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Barbituric acid-cyclohexadiene spiro compound with Boc amino and synthetic method of barbituric acid-cyclohexadiene spiro compound

A technology of aminobarbituric acid and spiro compounds, applied in the field of organic synthesis, to achieve the effects of wide application range, mild reaction conditions, and easy availability of raw materials

Active Publication Date: 2018-09-04
HENAN UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] A survey of the literature found that barbituric alkenes, often derived by condensation reactions between barbituric acids and the corresponding carbonyl derivatives (aldehydes and ketones), with acetylenic ketones, 3-isothiocyanatooxindole, or allenoic acid Cycloaddition between esters to construct barbituric acid-spiro derivatives, but directly from N,N′-disubstituted barbituric acid and 1,1-dicyano-1,3-diene The construction of barbituric acid-cyclohexene spiro compounds by tandem cyclization reaction is rarely reported

Method used

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  • Barbituric acid-cyclohexadiene spiro compound with Boc amino and synthetic method of barbituric acid-cyclohexadiene spiro compound
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  • Barbituric acid-cyclohexadiene spiro compound with Boc amino and synthetic method of barbituric acid-cyclohexadiene spiro compound

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Screening of reaction conditions

[0034] Formal [5+1] cyclization of 1,1-dicyano-1,3-diene and 1,3-dimethylbarbituric acid to construct two spirobarbituric acid compounds with different structures Reaction condition screening : Take the reaction of substrate 1a and 1,3-dimethylbarbituric acid as an example:

[0035] The reaction equation is as follows:

[0036]

[0037]

[0038]

Embodiment 2

[0040] Synthesis of barbituric acid-cyclohexene spiro compound 2 with imine group

[0041]

[0042] At room temperature, 1 (0.3mmol), 1,3-dimethylbarbituric acid (0.36mmol), tetrahydrofuran (0.6mL) were successively added to the reaction flask, and then the catalyst i-Pr 2 NH(5mol%) or Et 3 N (2mol%). After the reaction was completed, the corresponding target product 2 was obtained directly through silica gel column separation (petroleum ether / ethyl acetate=10 / 1). The specific experimental data are as follows:

[0043] =12.1Hz,1H); 3.91-3.80(m,1H),3.15(s,3H),3.15(s,3H),3.01(d,J=19.1Hz,1H); 13 CNMR (75MHz, CDCl 3 ):δ=169.1, 167.3, 166.6, 165.6, 150.1, 137.4, 135.8, 131.4, 129.3, 129.2, 129.1, 127.7, 127.5, 114.3, 109.6, 62.6, 47.3, 34.7, 28.8, 28.4; , CDCl 3 ): δ=131.3, 129.2, 129.1, 129.0, 127.6, 127.5, 47.3, 34.6, 28.8, 28.4; HRMS(ESI): m / z calcd for C 24 h 21 N 4 o 3 + [M+H] + 413.1608,found: 413.1608.

[0044] 3.88-3.78(m,1H),3.18(s,3H),3.16(s,3H),2.98(d...

Embodiment 3

[0058] Synthesis of Barbituric Acid-Cyclohexadiene Spiral Compound 4 with Boc Protected Amino

[0059] Compound 3a was treated with (Boc) in dichloromethane 2 A simple treatment of O can give the barbituric acid-cyclohexadiene spiro compound 4a with a Boc-protected amino group, as shown below, with a yield of 78%. The reaction equation is as follows:

[0060]

[0061] For this reason, the conditions for the synthesis of compound 3a were firstly optimized, and the results are as follows:

[0062]

[0063]

[0064] The best condition is to use DMAP as catalyst, 95% yield to get 3a

[0065]

[0066] Characterization data of compound 3a:

[0067] (2E,4E)-2-(amino(1,3-dimethyl-2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene)methyl)-3,5-diphenylpenta-2,4-dienenitrile(3a) Synthesis: Experimental steps: Add 1,1-dicyano-1,3-diene 1a and 1,3-dimethylbarbituric acid, catalyst, and solvent to the reaction flask in sequence, stir at room temperature, and monitor by TLC , 1a ...

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Abstract

The invention discloses a barbituric acid-cyclohexadiene spiro compound with Boc amino and a synthetic method of the barbituric acid-cyclohexadiene spiro compound and belongs to the technical field oforganic chemistry. The synthetic method comprises the following steps: adopting 1,1-dicyano-1,3-diene 1 and 1,3-dimethylbarbituricacid, carrying out an organic base catalytic reaction in an organic solvent, adding Boc2O into the reaction system when the raw material 1 is completely converted, and synthesizing the barbituric acid-cyclohexadiene spiro compound 4 with functional group Boc amino at high selectivity. The synthetic method can be applicable to multiple different 1,1-dicyano-1,3-diene compounds 1 and has the advantages of being readily available in raw materials, simple and convenient in operation, mild in conditions, high in reaction yield and capable of carrying out extensive reactions. According to the method disclosed by the invention, the reaction is carried out in a cycloaddition manner, and the atom economy is excellent; with the adoption of small-molecule organocatalysis, use of a transition metal catalyst is avoided, and heavy metal pollution does not exist in the product.

Description

technical field [0001] The invention relates to a preparation method of a class of spiro compounds, in particular to a class of Boc aminobarbituric acid-cyclohexadiene spiro compounds and a synthesis method thereof, belonging to the technical field of organic synthesis. Background technique [0002] Barbituric acid (also known as malonylurea), the chemical name is 2,4,6-pyrimidinetrione, which can be used as analytical reagent, raw material for organic synthesis, intermediate of plastics and dyes, catalyst for polymerization reaction, etc.; The two hydrogen atoms on the methylene group of malonylureide are replaced by hydrocarbon groups called barbituric acid derivatives, which are a class of compounds with important pharmacological activities, such as sedative, anesthetic, anxiolytic, anticonvulsant, sedative pain, anti-cancer, anti-AIDS and immune regulation (Bioorg.Med.Chem.2011,19,4985; CNS Neurosci.Ther.2009,15,24; CNS Drugs.2008,22,1037; Clin.CancerRes . 2004, 10, 403...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D239/70C07D409/04
CPCC07B2200/13C07D239/70C07D409/04
Inventor 汪游清完颜东艳张永娜刘颖
Owner HENAN UNIVERSITY
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