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A kind of tertiary amine derived from ansa-type ferrocene and its preparation method and application

A technology of ferrocene and diacetyl ferrocene is applied in the preparation of organic compounds, the preparation of amino compounds, chemical instruments and methods, etc., and can solve the problems of poor stability, expensive preparation, moisture and air sensitivity, and the like, Achieve mild reaction conditions, high catalytic activity, and good chemical stability.

Active Publication Date: 2019-04-30
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

After 10 years of development, many breakthroughs have been made in the field of FLP. However, compared with transition metal catalysis, there are still problems such as sensitivity to water vapor and air, poor stability, and expensive preparation costs.

Method used

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  • A kind of tertiary amine derived from ansa-type ferrocene and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] Example 1: Preparation of 1,1'-(1-methyl-3-oxygen-1,3-allyl)ferrocene IV

[0044] In a 250 mL three-necked flask, diacetylferrocene III (10.0 g, 37 mmol) was dissolved in dichloromethane (150 g); dry dimethylamine gas (24.2 g, 0.55 mol), adding AlCl in batches 3 (9.8 g, 74 mmol), slowly raised to room temperature and reacted for 30 hours; filtered the insoluble matter, concentrated the filtrate and separated it by silica gel (GF254, the same below) column chromatography (the eluent was petroleum ether and ethyl acetate, and the volume ratio was 50 : 1), obtained 6.9 g compound IV, m.p.: 85~86 ℃, yield 74%; 1 H NMR (400 MHz, CDCl 3 ) δ 2.15 (s, 3H), 4.27-4.53 (m, 8H), 6.35 (s,1H). 13 C NMR (100 MHz, CDCl 3 ) δ 26.0, 71.5 (2C), 72.3 (2C), 72.9 (2C), 73.0(2C), 84.7, 86.0, 133.2, 152.5, 197.0.

Embodiment 2

[0045] Example 2: Preparation of 1,1'-(1-methyl-3-oxygen-1,3-propyl)ferrocene V

[0046] In a 25 mL two-necked flask, 1,1'-(1-methyl-3-oxo-1,3-allyl)ferrocene IV (5.04 g, 20 mmol) was dissolved in anhydrous dichloromethane (20 g), add 5% Pd / C (0.1 g), under normal temperature and pressure in H 2 The reaction was carried out in the atmosphere for 8 hours; after the reaction was completed, it was suction filtered, and the obtained dichloromethane organic layer was concentrated and then separated by column chromatography (eluent was petroleum ether and ethyl acetate, the volume ratio was 30: 1), and 4.8 g of compound Ⅴ was obtained. , m.p.: 102~104 ℃, yield 96%; 1 H NMR (400MHz, CDCl 3 ) δ 1.25 (d, J = 6.4 Hz, 3H), 2.60 (dd, J = 2.8, 6.8 Hz, 1H), 3.21-3.27 (m, 2H), 3.97 (s, 1H), 4.08 (s, 1H), 4.33 (d, J = 15.2 Hz, 2H), 4.49 (s,1H), 4.67 (d, J = 14.8 Hz, 2H), 4.90 (s, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ22.70, 39.0, 52.2, 67.6, 68.4 (2C), 68.9 (2C), 69.9, 71.5, 72.3 (2C)...

Embodiment 3

[0047] Example 3: Preparation of 1,1'-(1-methyl-3-hydroxyl-1,3-propyl)ferrocene VI

[0048] Take a 50 mL two-necked flask, dissolve 1,1'-(1-methyl-3-oxo-1,3-propyl)ferrocene V (5.08 g, 20 mmol) in absolute ethanol (20 g) , adding NaBH 4 (0.76 g, 20 mmol) at N 2 The reaction was stirred under the atmosphere and protected from light for 6 hours. After the reaction was complete, the solvent was evaporated, and 5% aqueous sodium carbonate was added, extracted with ethyl acetate, and the resulting organic layer was concentrated and separated by column chromatography (eluent was petroleum ether and ethyl acetate). , with a volume ratio of 8 : 1), 4.7 g of compound VI was prepared, m.p.: 81~83 ℃, yield 95%; 1 H NMR (400 MHz, CDCl 3 ) δ 1.26 (d, J = 6.8 Hz, 3H), 1.98 (t, J = 11.2,12.0 Hz, 1H), 2.36-2.41 (m, 4H), 2.55 (t, J = 6.8, 7.2 Hz, 1H), 4.01-4.15 (m,8H), 4.43 (s, 1H), 4.54 (d, J = 6.8 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 20.8, 24.6, 51.6, 65.1, 66.3, 67.1, 67.3, 6...

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Abstract

The invention discloses ansa-ferrocene derived tertiary amine, and a preparation method and application thereof. The application is particularly as follows: the ansa-ferrocene derived tertiary amine and tri(pentafluorphenyl)boron according to the ratio of 1:1 form a hindered lewis acid and base pair catalyst, and the obtained catalyst is applied to catalysis of aniline hydrogenation reduction reaction. The catalyst has high stability, can replace a heavy metal catalyst to a certain degree, can avoid pollution of heavy metal in chemical products from the source, and has good application value and potential social and economic benefits.

Description

technical field [0001] The present invention relates to a tertiary amine derived from ansa-ferrocene and its preparation method and application, a "hindered" Lewis acid-base pair catalyst composed of a tertiary amine derived from ansa-ferrocene and tris(pentafluorophenyl)boron, Application of the catalyst in catalyzing imine hydrogenation reduction reaction. Background technique [0002] In the past few decades, catalytic hydrogenation reactions often use transition metal catalysts with ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt), etc. , there are problems such as high price and heavy metal residue. In particular, the pharmaceutical industry's strict restrictions on the content of heavy metals in food and drugs limit the application of noble metal catalysts in the synthesis of raw materials and intermediates to a certain extent. [0003] As a supplement to metal-catalyzed hydrogenation, metal-free catalytic hydrogenation reactions...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F17/02B01J31/22C07C209/52C07C211/45C07C211/52C07C213/02C07C217/84C07C217/58
CPCB01J31/2295B01J2231/641B01J2531/842C07C209/52C07C213/02C07F17/02C07C211/45C07C211/52C07C217/84C07C217/58
Inventor 钟为慧王辉苏为科
Owner ZHEJIANG UNIV OF TECH
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