A kind of gamma-(9-acridine) diazoacetoacetate, gamma-(9-acridine methylene)-beta-keto ester and preparation method thereof
A technology of acridine methylene group and diazoacetyl group, applied in directions such as organic chemistry, can solve problems such as difficulty in synthesizing exocyclic double bond acridine compounds, and achieve the effects of low cost, simple operation and high yield
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Embodiment 1
[0073] Example 1 Synthesis of 4-(10-methylacridine-9(10H)-alkylene)-3-oxobutanoic acid ethyl ester
[0074] Add 1 part of 2H-acridine compound a (R 1 is methyl, R 2 , R 3 is a hydrogen atom), 1 part of enol diazonium compound b (R 4 is a hydrogen atom, EWG is ethyl formate), 0.05 parts of ferric chloride, 2 parts of di-tert-butyl peroxide (DTBP) and an appropriate amount of dichloromethane. After stirring and reacting at room temperature for 12 h, the reaction solution was concentrated. Petroleum ether / ethyl acetate=10:1 mixed solvent is used as eluent and purified by column chromatography to obtain γ-(9-acridinyl)diazoacetoacetate c with a yield of 91%. Its structure is as follows Show:
[0075]
[0076] The NMR and high-resolution data of the compound are as follows:
[0077] 1 H NMR (400MHz, CDCl 3 )δ7.26–7.15(m,4H),6.95–6.87(m,4H),4.59(t,J=7.0Hz,1H),4.15(q,J=7.1Hz,2H),3.39(s,3H ), 3.11–3.06 (m, 2H), 1.23 (t, J=7.1Hz, 3H).
[0078] 13 C NMR (100MHz, CDCl 3 )δ ...
Embodiment 2
[0086] Example 2 Synthesis of ethyl 4-(10-benzylacridine-9(10H)-alkylene)-3-oxobutanoate
[0087] Add 1 part of 2H-acridine compound a (R 1 ~R 3 Respectively benzyl, hydrogen atom, hydrogen atom), 2 parts of enol diazo compound b (R 4 is a hydrogen atom, EWG is ethyl formate), 0.05 parts of cuprous bromide, 2 parts of tert-butyl hydroperoxide (TBHP) and an appropriate amount of dichloromethane. After stirring and reacting at room temperature for 48 hours, the reaction solution was concentrated , sherwood oil / ethyl acetate=10:1 mixed solvent can obtain gamma-(9-acridinyl) diazoacetoacetate c as eluent column chromatography purification, and yield is 72%, and its structure is as follows Shown:
[0088]
[0089] The NMR and high-resolution data of the compound are as follows:
[0090] 1 H NMR (400MHz, CDCl 3 )δ7.32–7.21(m,5),7.20–7.15(m,2),7.08–7.03(m,2),6.93–6.87(m,2),6.75–6.70(m,2),5.21( s,2),4.68(t,J=7.1Hz,1H),4.18(q,J=7.1Hz,2),3.16(d,J=7.1Hz,2),1.25(t,J=7.1Hz, 3). ...
Embodiment 3
[0099] Example 3 Synthesis of ethyl 4-(10-phenylacridine-9(10H)-alkylene)-3-oxobutanoate
[0100] Add 1 part of 2H-acridine compound a (R 1 ~R 3 Respectively phenyl, hydrogen atom, hydrogen atom), 2 parts of enol diazonium compound b (R 4 is a hydrogen atom, EWG is ethyl formate), 0.05 parts of zinc trifluoromethanesulfonate and a suitable amount of dichloromethane, at room temperature, after stirring and reacting for 72 hours in a standard atmospheric pressure oxygen atmosphere, the reaction solution is concentrated, petroleum ether / Ethyl acetate=10:1 mixed solvent can obtain gamma-(9-acridyl)diazoacetoacetate c as eluent column chromatography purification, yield is 75%, and its structure is as follows:
[0101]
[0102] The NMR and high-resolution data of the compound are as follows:
[0103] 1 H NMR (400MHz, CDCl 3 )δ7.64–7.59(m,2H),7.50(t,J=7.4Hz,1H),7.43–7.38(m,2H),7.28–7.23(m,2H),7.00–6.94(m,2H) ,6.90–6.82(m,2H),6.33–6.28(m,2H),4.74(t,J=7.1Hz,1H),4.16(q,J=7.1Hz...
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