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Mn-Anderson type heteropolyacid catalyst modified by (S)-1-(1-phenethyl) thiourea, and preparation method and application thereof

A technology of heteropolyacid and phenethyl group, which is applied in the field of catalytic chemistry, can solve the problems of high dosage, low catalyst activity, and difficult recycling, and achieve high catalytic activity, simple preparation method, and high enantioselectivity.

Active Publication Date: 2016-07-20
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

The invention solves the technical problems that the existing chiral organic small molecule catalyst has low activity, high dosage and difficult recycling

Method used

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  • Mn-Anderson type heteropolyacid catalyst modified by (S)-1-(1-phenethyl) thiourea, and preparation method and application thereof
  • Mn-Anderson type heteropolyacid catalyst modified by (S)-1-(1-phenethyl) thiourea, and preparation method and application thereof
  • Mn-Anderson type heteropolyacid catalyst modified by (S)-1-(1-phenethyl) thiourea, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Polyacid precursor [N(C 4 h 9 ) 4 ] 4 [α-Mo 8 o 26 ] preparation

[0030] 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

[0032] Preparation of (S)-1-(1-phenylethyl)isothiocyanate

[0033] 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 (S)-1-(1-phenylethyl)isothiocyanate. Yield 97%.

[0034] The NMR spectrum of (S)-1-(1-phenylethyl)isothiocyanate is shown in image 3 , the specific data are as follows:

[0035] 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

[0037] Preparation of Mn-Anderson Polyoxometalates Modified by Bilateral Amino Groups

[0038] 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.

[0039] The infrared spectrum of the Mn-Anderson type polyoxometalate modified with double amino group is as follows Figure 4 shown.

[0040] 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 Mn-Anderson type heteropolyacid catalyst modified by (S)-1-(1-phenethyl) thiourea, and a preparation method and application thereof. The preparation method comprises the following steps: firstly, reacting sodium molybdate and tetrabutylammonium bromide to generate [N(C4H9)4]4[alpha-Mo8O26], and then reacting [N(C4H9)4]4[alpha-Mo8O26] with tris(hydroxymethyl) aminomethane and manganese acetate to obtain organic bilateral amino-modified polyoxometallate; then with (R)-(+)-1-phenylethylamine as a raw material, synthesizing (S)-1-(1-phenethyl) isothiocyanate; and finally, reacting (S)-1-(1-phenethyl) isothiocyanate and organic bilateral amino-modified polyoxometallate to obtain the target catalyst. The preparation method is simple, and the reaction condition is mild and environmentally friendly; and the obtained catalyst is used for asymmetric dihydroxylation of olefin, has the advantages of high enantioselectivity, high catalytic activity, recoverability and the like and is applicable to industrial production.

Description

technical field [0001] The invention belongs to the technical field of catalytic chemistry, in particular to asymmetric selective catalysis, specifically a (S)-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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IPC IPC(8): B01J31/18B01J31/02C07B53/00C07C29/04C07C33/20C07C33/46C07C41/26C07C43/23
CPCB01J23/28B01J27/19B01J31/0271C07B53/00C07C29/04C07C41/26C07C33/20C07C33/46C07C43/23
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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