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2, 3-dihydro-1, 2-diazacyclobutene nitrogen oxide and preparation method thereof

A technology of diazepine and nitrogen oxides, applied in the direction of organic chemistry, etc., to achieve mild reaction conditions, a wide range of substrate adaptation, and good yields

Active Publication Date: 2021-12-03
CHENGDU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] So far, there is no further report on the universal and efficient synthesis of 2,3-dihydro-1,2-diazetidine nitrogen oxide. Based on this, it is necessary to develop an efficient synthetic method to build this Quaternary nitrogen-heterocyclic skeleton is very necessary

Method used

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  • 2, 3-dihydro-1, 2-diazacyclobutene nitrogen oxide and preparation method thereof
  • 2, 3-dihydro-1, 2-diazacyclobutene nitrogen oxide and preparation method thereof
  • 2, 3-dihydro-1, 2-diazacyclobutene nitrogen oxide and preparation method thereof

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Experimental program
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Embodiment 1

[0038] Embodiment 1: prepare following formula compound

[0039]

[0040] Preparation method 1: In a reaction tube, dissolve benzyl carbamate (0.1 mmol reactant concentration is 0.1 mol / L) in dichloromethane (1.0 mL), and then add α-bromoacetophenone oxime (0.12 mmol), 1,8-diazabicycloundec-7-ene (DBU) (0.25 mmol) and the reaction mixture was stirred and reacted at 30° C. for 48 hours (monitored by TLC). Separation and purification by column chromatography (petroleum ether: ethyl acetate = 8:1 ~ 5:1) to obtain the compound of the above formula, 14.2 mg, with a yield of 25%;

[0041] Preparation method 2: In a reaction tube, dissolve benzyl carbamate (0.1 mmol reactant concentration is 0.1 mol / L) in 1,2-dichloroethane (1.0 mL), and then add α-chlorobenzene in sequence The reaction mixture of acetoxime (0.12 mmol) and diisopropylethylamine (0.25 mmol) was stirred and reacted at 30° C. for 48 hours (monitored by TLC). Separation and purification by column chromatography (pet...

Embodiment 2

[0045] Embodiment 2: prepare following formula compound

[0046]

[0047]The preparation method is as follows: in a reaction tube, dissolve benzyl carbamate (0.2mmol reactant concentration is 0.1mol / L) in 1,2-dichloroethane (2.0mL), and then add α-bromopara The reaction mixture of fluoroacetophenone oxime (0.24 mmol) and diisopropylethylamine (0.8 mmol) was stirred and reacted at 50° C. for 4 hours (monitored by TLC). Separation and purification by column chromatography (petroleum ether: ethyl acetate = 8:1 ~ 5:1) to obtain the compound of the above formula, 48.1 mg, with a yield of 80%;

[0048] Structure Identification: 1 HNMR (300MHz, CDCl 3 )δ7.63(dd,J=8.7,5.5Hz,2H),7.49–7.42(m,2H),7.41–7.30(m,3H),7.11(t,J=8.7Hz,2H),5.33(s ,2H),4.52(s,2H); 13 CNMR (75MHz, CDCl 3 )δ163.0(d, J=250.9Hz, 1C), 156.0, 134.8, 134.2, 128.8, 128.4, 127.2(d, J=8.3Hz, 1C), 122.3(d, J=3.4Hz, 1C), 116.6 (d, J=22.3Hz, 1C), 68.8, 48.0.

Embodiment 3

[0049] Embodiment 3: preparation following formula compound

[0050]

[0051] The preparation method is as follows: in a reaction tube, dissolve benzyl carbamate (0.2mmol reactant concentration is 0.1mol / L) in 1,2-dichloroethane (2.0mL), and then add α-bromopara The reaction mixture of trifluoromethylacetophenone oxime (0.24mmol) and diisopropylethylamine (0.8mmol) was stirred and reacted at 50° C. for 4 hours (monitored by TLC). Separation and purification by column chromatography (petroleum ether: ethyl acetate = 8:1 ~ 5:1) to obtain the compound III-c of the above formula, 35.2 mg, with a yield of 50%;

[0052] Structure Identification: 1 HNMR (300MHz, DMSO-d 6 )δ7.90–7.82(m,4H),7.48–7.42(m,2H),7.42–7.32(m,3H),5.28(s,2H),4.79(s,2H); 13 CNMR (151MHz, DMSO-d 6 )δ154.9, 135.3, 134.2, 129.6, 128.9 (q, J = 32.0Hz, 1C), 128.5, 128.4, 128.2, 126.0 (q, J = 3.9Hz, 1C), 125.4, 123.9 (q, J = 272.0Hz, 1C), 67.8, 48.8.

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Abstract

The invention discloses a class of 2, 3-dihydro-1, 2-diazacyclobutene nitrogen oxides and a preparation method thereof, and belongs to the field of organic synthesis.The preparation method comprises the steps:an organic solvent is added into a mixture of alpha-halogenated acetophenone oxime, carbamate and alkali, stirring is conducted for 2-24 hours at a certain temperature for reaction, and after the reaction is completed, separation and purification are conducted to obtain the 2, 3-dihydro-1, 2-diazacyclobutene nitrogen oxides. According to the invention, synthesis of 2, 3-dihydro-1, 2-diazacyclobutene nitrogen oxide is realized through step-by-step [3 + 1] cycloaddition reaction, and the compound as a typical 1, 3-dipole can be used for constructing a series of other heterocyclic compounds through 1, 3-dipole cycloaddition reaction; and the preparation method disclosed by the invention has the advantages of mild reaction conditions, high conversion efficiency, simplicity and convenience in operation, wide substrate application range and the like.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a class of 2,3-dihydro-1,2-diazetidine nitrogen oxides and a preparation method thereof. Background technique [0002] Nitrogen-containing four-membered heterocyclic compounds widely exist in clinical drugs and biologically active compounds. For example, β-lactam antibiotics, including cephalosporins, penicillins and other drugs, all contain β-lactam core skeleton structures. In addition, four-membered nitrogen-containing heterocycles It can also be used as a ligand in metal-catalyzed chemical transformations or as a key intermediate in the synthesis of other nitrogen-containing heterocyclic compounds. Based on this, the university construction of quaternary nitrogen-containing heterocycles has attracted more and more attention of chemists. [0003] As a special class of nitrogen-containing heterocyclic rings with high ring tension, the four-membered ring of 2,3-dihydro-1,2-diaz...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D229/00
CPCC07D229/00Y02P20/55
Inventor 王振华袁伟成沈力文赵建强游勇
Owner CHENGDU UNIV