Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Aminothiazole compound dehydration and alkylation method

An aminothiazole and compound technology, applied in the field of synthesis of N-alkylaminothiazole and derivatives thereof, achieves the effects of reducing synthesis cost, good research and industrial application prospects, and mild reaction conditions

Inactive Publication Date: 2013-06-12
WENZHOU UNIVERSITY
View PDF2 Cites 4 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

According to reports, using metallic copper or iridium catalysts, alcohols as alkylating reagents, the alkylation reaction can be carried out on the exocyclic amino group with opposite selectivity to obtain 2-(N-alkylamino) benzothiazole compounds, but these There are still many obvious shortcomings in the method of borrowing hydrogen (especially the reaction catalyzed by metal iridium)

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Aminothiazole compound dehydration and alkylation method
  • Aminothiazole compound dehydration and alkylation method
  • Aminothiazole compound dehydration and alkylation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Preparation of N-(4-methoxybenzyl)-2-aminobenzothiazole by the reaction of 2-aminobenzothiazole and 4-methoxybenzyl alcohol

[0020]

[0021] Add 2-aminobenzothiazole (1mmol), 4-methoxybenzyl alcohol (1.5mmol, 1.5equiv.), NaOH (20mol%) in turn into a 20mL reaction tube, and directly seal and heat to 120°C for 3h under air , The conversion rate of the reaction was 99% as measured by GC-MS. The product was separated and purified by column chromatography, and the separation yield was 95%. 1 HNMR (500MHz, d 6 -DMSO):δ8.44(t,J=5.0Hz,1H),7.67(d,J=8.0Hz,1H),7.41(d,J=8.0Hz,1H),7.32(d,J=9.0Hz ,2H),7.25-7.21(m,1H),7.04-7.01(m,1H),6.92(d,J=8.5Hz,2H),4.53(d,J=5.5Hz,2H),3.74(S, 3H). 13 C NMR (125.4MHz, d 6 -DMSO): δ166.3, 158.6, 152.7, 130.9, 130.6, 129.0, 125.7, 121.07, 121.05, 118.2, 113.9, 55.2, 46.9. MS (EI): m / z (%) 270 (16, M+), 219 ( 4), 207(3), 121(100), 91(5), 77(8), 69(7), 63(5).

Embodiment 2

[0023] Preparation of N-(3-methoxybenzyl)-2-aminobenzothiazole by the reaction of 2-aminobenzothiazole and 3-methoxybenzyl alcohol

[0024]

[0025] Add 2-aminobenzothiazole (1mmol), 3-methoxybenzyl alcohol (1.5mmol, 1.5equiv.), NaOH (20mol%) in sequence to a 20mL reaction tube, and directly seal and heat to 120°C for 3h under air , GC-MS measured the conversion rate of 90%. The product was separated and purified by column chromatography, and the separation yield was 74%. 1 HNMR (500MHz, CDCl 3 ):δ7.55(d,J=8.0Hz,1H),7.38(d,J=8.0Hz,1H),7.26-7.23(m,2H),7.07-7.04(m,1H),6.98-6.93( m,3H),6.82(dd,J=2.5Hz,J=8.5Hz,1H),4.58(s,2H),3.74(s,3H). 13 CNMR (125.4MHz, CDCl 3 ):δ168.0,160.0,152.2,139.1,130.4,129.9,126.0,121.5,120.8,119.9,118.8,113.4,113.2,55.2,49.4.MS(EI):m / z(%)270(76,M+), 269(24), 255(8), 239(5), 136(62), 121(100), 91(49), 78(25), 77(23), 65(19).

Embodiment 3

[0027] Preparation of N-(2-methoxybenzyl)-2-aminobenzothiazole by the reaction of 2-aminobenzothiazole and 2-methoxybenzyl alcohol

[0028]

[0029] 2-Aminobenzothiazole (1mmol), 2-methoxybenzyl alcohol (1.5mmol, 1.5equiv.), NaOH (20mol%) were added sequentially into a 20mL reaction tube, and directly sealed and heated to 120°C for 3h under air , The conversion rate of the reaction was 99% as measured by GC-MS. The product was separated and purified by column chromatography, and the separation yield was 92%. 1 HNMR (500MHz, CDCl 3 ):δ7.54(d,J=8.0Hz,1H),7.46(d,J=8.0Hz,1H),7.36(dd,J=1.0Hz,J=7.5Hz,1H),7.26-7.24(m ,2H),7.06-7.02(m,1H),6.92-6.86(m,2H),6.48(b,1H),4.59(s,2H),3.82(s,3H). 13 CNMR (125.4MHz, CDCl 3):δ167.8,157.5,152.4,130.4,129.4,129.1,125.8,125.6,121.3,120.7,120.5,118.7,110.3,55.3,45.4.MS(EI):m / z(%)274(52,M+), 270(37),255(11),239(42),207(14),151(10),131(22),121(88),119(13),105(8),91(100), 77(13),69(32),65(22),

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention provides an aminothiazole compound dehydration and alkylation method. According to the method, any transition metal or non-transition metal catalyst is not required, and the aminothiazole compound can be directly reacted in the presence of a little alkali under the inert gas protection or air. The reaction conditions are mild, the reaction is easy to operate, the product is simply separated and purified, and the product recovery rate is high. The low-price readily available alcohol serves as an alkylating agent, and the synthesis cost is greatly reduced. In addition, the reaction is carried under solvent-free conditions, and the possible pollution of the organic solvent on the environment can be reduced to a certain degree; and moreover, the reaction requirements on the reaction conditions are low, the reaction can be performed under air conditions, and the method has good research and industrial application prospect.

Description

technical field [0001] The present invention relates to a synthesis method of N-alkylaminothiazole and its derivatives, in particular to a method for synthesizing N-alkylaminothiazole and its derivatives through dehydration N-alkylation reaction of alcohol and 2-aminothiazole compounds Methods. Background technique [0002] The N-alkylation reaction of amine compounds is one of the most important and basic methods for C-N bond formation and synthesis of amine derivatives. The traditional N-alkylation reaction uses a halogenated hydrocarbon as an alkylating agent and is realized by the Hofmann reaction. However, this method has many disadvantages. It requires the use of a large amount of alkali, produces a lot of waste, and has low reaction selectivity, resulting in difficulty in product separation. In recent years, through the "hydrogen borrowing" method catalyzed by transition metals, green, low-toxic and low-priced alcohol compounds can be used to replace halogenated hydr...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Applications(China)
IPC IPC(8): C07D277/82C07D417/12C07D277/42
Inventor 徐清李双艳李强
Owner WENZHOU UNIVERSITY
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com