[2.2] paracyclophane derivative as well as preparation method and application thereof

A technology for cyclamen and its derivatives, applied in the application field of catalytic hydrogenation reduction reaction, can solve the problems of high cost of catalyst preparation, lack of universal applicability of catalyst, difficulty in recovery and mechanical application, etc., to avoid heavy metal pollution, good application value, The effect of high catalytic activity

Active Publication Date: 2014-03-05
安徽艾博生物科技有限公司
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  • Abstract
  • Description
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  • Application Information

AI Technical Summary

Problems solved by technology

[0009] Although many non-metallic catalytic hydrogenation catalysts have been discovered so far, the catalysts are sensitive to moisture and air, and their stability is generally poor; in addition, the catalysts are expensive to prepare, difficult to recycle, and have no universal applicability, and have many limitations on substrates.

Method used

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  • [2.2] paracyclophane derivative as well as preparation method and application thereof
  • [2.2] paracyclophane derivative as well as preparation method and application thereof
  • [2.2] paracyclophane derivative as well as preparation method and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0065] Embodiment 1: [2.2] the preparation of cyclofenene VII

[0066] (1) In a 100mL three-neck flask, dissolve [2.2] p-Cyclofan V (20.8g, 100mmol) in 110g of carbon tetrachloride, add the initiator azobisisobutyronitrile (0.17g, 1mmol), slowly drop Add bromine (17.6g, 110mmol), after the dropwise addition, heat and reflux for 2 hours, TLC tracking until the reaction is complete, cool after the reaction, filter, and the filtrate is concentrated and then subjected to silica gel column chromatography, the eluent is petroleum ether: Ethyl acetate=60:1 (V:V), collect the eluate containing 1-bromo[2.2] p-cyclophane VI, concentrate under reduced pressure, and dry to obtain 1-bromo[2.2] p-cyclophane VI is 15.2 g, mp: 119-121℃, yield 53%; 1 H NMR (400MHz, CDCl 3 )δ2.80-2.85(m,4H),3.21(dd,J=12.4,8.0Hz,1H),3.46(dd,J=12.4,8.0Hz,1H),5.46(t,J=8.0Hz,1H ),7.05-7.11(m,6H),7.30(d,J=7.6Hz,2H). 13 C NMR (100MHz, CDCl 3 )δ44.4,45.5,46.3,62.6,124.4,125.1,126.6,128.7,129.5.133.4,134.0,135.2,1...

Embodiment 2

[0068] Embodiment 2: [2.2] the preparation of cyclofenene VII

[0069](1) In a 500mL three-neck flask, dissolve [2.2] p-Cyclofan V (20.8g, 100mmol) in 400g of carbon tetrachloride, add the initiator azobisisobutyronitrile (1.6g, 10mmol), slowly drop Add bromine (24.0g, 150mmol). After the dropwise addition, heat and reflux for 12 hours. After the reaction, cool and filter. After the filtrate is concentrated, it is subjected to silica gel column chromatography. The eluent is petroleum ether: ethyl acetate = 60: 1 (V:V), collect the eluate containing 1-bromo[2.2]-p-cyclophenone VI, concentrate under reduced pressure, and dry to obtain 17.8g of 1-bromo[2.2]-p-cyclophenone VI, mp: 118 -120℃, yield 62%;

[0070] (2) In a 100mL three-neck flask, dissolve 1-bromo[2.2]p-cyclophenone VI (7.2g, 25mmol) in 70g dimethyl sulfoxide, add potassium tert-butoxide (8.4g, 75mmol) in batches, Heat to 40-50°C and react for 6 hours, cool down after the reaction, add 10mL of water to quench, add t...

Embodiment 3

[0071] Embodiment 3: [2.2] the preparation of cyclofenene VII

[0072] (1) In a 250mL three-neck flask, dissolve [2.2] p-Cyclofan V (20.8g, 100mmol) in 200g of carbon tetrachloride, add the initiator azobisisobutyronitrile (0.8g, 5mmol), slowly drop Add bromine (19.2g, 120mmol). After the dropwise addition, heat and reflux for 6 hours. After the reaction, cool and filter. The filtrate is concentrated and then subjected to silica gel column chromatography. The eluent is petroleum ether: ethyl acetate = 60: 1 (V:V), collect the eluate containing 1-bromo[2.2]-p-cyclophenone VI, concentrate under reduced pressure, and dry to obtain 18.7g of 1-bromo[2.2]-p-cyclophenone VI, mp: 119 -121℃, yield 65%;

[0073] (2) In a 100mL three-necked flask, dissolve 1-bromo[2.2]p-cyclophenone VI (7.2g, 25mmol) in 60g dimethyl sulfoxide, add potassium tert-butoxide (5.6g, 50mmol) in batches, Heat to 40-50°C to react for 4 hours, cool down after the reaction, add 10mL water to quench, add toluene ...

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Abstract

The invention discloses a [2.2] paracyclophane derivative as shown in the general formula (A), wherein R is phenyl or 2,4,6-trimethylphenyl, and the two R groups in the general formula (A) are same. The invention also discloses a preparation method of the compound and an application of the compound as a nonmetallic catalyst to the catalytic hydrogenation reduction reaction of imide compounds. The [2.2] paracyclophane derivative as shown in the general formula (A) is novel in structure, is mild in reaction condition and high in reaction yield in the preparation process and has the characteristics of high catalytic activity, recycling and no heavy metal residues in products when being used for the catalytic hydrogenation reduction reaction of the imide compounds so as to have wider application prospect and higher societal and economic benefits.

Description

(1) Technical field [0001] The present invention relates to [2.2] p-cyclophane derivatives, in particular to 1-bis(phenyl)phosphino-2-bis(pentafluorophenyl)boryl-[2.2] p-cyclophane and 1-bis(2,4 ,6-trimethylphenyl)phosphino-2-bis(pentafluorophenyl)boryl-[2.2]p-cyclophane and its preparation method, and its catalytic hydrogenation reduction reaction in imine compounds as non-metallic catalyst in the application. (2) Background technology [0002] Lewis acid-base theory is one of the most important basic theories in classical chemistry. It expands the concept and scope of acids and bases, enables people to better understand acid-base reactions, and is used to explain numerous reaction mechanisms. When a Lewis acid and a base meet, the Lewis base provides a lone pair of electrons, and the Lewis acid provides an empty orbital, and the two are combined through a coordination bond to form a stable Lewis acid-base adduct, such as Et 2 O·BF 3 , H 3 N·BH 3 Wait. There is also a...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/50B01J31/02C07C209/52C07C211/48C07C211/52C07C211/45C07C217/84C07C213/02
Inventor 钟为慧王冠苏为科
Owner 安徽艾博生物科技有限公司
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