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Method of synthesizing dibenzodihydro-1,3-diazepine derivatives

A technology for diazepines and derivatives, applied in the field of synthesizing dibenzodihydro-1,3-diazepine derivatives, which can solve the problem of difficult preparation of substituent types with diverse functional group-modified dibenzo Dihydro-1 and other problems, to achieve the effect of simple operation

Inactive Publication Date: 2015-04-08
TIANJIN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0015] Due to the potential pharmacological activity of dibenzodihydro-1,3-diazepines (I), it is necessary to prepare derivatives with various types of substituents for pharmacological activity research, but the current methods are difficult to prepare Dibenzodihydro-1,3-diazepine compounds with diverse types of substituents and easy functional group modification have not been reported in the literature. 2-amido-N-phenylbenzamide derivatives are used as raw materials , to prepare dibenzodihydro-1,3-diazepines by oxidative rearrangement of hypervalent iodine reagents

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  • Method of synthesizing dibenzodihydro-1,3-diazepine derivatives
  • Method of synthesizing dibenzodihydro-1,3-diazepine derivatives
  • Method of synthesizing dibenzodihydro-1,3-diazepine derivatives

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Embodiment 1

[0033] The method for synthesizing dibenzodihydro-1,3-diazepine derivatives (I), comprises the steps:

[0034] (a) Preparation of 2-amino-N-methyl-N-phenylbenzamide (III-a):

[0035] Add anthranilic acid (2.74g, 20mmol) and dichloromethane (67mL) successively in a 250mL round bottom flask with magnetic stirring, slowly add thionyl chloride (4.4mL, 60mmol) dropwise under stirring, dropwise After completion, stir at room temperature for 5 h. Then slowly heated to reflux, after half an hour, concentrated under reduced pressure to distill off the solvent to obtain anthranilic acid chloride. Dichloromethane (67mL) was added to the flask, and a mixture of triethylamine (5.6mL, 40mmol) and N-methylaniline (2.2mL, 20mml) was slowly added dropwise in an ice-water bath. After the dropwise addition, the ice-water bath was removed and stirred at room temperature. The solvent was evaporated by concentration under reduced pressure, diluted with water (100 mL), extracted with ethyl acetat...

Embodiment 2

[0041] The method for synthesizing dibenzodihydro-1,3-diazepine derivatives (I), comprises the steps:

[0042] (a) With reference to the preparation method of (III-a) in Example 1, prepare 2-amino-N-(3-methoxyphenyl)-N-methylbenzamide (III-b), yellow oil , the yield is 26%, 1 H NMR (600MHz, CDCl 3 )δ7.11(t,J=8.1Hz,1H),6.98(td,J=8.2,1.5Hz,1H),6.76(dd,J=7.8,1.4Hz,1H),6.67–6.64(m,2H ),6.62–6.60(m,2H),6.36–6.33(m,1H),4.43(brs,2H),3.67(s,3H),3.47(s,3H). 13 C NMR (150MHz, CDCl 3 )δ171.1, 160.0, 146.7, 146.1, 130.5, 129.7, 129.4, 120.0, 118.5, 116.8, 116.4, 112.2, 112.1, 55.3, 37.9.

[0043] (b) Referring to the preparation method of (II-a) in Example 1, prepare 2-acetamido-N-(3-methoxyphenyl)-N-methylbenzamide (II-b), white solid , the yield is 46%, melting point: 142-144℃. 1 H NMR (600MHz, CDCl 3 )δ9.46(s,1H),8.22(d,J=7.9Hz,1H),7.21(t,J=7.6Hz,1H),7.10(t,J=8.0Hz,1H),6.90(d, J=6.6Hz,1H),6.72-6.68(m,2H),6.58–6.55(m,2H),3.66(s,3H),3.49(s,3H),2.20(s,3H). 13 C NMR (150MHz, CDCl ...

Embodiment 3

[0046] The method for synthesizing dibenzodihydro-1,3-diazepine derivatives (I), comprises the steps:

[0047] (a) With reference to the preparation method of (III-a) in Example 1, prepare 2-amino-N-(3,4-dimethoxyphenyl)-N-methylbenzamide (III-c), Pale yellow solid, yield 53%, melting point: 119-121°C. 1 H NMR (600MHz, CDCl 3 )δ6.95(t,J=7.3Hz,1H),6.75(d,J=7.5Hz,1H),6.69(d,J=8.4Hz,1H),6.66(d,J=8.4Hz,1H) ,6.60(d,J=8.0Hz,1H),6.57(s,1H),6.35(t,J=7.3Hz,1H),4.61(brs,2H),3.80(s,3H),3.69(s, 3H),3.45(s,3H). 13 C NMR (150MHz, CDCl 3 )δ171.0, 148.9, 147.4, 146.4, 138.0, 130.3, 129.2, 120.3, 117.9, 116.8, 116.2, 111.0, 110.3, 55.9, 38.0.

[0048] (b) With reference to the preparation method of (II-a) in Example 1, prepare 2-acetylamino-N-(3,4-dimethoxyphenyl)-N-methylbenzamide (II-c) , white solid, the yield is 88%, melting point: 140-142℃. 1 H NMR (600MHz, CDCl 3 )δ9.38(s,1H),8.15(s,1H),7.20(s,1H),6.87(s,1H),6.72–6.68(m,2H),6.58(d,J=5.4Hz,1H ),6.49(s,1H),3.80(s,3H),3.68(s,3H),3....

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Abstract

The invention discloses a method of synthesizing dibenzodihydro-1,3-diazepine derivatives (I), and the method comprises the following steps of: adding 2-acylamino-N-phenyl benzamide derivatives (II), diacetoxyl iodobenzene and acetonitrile into a container; heating until refluxing; monitoring by a TLC (Thin-Layer Chromatography) until reaction is complete; decompressing and concentrating reaction liquor to evaporate out a solvent; adding water to dilute, using ethyl acetate to extract, combining organic phases, decompressing and concentrating to evaporate out the solvent; and obtaining dibenzodihydro-1,3-diazepine derivatives (I) by column chromatography separation, wherein a reaction formula is shown in the specification. The method disclosed by the invention has the advantages that operation is simple, a reagent is cheap and easily available, and product substituent group types are various.

Description

technical field [0001] The invention relates to a method for synthesizing dibenzodihydro-1,3-diazepine derivatives. Background technique [0002] Dibenzodihydro-1,3-diazepines are a class of biphenyl compounds with axial chirality [1] , and its derivative (A) can be used as a ligand for palladium-catalyzed reactions [2] , 6-Amino-substituted dibenzo[d,f][1,3]-diazepine derivatives (B-E) were used to study anticonvulsant and antiepileptic effects [3] , a dibenzodihydro-1,3-diazepine derivative (F) obtained by modifying the structure of the natural product Erysotrine alkaloid Erysotrine is also considered to have pharmacological activity similar to Erysotrine [4] . [0003] [0004] At present, the synthesis methods of dibenzodihydro-1,3-diazepines mainly include the following categories: (1) 2,2′-diaminobiphenyl is used as raw material, combined with 1,1′- Double electrophile reaction preparation [1][5-7] ; (2) Using 1-(2-bromobenzene)-1,3-dimethyl-3-phenylurea as raw...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D243/04
CPCC07D243/04
Inventor 杜云飞尚巳耘赵康
Owner TIANJIN UNIV