3-halo-1,1-bialkyl sulphide-1,3-butadiene derivatives and synthesis thereof

A technology of alkyl and alkoxy, which is applied in the field of carbonyl protection reagents in organic synthesis, which can solve the problems of high price, inconvenient transportation, and low-level mercaptans are easy to volatilize, and achieve the effect of low price, no peculiar smell, and convenient transportation and storage

Inactive Publication Date: 2004-04-21
NORTHEAST NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0002] At present, mercaptans are widely used in thioketal (aldehyde) reactions, but there are disadvantages such as high price, toxicity, inconvenient transportation, etc., especially l

Method used

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  • 3-halo-1,1-bialkyl sulphide-1,3-butadiene derivatives and synthesis thereof
  • 3-halo-1,1-bialkyl sulphide-1,3-butadiene derivatives and synthesis thereof
  • 3-halo-1,1-bialkyl sulphide-1,3-butadiene derivatives and synthesis thereof

Examples

Experimental program
Comparison scheme
Effect test

Example Embodiment

[0019] Example 1:

[0020] Add 30 ml of a mixed solvent of dimethylacetamide and ethyl acetate to a 100 ml three-necked flask equipped with a condenser tube, a constant pressure funnel and a thermometer, control the temperature at -5°C, and add 2 mmol chlorine dropwise to the three-necked flask. The sulfoxide was dissolved, and the solution was slightly red at this point. After stirring for 30 min, a chloroform solution of 2-[1,3]dithi-2-ylidene-3-carbonyl-butyric acid methyl ester (3) (232 mg, 1.0 mmol) was added in one portion, stirred for 10 hours, and the substrate was monitored by TLC disappear. The reaction solution was poured into ice water and stirred until a large amount of precipitate formed. It was filtered to obtain 208.46 mg of methyl 3-chloro-2-[1,3]dithi-2-ylidene-3-butenoate (4) in a yield of 87%. (See the following formula for the reaction).

[0021]

[0022] Structure Characterization:

[0023] Yield: 87% m.p.66-68°C 1 HNMR: 2.19 (2H, m, -CH 2 -),...

Example Embodiment

[0024] Example 2:

[0025] p-Nitrobenzaldehyde (5) (151 mg, 1.0 mmol) and methyl 3-chloro-2-[1,3]dithi-2-ylidene-3-butenoate (4) (2 mmol) were added to In a round-bottomed flask equipped with a condenser, a mixture of absolute ethanol and tetrahydrofuran was used as a solvent. The reaction temperature was controlled at 65°C, stirred for 36 hours, and monitored by TLC until the disappearance of the substrate. The product 2-(4-nitrophenyl-[1,3]dithiane (6) 229 mg was isolated by column chromatography, and the yield was 95%. (The reaction is shown in the following formula).

[0026]

Example Embodiment

[0027] Example 3:

[0028] To a 100-mL three-necked flask equipped with a condenser tube, a constant pressure funnel, and a thermometer, add 1 mmol of 3-(dimethylthio)methylene-2,4-pentanedione (7), and mix with benzene, ether and DMF. Dissolve it with 40 ml of solvent, control the temperature at 0°C, and add 4 mmol of phosphorus trichloride dropwise to the three-necked flask, and the solution is slightly red at this time. After stirring at room temperature for 5 hours, the color of the system deepened. TLC monitoring until the disappearance of the substrate. The reaction solution was poured into ice water and stirred until a large amount of precipitate formed. The product 3-(bismethylthio)methylene-2,4-dichloro-1,4-pentadiene (8) 236 mg was obtained by filtration, and the yield was 98%. (See the following formula for the reaction).

[0029]

[0030] Structure Characterization:

[0031] Yield: 98% m.p: 38-40°C 1 HNMR: 2.39(6H,s,-SCH 3 ), 5.43(2H,s,=-H), 5.64(2H,s,=...

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Abstract

A 3-halo-1,1-bialkylthio-1,3-butadiene derivative used as the carbonyl protecting agent and its preparing process are disclosed. It can be used in thioketalization reaction. Its advantages are high performance, low cost and no odor.

Description

Technical field: [0001] The invention discloses a new compound 3-halo-1,1-bisalkylthio-1,3-butadiene derivative as a carbonyl protection reagent, and provides its synthesis method, which belongs to the carbonyl protection reagent technology of organic synthesis field. Background technique: [0002] At present, mercaptans are widely used in thioketal (aldehyde) reactions, but there are disadvantages such as high price, toxicity, inconvenient transportation, etc., especially low-level mercaptans are volatile and have a strong smell, which is difficult to obtain. The unbearable, penetrating smell of rotten eggs often fills the entire laboratory with a foul smell. Even so, given their important role in synthesis, thioketal (aldehyde) reactions have been widely used, and thiols and their derivatives are still the preferred reagents. It can be seen that no matter from the basic research itself or from the aspect of social and economic benefits, it is possible to develop a cheap,...

Claims

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Application Information

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IPC IPC(8): C07C323/05C07D339/00C07D339/06C07D339/08
Inventor 刘群车广波孙然赵玉龙
Owner NORTHEAST NORMAL UNIVERSITY
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