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Preparation method of aromatic sulfinic acid compound

A technology for aromatic sulfinic acid and aromatic compounds, applied in a new field of preparation, can solve the problems of harsh reaction conditions and expensive catalysts, achieve mild reaction conditions, omit chlorosulfonation reaction steps, and facilitate storage and transportation Effect

Inactive Publication Date: 2017-08-29
TIANJIN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Literature [Angew.Chem.2013,125,12911] utilizes aryl lithium to react with DABSO to generate lithium arylsulfinate; literature [Org.Lett.2014,16,150] utilizes Grignard reagent to react with DABSO to prepare the corresponding Sulfonic acid and participate in the next reaction, but the reaction needs to be carried out at -40 °C; literature [Angew.Chem.2016,128,757] utilizes aromatic boric acid and DABSO to prepare aromatic sulfinic acid under the catalysis of palladium acetate; literature [Tetrahedron Letters, 2016, 57, 533] using aryl bromide and DABSO to react to obtain the corresponding aryl sulfinic acid sodium salt; the above reactions have certain limitations, such as harsh reaction conditions, special substrates are required, catalysts are expensive, etc.

Method used

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  • Preparation method of aromatic sulfinic acid compound
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  • Preparation method of aromatic sulfinic acid compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] The preparation of embodiment 1:4-sodium methylbenzene sulfinate

[0024] 1) DABSO (1,4-diazabicyclo[2.2.2]octane and SO 2 The preparation of the adduct):

[0025] In a 100mL three-necked flask connected with a tail gas absorption device, add 50mmol of 1,4-diazabicyclo[2.2.2]octane and 50mL of dichloromethane in sequence, and then slowly introduce 60mmol of SO at room temperature. 2 Gas, react at room temperature for 4 hours after passing through, filter with suction, dry, and store the obtained solid for later use;

[0026] 2) Preparation of sodium 4-methylbenzenesulfinate:

[0027] Under normal pressure, into a 100mL three-necked flask with mechanical stirring, add 40mL of dichloromethane, 8.0mmol of toluene, 25.0mmol of aluminum trichloride, and 8.2mmol of the above-mentioned self-made DABSO at 20°C, and then heat up to 25-30°C, react for 8-10 hours, and when the liquid chromatography detects that the toluene content in the reaction solution is lower than 10% and ...

Embodiment 2

[0031] Embodiment 2: the preparation of sodium 4-acetamidobenzenesulfinate

[0032] DABSO (1,4-diazabicyclo[2.2.2]octane and SO 2 The preparation of the adduct) is the same as in Example 1, the same below.

[0033] Under normal pressure, add 20mL of 1,2-dichloroethane, 3.0mmol of N-acetanilide, 24.0mmol of aluminum trichloride, 3.0mmol of the above self-made DABSO, then heated up to 25-40°C, reacted for 20-24h, and when the N-acetanilide content in the reaction liquid was detected by liquid chromatography to be lower than 1%, the reaction ended. The post-processing operation was the same as in Example 1 to obtain 0.53 g of white solid powder of sodium 4-acetamidobenzenesulfinate with a yield of 80%. Its reaction formula is as follows:

[0034]

[0035] The NMR data are as follows:

[0036] Sodium 4-acetamidobenzenesulfinate: 1 H NMR (400MHz, Methanol-d 4 ,δ):7.67-7.63(d,2H,aromatic),7.62-7.58(d,2H,aromatic),2.15(s,3H,COCH 3 ).

Embodiment 3

[0037] Embodiment 3: the preparation of sodium 4-chlorobenzenesulfinate

[0038]Under normal pressure, add 25mL of dichloromethane, 6.2mmol of chlorobenzene, 18.8mmol of aluminum trichloride, and 6.2mmol of the above-mentioned self-made DABSO at 25°C to a 100mL three-necked flask with mechanical stirring, and then heat up to 30-35°C, react for 12-14 hours, and when the liquid chromatographic detection shows that the chlorobenzene content in the reaction solution is lower than 5% and no longer decreases, the reaction ends. The post-processing operation was the same as that of Example 1, and 1.08 g of white solid powder of sodium 4-chlorobenzenesulfinate was obtained, with a yield of 88%. Its reaction formula is as follows:

[0039]

[0040] The NMR data are as follows:

[0041] Sodium 4-chlorobenzenesulfinate: 1 H NMR (400MHz, Methanol-d 4 ,δ):7.68-7.60(m,2H,aromatic),7.46-7.42(m,2H,aromatic).

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Abstract

The invention relates to a preparation method of an aromatic sulfinic acid compound. The preparation method includes the steps of: with Lewis acid as a catalyst, performing a Friedel-Crafts acylation reaction to an aromatic compound as a raw material with 1,4-diazabicyclo[2.2.2]octane (DABSO) in a solvent to generate a corresponding aromatic sulfinic acid compound. Compared with industrial preparation methods for the aromatic sulfinic acid compound in the prior art, the method can synthesize the aromatic sulfinic acid compound in one step, so that experiment operations are simplified and a high-polluting chlorosulfonation step is avoided. The method has mild reaction conditions, wherein the reaction can be carried out under a common normal temperature condition, so that a large amount of energy consumption in production is reduced. The DABSO, compared with gas-phase SO2, is convenient to store and transport, has stable properties at normal temperature and under normal pressure and has safe and simple operations. The raw materials are low in cost and easy to obtain, thus reducing production cost. The method has huge potential in practical use.

Description

technical field [0001] The invention belongs to the field of organic synthesis and relates to a new preparation method of aromatic sulfinic acid compounds. They are available in the form of their sodium salts. Background technique [0002] As a class of important reaction intermediates, aromatic sulfinic acid compounds are widely used in the fields of medicine, printing and dyeing, pesticides, and organic synthesis. Such compounds can be prepared by reduction of sulfuryl chloride with zinc powder or sodium sulfite and other reducing agents, Friedel-Crafts reaction between sulfur dioxide and aromatic hydrocarbons, oxidation of mercaptans, and reaction of sulfur dioxide with Grignard reagents or aromatic diazonium salts. Knoevenagel et al. [Chemische Berichte 1908, 41, 3315] first prepared aromatic sulfinic acids by Friedel-Crafts reaction. The literature reports a method for synthesizing aromatic sulfinic acid by a gas-liquid two-phase method by passing sulfur dioxide into ...

Claims

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Application Information

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IPC IPC(8): C07C313/04
CPCC07C313/04C07D487/08
Inventor 张旭斌王天磊吴博韬王富民倪汝伟倪昊
Owner TIANJIN UNIV
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