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(R)-1-(1-phenethyl) thiourea modified Mn-Anderson type heteropolyacid catalyst as well as preparation method and application thereof

A technology of heteropoly acid and phenethyl, applied in the field of catalytic chemistry, can solve the problems of low activity, difficult recycling and high dosage, and achieve the effects of high catalytic activity, high enantioselectivity and simple preparation method

Active Publication Date: 2016-07-27
上海元革新材料科技有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of (R)-1-(1-phenylethyl) thiourea modified Mn-Anderson type heteropolyacid catalyst, preparation method and application thereof, the present invention Solve the technical problems of low activity, high consumption and difficult recycling of existing chiral organic small molecule catalysts

Method used

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  • (R)-1-(1-phenethyl) thiourea modified Mn-Anderson type heteropolyacid catalyst as well as preparation method and application thereof
  • (R)-1-(1-phenethyl) thiourea modified Mn-Anderson type heteropolyacid catalyst as well as preparation method and application thereof
  • (R)-1-(1-phenethyl) thiourea modified Mn-Anderson type heteropolyacid catalyst as well as preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Polyacid precursor [N(C 4 h 9 ) 4 ] 4 [α-Mo 8 o 26 ] preparation

[0029] In a 50mL flask, Na 2 MoO 4 2H 2O5.00g (20.7mmol) was dissolved in 12mL of deionized water, and 5.17mL of 6.0N hydrochloric acid solution was added, and vigorously stirred at room temperature for 1-2min. Then 3.34 g (10.4 mmol) of tetrabutylammonium bromide was dissolved in 10 ml of deionized water, and added to the flask under vigorous stirring to form a white precipitate immediately. After the mixture was stirred for 10 minutes, the precipitate was collected on a medium porosity filter by suction and washed with 20 mL of water, 20 mL of ethanol, 20 mL of acetone and 20 mL of diethyl ether, respectively. This crude product (4.78g) was dissolved in 35mL of acetonitrile and allowed to stand at -10°C for 24h. Clear, colorless, block-like crystals were collected by suction filtration and dried under vacuum for 12 hours. The clarity of the crystals is lost as they dry. Yield 3.58g (1.66mmo...

Embodiment 2

[0031] Preparation of (R)-1-(1-phenylethyl)isothiocyanate

[0032] Add (R)-(+)-1-phenylethylamine (0.606g, 5mmol) into a dry reaction vessel, dissolve it with 20mL of ethyl acetate, then slowly add CS 2 (0.1142g, 15mmol) and triethylamine (0.506mg, 5mmol), after stirring the reaction at room temperature for 1h, then adding di-tert-butyl dicarbonate (Boc 2 O) (1.091mg, 5mmol) and 4-dimethylaminopyridine (DMAP) (18mg, 0.15mmol), after stirring and reacting at room temperature for 2h (gas is generated during the stirring process, attention should be paid to degassing and decompression), which can be obtained 0.79 g of (R)-1-(1-phenylethyl)isothiocyanate. Yield 97%.

[0033] The NMR spectrum of (R)-1-(1-phenylethyl)isothiocyanate is shown in image 3 , the specific data are as follows:

[0034] 1 HNMR (501MHz, CDCl 3 )δ7.3-7.5(dt, J=12.3,7.7Hz,5H),4.90-4.95(q,J=6.7Hz,1H),1.65-1.70(d,J=6.8Hz,3H).

Embodiment 3

[0036] Preparation of Mn-Anderson Polyoxometalates Modified by Bilateral Amino Groups

[0037] Take [N(C 4 h 9 ) 4 ] 4 [α-Mo 8 o 26 ] (8.00g, 3.7mmol), Mn(CH 3 COO) 3 2H 2 O (1.49g, 5.6mmol) and (HOCH 2 ) 3 CNH 2 (1.56g, 12.8mmol), in 150mL of acetonitrile solution was refluxed for 16h. The orange solution was cooled to room temperature and filtered to remove a very fine black solid. The filtrate was exposed to ether vapor. After 2 hours, the white precipitate was filtered off. The orange filtrate was again exposed to ether vapor for several days. Plenty of orange crystals were obtained. They were isolated by filtration, washed with acetonitrile and a small amount of ether, and dried under vacuum.

[0038] The infrared spectrum of the Mn-Anderson type polyoxometalate modified with double amino group is as follows Figure 4 shown.

[0039] The nuclear magnetic spectrum of Mn-Anderson type polyoxometalate modified with double amino group is as follows Figure ...

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Abstract

The invention discloses a (R)-1-(1-phenethyl) thiourea modified Mn-Anderson type heteropolyacid catalyst as well as a preparation method and an application thereof. The preparation method comprises steps as follows: firstly, sodium molybdate and tetrabutylammonium bromide are subjected to a reaction to generate [N(C4H9)4]4[alpha-Mo8O26], [N(C4H9)4]4[alpah-Mo8O26] is subjected to a reaction with tris(hydroxymethyl)aminomethane and manganese acetate, and organic bilateral amino modified polyoxometallate is obtained; (R)-(+)-1-phenylethylamine is taken as a raw material to synthesize (R)-1-(1-phenethyl) isothiocyanic acid; finally, (R)-1-(1-phenethyl) isothiocyanic acid is subjected to a reaction with the organic bilateral amino modified polyoxometallate, and the target catalyst is obtained. The preparation method is simple, and reaction conditions are mild and environment friendliness is realized; the catalyst can be applied to asymmetric dihydroxylation of olefin, has the advantages of high enantioselectivity, high catalytic activity, recyclability and the like and is suitable for industrial production.

Description

technical field [0001] The invention belongs to the technical field of catalytic chemistry, in particular to asymmetric selective catalysis, specifically a (R)-1-(1-phenylethyl)thiourea-modified Mn-Anderson type heteropolyacid catalyst, a preparation method and its application. Background technique [0002] Professor Noyori, a Nobel Prize winner in 2001, pointed out: "Future synthetic chemistry must be economical, safe, environmentally friendly, and resource- and energy-saving chemistry. Chemists need to work hard to achieve 'perfect reaction chemistry', that is, Only the desired product is produced with 100% selectivity and 100% yield and no waste is generated". Chiral catalytic synthesis is one of the important ways to realize "perfect synthetic chemistry". Among them, chiral catalyst is the core scientific problem in the research of chiral catalysis. From the perspective of the reaction principle, chiral organic small molecule catalysis is to reversibly form an active i...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/16B01J27/19C07C29/04C07C33/26C07C33/46C07C41/26C07C43/23
CPCB01J27/19B01J31/0249B01J31/32B01J2231/32C07C29/04C07C33/26C07C33/46C07C41/26C07C43/23
Inventor 余焓戴国勇翟永彦茹诗韩生
Owner 上海元革新材料科技有限公司
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