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A kind of method that adopts arylsulfonylbenzaldehyde hydrazone to ring-open cyclopropane compound

A technology of arylsulfonylbenzaldehyde hydrazone and arylsulfonylbenzaldehyde, which is applied in the field of organic synthesis, can solve problems such as ring-opening reactions that are rarely reported, and achieve the effects of strong practical application value, reduced dosage, and mild reaction conditions

Active Publication Date: 2018-08-03
TAIYUAN UNIV OF TECH
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Problems solved by technology

[0005] Although this method realizes the heteroatom ring-opening reaction of sulfur atom and oxygen atom to cyclopropane, the reaction is only for the thioopenation reaction of aromatic thiols.
[0006] In summary, although the research on the ring-opening reaction of cyclopropane compounds under the catalysis of Lewis acid has made some progress, there is little research on the ring-opening reaction of arylsulfonyl-protected benzaldehyde hydrazone as a nucleophile with cyclopropane. to report

Method used

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  • A kind of method that adopts arylsulfonylbenzaldehyde hydrazone to ring-open cyclopropane compound
  • A kind of method that adopts arylsulfonylbenzaldehyde hydrazone to ring-open cyclopropane compound
  • A kind of method that adopts arylsulfonylbenzaldehyde hydrazone to ring-open cyclopropane compound

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Add 0.1mmol of p-toluenesulfonylbenzaldehyde hydrazone 1a, 0.35mmol of cyclopropane as shown in 2a, 1.5mg of Sc(OTf) in the reaction test tube 3 , 1.4 mg ZnCl 2 , 20mg Toluene 0.5mL, heated to 30°C and stirred for 16h, the crude product was obtained by extraction, washing and drying. The crude product was purified by silica gel chromatography to obtain a ring-opened product with a single configuration. The structural formula is shown in Table 1 as 3a. The product was characterized by nuclear magnetic resonance and high-resolution mass spectrometry to confirm the structure of the product.

[0035] Table 1 Reaction of p-toluenesulfonylhydrazone 1a and cyclopropane 2a

[0036]

[0037] 3a The product was obtained (petroleum ether / ethyl acetate=10:1(v / v)) as a colorless liquid; 1 H NMR (400MHz, CDCl 3 ): δ7.44(d, J=8.3Hz, 2H), 7.33-7.23(m, 3H), 7.20(d, J=8.0Hz, 2H), 7.13-7.10(m, 2H), 4.26(dd, J=4.5,11.1Hz,1H),4.18-4.04(m,4H),3.27(dd,J=5.4,9.8Hz,1H),2.98-2.90(m,1H),...

Embodiment 2

[0039]Add 0.1mmol of p-toluenesulfonylbenzaldehyde hydrazone 1a, 0.30mmol of cyclopropane as shown in 2b, 1.1mg of In(OTf) in the reaction test tube 3 , 3.1mg SnCl 4 , 20mg Toluene 0.7mL, heated to 30°C and stirred for 10h, the crude product was obtained by extraction, washing and drying. The crude product was purified by silica gel chromatography to obtain a ring-opened product with a single configuration. The structural formula is shown in 3b in Table 2. The product was characterized by nuclear magnetic resonance and high-resolution mass spectrometry to confirm the structure of the product.

[0040] Table 2 Reaction of p-toluenesulfonylhydrazone 1a and cyclopropane 2b

[0041]

[0042] 3b The product was obtained (petroleum ether / ethyl acetate=10:1(v / v)) as a colorless liquid; 1 H NMR (600MHz, CDCl 3 ): δ7.45(d, J=8.2Hz, 2H), 7.42(dd, J=1.7, 7.6Hz, 2H), 7.24(td, J=1.3, 7.2Hz, 1H), 7.20(t, J= 8.1Hz, 3H), 7.05-7.02(m, 1H), 6.90(d, J=7.2Hz, 1H), 4.67(dd, J=4.4, 11.0Hz,...

Embodiment 3

[0044] Add 0.2mmol of p-toluenesulfonylbenzaldehyde hydrazone 1a, 0.35mmol of cyclopropane as shown in 2c, 5.0mg of Sc(OTf) in the reaction test tube 3 , 5.2 mg GaCl 3 , 20mg Toluene 1.0mL, heated to 40°C and stirred for 14h, the crude product was obtained by extraction, washing and drying. The crude product was purified by silica gel chromatography to obtain a ring-opened product with a single configuration. The structural formula is shown in 3c in Table 3. The product was characterized by nuclear magnetic resonance and high-resolution mass spectrometry to confirm the structure of the product.

[0045] Table 3 Reaction of p-toluenesulfonylhydrazone 1a and cyclopropane 2c

[0046]

[0047] 3c The product was obtained (petroleum ether / ethyl acetate=10:1(v / v)) as a colorless liquid; 1 H NMR (600MHz, CDCl 3 ): δ7.46(d, J=8.3Hz, 2H), 7.21(d, J=8.0Hz, 2H), 7.15-7.10(m, 2H), 6.93(s, 1H), 6.90(d, J= 7.2Hz, 1H), 4.21(dd, J=4.4, 11.2Hz, 1H), 4.17-4.10(m, 4H), 3.26(q, J=7.2Hz, ...

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Abstract

The invention discloses a method using aryl sulfonyl benzaldehyde hydrazone to perform ring opening on a cyclopropane compound. The method includes: using a 1, 1-diester-2-aryl cyclopropane compound as the initial raw material, and using the aryl sulfonyl benzaldehyde hydrazone as the nucleophilic reagent; under the effect of trifluoromethanesulfonic acid metal type and halogeneated metal type double Lewis acid catalysts, performing the ring opening reaction of cyclopropane and hydrazone in a benzene solvent to obtain an aromatic-fat multi-functionalized sulfone product, wherein the reaction temperature is 25-50 DEG C. The method has the advantages that the method is simple to operate, the synthesizing method is high in universality, and high yield of the reactions of the diester cyclopropane and aryl sulfonyl benzaldehyde hydrazone of different structures can be achieved.

Description

technical field [0001] The invention relates to a method for ring-opening cyclopropane compounds by using arylsulfonylbenzaldehyde hydrazone, and belongs to the technical field of organic synthesis. Background technique [0002] Effective utilization of ring tension has considerable advantages in the construction of complex molecules, among which cyclopropane is widely used in synthesis as an important organic synthesis building block. In recent years, cyclopropane, as an important raw material for the synthesis of natural products and drugs, has become the subject of intense research by scientists. Although it has a large ring tension, it is still difficult to cause C-C bond breakage under normal circumstances. Among the cyclopropanes with different substituents, the cyclopropane compound with both the withdrawing and donating groups can use the push-pull effect to induce the formation of highly polarized C-C bonds, reduce the activation barrier, and improve the reactivity ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C315/00C07C317/44B01J31/26B01J31/30
CPCB01J31/26B01J31/30B01J2231/48C07C315/00C07C317/44
Inventor 李兴闫文静张照昱常宏宏魏文珑李彦威
Owner TAIYUAN UNIV OF TECH
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