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Process for alkyl aryl sulfide derivatives and new sulfide compounds

A technology for alkyl aryl and aryl halides, applied in the field of alkyl aryl sulfide derivatives and new sulfides, can solve the problems of troublesome methods, easy formation of disulfides, difficult to handle and the like

Inactive Publication Date: 2007-10-03
SEOUL NAT UNIV R&DB FOUND
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  • Abstract
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Problems solved by technology

[0012] 1) In the method shown in reaction scheme (1), thiophenol has a very large pungent odor, which makes it difficult to handle
It is unstable in air and easily forms unwanted aryl disulfides (R-SS-R), and there are not many commercially available varieties, but the price is higher than aryl halides
[0013] 2) Although the method shown in reaction scheme (2) has a higher final product yield (greater than or equal to 80%), the reaction conditions are harsh (greater than or equal to 100 ° C), and the reaction time is longer, which is 10 hours ~24 hours
However, since the substance represented by chemical formula (8) is prone to form disulfides and cause storage problems, it should be reacted with halides and inorganic salts immediately after synthesis
In addition, this method has limitations as a method for preparing various sulfides because the position of the -SH group introduced by sulfonyl chloride is mainly at the para
[0015] 4) In the reaction scheme (3), the method for preparing the compound of the chemical formula (10) is very troublesome, because the thiol compound (8) must be prepared according to the scheme, and then be separated and purified before the subsequent reaction
However, this method also has the following problems: disulfides are easily formed, and the LiAlH used in the reduction 4 Unstable in air, which can cause problems for mass production

Method used

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  • Process for alkyl aryl sulfide derivatives and new sulfide compounds
  • Process for alkyl aryl sulfide derivatives and new sulfide compounds
  • Process for alkyl aryl sulfide derivatives and new sulfide compounds

Examples

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preparation example Construction

[0040] In the production method according to the present invention, the compound of the chemical formula (I) used as a raw material is widely known in the art and can be obtained commercially.

[0041] The preparation method according to the present invention will be described in detail below.

[0042] [Method A] Production of an alkylaryl sulfide represented by the chemical formula (III) having an electron-donating or electron-withdrawing substituent

[0043] The alkylaryl sulfide represented by the chemical formula (III) is obtained by reacting the compound represented by the chemical formula (I) with an alkyllithium organometallic reagent and sulfur, and then reacting with the compound represented by the chemical formula (II).

[0044] A dry solvent such as diethyl ether, tetrahydrofuran, hexane, and heptane can be used alone or a mixture of two or more of them can be used in this method. Among them, diethyl ether, tetrahydrofuran, and a mixture of diethyl ether and tetrah...

Embodiment 1

[0058] [Example 1] The preparation of benzyl 2-trifluoromethylphenyl sulfide

[0059]

[0060] Under a nitrogen atmosphere, 271 µl of 1-bromo-2-(trifluoromethyl)-benzene was completely dissolved in 15 ml of dry tetrahydrofuran, and the mixture was cooled to -78°C. To this mixture was slowly added 1.25 ml of n-butyllithium (1.6M in cyclohexane, 1.0 eq.) over 1 minute. After stirring for another 10 minutes, 64 mg (2 mmol, 1.0 equivalent) of sulfur powder was added at the same temperature at one time. The mixture was further stirred at the same temperature for 10 minutes to completely dissolve sulfur, and then 236 µl (2 mmol, 1.0 equivalent) of benzyl bromide was slowly added thereto. The reaction was carried out allowing the overall temperature of the reaction mixture to rise to room temperature within 20 minutes. The reaction was monitored by TLC, and at the end of the reaction, 15 ml of ammonium chloride aqueous solution was added thereto to terminate the reaction. The o...

Embodiment 2

[0063] [embodiment 2] the preparation of benzyl 3-trifluoromethyl phenyl sulfide

[0064]

[0065] The same procedure as described in Example 1 was repeated except that 276 µl (2 mmol) of 1-bromo-3-(trifluoromethyl)-benzene was used instead of 1-bromo-2-(trifluoromethyl)-benzene. After purification, 381 mg of the title compound was obtained (yield: 71%).

[0066] 1 H-NMR (300MHz, CDCl 3 )δ: 7.51 (br s, 1H), 7.39 (t, 2H), 7.33 (d, 1H), 7.28 (m, 5H), 4.13 (s, 2H).

[0067] 13C-NMR (75.5MHz, CDCl 3 )δ: 138.3, 137.0, 133.0, 131.6 (q, J=32Hz), 129.5, 129.2, 129.0, 128.9, 127.9, 126.5 (q, J=3.7Hz), 123.3, 39.1.

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Abstract

The present invention provide a process for preparing an alkyl aryl sulfide of Chemical Formula (I I I) characterized in that an aryl halogen compound of Chemical Formula (I) is substituted with an alkyl lithium organometallic reagent, and subseq uently reacted with a compound of Chemical Formula (I I ) , or an aryl halogen compound of Chemical Formula (I) is reacted with Grignard reagent to protect the hyd rogen-donating substituent, and then reacted with an alkyl lithium orga nometallic reagent, and subsequently with sulfur and a compound of Chemical Formula (I I) . According to the process of the invention , an alkyl aryl sulfide of C hemical Formula (I I I ) can be prepared via one-step reaction without separation or purif ication of an intermediate compound from various aryl halogen compounds in a short reaction time with high yield. Several compounds among those compounds represented by Chemical Formula (I I I) are novel compounds.

Description

technical field [0001] The present invention relates to a method for preparing sulfides by a one-step reaction from aryl halides having various electron-donating, electron-withdrawing or hydrogen-donating substituents, and sulfide derivatives prepared by said method. More specifically, the present invention relates to a method for preparing various alkylaryl sulfides represented by formula (III), which play an important role in the synthesis of organic chemistry and medicinal chemistry, by a one-step reaction . Background technique [0002] The alkylaryl sulfides represented by formula (III) have a very wide range of applications in organic chemistry and medicinal chemistry. Therefore, various methods for preparing such sulfides have been developed by many researchers. Among these methods, the most common method is in the presence of strong base, the synthetic method (Synthesis 1972,101,1977,357, 1972,101,1977,357, Chemical Reviews 1978, 78, 363). As another synthetic me...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C323/09
CPCC07C319/14C07D277/26C07D317/22C07D405/12C07C323/09C07C323/14C07C323/19C07C323/20C07C323/21C07C323/22C07C323/32C07C323/36C07C323/52C07C323/60C07C323/62C07C321/28
Inventor 姜宪中咸政烨高在濚
Owner SEOUL NAT UNIV R&DB FOUND
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