Preparation method for aryl tin compound

A technology of tin compounds and compounds, applied in the direction of tin organic compounds, etc., can solve problems such as harsh reaction conditions, unfriendly environment, complicated operation, etc., and achieve the effects of low preparation cost, low reaction cost and high reaction efficiency

Inactive Publication Date: 2014-03-26
PEKING UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The disadvantages of the above method are: (1) The raw materials are single, and they are all synthesized from aromatic halides
(2) Use metal reagents as raw materials or use noble metal catalysts. The former requires the use of equivalent aryl metal reagents, which is less economical, while the latter is more expensive and requires the use of expensive palladium catalysts
(3) Unfriendly to the environment and complex operation
[0005] The above methods all require relatively harsh reaction conditions. The first method needs to be carried out under low temperature conditions. The use of aryl metal reagents has certain risks and requires strict anhydrous and oxygen-free conditions; heating at high temperature

Method used

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  • Preparation method for aryl tin compound
  • Preparation method for aryl tin compound
  • Preparation method for aryl tin compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Synthesis of ethyl p-trimethylstannyl benzoate

[0038] Add 50mg (ie 0.3mmol) ethyl p-aminobenzoate, 62mg (ie 0.36mmol) p-toluenesulfonic acid, 1.5mL 1,2-dichloroethane into a 10mL long tube reaction bottle, and then weigh 62mg (ie 0.6mmol) tert-butyl nitrite and 108mg (ie 0.33mmol) hexamethyldistannane, react at 0°C for 4h, concentrate after reaction, wash with petroleum ether: ethyl acetate = 50:1 Purification by deagent column chromatography can obtain ethyl p-trimethylstannyl benzoate, and its structure is shown in the following formula:

[0039]

[0040] The compound is a light yellow liquid with a yield of 76%, and its NMR data are as follows:

[0041] 1 HNMR (400MHz, CDCl 3 )δ7.98(d,J=7.2Hz,2H),7.57(d,J=7.2Hz,2H),4.37(q,J=6.7Hz,2H),1.39(t,J=6.7Hz,3H) ,0.31(s,9H); 13 CNMR (100MHz, CDCl 3 )δ166.9, 149.4, 135.7, 130.2, 128.5, 60.9, 14.4, -9.5;

Embodiment 2

[0043] Synthesis of p-methylphenyltrimethylstannane

[0044] Add 32mg (ie 0.3mmol) p-toluidine, 62mg (ie 0.36mmol) p-toluenesulfonic acid, 1.5mL 1,2-dichloroethane into a 10mL long tube reaction bottle, and then weigh 62mg (ie 0.6mmol) of tert-butyl nitrite and 108mg (ie 0.33mmol) of hexamethyldistannane were reacted at 30°C for 4h, concentrated after the reaction, and purified by column chromatography using petroleum ether as eluent to obtain p-formazan phenyl trimethylstannane, its structure is shown in the following formula:

[0045]

[0046] The compound is a colorless liquid with a yield of 53%, and its NMR data are as follows:

[0047] 1 HNMR (400MHz, CDCl 3 )δ7.39(d,J=7.5Hz,2H),7.17(d,J=7.5Hz,2H),2.34(s,3H),0.27(s,9H); 13 CNMR (100MHz, CDCl 3 )δ138.2, 138.0, 135.8, 128.9, 21.4, -9.5;

Embodiment 3

[0049] Synthesis of p-Methoxyphenyltrimethylstannane

[0050] Add 37mg (ie 0.3mmol) p-methoxyaniline, 62mg (ie 0.36mmol) p-toluenesulfonic acid, 1.5mL 1,2-dichloroethane into a 10mL long tube reaction bottle, and then weigh 62mg (ie 0.6mmol) tert-butyl nitrite and 108mg (ie 0.33mmol) hexamethyldistannane, reacted at 25°C for 3h, concentrated after the reaction, and purified by column chromatography with petroleum ether as eluent to obtain P-methoxyphenyltrimethylstannane, its structure is shown in the following formula:

[0051]

[0052] The compound is a colorless liquid with a yield of 49%, and its NMR data are as follows:

[0053] 1 HNMR (400MHz, CDCl 3 )δ7.41(d,J=8.4Hz,2H),6.92(d,J=8.4Hz,2H),3.80(s,3H),0.26(s,9H); 13 CNMR (100MHz, CDCl 3 )δ159.9, 136.9, 132.4, 114.0, 55.0, -9.5;

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Abstract

The invention discloses a preparation method for an aryl tin compound. The aryl tin compound is prepared from reaction of aromatic amine Ar-NH2, distannanes, alkyl nitrous acid ester and Lewis acid in an organic solution, wherein Ar represents a substitutional or non-substitutional benzene ring or an aromatic heterocyclic ring group, and the reaction is prominently quickened by the adopted Lewis acid. According to the invention, the preparation method enables a one-step conversion of the aromatic amine into the aryl tin compound under mild condition for the first time, and is high in reaction rate and low in reaction cost; the reaction involved in the method disclosed by the invention requires no strict water-free and oxygen-free conditions, occurs smoothly in the air and is easy to operate, and meanwhile has an excellent tolerance and universality for the functional group, therefore, the method can be widely used for the preparation of aryl tin compounds.

Description

technical field [0001] The invention belongs to the field of organic synthesis, in particular to a preparation method of an aryl tin compound. Background technique [0002] Aryltin compounds are an important class of small organic molecules, which are widely used in scientific research, drug design and industrial synthesis. In scientific research and drug design, aryl tin compounds are mainly used in organic synthesis. They can be used as molecular building blocks to construct more complex target compounds by participating in Stille coupling reactions or other functional group transformations; in industrial synthesis, aryl tin compounds Base tin compounds are mainly used in the synthesis of liquid crystals or the synthesis of luminescent materials. [0003] For a long time, people are looking for a simple and convenient method for synthesizing aryl tin compounds. Currently known synthetic methods are still very limited, and mainly all are to prepare aryl tin compounds by t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/22
Inventor 王剑波邱頔叶宇轩邓亦范张艳
Owner PEKING UNIV
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