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Stable aza [3.3.3] propellane carbene and preparation method thereof

A propane, stable technology, applied in the field of aza[3.3.3]propane carbene and its preparation, can solve the problems of limited scope of application, high risk, trouble, etc.

Active Publication Date: 2019-03-12
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in this route, the precursor salt and strong base are indispensable; in many cases, the solubility of the precursor salt will become troublesome; the raw material thione of route 2 is not easy to obtain, and the preparation needs to be carried out under vacuum conditions, and Potassium metal is required, which is highly dangerous; the preparation of raw materials for route 3 is inconvenient, and requires high-temperature pyrolysis under ultra-vacuum conditions, so the scope of application is very limited
As a highly sensitive active intermediate, the above preparation methods all require special conditions, such as glove box, dehydration, dehumidification and inert gas protection, which is very troublesome

Method used

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  • Stable aza [3.3.3] propellane carbene and preparation method thereof
  • Stable aza [3.3.3] propellane carbene and preparation method thereof
  • Stable aza [3.3.3] propellane carbene and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0113] Preparation of 2,4,6,8,10-pentabenzyl-3,7,9,11-tetraoxo-2,4,6,8,10-pentaaza[3.3.3]propeller

[0114] Under an argon atmosphere, 3.01 g (10 mmol) of 10-benzyl-3,7,9,11-tetraoxo-2,4,6,8,10-pentaaza[3.3.3]propeller Dissolve 10.26g (60mmol) benzyl bromide in 15ml of the first solvent, cool to 0°C with an ice bath, slowly add 50mmol (1.20g) sodium hydride solid and continue stirring for 1h; after the white bubbles in the reaction mixture disappear, add The reaction system was raised to room temperature; the progress of the reaction was detected by thin-layer chromatography, and when the raw materials were detected by thin-layer chromatography, the reaction mixture was cooled to 0°C again with an ice bath; the reaction mixture was diluted with ethyl acetate, and dilute hydrochloric acid was slowly added dropwise To quench the unreacted hydride, adjust the pH of the solution to neutral; add water to the resulting mixture, and extract three times with ethyl acetate; combine the...

Embodiment 2

[0123] 2,4,6,8-Tetrakis(4-methylbenzyl)-3,7,9,11-tetraoxo-10-benzyl-2,4,6,8,10-pentaaza[3.3 .3] Preparation of propane

[0124] 4-methylbenzyl bromide was used instead of benzyl bromide in Example 1, and the others were the same as in Example 1 to obtain a white solid product with a mass of 2.66 g, a yield of 37%, and a melting point of 172.4°C to 172.9°C.

[0125] Structural characterization related tests were carried out on the product, and the test results were as follows: Figure 5 ~ Figure 8 Shown:

[0126] 1 H NMR (400MHz, CDCl 3 )δ7.37–6.69(m,21H),4.41(s,8H),4.25(d,J=14.7Hz,2H),2.22(s,12H); 13 C NMR (100MHz, CDCl 3 )δ166.13(s),156.07(s),136.04(s),132.69(d),128.26(s),127.65(d),127.17(s),125.97(s),74.32(s),44.38( s), 41.52 (s), 20.09 (d); -1 ; HRMS (ESI + ):calcd.for C 45 h 43 N 5 o 4[M+H] + 718.3388, found 718.3378.

[0127] The above data indicate that the product is 2,4,6,8-tetra(4-methylbenzyl)-3,7,9,11-tetraoxo-10-benzyl-2,4,6,8,10- Pentaaza[3.3.3] pro...

Embodiment 3

[0130] 2,4,6,8-Tetrakis(4-fluorobenzyl)-3,7,9,11-tetraoxo-10-benzyl-2,4,6,8,10-pentaaza[3.3. 3] Preparation of propane

[0131] 4-fluorobenzyl bromide was used to replace the benzyl bromide in Example 1, and the others were the same as in Example 1 to obtain a white solid product with a mass of 3.52 g, a yield of 48%, and a melting point of 108.4°C to 110.1°C.

[0132] Structural characterization related tests were carried out on the product, and the test results were as follows: Figure 9 ~ Figure 12 Shown:

[0133] 1 H NMR (400MHz, DMSO) δ7.55–6.49 (m, 21H), 5.06–4.11 (m, 10H). 13 C NMR (100 MHz, DMSO) δ167.19(s), 162.99(s), 160.57(s), 157.26(s), 134.79(s), 133.58(d), 129.53–128.96(m), 128.33(s ), 115.58(d), 115.41–115.23(m), 75.16(s), 44.82(s); 947,844,815,736,698,665,526,491cm -1 ; HRMS (ESI + ):calcd.for C 41 h 31 f 4 N 5 o 4 [M+H] + 734.2385, found 734.2374.

[0134] The above data indicate that the product is 2,4,6,8-tetra(4-fluorobenzyl)-3,7,9,11-tetraoxo...

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Abstract

The invention relates to a stable aza [3.3.3] propellane carbene and a preparation method thereof and belongs to the field of organic chemistry. The stable aza [3.3.3] propellane carbene is 2, 4, 6, 8, 10-substituted-2, 4, 6, 8, 10-aza [3.3.3] propellane carbene, which is high in stability. The 2, 4, 6, 8, 10-pentasubstituted-2, 4, 6, 8, 10-aza [3.3.3] propellane carbene is prepared by preparing 2, 4, 6, 8, 10-substituted-3, 7, 9, 11-oxo-2, 4, 6, 8, 10-aza [3.3.3] propellane from 10-substituted-3, 7, 9, 11-oxo-2, 4, 6, 8, 10-aza [3.3.3] propellane and alkyl halide, reducing carbonyl and lastlyadding in palladium catalysts. The stable aza [3.3.3] propellane carbene saves deoxygenization, dehumidification and inert gas protection during preparation and storage and does not require preparation of reaction precursor into salts. The preparation method of the stable aza [3.3.3] propellane carbene is simple, mild in reaction condition, convenient to postprocess, high in yield and applicableto industrialized production, storage and usage.

Description

technical field [0001] The present invention relates to a stable aza[3.3.3] propeller alkane carbene and a preparation method thereof, specifically, the carbene is 2,4,6,8,10-pentasubstituted-2,4,6, 8,10-pentaaza[3.3.3]propeller carbene, belongs to the field of organic chemistry. Background technique [0002] Carbene, also known as carbene and carbene, is usually formed by eliminating a neutral molecule from a molecule containing an easy-leaving group, and its simplified formula is H 2 C: and its substituted derivatives. Carbene is an electrically neutral divalent carbon atom and a highly reactive intermediate containing two unbonded electrons. The lifetime of carbene is much lower than 1 second, and it can only be trapped at low temperature (below 77K), separated and observed in the crystal lattice. [0003] Carbenes have long been considered reactive intermediates that are not stable at room temperature. In view of the introduction of heteroatoms such as nitrogen, phos...

Claims

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Application Information

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IPC IPC(8): C07D487/18
CPCC07D487/18
Inventor 李加荣周光伟陈芊竹薛亚涵张莉珠张凯苏子琦藤青湖
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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