.17 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ166.5, 166.3, 163.0, 143.6, 135.6, 132.6, 130.3, 128.9, 127.1, 113.9, 64.5, 61.7, 55.6, 44.3, 13.9; HRMS (ESI-TOF): Anal. Calcd. For C 19H 21NO 8S 2+Na +: 478.0601, Found: 478.0632; IR (neat, cm -1): υ 3008, 2928, 1743, 1618, 1594, 1311, 1284, 1113, 1087, 826, 801。 1 H NMR (400 MHz, CDCl 3 ) δ 8.03 (s, 4H), 7.73 (d, J = 8.9 Hz, 2H), 6.92 (d, J = 8.9 Hz, 2H), 4.78 (s, 2H), 4.07 (q, J = 7.1 Hz, 2H), 3.84 (s, 3H), 3.09 (s, 3H), 1.17 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ166.5 , 166.3, 163.0, 143.6, 135.6, 132.6, 130.3, 128.9, 127.1, 113.9, 64.5, 61.7, 55.6, 44.3, 13.9; HRMS (ESI-TOF): Anal. Calcd. For C 19 H 22 NO 8 Na + : 478.0601, Found: 478.0632; IR (neat, cm -1 ): υ 3008, 2928, 1743, 1618, 1594, 1311, 1284, 1113, 1087, 826, 801.
实施例五。Embodiment five.
Figure 999592dest_path_image010
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Figure 999592dest_path_image010
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向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率62%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 62%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 8.00–7.94 (m, 2H), 7.80–7.75 (m, 2H), 7.17–7.13 (m, 2H), 6.95–6.89 (m, 2H), 4.73 (s, 2H), 4.04 (q, J = 7.1 Hz, 2H), 3.84 (s, 3H), 1.16 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 167.0, 166.7, 164.1, 162.8, 133.4, 132.5 (d, J = 9.2 Hz), 128.8, 126.4, 115.5, 115.3, 113.8, 64.3, 61.5, 55.5, 13.9; 19F NMR (376 MHz, CDCl 3) δ = -104.90 (s, 1F); HRMS (ESI-TOF): Anal. Calcd. For C 18H 18FNO 6S+Na +: 418.0731, Found: 418.0727; IR (neat, cm -1): υ 3073, 2941, 1744, 1616, 1376, 1297, 1089, 815, 806。 1 H NMR (400 MHz, CDCl 3 ) δ 8.00–7.94 (m, 2H), 7.80–7.75 (m, 2H), 7.17–7.13 (m, 2H), 6.95–6.89 (m, 2H), 4.73 (s , 2H), 4.04 (q, J = 7.1 Hz, 2H), 3.84 (s, 3H), 1.16 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.0, 166.7, 164.1, 162.8, 133.4, 132.5 (d, J = 9.2 Hz), 128.8, 126.4, 115.5, 115.3, 113.8, 64.3, 61.5, 55.5, 13.9; 19 F NMR (376 MHz, CDCl 3 ) δ9 = -104. , 1F); HRMS (ESI-TOF): Anal. Calcd. For C 18 H 18 FNO 6 S+Na + : 418.0731, Found: 418.0727; IR (neat, cm -1 ): υ 3073, 2941, 1744, 1616 , 1376, 1297, 1089, 815, 806.
实施例六。Embodiment six.
Figure 531067dest_path_image011
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Figure 531067dest_path_image011
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向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率54%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 54%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 7.87 (d, J = 8.6 Hz, 2H), 7.77 (d, J = 8.9 Hz, 2H), 7.45 (d, J = 8.6 Hz, 2H), 6.92 (d, J = 8.9 Hz, 2H), 4.74 (s, 2H), 4.05 (d, J = 7.1 Hz, 2H), 3.85 (s, 3H), 1.17 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 167.1, 166.6, 162.8, 139.3, 131.1, 128.8, 128.7, 128.5, 113.8, 64.3, 61.6, 55.6, 14.0; HRMS (ESI-TOF): Anal. Calcd. For C 18H 18 35ClNO 6S+Na +: 436.0436, Found: 436.0441. Anal. Calcd. For C 18H 18 37ClNO 6S +Na +: 436.0406, Found: 436.0413; IR (neat, cm -1): υ 3073, 2987, 1754, 1609, 1463, 1382, 1145, 1088, 835, 806。 1 H NMR (400 MHz, CDCl 3 ) δ 7.87 (d, J = 8.6 Hz, 2H), 7.77 (d, J = 8.9 Hz, 2H), 7.45 (d, J = 8.6 Hz, 2H), 6.92 (d , J = 8.9 Hz, 2H), 4.74 (s, 2H), 4.05 (d, J = 7.1 Hz, 2H), 3.85 (s, 3H), 1.17 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.1, 166.6, 162.8, 139.3, 131.1, 128.8, 128.7, 128.5, 113.8, 64.3, 61.6, 55.6, 14.0; HRMS (ESI-TOF): Anal. Calcd . For C 18 35 ClNO 6 S+Na + : 436.0436, Found: 436.0441. Anal. Calcd. For C 18 H 18 37 ClNO 6 S +Na + : 436.0406, Found: 436.0413; IR (neat, cm -1 ): υ 3073, 2987 , 1754, 1609, 1463, 1382, 1145, 1088, 835, 806.
实施例七。Embodiment seven.
Figure 874324dest_path_image012
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Figure 874324dest_path_image012
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向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率63%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 63%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 7.80–7.75 (m, 4H), 7.61 (d, J = 8.5 Hz, 2H), 6.93 (d, J = 8.5 Hz, 2H), 4.74 (s, 2H), 4.05 (q, J = 7.1 Hz, 2H), 3.85 (s, 3H), 1.17 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 167.2, 166.6, 162.8, 133.3, 131.4, 131.2, 129.2, 128.8, 127.8, 113.8, 64.3, 61.6, 55.6, 14.0; HRMS (ESI-TOF): Anal. Calcd. For C 18H 18 79BrNO 6S+Na +: 477.9930, Found: 477.9920. Anal. Calcd. For C 18H 18 81BrNO 6S+Na +: 479.9910, Found: 479.9919; IR (neat, cm -1): υ 2923, 2851, 1753, 1589, 1357, 1295, 1203, 1141, 835, 802。 1 H NMR (400 MHz, CDCl 3 ) δ 7.80–7.75 (m, 4H), 7.61 (d, J = 8.5 Hz, 2H), 6.93 (d, J = 8.5 Hz, 2H), 4.74 (s, 2H) , 4.05 (q, J = 7.1 Hz, 2H), 3.85 (s, 3H), 1.17 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.2, 166.6, 162.8, 133.3 , 131.4, 131.2, 129.2, 128.8, 127.8, 113.8, 64.3, 61.6, 55.6, 14.0; HRMS (ESI-TOF): Anal. Calcd. For C 18 H 18 79 BrNO 6 S+Na + : 477.9930, Found: 2077 . Anal. Calcd. For C 18 H 18 81 BrNO 6 S+Na + : 479.9910, Found: 479.9919; IR (neat, cm -1 ): υ 2923, 2851, 1753, 1589, 1357, 1295, 1203, 1141, 835, 802.
实施例八。Embodiment eight.
Figure 47816dest_path_image013
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Figure 47816dest_path_image013
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率42%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 42%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 8.14 (d, J = 7.8 Hz, 1H), 8.01 (s, 1H), 7.82 (d, J = 7.8 Hz, 1H), 7.73 (d, J = 8.9 Hz, 2H), 7.64–7.60 (m, 1H), 6.91 (d, J = 8.9 Hz, 2H), 4.79 (s, 2H), 4.09 (q, J = 7.1 Hz, 2H), 3.85 (s, 3H), 1.20 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 166.5, 163.0, 133.1, 131.3, 120.0, 128.7, 126.1, 113.9, 64.4, 61.7, 55.6, 14.0; 19F NMR (376 MHz, CDCl 3) δ = -62.84 (s, 3F); HRMS (ESI-TOF): Anal. Calcd. For C 19H 18F 3NO 6S+Na +: 468.0699, Found: 468.0695; IR (neat, cm -1): υ 2975, 1747, 1615, 1377, 1263, 1130, 1090, 1014, 825, 804。 1 H NMR (400 MHz, CDCl 3 ) δ 8.14 (d, J = 7.8 Hz, 1H), 8.01 (s, 1H), 7.82 (d, J = 7.8 Hz, 1H), 7.73 (d, J = 8.9 Hz , 2H), 7.64–7.60 (m, 1H), 6.91 (d, J = 8.9 Hz, 2H), 4.79 (s, 2H), 4.09 (q, J = 7.1 Hz, 2H), 3.85 (s, 3H) , 1.20 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 166.5, 163.0, 133.1, 131.3, 120.0, 128.7, 126.1, 113.9, 64.4, 61.7, 55.6, 19 F.0; NMR (376 MHz, CDCl 3 ) δ = -62.84 (s, 3F); HRMS (ESI-TOF): Anal. Calcd. For C 19 H 18 F 3 NO 6 S+Na + : 468.0699, Found: 468.0695; IR (neat, cm -1 ): υ 2975, 1747, 1615, 1377, 1263, 1130, 1090, 1014, 825, 804.
实施例九。Embodiment nine.
Figure 792918dest_path_image014
。
Figure 792918dest_path_image014
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率53%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 53%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 7.82 (d, J = 8.5 Hz, 2H), 7.75 (d, J = 8.9 Hz, 2H), 7.62 (d, J = 8.5 Hz, 2H), 6.92 (d, J = 8.9 Hz, 2H), 4.73 (s, 2H), 4.04 (q, J = 7.1 Hz, 2H), 3.84 (s, 3H), 1.16 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 167.4, 166.6, 162.8, 137.3, 133.2, 131.0, 129.7, 128.8, 113.8, 100.4, 64.3, 61.5, 55.6, 13.9; HRMS (ESI-TOF): Anal. Calcd. For C 18H 18INO 6S+Na +: 525.9792, Found: 525.9776; IR (neat, cm -1): υ 3028, 2978, 1753, 1589, 1499, 1295, 1263, 1140, 833, 802。 1 H NMR (400 MHz, CDCl 3 ) δ 7.82 (d, J = 8.5 Hz, 2H), 7.75 (d, J = 8.9 Hz, 2H), 7.62 (d, J = 8.5 Hz, 2H), 6.92 (d , J = 8.9 Hz, 2H), 4.73 (s, 2H), 4.04 (q, J = 7.1 Hz, 2H), 3.84 (s, 3H), 1.16 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.4, 166.6, 162.8, 137.3, 133.2, 131.0, 129.7, 128.8, 113.8, 100.4, 64.3, 61.5, 55.6, 13.9; HRMS (ESI-TOF): Anal . H 18 INO 6 S+Na + : 525.9792, Found: 525.9776; IR (neat, cm -1 ): υ 3028, 2978, 1753, 1589, 1499, 1295, 1263, 1140, 833, 802.
实施例十。Embodiment ten.
Figure 619929dest_path_image015
。
Figure 619929dest_path_image015
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率49%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 49%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 7.80 (d, J = 9.0 Hz, 2H), 6.94 (d, J = 9.0 Hz, 2H), 4.60 (s, 2H), 4.07 (q, J = 7.1 Hz, 2H), 3.84 (s, 3H), 2.95 (q, J = 7.6 Hz, 2H), 1.29 (t, J = 7.6 Hz, 3H), 1.16 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 175.7, 166.7, 162.8, 133.4, 128.7, 113.8, 63.7, 61.4, 55.5, 26.9, 13.9, 10.2; HRMS (ESI-TOF): Anal. Calcd. For C 14H 19NO 6S+Na +: 352.0825, Found: 352.0833; IR (neat, cm -1): υ 3226, 2979, 2849, 1753, 1593, 1499, 1143, 1110, 833, 803, 722。 1 H NMR (400 MHz, CDCl 3 ) δ 7.80 (d, J = 9.0 Hz, 2H), 6.94 (d, J = 9.0 Hz, 2H), 4.60 (s, 2H), 4.07 (q, J = 7.1 Hz , 2H), 3.84 (s, 3H), 2.95 (q, J = 7.6 Hz, 2H), 1.29 (t, J = 7.6 Hz, 3H), 1.16 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 175.7, 166.7, 162.8, 133.4, 128.7, 113.8, 63.7, 61.4, 55.5, 26.9, 13.9, 10.2; HRMS (ESI-TOF): Anal. Calcd. For C 14 H 19 NO 6 S+Na + : 352.0825, Found: 352.0833; IR (neat, cm -1 ): υ 3226, 2979, 2849, 1753, 1593, 1499, 1143, 1110, 833, 803, 722.
实施例十一。Embodiment eleven.
Figure 450482dest_path_image016
。
Figure 450482dest_path_image016
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率62%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 62%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 8.16 (d, J = 8.6 Hz, 2H), 7.78 (d, J = 8.9 Hz, 2H), 7.45 (d, J = 8.6 Hz, 2H), 6.95 (d, J = 8.9 Hz, 2H), 4.60 (s, 2H), 4.08 (q, J = 7.1 Hz, 2H), 3.86 (s, 3H), 3.31–3.25 (m, 2H), 3.22–3.18 (m, 2H), 1.17 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 172.6, 166.5, 163.0, 147.3, 146.8, 132.9, 129.4, 128.8, 123.8, 113.9, 63.9, 61.5, 55.6, 34.3, 31.7, 14.0; HRMS (ESI-TOF): Anal. Calcd. For C 20H 22N 2O 8S+Na +: 473.0989, Found: 473.0993; IR (neat, cm -1): υ 2981, 2847, 1745, 1617, 1595, 1381, 1345, 1111, 833, 803, 687。 1 H NMR (400 MHz, CDCl 3 ) δ 8.16 (d, J = 8.6 Hz, 2H), 7.78 (d, J = 8.9 Hz, 2H), 7.45 (d, J = 8.6 Hz, 2H), 6.95 (d , J = 8.9 Hz, 2H), 4.60 (s, 2H), 4.08 (q, J = 7.1 Hz, 2H), 3.86 (s, 3H), 3.31–3.25 (m, 2H), 3.22–3.18 (m, 2H), 1.17 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.6, 166.5, 163.0, 147.3, 146.8, 132.9, 129.4, 128.8, 123.8, 113.9, 61.59, 6 55.6, 34.3, 31.7, 14.0; HRMS (ESI-TOF): Anal. Calcd. For C 20 H 22 N 2 O 8 S+Na + : 473.0989, Found: 473.0993; IR (neat, cm -1 ): υ 2981 , 2847, 1745, 1617, 1595, 1381, 1345, 1111, 833, 803, 687.
实施例十二。Embodiment twelve.
Figure 896507dest_path_image017
。
Figure 896507dest_path_image017
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率34%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 34%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 7.88 (d, J = 8.8 Hz, 2H), 7.67 (d, J = 8.4 Hz, 2H), 7.47 (d, J = 8.4 Hz, 2H), 7.19 (d, J = 2.3 Hz, 1H), 6.99 (d, J = 8.8 Hz, 2H), 6.93 (d, J = 9.0 Hz, 1H), 6.70–6.67 (m, 1H), 4.54 (s, 2H), 4.39 (s, 2H), 4.04 (q, J = 7.1 Hz, 2H), 3.88 (s, 3H), 3.85 (s, 3H), 2.40 (s, 3H), 1.12 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 171.6, 168.3, 166.3, 163.0, 156.1, 139.3, 136.6, 133.8, 133.1, 131.2, 130.6, 129.1, 128.8, 114.8, 114.0, 112.1, 111.6, 101.3, 64.1, 61.4, 55.7, 55.6, 28.4, 13.9, 13.6; HRMS (ESI-TOF): Anal. Calcd. For C 30H 29 35ClN 2O 8S+Na +: 635.1225, Found: 635.1228. Anal. Calcd. For C 30H 29 37ClN 2O 8S +Na +: 637.1196, Found: 637.1199; IR (neat, cm -1): υ 2986, 2923, 1757, 1590, 1383, 1067, 1039, 828, 800, 773。 1 H NMR (400 MHz, CDCl 3 ) δ 7.88 (d, J = 8.8 Hz, 2H), 7.67 (d, J = 8.4 Hz, 2H), 7.47 (d, J = 8.4 Hz, 2H), 7.19 (d , J = 2.3 Hz, 1H), 6.99 (d, J = 8.8 Hz, 2H), 6.93 (d, J = 9.0 Hz, 1H), 6.70–6.67 (m, 1H), 4.54 (s, 2H), 4.39 (s, 2H), 4.04 (q, J = 7.1 Hz, 2H), 3.88 (s, 3H), 3.85 (s, 3H), 2.40 (s, 3H), 1.12 (t, J = 7.1 Hz, 3H) ; 13 C NMR (100 MHz, CDCl 3 ) δ 171.6, 168.3, 166.3, 163.0, 156.1, 139.3, 136.6, 133.8, 133.1, 131.2, 130.6, 129.1, 128.8, 114.8, 114.0, 112.1, 111.6, 101.3, 64.1, 61.4, 55.7, 55.6, 28.4, 13.9, 13.6; HRMS (ESI-TOF): Anal. Calcd. For C 30 H 29 35 ClN 2 O 8 S+Na + : 635.1225, Found: 635.1228. 30 H 29 37 ClN 2 O 8 S +Na + : 637.1196, Found: 637.1199; IR (neat, cm -1 ): υ 2986, 2923, 1757, 1590, 1383, 1067, 1039, 828, 800, 773.
实施例十三。Embodiment thirteen.
Figure 496115dest_path_image018
。
Figure 496115dest_path_image018
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率48%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 48%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 7.79 (d, J = 8.8 Hz, 2H), 6.94 (d, J = 8.8 Hz, 2H), 6.80 (d, J = 7.8 Hz, 3H), 4.59 (s, 2H), 4.08 (q, J = 7.1 Hz, 2H), 3.87 (s, 3H), 3.85 (s, 6H), 3.24–3.20 (m, 2H), 3.05–3.01 (m, 2H), 1.17 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 173.8, 166.7, 162.9, 148.9, 147.6, 133.3, 132.3, 129.4, 128.8, 120.3, 114.2, 113.9, 111.7, 111.3, 63.8, 61.4, 55.9, 55.8, 55.6, 35.3, 31.7, 14.0; HRMS (ESI-TOF): Anal. Calcd. For C 22H 27NO 8S+Na +: 488.1350, Found: 488.1367; IR (neat, cm -1): υ 3283, 2981, 1739, 1595, 1515, 1499, 1257, 1151, 1094, 1023, 803, 720, 686。 1 H NMR (400 MHz, CDCl 3 ) δ 7.79 (d, J = 8.8 Hz, 2H), 6.94 (d, J = 8.8 Hz, 2H), 6.80 (d, J = 7.8 Hz, 3H), 4.59 (s , 2H), 4.08 (q, J = 7.1 Hz, 2H), 3.87 (s, 3H), 3.85 (s, 6H), 3.24–3.20 (m, 2H), 3.05–3.01 (m, 2H), 1.17 ( t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 173.8, 166.7, 162.9, 148.9, 147.6, 133.3, 132.3, 129.4, 128.8, 120.3, 114.2, 113.73, 111.1 , 61.4, 55.9, 55.8, 55.6, 35.3, 31.7, 14.0; HRMS (ESI-TOF): Anal. Calcd. For C 22 H 27 NO 8 S+Na + : 488.1350, Found: 488.1367 ; 1 ): υ 3283, 2981, 1739, 1595, 1515, 1499, 1257, 1151, 1094, 1023, 803, 720, 686.
实施例十四。Embodiment Fourteen.
Figure 241830dest_path_image019
。
Figure 241830dest_path_image019
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率48%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 48%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 8.88 (s, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.90–7.86 (m, 3H), 7.50–7.43 (m, 2H), 6.97 (d, J = 8.9 Hz, 2H), 4.73 (s, 2H), 4.12 (q, J = 7.1 Hz, 2H), 3.87 (s, 3H), 1.20 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 166.5, 162.8, 160.3, 142.3, 138.7, 135.7, 133.8, 128.6, 126.5, 125.1, 122.2, 113.9, 64.4, 61.6, 55.6, 14.0; HRMS (ESI-TOF): Anal. Calcd. For C 20H 19NO 6S 2+H +: 434.0727, Found: 434.0727; IR (neat, cm -1): υ 3100, 2964, 1753, 1603, 1590, 1247, 1108, 1024, 838, 802, 681。 1 H NMR (400 MHz, CDCl 3 ) δ 8.88 (s, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.90–7.86 (m, 3H), 7.50–7.43 (m, 2H), 6.97 ( d, J = 8.9 Hz, 2H), 4.73 (s, 2H), 4.12 (q, J = 7.1 Hz, 2H), 3.87 (s, 3H), 1.20 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 166.5, 162.8, 160.3, 142.3, 138.7, 135.7, 133.8, 128.6, 126.5, 125.1, 122.2, 113.9, 64.4, 61.6, 55.6, HR14.0: AnTOI; Calcd. For C 20 H 19 NO 6 S 2 +H + : 434.0727, Found: 434.0727; IR (neat, cm -1 ): υ 3100, 2964, 1753, 1603, 1590, 1247, 1108, 1024, 838, 802 , 681.
实施例十五。Embodiment fifteen.
Figure 559679dest_path_image020
。
Figure 559679dest_path_image020
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率52%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 52%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 10.68 (s, 1H), 7.94–7.88 (m, 2H), 7.72–7.70 (m, 1H), 7.67–7.66 (m, 1H), 7.51–7.48 (m, 1H), 7.39–7.35 (m, 1H), 7.20–7.13 (m, 1H), 7.02–6.95 (m, 2H), 4.75 (s, 2H), 4.12 (q, J = 7.1 Hz, 2H), 3.87 (s, 3H), 1.19 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ166.9, 162.9, 158.1, 138.5, 133.3, 126.8, 124.3, 121.3, 114.8, 114.0, 112.7, 64.0, 61.5, 55.6, 14.0; HRMS (ESI-TOF): Anal. Calcd. For C 20H 20N 2O 6S+Na +: 439.0934, Found: 439.0932; IR (neat, cm -1): υ 3578, 3222, 2922, 1753, 1570, 1084, 1023, 825, 802, 742。 1 H NMR (400 MHz, CDCl 3 ) δ 10.68 (s, 1H), 7.94–7.88 (m, 2H), 7.72–7.70 (m, 1H), 7.67–7.66 (m, 1H), 7.51–7.48 (m , 1H), 7.39–7.35 (m, 1H), 7.20–7.13 (m, 1H), 7.02–6.95 (m, 2H), 4.75 (s, 2H), 4.12 (q, J = 7.1 Hz, 2H), 3.87 (s, 3H), 1.19 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ166.9, 162.9, 158.1, 138.5, 133.3, 126.8, 124.3, 121.3, 114.8, 114.0 , 112.7, 64.0, 61.5, 55.6, 14.0; HRMS (ESI-TOF): Anal. Calcd. For C 20 H 20 N 2 O 6 S+Na + : 439.0934, Found: 439.0932; IR (neat, cm -1 ) : υ 3578, 3222, 2922, 1753, 1570, 1084, 1023, 825, 802, 742.
实施例十六。Embodiment sixteen.
Figure 543815dest_path_image021
。
Figure 543815dest_path_image021
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率64%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 64%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 7.89–7.87 (m, 2H), 7.58–7.55 (m, 1H), 7.51–7.47 (m, 2H), 4.61 (s, 2H), 4.06 (q, J = 7.1 Hz, 2H), 2.57 (s, 3H), 1.14 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 172.9, 166.5, 141.1, 132.6, 128.7, 126.5, 63.9, 61.4, 19.8, 13.8; HRMS (ESI-TOF): Anal. Calcd. For C 12H 15NO 5S+Na +: 308.0563, Found: 308.0568; IR (neat, cm -1): υ 3251, 2974, 2873, 1723, 1597, 1154, 1088, 854, 719, 686。 1 H NMR (400 MHz, CDCl 3 ) δ 7.89–7.87 (m, 2H), 7.58–7.55 (m, 1H), 7.51–7.47 (m, 2H), 4.61 (s, 2H), 4.06 (q, J = 7.1 Hz, 2H), 2.57 (s, 3H), 1.14 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.9, 166.5, 141.1, 132.6, 128.7, 126.5, 63.9 , 61.4, 19.8, 13.8; HRMS (ESI-TOF): Anal. Calcd. For C 12 H 15 NO 5 S+Na + : 308.0563, Found: 308.0568; IR (neat, cm -1 ): υ 3251, 2974, 2873, 1723, 1597, 1154, 1088, 854, 719, 686.
实施例十七。Embodiment seventeen.
Figure 263509dest_path_image022
。
Figure 263509dest_path_image022
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率66%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 66%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 7.76 (d, J = 8.0 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 4.61 (s, 2H), 4.11–4.05 (m, 2H),2.55 (s, 3H), 2.41 (s, 3H), 1.16 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 172.7, 166.6, 143.5, 138.4, 129.4, 126.7, 63.9, 61.5, 21.5, 19.8, 13.9; HRMS (ESI-TOF): Anal. Calcd. For C 13H 17NO 5S+Na +: 322.0720, Found: 322.0726; IR (neat, cm -1): υ 2954, 2922, 1755, 1612, 1461, 1156, 1072, 1173, 1027, 814, 706。 1 H NMR (400 MHz, CDCl 3 ) δ 7.76 (d, J = 8.0 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 4.61 (s, 2H), 4.11–4.05 (m, 2H) ,2.55 (s, 3H), 2.41 (s, 3H), 1.16 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.7, 166.6, 143.5, 138.4, 129.4, 126.7, 63.9, 61.5, 21.5, 19.8, 13.9; HRMS (ESI-TOF): Anal. Calcd. For C 13 H 17 NO 5 S+Na + : 322.0720, Found: 322.0726; IR (neat, cm -1 ): υ 2954 , 2922, 1755, 1612, 1461, 1156, 1072, 1173, 1027, 814, 706.
实施例十八。Embodiment eighteen.
Figure 432323dest_path_image023
。
Figure 432323dest_path_image023
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率53%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 53%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 8.02–8.00 (m, 1H), 7.47–7.43 (m, 1H), 7.32–7.26 (m, 2H), 4.63 (s, 2H), 4.07 (q, J = 7.1 Hz, 2H), 2.62 (s, 3H), 2.57 (s, 3H), 1.15 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ173.1, 166.6, 139.1, 137.7, 132.2, 128.1, 125.8, 63.8, 61.5, 20.2, 20.1, 13.9; HRMS (ESI-TOF): Anal. Calcd. For C 13H 17NO 5S+Na +: 322.0720, Found: 322.0731; IR (neat, cm -1): υ 3066, 2874, 2706, 1678, 1478, 1371, 1168, 1158, 775, 709。 1 H NMR (400 MHz, CDCl 3 ) δ 8.02–8.00 (m, 1H), 7.47–7.43 (m, 1H), 7.32–7.26 (m, 2H), 4.63 (s, 2H), 4.07 (q, J = 7.1 Hz, 2H), 2.62 (s, 3H), 2.57 (s, 3H), 1.15 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ173.1, 166.6, 139.1 , 137.7, 132.2, 128.1, 125.8 , 63.8, 61.5, 20.2, 20.1, 13.9 ; HRMS( ESI - TOF): Anal. Calcd. neat, cm -1 ): υ 3066, 2874, 2706, 1678, 1478, 1371, 1168, 1158, 775, 709.
实施例十九。Embodiment nineteen.
Figure 237468dest_path_image024
。
Figure 237468dest_path_image024
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率55%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 55%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 8.47 (s, 1H), 7.99–7.82 (m, 4H), 7.67–7.56 (m, 2H), 4.63 (s, 2H), 4.03 (q, J = 7.1 Hz, 2H), 2.62 (s, 3H), 1.08 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 172.9, 166.5, 138.1, 134.8, 131.9, 129.3, 129.1, 128.8, 127.8, 127.7, 127.4, 122.3, 64.0, 61.5, 20.0, 13.8; HRMS (ESI-TOF): Anal. Calcd. For C 16H 17NO 5S+Na +: 358.0720, Found: 358.0720; IR (neat, cm -1): υ 3063, 2912, 1753, 1613, 1157, 1130, 1061, 752, 691。 1 H NMR (400 MHz, CDCl 3 ) δ 8.47 (s, 1H), 7.99–7.82 (m, 4H), 7.67–7.56 (m, 2H), 4.63 (s, 2H), 4.03 (q, J = 7.1 Hz, 2H), 2.62 (s, 3H), 1.08 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.9, 166.5, 138.1, 134.8, 131.9, 129.3, 129.1, 128.8 , 127.8, 127.7, 127.4, 122.3, 64.0, 61.5, 20.0, 13.8; HRMS ( ESI - TOF): Anal . Calcd . cm -1 ): υ 3063, 2912, 1753, 1613, 1157, 1130, 1061, 752, 691.
实施例二十。Embodiment 20.
Figure 25295dest_path_image025
。
Figure 25295dest_path_image025
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率74%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 74%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 7.90 (d, J = 8.0 Hz, 1H), 7.60–7.52 (m, 2H), 7.36–7.32 (m, 1H), 4.73 (s, 2H), 4.57 (s, 2H), 4.16 (q, J = 7.1 Hz, 2H), 2.43 (s, 3H), 1.25 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 174.0, 166.0, 163.5, 149.3, 130.2, 124.0, 122.4, 120.7, 109.7, 63.9, 61.6, 51.2, 20.1, 13.9; HRMS (ESI-TOF): Anal. Calcd. For C 14H 16N 2O 6S+Na +: 363.0621, Found: 363.0621; IR (neat, cm -1): υ 2990, 2939, 1757, 1612, 1306, 1172, 1077, 1046, 802, 750, 737。 1 H NMR (400 MHz, CDCl 3 ) δ 7.90 (d, J = 8.0 Hz, 1H), 7.60–7.52 (m, 2H), 7.36–7.32 (m, 1H), 4.73 (s, 2H), 4.57 ( s, 2H), 4.16 (q, J = 7.1 Hz, 2H), 2.43 (s, 3H), 1.25 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 174.0, 166.0 , 163.5, 149.3, 130.2, 124.0, 122.4, 120.7, 109.7, 63.9, 61.6, 51.2, 20.1, 13.9; HRMS (ESI-TOF): Anal. Calcd. For C 14 H 16 N 2 O 6 S+Na + : 363.0621, Found: 363.0621; IR (neat, cm -1 ): υ 2990, 2939, 1757, 1612, 1306, 1172, 1077, 1046, 802, 750, 737.
实施例二十一。Embodiment 21.
Figure 599496dest_path_image026
。
Figure 599496dest_path_image026
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率90%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 90%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 7.65 (d, J = 3.7 Hz, 1H), 7.59 (d, J = 5.0 Hz, 1H), 7.08–7.03 (m, 1H), 4.67 (s, 2H), 4.14 (q, J = 7.1 Hz, 2H), 2.56 (s, 3H), 1.21 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 173.0, 166.3, 142.0, 132.0, 131.7, 126.8, 64.0, 61.4, 19.7, 13.8; HRMS (ESI-TOF): Anal. Calcd. For C 10H 13NO 5S 2+Na +: 314.0127, Found: 314.0126; IR (neat, cm -1): υ 3099, 2984, 2918, 1751, 1607, 1302, 1153, 1067, 1016, 855, 724, 679。 1 H NMR (400 MHz, CDCl 3 ) δ 7.65 (d, J = 3.7 Hz, 1H), 7.59 (d, J = 5.0 Hz, 1H), 7.08–7.03 (m, 1H), 4.67 (s, 2H) , 4.14 (q, J = 7.1 Hz, 2H), 2.56 (s, 3H), 1.21 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 173.0, 166.3, 142.0, 132.0 , 131.7, 126.8, 64.0, 61.4, 19.7, 13.8; HRMS (ESI-TOF): Anal. Calcd. For C 10 H 13 NO 5 S 2 +Na + : 314.0127, Found: 314.0126 ; ): υ 3099, 2984, 2918, 1751, 1607, 1302, 1153, 1067, 1016, 855, 724, 679.
实施例二十二。Embodiment twenty-two.
Figure 80156dest_path_image027
。
Figure 80156dest_path_image027
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率39%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 39%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 8.96 (d, J = 7.1 Hz, 1H), 7.86 (d, J = 9.1 Hz, 1H), 7.59–7.53 (m, 1H), 7.21–7.17 (m, 1H), 4.63 (s, 2H), 4.00 (q, J = 7.1 Hz, 2H), 3.63 (q, J = 7.4 Hz, 2H), 2.70 (s, 3H), 1.41 (t, J = 7.4 Hz, 3H), 1.12 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 175.0, 166.1, 145.1, 144.3, 129.1, 127.3, 119.1, 116.3, 64.5, 61.5, 49.5, 20.6, 13.8, 6.8; HRMS (ESI-TOF): Anal. Calcd. For C 15H 19N 3O 7S 2+Na +: 440.0557, Found: 440.0572; IR (neat, cm -1): υ 3272, 3077, 2983, 1752, 1587, 1312, 1165, 1134, 857, 827, 760, 733。 1 H NMR (400 MHz, CDCl 3 ) δ 8.96 (d, J = 7.1 Hz, 1H), 7.86 (d, J = 9.1 Hz, 1H), 7.59–7.53 (m, 1H), 7.21–7.17 (m, 1H), 4.63 (s, 2H), 4.00 (q, J = 7.1 Hz, 2H), 3.63 (q, J = 7.4 Hz, 2H), 2.70 (s, 3H), 1.41 (t, J = 7.4 Hz, 3H), 1.12 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 175.0, 166.1, 145.1, 144.3, 129.1, 127.3, 119.1, 116.3, 64.5, 61.5, 49.5, 20. 13.8, 6.8; HRMS (ESI-TOF): Anal. Calcd. For C 15 H 19 N 3 O 7 S 2 +Na + : 440.0557, Found: 440.0572; IR (neat, cm -1 ): υ 3272, 3077, 2983, 1752, 1587, 1312, 1165, 1134, 857, 827, 760, 733.
实施例二十三。Embodiment twenty-three.
Figure 982384dest_path_image028
。
Figure 982384dest_path_image028
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率47%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 47%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 7.87 (d, J = 8.7 Hz, 2H), 7.45 (d, J = 8.7 Hz, 2H), 7.18 (d, J = 8.0 Hz, 2H), 7.11 (d, J = 8.0 Hz, 2H), 6.73 (s, 1H), 4.61 (s, 2H), 4.10 (q, J = 7.1 Hz, 2H), 2.58 (s, 3H), 2.37 (s, 3H), 1.18 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 173.4, 166.4, 145.2, 142.5, 140.6, 139.7, 129.7, 128.7, 127.7, 125.7, 125.2, 106.2, 64.0, 61.6, 21.3, 20.1, 14.0; 19F NMR (376 MHz, CDCl 3) δ = -62.48 (s, 3F); HRMS (ESI-TOF): Anal. Calcd. For C 23H 22F 3N 3O 5S+Na +: 532.1124, Found: 532.1105; IR (neat, cm -1): υ 3078, 2990, 2925, 1756, 1608, 1406, 1131, 843, 817, 654。 1 H NMR (400 MHz, CDCl 3 ) δ 7.87 (d, J = 8.7 Hz, 2H), 7.45 (d, J = 8.7 Hz, 2H), 7.18 (d, J = 8.0 Hz, 2H), 7.11 (d , J = 8.0 Hz, 2H), 6.73 (s, 1H), 4.61 (s, 2H), 4.10 (q, J = 7.1 Hz, 2H), 2.58 (s, 3H), 2.37 (s, 3H), 1.18 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 173.4, 166.4, 145.2, 142.5, 140.6, 139.7, 129.7, 128.7, 127.7, 125.7, 125.2, 106.2, 61. 21.3, 20.1, 14.0; 19 F NMR (376 MHz, CDCl 3 ) δ = -62.48 (s, 3F); HRMS (ESI-TOF): Anal. Calcd. For C 23 H 22 F 3 N 3 O 5 S+ Na + : 532.1124, Found: 532.1105; IR (neat, cm -1 ): υ 3078, 2990, 2925, 1756, 1608, 1406, 1131, 843, 817, 654.
实施例二十四。Embodiment twenty-four.
Figure 573902dest_path_image029
。
Figure 573902dest_path_image029
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率48%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 48%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 7.79–7.77 (m, 1H), 7.42–7.33 (m, 1H), 6.76–6.72 (m, 1H), 6.56–6.54 (m, 1H), 6.28–6.26 (m, 1H), 4.66 (s, 2H), 4.27–4.21 (m, 2H), 4.03 (q, J = 7.1 Hz, 2H), 3.96 (d, J = 5.2 Hz, 2H), 2.55 (s, 3H), 1.29 (t, J = 7.1 Hz, 3H), 1.13 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 172.8, 169.9, 166.7, 144.9, 134.5, 129.1, 122.9, 116.1, 111.7, 64.1, 61.4, 61.3, 19.9, 14.1, 13.9; HRMS (ESI-TOF): Anal. Calcd. For C 16H 22N 2O 7S+Na +: 409.1040, Found: 409.1046; IR (neat, cm -1): υ 3395, 2956, 2917, 1739, 1600, 1204, 1153, 803, 746。 1 H NMR (400 MHz, CDCl 3 ) δ 7.79–7.77 (m, 1H), 7.42–7.33 (m, 1H), 6.76–6.72 (m, 1H), 6.56–6.54 (m, 1H), 6.28–6.26 (m, 1H), 4.66 (s, 2H), 4.27–4.21 (m, 2H), 4.03 (q, J = 7.1 Hz, 2H), 3.96 (d, J = 5.2 Hz, 2H), 2.55 (s, 3H), 1.29 (t, J = 7.1 Hz, 3H), 1.13 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.8, 169.9, 166.7, 144.9, 134.5, 129.1, 122.9 , 116.1 , 111.7, 64.1, 61.4, 61.3, 19.9, 14.1, 13.9; HRMS ( ESI - TOF): Anal. Calcd. (neat, cm -1 ): υ 3395, 2956, 2917, 1739, 1600, 1204, 1153, 803, 746.
实施例二十五。Embodiment twenty-five.
Figure 2609dest_path_image030
。
Figure 2609dest_path_image030
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率47%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 47%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 7.68 – 7.61 (m, 2H), 6.58 – 6.53 (m, 2H), 4.57 (d, J = 1.8 Hz, 2H), 4.24 – 4.16 (m, 2H), 4.12 (s, 2H), 4.09 – 4.01 (m, 2H), 3.88 (d, J = 5.3 Hz, 1H), 2.47 (s, 3H), 1.25 (t, J = 7.1 Hz, 3H), 1.14 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 172.0, 171.9, 170.1, 169.7, 166.7, 151.0, 150.3, 129.6, 129.1, 128.7, 128.6, 111.7, 111.3, 63.7, 61.6, 61.4, 61.4, 53.2, 44.9, 19.6, 19.5, 14.10, 14.07,13.9; HRMS (ESI-TOF): Anal. Calcd. For C 16H 22N 2O 7S+Na +: 409.1040, Found: 409.1014; IR (neat, cm -1): υ 3383, 2972, 2905, 1735, 1596, 1375, 1148, 819, 745。 1 H NMR (400 MHz, CDCl 3 ) δ 7.68 – 7.61 (m, 2H), 6.58 – 6.53 (m, 2H), 4.57 (d, J = 1.8 Hz, 2H), 4.24 – 4.16 (m, 2H), 4.12 (s, 2H), 4.09 – 4.01 (m, 2H), 3.88 (d, J = 5.3 Hz, 1H), 2.47 (s, 3H), 1.25 (t, J = 7.1 Hz, 3H), 1.14 (t , J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 172.0, 171.9, 170.1, 169.7, 166.7, 151.0, 150.3, 129.6, 129.1, 128.7, 128.6, 111.7, 61.7, 61.1 61.4, 61.4, 53.2, 44.9, 19.6, 19.5, 14.10 , 14.07,13.9 ; HRMS ( ESI - TOF): Anal. Calcd. (neat, cm -1 ): υ 3383, 2972, 2905, 1735, 1596, 1375, 1148, 819, 745.
实施例二十六。Embodiment twenty-six.
Figure 388591dest_path_image031
。
Figure 388591dest_path_image031
.
向试管中加入酰胺（0.5 mmol）、磺酰胺（0.75 mmol）、硫酸铁（20 %mmol）、硫酸氢钾（2.0 eq），然后加入环己烷（2 mL），最后加入重氮乙酸乙酯 EDA（3.0 mmol），将混合物在空气气氛下油浴90℃反应24小时。 反应完成后用饱和氯化钠溶液淬灭 ，乙酸乙酯提取，有机相合并后无水硫酸镁干燥，减压旋干溶剂。用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物，产率71%。所制得产物的主要测试数据如下，通过分析可知，实际合成产物与理论分析一致。 Add amide (0.5 mmol), sulfonamide (0.75 mmol), ferric sulfate (20 % mmol), potassium bisulfate (2.0 eq) to the test tube, then cyclohexane (2 mL), and finally ethyl diazoacetate EDA (3.0 mmol), the mixture was reacted in an oil bath at 90 °C for 24 h under an air atmosphere. After the reaction was completed, it was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was spin-dried under reduced pressure. The product can be obtained by column chromatography with a mixed solvent of ethyl acetate and petroleum ether, and the yield is 71%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.
1H NMR (400 MHz, CDCl 3) δ 7.88 (d, J = 7.6 Hz, 2H), 7.58–7.55 (m, 1H), 7.47–7.43 (m, 2H), 4.99 (d, J = 15.6 Hz, 1H), 4.84 (d, J = 15.6 Hz, 1H), 4.61–4.58 (m, 1H), 4.36 (d, J = 2.6 Hz, 1H), 4.32–4.16 (m, 6H), 3.91–3.87 (m, 1H), 3.73 (d, J = 12.9 Hz, 1H), 1.52 (s, 3H), 1.46 (s, 3H), 1.39 (s, 3H), 1.32 (s, 3H), 1.29 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl 3) δ 170.6, 166.4, 133.0, 129.7, 129.2, 128.2, 109.1, 109.0, 100.7, 69.8, 64.5, 61.8, 61.2, 26.4, 25.7, 25.1, 23.9, 14.0; HRMS (ESI-TOF): Anal. Calcd. For C 23H 31NO 11S+Na +: 552.1510, Found: 552.1505; IR (neat, cm -1): υ 2990, 2939, 1757, 1612, 1381, 1307, 1207, 1074, 803, 777, 751。 1 H NMR (400 MHz, CDCl 3 ) δ 7.88 (d, J = 7.6 Hz, 2H), 7.58–7.55 (m, 1H), 7.47–7.43 (m, 2H), 4.99 (d, J = 15.6 Hz, 1H), 4.84 (d, J = 15.6 Hz, 1H), 4.61–4.58 (m, 1H), 4.36 (d, J = 2.6 Hz, 1H), 4.32–4.16 (m, 6H), 3.91–3.87 (m , 1H), 3.73 (d, J = 12.9 Hz, 1H), 1.52 (s, 3H), 1.46 (s, 3H), 1.39 (s, 3H), 1.32 (s, 3H), 1.29 (t, J = 7.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 170.6, 166.4, 133.0, 129.7, 129.2, 128.2, 109.1, 109.0, 100.7, 69.8, 64.5, 61.8, 51.2, 25.9, 1 , 14.0; HRMS (ESI-TOF): Anal. Calcd. For C 23 H 31 NO 11 S+Na + : 552.1510, Found: 552.1505; IR (neat, cm -1 ): υ 2990, 2939, 1757, 1612, 1381, 1307, 1207, 1074, 803, 777, 751.

Claims (10)

  1. 一种制备 N-磺酰亚胺的方法，其特征在于：以酰胺、重氮乙酸乙酯、磺酰胺为反应底物，在催化剂与助剂作用下，在有机溶剂中反应得到 N-磺酰亚胺；或者以酰胺、重氮乙酸乙酯、和磺酰胺为反应底物，在助剂作用下，在有机溶剂中反应得到 N-磺酰亚胺； A method for preparing N -sulfonyl imide, characterized in that: using amide, ethyl diazoacetate, and sulfonamide as reaction substrates, under the action of catalyst and auxiliary agent, react in an organic solvent to obtain N -sulfonyl Imine; or with amide, ethyl diazoacetate, and sulfonamide as reaction substrate, under the effect of auxiliary agent, react in organic solvent to obtain N -sulfonimide;
    其中，所述酰胺的化学结构通式为：
    Figure 356630dest_path_image001
    ；式中，R 1、R 2、R 3独立的选自烷基、杂芳香烃、取代芳基；     Wherein, the general chemical structure formula of described amide is:
    Figure 356630dest_path_image001
    ; In the formula, R 1 , R 2 , and R 3 are independently selected from alkyl groups, heteroaromatic hydrocarbons, and substituted aryl groups;
    所述磺酰胺的化学结构通式为：
    Figure 27914dest_path_image002
    ；式中，R 5选自烷基、杂芳香烃、萘环或者取代芳基；     The general chemical structure formula of described sulfonamide is:
    Figure 27914dest_path_image002
    ; In the formula, R 5 is selected from an alkyl group, a heteroaromatic hydrocarbon, a naphthalene ring or a substituted aryl group;
    所述 N-磺酰亚胺的化学结构式为：
    Figure 46686dest_path_image003
    。     The chemical structural formula of described N -sulfonylimide is:
    Figure 46686dest_path_image003
    .
  2. 根据权利要求1所述制备 N-磺酰亚胺的方法，其特征在于：所述反应的反应温度为25～100℃，时间为12～48小时。 The method for preparing N -sulfonimide according to claim 1, characterized in that: the reaction temperature of the reaction is 25-100° C., and the time is 12-48 hours.
  3. 根据权利要求1所述制备 N-磺酰亚胺的方法，其特征在于：所述取代芳基的结构通式为：
    Figure 193633dest_path_image004
    ，其中R 4选自氢、烷基、氟、氯、溴、烷氧基、三氟甲基或者砜基。     The method for preparing N -sulfonimide according to claim 1, is characterized in that: the structural general formula of described substituted aryl is:
    Figure 193633dest_path_image004
    , wherein R 4 is selected from hydrogen, alkyl, fluorine, chlorine, bromine, alkoxy, trifluoromethyl or sulfone.
  4. 根据权利要求1所述制备 N-磺酰亚胺的方法，其特征在于：所述催化剂为硫酸铁、硫酸钴、乙酰丙酮钴、乙酰丙酮铁、硫酸亚铁、三氧化铁、三氯化铁中的一种；所述助剂为硫酸氢钾、磷酸二氢钠、磷酸二氢钾中的一种；有机溶剂为环己烷、己烷、乙腈、硝基甲烷、1,2-二氯乙烷、1,4-二氧六环中的一种。 The method for preparing N -sulfonylimide according to claim 1, is characterized in that: the catalyst is ferric sulfate, cobalt sulfate, cobalt acetylacetonate, iron acetylacetonate, ferrous sulfate, ferric oxide, ferric chloride The one in; the auxiliary agent is one in potassium hydrogen sulfate, sodium dihydrogen phosphate, potassium dihydrogen phosphate; the organic solvent is cyclohexane, hexane, acetonitrile, nitromethane, 1,2-dichloro One of ethane and 1,4-dioxane.
  5. 根据权利要求1所述制备 N-磺酰亚胺的方法，其特征在于：所述催化剂的用量为酰胺摩尔量的5～30%。 The method for preparing N -sulfonimide according to claim 1, characterized in that: the amount of the catalyst is 5-30% of the molar weight of the amide.
  6. 根据权利要求1所述制备 N-磺酰亚胺的方法，其特征在于：所述重氮乙酸乙酯的用量为酰胺摩尔量的6倍；磺胺的用量为酰胺摩尔量的1.5倍。 The method for preparing N -sulfonimide according to claim 1 is characterized in that: the consumption of said ethyl diazoacetate is 6 times of the molar weight of amide; the consumption of sulfonamide is 1.5 times of the molar weight of amide.
  7. 根据权利要求1所述制备 N-磺酰亚胺的方法，其特征在于：所述反应在空气中进行。 The method for preparing N -sulfonimide according to claim 1, characterized in that: said reaction is carried out in air.
  8. 根据权利要求1所述制备 N-磺酰亚胺的方法，其特征在于：所述助剂的用量为酰胺摩尔量的1～3倍。 The method for preparing N -sulfonimide according to claim 1, characterized in that: the amount of the auxiliary agent is 1 to 3 times the molar weight of the amide.
  9. 根据权利要求1所述制备N-磺酰亚胺的方法制备的N-磺酰亚胺。The N-sulfonimide prepared by the method for preparing N-sulfonimide according to claim 1.
  10. 催化剂和/或助剂在以酰胺、重氮乙酸乙酯、和磺酰胺为反应底物制备N-磺酰亚胺中的应用。Application of catalyst and/or auxiliary agent in preparing N-sulfonimide with amide, ethyl diazoacetate and sulfonamide as reaction substrates.
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Citations (3)

* Cited by examiner, † Cited by third party
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CN107459509A (en) * 2016-06-06 2017-12-12 南开大学 A kind of nitrogenous sulfur-bearing sulfimide derivative and its production and use
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