A kind of synthetic method of nitrogen heterocyclic substituted p-quinone skeleton spiro compound

A technology of spiro compound and synthesis method, which is applied in the field of synthesis of nitrogen heterocyclic substituted p-quinone skeleton spiro compound, can solve the problem of hindering dearomatization of hydrogen migration/cyclization reaction, unable to realize dearomatization of condensed ring aromatics, and not It is suitable for the efficient synthesis of quinone compounds and other problems, and achieves the effect of complete conversion of raw materials, convenient separation of products, and high yield

Active Publication Date: 2020-05-19
QINGDAO AGRI UNIV
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Problems solved by technology

However, for the synthesis of p-quinone compounds belonging to non-aromatic, α,β-unsaturated ketones, the above two strategies are not suitable for the efficient synthesis of p-quinone compounds because the dearomatization of fused-ring aromatics cannot be achieved.
[0007] Moreover, using the tandem [1,n]-hydrogen migration / cyclization reaction (tertiary amino group effect) in the reaction process, there are other competing reactions, for example, the iminium ion generated by the hydrogen migration of the meta-position of the hydroxyl group can construct the seven-membered ring, the hydroxyl attacking the positive ion can generate an eight-membered ring, and because benzoquinone has a strong tendency to return to the benzene ring structure, which hinders the effective dearomatization of the hydrogen transfer / cyclization reaction, it is difficult to form a stable p-quinone compound

Method used

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  • A kind of synthetic method of nitrogen heterocyclic substituted p-quinone skeleton spiro compound
  • A kind of synthetic method of nitrogen heterocyclic substituted p-quinone skeleton spiro compound
  • A kind of synthetic method of nitrogen heterocyclic substituted p-quinone skeleton spiro compound

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039]

[0040] take compound A 1 (2,6-di-tert-butylphenol) 0.13mmol, Compound B 1 (2-Pyrrolidinylbenzaldehyde) 0.1mmol and piperidine 0.2mmol in a reaction flask, add 1mL of toluene, stir and react at 120°C for 12h, then cool to room temperature;

[0041] Subsequently, 1 mL of hexafluoroisopropanol HFIP was added to the reaction system, and stirred at 25° C. for 10 min. After the reaction was completed, the reaction product was concentrated by rotary evaporation, and purified and separated on a silica gel column.

[0042] The isolated product was detected and analyzed, and the results of the analyzed data were as follows, the obtained product was the target product, and the yield was 60%.

[0043] Chemical formula: C 25 h 33 NO

[0044] Exact molecular weight: 363.2562

[0045] Molecular weight: 363.5450

[0046] Structural formula:

[0047] Yield: 60%

[0048] 1 H NMR (500MHz, CDCl 3 )δ7.14(t, J=7.7Hz, 1H), 6.99(d, J=7.4Hz, 1H), 6.62(t, J=7.3Hz, 1H), 6.51(d, J...

Embodiment 2

[0050] take compound A 1 (2,6-di-tert-butylphenol) 0.13mmol, compound B 1 (2-Pyrrolidinylbenzaldehyde) 0.1mmol and piperidine 0.2mmol were placed in a reaction flask, 1mL of toluene was added, and the reaction was stirred at 120°C for 12h, then cooled to room temperature, and the reaction intermediate was separated and purified;

[0051] The reaction intermediate was added into 2 mL of hexafluoroisopropanol HFIP, and stirred at 25° C. for 10 min. After the reaction was completed, the reaction product was concentrated by rotary evaporation, and purified and separated on a silica gel column.

[0052] Detection and analysis were carried out on the isolated product, and the results of the analysis data were as follows, the obtained product was the target product, and the yield was 90%.

[0053] Chemical formula: C 25 h 33 NO

[0054] Exact molecular weight: 363.2562

[0055] Molecular weight: 363.5450

[0056] Structural formula:

[0057] Yield: 90%

[0058] 1 H NMR (50...

Embodiment 3

[0061] Raw materials: 4-bromo-2-pyrrolidinylbenzaldehyde, 2,6-di-tert-butylphenol

[0062] Product: Chemical formula: C 25 h 32 BrNO

[0063] Exact molecular weight: 441.1667

[0064] Molecular weight: 442.4410

[0065] Structural formula:

[0066] Yield: 50%

[0067] 1 H NMR (500MHz, CDCl 3 )δ6.83(d, J=7.8Hz, 1H), 6.72(dd, J=7.9, 1.9Hz, 1H), 6.61(d, J=1.9Hz, 1H), 6.33(d, J=2.9Hz, 1H), 6.24(d, J=2.9Hz, 1H), 3.61(dd, J=9.5, 6.0Hz, 1H), 3.43(td, J=8.8, 3.2Hz, 1H), 3.20(dd, J=16.4 ,8.7Hz,1H),3.08(dd,J=15.8,0.8Hz,1H),2.51(d,J=15.8Hz,1H),1.98–1.84(m,2H),1.79(dtd,J=10.0, 6.4,3.2Hz,1H),1.29–1.23(m,11H),1.13(s,10H); 13 C NMR (126MHz, CDCl 3 )δ186.7, 149.4, 148.5, 144.5, 143.7, 138.7, 130.2, 121.3, 118.5, 117.5, 113.1, 77.3, 77.0, 76.8, 64.1, 47.5, 39.5, 38.0, 35.0, 34.9, 29.5, 29.5, 27 Resolution mass spectrometry (ESI): calcd.forC 25 h 32 BrNO[M+H] + :442.1667, actual value: 442.1677.

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Abstract

The invention relates to a synthetic method of an N-heterocycle substituted para-quinone skeleton spiro compound. The synthetic method is a construction strategy of realizing the para-quinone compoundthrough hydrogen transfer reaction by adopting para-methylene benzoquinone as a hydrogen acceptor, 2,6-di-tert-butylphenol and an amino-formaldehyde compound takes aromatizing as driving force, and the spiro para-quinone compound is finally obtained through a 'one-pot method'. According to the synthetic method provided by the invention, a para substituent group has no need to be pre-synthesized,and chemoselectivity and locus specificity of intermolecular phenolic dearomatization are realized. According to the synthetic method provided by the invention, raw materials are simple and easy to obtain; reaction can be carried out at room temperature, the reaction conditions are mild, no metal or proton catalyst is required, and the method is convenient to operate, economical and high-efficient; according to the method provided by the invention, the reaction activity is high, the yield reaches up to 99 percent, and the raw material conversion is complete; the products are conveniently separated, and the reaction is green, economical, and friendly to the environment.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to a synthesis method of a nitrogen heterocyclic substituted p-quinone skeleton spiro compound. Background technique [0002] There are a large number of p-quinones in various natural and non-natural products with biological activity. Their artificial synthesis and functional transformation have attracted extensive attention from researchers in organic synthesis, pharmaceuticals and other industries. [0003] [0004] In the organic synthesis strategy of substituted p-quinones, through the catalytic dearomatization reaction of phenols and anilines, the efficient functional transformation of p-quinones can be realized, and many compounds containing quaternary carbon centers, spiro rings or bridged rings can be synthesized. three-dimensional structure of compounds. For example, the above two natural molecules have been synthesized by catalytic dearomatizatio...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D471/10C07D487/10C07D471/20C07D221/20
CPCC07D221/20C07D471/10C07D471/20C07D487/10
Inventor 肖建朱帅李帅帅
Owner QINGDAO AGRI UNIV
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