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Synthesis method and applications of N heteroatom polysubstituted benzoquaternary cycloketone

A synthesis method and multi-substitution technology, which is applied in the field of synthesis of N-heteroatom multi-substituted benzotetracyclic ketones, can solve problems such as the difficulty of benzocyclobutanone, and achieve high applicability and high yield

Active Publication Date: 2020-03-03
OCEAN UNIV OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, it is still difficult to prepare benzocyclobutanones with different substituents. The benzocyclobutanones with oxygen substituents have been prepared on a large scale, while N heteroatom multi-substituted benzocyclobutanones have not been reported yet.

Method used

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  • Synthesis method and applications of N heteroatom polysubstituted benzoquaternary cycloketone
  • Synthesis method and applications of N heteroatom polysubstituted benzoquaternary cycloketone
  • Synthesis method and applications of N heteroatom polysubstituted benzoquaternary cycloketone

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] first step:

[0033]

[0034] Three THF solutions of compound A were prepared, and commercially available LDA (1.08 mmol, 0.54 mL, 2M hexane / THF solution) was added to a solution of compound A (1 mmol) in THF (2 mL) at -78 ° C, and the reactant Stir at this temperature for 20 minutes, add iodomethane, iodoethane and benzyl bromide (63uL) to the three solutions respectively, then continue to stir at room temperature for 1 hour, after the reaction is completed, wash with NH 4 Quenched with aqueous Cl. Extracted with ethyl acetate, washed with brine, MgSO 4 Drying, concentration and purification by silica gel chromatography afforded compound B1 (R 2 =CH 3 ), B2(R 2 =Et), B3(R 2 =Bn), the yield was 80-91%.

[0035] B1:R f =0.55, (PE:EA=5:1), 1 H NMR (500MHz, Chloroform-d) δ7.27 (td, J = 8.2, 1.2Hz, 1H), 6.73–6.60 (m, 1H), 6.51 (dd, J = 8.4, 1.4Hz, 1H), 2.94 ( d,J=1.3Hz,3H). 13 C NMR (126MHz, Chloroform-d) δ150.83, 150.76, 130.48, 120.15, 117.60, 109.59, 109.58,...

Embodiment 2

[0063]

[0064] Concrete experimental operation is with embodiment one, and the product that makes is as follows:

[0065] F4:R f =0.7, (PE:EA=5:1) 1 H NMR (400MHz, Chloroform-d) δ7.40(s,1H),7.17(s,1H),3.94(s,2H),3.36(s,3H).

[0066] F5:R f =0.6, (PE:EA=5:1) 1 H NMR (400MHz, Chloroform-d) δ7.24(s,1H),7.01(s,1H),3.84(s,2H),3.26(s,3H).

[0067] F6:R f =0.75, (PE:EA=5:1) 1 H NMR (400MHz, Chloroform-d) δ7.45(s,1H),7.23(s,1H),3.9(s,2H),3.36(s,3H).

[0068] F7:R f =0.7, (PE:EA=5:1) 1 H NMR (400MHz, Chloroform-d) δ7.38(s,1H),7.15(s,1H),3.92(s,2H),3.33(s,3H).

Embodiment 3

[0070]

[0071] Concrete experimental operation is with embodiment one, and the product that makes is as follows:

[0072] F8:R f =0.52, (PE:EA=5:1) 1 H NMR (400MHz, Chloroform-d) 1 H NMR (400MHz, Chloroform-d) δ7.40(d, J=7.26Hz, 1H), 7.14(d, J=7.26Hz, 1H), 6.88(s, 1H), 3.82(s, 2H), 3.09 (s,3H).

[0073] F9:R f =0.57, (PE:EA=5:1) 1 H NMR (400MHz, Chloroform-d) 1 H NMR (400MHz, Chloroform-d) δ7.42 (d, J = 7.26Hz, 1H), 7.16 (d, J = 7.26Hz, 1H), 6.88 (s, 1H), 3.82 (s, 2H), 3.09 (s,3H).

[0074] F10:R f =0.6, (PE:EA=5:1) 1 H NMR (400MHz, Chloroform-d) δ7.32(d, J=4.8Hz, 4H), 7.30–7.26(m, 1H), 7.21(t, J=4.8Hz, 1H), 6.7(d, J= 7.0Hz, 1H), 6.45(d, J=8.4Hz, 1H), 4.64(s, 2H), 3.80(s, 2H).

[0075] Part II: Application of N heteroatom multi-substituted benzotetracyclic ketones

[0076] The first step, the preparation of acid chloride:

[0077] figure 1 Among them, the preparation process of the required acid chlorides for Gb, Gd, Ge, Gq, Gt is consistent, as follows:

[...

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Abstract

The invention discloses an N heteroatom polysubstituted benzoquaternary cycloketone synthesis method. According to the invention, the synthetic route starts from a known aniline compound A, the hundred g-scale preparation can be achieved, the yield can achieve more than 90%, and each step of the synthetic route can achieve reactions with scale of more than 20 g; the synthetic route provides a concise and effective approach for the synthesis of compounds having biological activity, is high in yield, and is suitable for large-scale preparation; the invention discloses applications of the N heteroatom polysubstituted benzoquaternary cycloketone, wherein different products can be prepared by carrying out reactions on the N heteroatom polysubstituted benzoquaternary cycloketone and different acyl chlorides, so that the N heteroatom polysubstituted benzoquaternary cycloketone has wide application prospect.

Description

technical field [0001] The invention relates to a benzo four-membered ring ketone, in particular to a synthesis method and application of a N heteroatom multi-substituted benzo four-membered ring ketone. Background technique [0002] The four-membered ring in benzocyclobutanone has a large ring tension. At present, this type of compound is widely used in the activation of carbon-carbon bonds. Different substituents of benzocyclobutanone can be activated through carbon-carbon bonds under appropriate conditions. Various types of products are obtained, such as spiro rings, parallel rings and other types of compounds. However, it is still difficult to prepare benzocyclobutanones with different substituents. The benzocyclobutanones with oxygen substituents have been prepared on a large scale, but the N heteroatom multi-substituted benzocyclobutanones have not been reported yet. Contents of the invention [0003] In order to solve the above technical problems, the present inven...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C221/00C07C225/22C07C231/02C07C233/33
CPCC07C221/00C07C231/02C07C269/06C07C303/30C07C2602/06C07C225/22C07C271/30C07C309/65C07C233/33
Inventor 徐涛邱波张建宇战俊玲李晓彤
Owner OCEAN UNIV OF CHINA
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