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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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

At present, there are many reports on the construction of aromatic benzothiazole compounds through intramolecular C-

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

Examples

Experimental program
Comparison scheme
Effect test

Example Embodiment

[0035] Example 1

[0036]

[0037] Add 2-(methyl(phenyl)carbamoyl) dimethyl malonate (56.2mg, 0.2mmol), anhydrous cobalt bromide (4.4mg, 0.02mmol), DDQ (90.8mg, 0.4mmol) Add 4 mL of anhydrous acetonitrile to the reaction flask. When reacting at room temperature for 4 hours, TLC detects that the raw materials are completely consumed. The reaction is quenched by adding saturated sodium thiosulfate solution (4 mL). The organic phase is extracted with dichloromethane and then saturated carbonic acid. The organic phase was washed twice with sodium hydrogen solution, the organic phase was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography to obtain 55.1 mg of pure product, the structure of which was shown in formula (2-1), and the yield was 99%. NMR 1 H NMR, 13 The CNMR spectrum is as figure 1 As shown, the product: 1 HNMR(500MHz, CDCl 3 )δ7.60(dd,J=7.8,0.5 Hz,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...

Example Embodiment

[0039] Example 2

[0040]

[0041] The experimental method of this example is basically the same as that of example 1. The raw material used in this example is dimethyl 2-((4-methoxyphenyl)(methyl)carbamoyl)malonate, at room temperature The reaction time is 5 hours, and the obtained product is shown in the structural formula (2-2). The yield was 91%. NMR 1 H NMR, 13 The C NMR spectrum is 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, CDCl 3 )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.

Example Embodiment

[0043] Example 3

[0044]

[0045] The experimental method of this example is basically the same as that of example 1. The raw material used in this example is dimethyl 2-(methyl(p-tolyl)carbamoyl)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%. NMR 1 H NMR, 13 The C NMR spectrum is 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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