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2-substituted methylene dihydrobenzo[d]thiazole derivative and synthesis method and application thereof

A technology of methylene dihydrobenzene and synthesis method, applied in the direction of organic chemistry, etc., to achieve the effects of high chemoselectivity and position selectivity, economical steps, and simple operation

Active Publication Date: 2020-05-08
EAST CHINA NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, there are many reports on the construction of aromatic benzothiazole compounds through intramolecular C-S coupling, but there are few reports on the method of synthesizing the non-aromatic dihydrobenzothiazole compounds.

Method used

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  • 2-substituted methylene dihydrobenzo[d]thiazole derivative and synthesis method and application thereof
  • 2-substituted methylene dihydrobenzo[d]thiazole derivative and synthesis method and application thereof
  • 2-substituted methylene dihydrobenzo[d]thiazole derivative and synthesis method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036]

[0037] Dimethyl 2-(methyl(phenyl)carbamoyl)malonate (56.2 mg, 0.2 mmol), anhydrous cobalt bromide (4.4 mg, 0.02 mmol), DDQ (90.8 mg, 0.4 mmol) were added To the reaction bottle, add anhydrous acetonitrile 4mL, react at room temperature for 4 hours, TLC detects that the raw materials are completely consumed, add saturated sodium thiosulfate solution (4mL) to quench the reaction, the organic phase is extracted with dichloromethane, and then saturated carbonic acid The organic phase was washed twice with sodium hydrogen solution, and the organic phase was concentrated under reduced pressure. The residue was separated by silica gel column chromatography to obtain 55.1 mg of pure product, whose structure was shown in formula (2-1), and the yield was 99%. nuclear magnetic resonance 1 H NMR, 13 CNMR spectrum such as figure 1 As shown, the product: 1 HNMR (500MHz, CDCl 3 )δ7.60(dd,J=7.8,0.5Hz,1H),7.41–7.37(m,1H),7.23(ddd,J=13.8,10.4,4.5Hz,2H),3.84(s,6H), 3.50 (s,3H)....

Embodiment 2

[0040]

[0041] The experimental method of this embodiment is basically the same as that of Example 1. The raw material used in this embodiment is 2-((4-methoxyphenyl) (methyl) carbamoyl) dimethyl malonate. The reaction time is 5 hours, and the obtained product is shown in structural formula (2-2). The yield was 91%. nuclear magnetic resonance 1 H NMR, 13 C NMR spectrum as figure 2 As shown, the product: 1 HNMR (500MHz, CDCl 3 )δ7.39(s,1H),7.18(dd,J=8.3,0.7Hz,1H),7.09(d,J=8.3Hz,1H),3.83(s,6H),3.48(s,3H), 2.41(s,3H). 13 C NMR (126MHz, CDCl3 )δ167.42, 167.10, 139.54, 133.85, 127.55, 127.42, 121.80, 111.09, 87.14, 51.76, 37.30, 21.04.

[0042] HRMS(EI)m / z calculated for C 14 h 15 NO 5 S[M] + 309.0671,found 309.0673.

Embodiment 3

[0044]

[0045] The experimental method of this embodiment is basically the same as that of Example 1. The raw material used in this embodiment is 2-(methyl (p-tolyl) carbamoyl) dimethyl malonate, and the reaction time is 4 hours at room temperature. The obtained product is shown in structural formula (2-3). The yield was 87%. nuclear magnetic resonance 1 H NMR, 13 C NMR spectrum as image 3 As shown, the product: 1 H NMR (500MHz, CDCl 3 )δ7.31(s,1H),7.10(d,J=8.3Hz,1H), 7.01(d,J=8.3Hz,1H),3.75(s,6H),3.39(s,3H),2.33( s,3H). 13 C NMR (126MHz, CDCl 3 )δ167.40, 167.06, 139.52, 133.83, 127.54, 127.40, 121.78, 111.08, 87.14, 51.75, 37.29, 21.03.

[0046] HRMS(EI)m / z calculated for C 14 h 15 NO 4 S[M] + 293.0722, found 293.0724.

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Abstract

The invention discloses a 2-substituted methylene dihydrobenzo[d]thiazole derivative and a synthesis method thereof. According to the method, an N-alkyl / N-aryl thioamide derivative as shown in a formula (1) is used as a raw material and undergoes intramolecular alkene-thiol interconversion and then further undergoes C-S coupling dehydrogenation coupling reaction in series in an organic solvent inthe presence of an oxidant and a catalyst under mild reaction conditions so as to obtain the 2-substituted methylene dihydrobenzo[d]thiazole derivative. The synthesis method of the 2-substituted methylene dihydrobenzo[d]thiazole derivative has the advantages of mild conditions, economic atomic steps, high yield and the like through condition control, has high chemical selectivity and regioselectivity, and has wide application prospects. The invention also discloses application of the 2-substituted methylene dihydrobenzo[d]thiazole derivative in medicine and material science.

Description

technical field [0001] The invention belongs to the field of synthetic medicine and chemical industry, and mainly relates to a class of 2-substituted methylene dihydrobenzo[d]thiazole derivatives and their synthesis method and application. Background technique [0002] Benzoheterocyclic bicyclic compounds widely exist in nature, especially the heterocyclic structures containing N, O, S and other elements are commonly found in natural products and bioactive molecules. Both benzothiazole and dihydrobenzothiazole are special bicyclic heterocyclic substances containing both N and S elements, and are widely used in medicine and material science. At present, there are many reports on the construction of aromatic benzothiazole compounds through intramolecular C-S coupling, but there are few reports on methods for synthesizing the non-aromatic dihydrobenzothiazole compounds. Contents of the invention [0003] The object of the present invention is to provide a class of 2-substitu...

Claims

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Application Information

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IPC IPC(8): C07D277/64C07D277/84C07D513/04
CPCC07D277/64C07D277/84C07D513/04
Inventor 姜丽琴姚智杨俊蔡忠良于淼
Owner EAST CHINA NORMAL UNIVERSITY
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