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Synthesis method of methyl thiomethylene ester compound

A technology of methyl thiomethylene ester and synthesis method, applied in the directions of organic chemistry, sulfide preparation, etc., can solve problems such as unfavorable industrial production, hydrogen generation, expensive electrodes, etc., and achieve cost saving, simple production, and reaction yield. high rate effect

Pending Publication Date: 2022-05-03
NANJING NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0014] The electrodes required for this reaction are relatively expensive, and hydrogen gas will be generated, which has certain safety hazards and is not conducive to industrial production.

Method used

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  • Synthesis method of methyl thiomethylene ester compound
  • Synthesis method of methyl thiomethylene ester compound
  • Synthesis method of methyl thiomethylene ester compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0047] Embodiment 1: the synthesis of p-methoxybenzoic acid methylsulfomethylene ester

[0048] Add p-methoxybenzoic acid (45.6mg, 1.0eq), dimethylsulfonium bromide (100mg, 1.5eq), triethylamine (91.1mg, 125uL, 3.0eq ) and 3 mL of acetonitrile. In a nitrogen atmosphere, the temperature was gradually raised to room temperature at 0° C. and reacted for 18 h. After the reaction was completed, distilled water was added to quench the reaction, extracted 3 times with ethyl acetate, 10 mL each time, the combined organic phase was concentrated by rotary evaporation, and then column chromatography was carried out to obtain methylsulfomethylene p-methoxybenzoate The ester was 57.5 mg, and the yield was 90%.

[0049] Product Methylsulfomethylene p-methoxybenzoate: 1 H NMR (400MHz, CDCl 3 )δ8.03(d, J=8.8Hz, 2H), 6.94(d, J=8.8Hz, 2H), 5.35(s, 2H), 3.85(s, 3H), 2.29(s, 3H). 13 C NMR (101MHz, CDCl 3 )δ165.9, 163.5, 131.75, 122.1, 113.6, 68.4, 55.4, 15.4.

Embodiment 2

[0050] Embodiment 2: the synthesis of 2-naphthoic acid methylsulfomethylene ester

[0051] Add 2-naphthoic acid (51.7mg, 1.0eq), dimethylsulfonium bromide (100mg, 1.5eq), triethylamine (91.1mg, 125uL, 3.0eq) and 3 mL of acetonitrile. In a nitrogen atmosphere, the temperature was gradually raised to room temperature at 0° C. and reacted for 18 h. After the reaction was completed, distilled water was added to quench the reaction, extracted 3 times with ethyl acetate, 10 mL each time, the combined organic phase was concentrated by rotary evaporation, and then column chromatography was carried out to obtain 2-naphthoic acid methylsulfomethylene ester 60.0 mg, the yield was 86%.

[0052] Product 2-Naphthoic acid methylsulfomethylene ester: 1 H NMR (400MHz, CDCl 3 )δ8.64(s,1H),8.12–8.03(m,1H),7.99–7.94(m,1H),7.91–7.85(m,2H),7.63–7.51(m,2H),5.46(s, 2H), 2.36(s, 3H). 13 C NMR (101MHz, CDCl 3 )δ166.3, 135.6 132.3, 131.3 129.3, 128.4, 128.2, 127.7, 126.9, 126.7, 125.1, 68.9 15.5....

Embodiment 3

[0053] Embodiment 3: the synthesis of piperic acid methylsulfomethylene ester

[0054] Add piperic acid (50.0 mg, 1.0 eq), dimethylsulfonium bromide (100 mg, 1.5 eq), triethylamine (91.1 mg, 125 uL, 3.0 eq) and 3 mL of acetonitrile into a Schlenk reaction tube equipped with a magnetic stir bar . In a nitrogen atmosphere, the temperature was gradually raised to room temperature at 0° C. and reacted for 18 h. After the reaction was completed, distilled water was added to quench the reaction, and ethyl acetate was used to extract 3 times, 10 mL each time, the combined organic phase was concentrated by rotary evaporation, and then column chromatography was carried out to obtain 57.3 mg of methylsulfomethylene piperonate. The yield was 88%.

[0055] Product Methylsulfomethylene piperonate: 1 H NMR (400MHz, CDCl 3 )δ7.71–7.56(m,1H),7.45(d,J=1.8Hz,1H),6.82(d,J=8.2Hz,1H),6.02(s,2H),5.33(s,2H), 2.27(s,3H). 13 C NMR (101MHz, CDCl 3 )δ165.4, 151.8, 147.6, 125.5, 123.6, 109.4, 107....

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Abstract

The invention discloses a synthetic method of a methyl thiomethylene ester compound. According to the method, in the presence of nitrogen and alkali, a carboxylic acid compound reacts with an esterification reagent to form a methyl thiomethylene ester compound; wherein the esterification reagent is brominated dimethyl sulfonium; the alkali is organic alkali or inorganic alkali, and the carboxylic acid compound is p-methoxybenzoic acid, a benzoic acid derivative containing a substituent group on a benzene ring, conjugated carboxylic acid, amino acid and a carboxylic acid compound containing other functional groups or heteroatoms; the raw materials required by the method are simple and easy to obtain, the reaction conditions are simple and convenient, the method is green and energy-saving, the reaction yield is high, the compatibility of substrate functional groups is excellent, and the method has high application value.

Description

technical field [0001] The invention relates to the technical field of organic intermediate synthesis, in particular to a method for synthesizing methylsulfomethylene ester compounds. Background technique [0002] As a very important class of organic molecular intermediates, methylsulfomethylene esters widely exist in natural products and synthetic compounds with biological and pharmacological activities, and can be used to synthesize non-steroidal anti-inflammatory drugs. It occupies a very important position in life and can be used as a flavor additive in dairy products. In addition, it also has special chemical properties under photochemical conditions. Based on cleavage under neutral non-hydrolytic conditions, methylsulfomethylene esters can also serve as useful carboxyl protecting groups in peptide synthesis. Currently, there are many drugs containing carboxyl functional groups on the market, such as aspirin, ibuprofen, adapalene, etc. Therefore, the synthesis of rel...

Claims

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Application Information

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IPC IPC(8): C07C319/14C07C323/12
CPCC07C319/14C07C323/12Y02E60/10
Inventor 谢兰贵沈健董博
Owner NANJING NORMAL UNIVERSITY
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