A kind of synthetic method of synthesizing benzo[1,3]oxazine-2-thione by isothiocyanate and 2-sulfonylalkylphenol

A technology of sulfonyl alkylphenol and isothiocyanate, which is applied in the field of synthesis of benzo[1,3]oxazine-2-thione, can solve the problem of weak catalyst and o-QMs, short life, Not suitable for problems such as acidic catalysts

Active Publication Date: 2020-06-09
QINGDAO UNIV OF SCI & TECH +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the difficulty of catalytic asymmetric [4+2] cycloaddition involving o-QMs lies not only in its short lifetime, but also in the fact that the catalyst and o-QMs are too weak to promote the reaction.
Moreover, among the various production mechanisms of o-QMs, Lewis acid and Acid-catalyzed substituent removal is easy to operate and has a wide range of applications, but o-QMs precursors containing acid-sensitive functional groups (such as phenolic hydroxyl groups) are not suitable for these acidic catalysts

Method used

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  • A kind of synthetic method of synthesizing benzo[1,3]oxazine-2-thione by isothiocyanate and 2-sulfonylalkylphenol
  • A kind of synthetic method of synthesizing benzo[1,3]oxazine-2-thione by isothiocyanate and 2-sulfonylalkylphenol
  • A kind of synthetic method of synthesizing benzo[1,3]oxazine-2-thione by isothiocyanate and 2-sulfonylalkylphenol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039]

[0040] Take 0.2 mmol of 2-(α-phenyl-p-toluenesulfonyl)phenol in a reaction flask, add 2 mL of solvent, 0.3 mmol of phenyl isothiocyanate, and finally add 0.5 mmol of alkaline reagent. The temperature of the system was controlled at 25°C, the stirring was continued, and the reaction was tracked by spotting samples on a thin-layer chromatographic plate until the reaction of the raw materials was complete.

[0041] After the reaction is completed, a silica gel column is used for separation and purification, and the purified product is rotary evaporated to obtain the target product.

[0042] Using the above reaction formula, set up 10 parallel test groups, using different alkaline reagents, solvents and reaction times. Alkaline reagents are cesium carbonate Cs 2 CO 3 , potassium carbonate K 2 CO 3, Triethylamine TEA, 1,8-diazabicyclo[5.4.0]undec-7-ene DBU, tetramethylguanidine TMG. The solvents were dichloromethane DCM, tetrahydrofuran THF, and dioxane Dioxane, re...

Embodiment 2

[0048] According to the operating steps and reagent consumption of Example 1, in the reaction system, 2-(α-phenyl-p-toluenesulfonyl)phenol is mixed with 4-cyanophenyl isothiocyanate and 4-nitrophenyl isothiocyanate respectively. For the reaction of cyanate and ethyl isothiocyanate, the basic reagent is 0.5 mmol of cesium carbonate, and 2 mL of DCM is used as a solvent, and the reaction is continuously stirred at 25 ° C, and the reaction is completed after 12 hours.

[0049]

[0050]

[0051] According to the analysis of the above test results, one of the reaction raw materials is isothiocyanate with different electrical substituents. During the reaction process, it undergoes [4+2] cycloaddition with o-QMs to obtain different addition products. The yield of benzo[1,3]oxazine-2-thione will be significantly lower.

Embodiment 3

[0054] Raw materials: 2-(α-phenyl-p-toluenesulfonyl)phenol, phenyl isothiocyanate

[0055] Product: Chemical formula: C 20 h 15 NOS

[0056] Molecular weight: 318.4126

[0057] Structural formula:

[0058] Yield: 92%

[0059] 1 H NMR (500MHz, CDCl 3 )δ7.39–7.31(m,8H),7.21–7.14(m,3H),7.04(d,J=7.1Hz,3H),5.69(s,1H). 13 C NMR (125MHz, CDCl 3 )δ=182.9, 147.9, 143.8, 140.2, 129.6, 129.5, 129.2, 128.9, 128.5, 127.6, 127.4, 126.2, 125.5, 121.8, 116.5, 67.1. HRMS (ESI) Calcd for C 20 h 15 NOS[M+H] + :318.4121,Found:318.4126.

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Abstract

The invention relates to a synthetic method for synthesizing benzo[1,3]oxazine-2-thioketone by virtue of isothiocyanate and 2-sulfonyl alkyl phenol under weak alkali condition. The 2-sulfonyl alkyl phenol and isothiocyanate are used as substrates to synthesize multi-functional-group benzo[1,3]oxazine-2-thioketone comprising a nitrogen, oxygen and sulfur heterocyclic ring structure in a one-step method, so that the application of the reaction method of the isothiocyanate and o-QMs can be enlarged. The synthetic method provided in the invention can perform the reaction at room temperature, and is mild in reaction condition, good in substrate universality, free from catalyst, simple and easy in obtaining an alkaline reagent, convenient in operation, economical and high in efficiency; the synthetic method of the invention is high in reaction activity, the yield reaches 92 percent, and the raw materials can be completely converted; and a product is convenient to separate, and the reaction is pollution-free and economical and environment-friendly.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis and relates to a method for synthesizing benzo[1,3]oxazine-2-thione through isothiocyanate and 2-sulfonylalkylphenol. Background technique [0002] Heterocyclic compounds have become a hot spot in the field of drug research due to their wide range of biological activities. Among them, oxazine-2-thione belongs to a class of polycyclic compounds containing nitrogen, oxygen, and sulfur heteroatoms. This type of compound has anticancer, anti Tumor, analgesic, insecticidal and bactericidal and other biological activities. For example, Tanaproget, a non-steroidal synthetic progestin, entered Phase II clinical trials in 2010 and may be used as an effective contraceptive in the future. [0003] [0004] However, the current synthetic method for oxazin-2-thione includes using the corresponding oxazin-2-one as substrate and Lawesson reagent to carry out substitution reaction (Bioorg.Med.Chem....

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D279/08
CPCC07D279/08
Inventor 于丽萍于世涛肖建
Owner QINGDAO UNIV OF SCI & TECH
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