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Synthetic method of succinimide type trifluoromethyl sulfuration reagent

A succinimide-type and succinimide technology is applied in the field of synthesis of succinimide-type trifluoromethane vulcanization reagents, and can solve the problems that limit the practicability of the synthesis method, affect the accuracy of experimental results, transition metal Element residues and other problems, to achieve the effect of reducing synthesis costs, facilitating industrial production, and mild conditions

Active Publication Date: 2021-05-11
SHANDONG LINGHAI BIOTECHNOLOGY CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, most of the current synthetic methods need to use expensive silver trifluoromethyl sulfide as the methyl trifluoromethyl sulfide donor to synthesize the reagent, which causes the price of the reagent to be relatively expensive, which limits the practicability of these synthetic methods. Participation, there may be residues of transition metal elements, which will affect the accuracy of the experimental results

Method used

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  • Synthetic method of succinimide type trifluoromethyl sulfuration reagent
  • Synthetic method of succinimide type trifluoromethyl sulfuration reagent
  • Synthetic method of succinimide type trifluoromethyl sulfuration reagent

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Example 1: In this example, N-chlorosuccinimide and 4-phenylbenzoic acid trifluoromethyl thioester (S-(trifluoromethyl)[1,1'-biphenyl]-4-carbothioate) were used The reaction synthesizes the trifluoromethyl sulfide reagent:

[0031] The reaction equation is:

[0032]

[0033] The synthesis steps and process are as follows: to a 10 mL reaction tube equipped with a magnetic stirring bar, add 4-phenylbenzoic acid trifluoromethyl thioester 3a (0.4 mmol, 112.8 mg), tetrabutylammonium fluoride (0.5 mmol, 130.5 mg), 3.5 mL of acetonitrile, and after mixing, N-chlorosuccinimide 2a (0.4 mmol, 53.4 mg) was added; the reaction tube was fixed on a magnetic stirrer, reacted at 25 °C for 12 hours, and separated and purified after completion. The target product 1 was obtained with a yield of 62%.

[0034] The NMR data of compound (1) are:

[0035] 1 H NMR (600 MHz, Chloroform-d): δ 2.96 (s, 4 H).

[0036] 13 C NMR (151 MHz, Chloroform-d): δ 127.70 (q, J = 313.5 Hz), 28.46

[...

Embodiment 2

[0038] Example 2: In this example, N-bromosuccinimide and 4-phenylbenzoic acid trifluoromethyl thioester (S-(trifluoromethyl)[1,1'-biphenyl]-4-carbothioate) were used The reaction synthesizes the trifluoromethyl sulfide reagent:

[0039] The reaction equation is:

[0040]

[0041]The synthesis steps and process are as follows: to a 10 mL reaction tube equipped with a magnetic stirring bar, 4-phenylbenzoic acid trifluoromethyl thioester 3a (0.4 mmol, 112.8 mg) and potassium fluoride (0.6 mmol, 34.8 mg) were successively added. , 18-crown ether-6 (1.0 mmol, 264 mg), 4.0 mL of trifluorotoluene, N-bromosuccinimide 2b (0.45 mmol, 80.1 mg); the reaction tube was fixed on a magnetic stirrer, in The reaction was carried out at 30° C. for 6 hours, and after completion, the target product 1 was obtained by separation and purification with a yield of 58%.

Embodiment 3

[0042] Example 3: In this example, N-iodosuccinimide and 4-phenylbenzoic acid trifluoromethyl thioester (S-(trifluoromethyl)[1,1'-biphenyl]-4-carbothioate) were used The reaction synthesizes the trifluoromethyl sulfide reagent:

[0043] The reaction equation is:

[0044]

[0045] The synthesis steps and process are as follows: 4-phenylbenzoic acid trifluoromethylthioester 3a (0.4 mmol, 112.8 mg) and silver fluoride (0.45 mmol, 57.2 mg) were successively added to a 10 mL reaction tube equipped with a magnetic stirring bar. , 3.0 mL of acetonitrile, and after mixing, N-iodosuccinimide 2c (0.4 mmol, 90.0 mg) was added; the reaction tube was fixed on a magnetic stirrer, and the reaction was carried out at 50 °C for 24 hours. After completion, the target was separated and purified. Product 1, 45% yield.

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Abstract

The invention belongs to the technical field of synthesis of organic compounds, and relates to a synthesis method of a succinimide type trifluoromethyl sulfide reagent. The CAS number of the reagent is 183267-04-1, and the structural formula of the reagent is shown in a formula (1) as described in the specification. According to the synthetic method of the succinimide type trifluoromethyl sulfide reagent, a nitrogen halogenated compound containing a succinimide structural framework, trifluoromethanesulfonate, nonafluorobutyl sulfonate, methanesulfonate and p-toluenesulfonate are used as reaction substrates and trifluoromethylthioester is used as a trifluoromethylthio source, for synthesis of the trifluoromethyl sulfuration reagent. According to the method, trifluoromethylthioester is taken as the trifluoromethylthio source, generates trifluoromethylthio negative ions under activation of fluorine negative ions, and conducts nucleophilic substitution on a reaction substrate, so the construction of a nitrogen-sulfur bond is realized, and the trifluoromethyl sulfuration reagent is obtained after separation and purification. According to the synthesis method of the trifluoromethyl sulfuration reagent, the raw materials are easy to prepare, the reaction reagent is low in price, the synthesis cost of the trifluoromethyl sulfuration reagent is remarkably reduced, and industrial production is facilitated; synthesis conditions are mild, and operation is simple and safe; and transition metal elements are not needed, and the method is green and environment-friendly.

Description

technical field [0001] The invention belongs to the technical field of organic compound synthesis, and relates to a method for synthesizing a succinimide-type trifluoromethyl sulfide reagent. Background technique [0002] Fluorine atoms play an important role in modern drug design and synthesis (Liu X, Xu C, Wang M, etal. Trifluoromethyltrimethylsilane: nucleophilic trifluoromethylation and beyond[J]. Chem Rev, 2015, 115(2):683-730.), According to statistics, 15% to 20% of modern drugs contain fluorine-containing groups (Hui R, Zhang S, Tan Z, et al. Research Progress of Trifluoromethylation with Sodium Trifluoromethanesulfinate[J]. Chin J OrgChem (Organic Chemistry), 2017, 37(12):3060-3075). The presence of fluorine-containing groups helps to increase the lipophilicity and metabolic stability of drug molecules (Yang B, Xu XH, Qing FL. Copper-mediated radical 1,2-bis(trifluoromethylation) of alkenes with sodium trifluoromethanesulfinate[J]. Org Lett, 2015, 17(8):1906-1909....

Claims

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Application Information

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IPC IPC(8): C07D207/48
CPCC07D207/48
Inventor 史大永田阳许凤刘瑞华
Owner SHANDONG LINGHAI BIOTECHNOLOGY CO LTD
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