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(S)-1-(1-hydroxyethyl-1-isopropyl) thiourea modified Mn-Anderson type heteropoly acid catalyst, and preparation method and application thereof

An isopropyl and heteropolyacid technology, 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, environmental friendliness 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

AI Technical Summary

Problems solved by technology

The invention solves the technical problems of the existing chiral organic small molecule catalysts such as low activity, high dosage and difficult recycling, and at the same time, starting from the design idea of ​​organic small molecule catalysts, it innovatively proposes the use of "acid-base" synergistic catalytic strategy , using chiral small organic molecules with potential catalytic activity as precursors, through organic modification and other methods, skillfully combine small organic molecules with high Bronsted acidic vacant polyanions to construct chiral polyacid catalysts

Method used

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  • (S)-1-(1-hydroxyethyl-1-isopropyl) thiourea modified Mn-Anderson type heteropoly acid catalyst, and preparation method and application thereof
  • (S)-1-(1-hydroxyethyl-1-isopropyl) thiourea modified Mn-Anderson type heteropoly acid catalyst, and preparation method and application thereof
  • (S)-1-(1-hydroxyethyl-1-isopropyl) thiourea modified Mn-Anderson type heteropoly acid catalyst, and preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Polyacid precursor [N(C 4 h 9 ) 4 ] 4 [α-Mo 8 o 26 ] preparation

[0035] In a 50mL flask, Na 2 MoO 4 2H 2 O5.00g (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.

[0036] The clarity of the crystals is lost as they dry. Yield 3.58...

Embodiment 2

[0038] Preparation of (S)-1-(1-hydroxyethyl-1-isopropyl)isothiocyanate

[0039] Add L-valinol (0.7560g, 5mmol) to the dry reaction vessel, dissolve it with 20mL ethanol, 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 0.7818 g (S)-1-(1-hydroxyethyl-1-isopropyl)isothiocyanate. The yield was 80.9%.

[0040] The NMR spectrum of (S)-1-(1-hydroxyethyl-1-isopropyl)isothiocyanate is shown in image 3 , the specific data are as follows:

[0041] 1 HNMR (501MHz, CDCl 3 )δ8.17(s, 1H), 4.62(t, J=9.1Hz, 1H), 4.32(t, J=7.8Hz, 1H), 3.78(d, J=7.4Hz, 1H), 1.86–1.71( m,1H),0.89(dd,J=24.8,6.7Hz,6H).

Embodiment 3

[0043] Preparation of Mn-Anderson Polyoxometalates Modified by Bilateral Amino Groups

[0044] 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.

[0045] The infrared spectrum of the Mn-Anderson type polyoxometalate modified with double amino group is as follows Figure 4 shown.

[0046] 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 (S)-1-(1-hydroxyethyl-1-isopropyl) thiourea modified Mn-Anderson type heteropoly acid catalyst, and a preparation method and an application thereof. The preparation method comprises the following steps: causing sodium molybdate react with tetrabutylammonium bromide to generate [N(C4H9)4]4[alpha-Mo8O26]; causing [N(C4H9)4]4[alpha-Mo8O26] react with trihydroxyamino methane and manganese acetate, thereby acquiring an organic bilateral amino-modified polyoxometallate; synthesizing (S)-1-(1-hydroethyl-1-isopropyl) isothiocyanic acid from L-valinol; lastly, causing (S)-1-(1-hydroethyl-1-isopropyl) isothiocyanic acid react with the organic bilateral amino-modified polyoxometallate, thereby acquiring a target catalyst. The preparation method provided by the invention is mild in reaction condition and is environmentally friendly; applied to the olefin asymmetric double-hydroxylation reaction, the acquired catalyst has high catalytic activity and high corresponding selectivity; the catalyst is recyclable and is fit for industrial production.

Description

technical field [0001] The invention belongs to the technical field of catalytic chemistry, in particular to asymmetric selective catalysis, specifically (S)-1-(1-hydroxyethyl-1-isopropyl)thiourea-modified Mn-Anderson type heteropolyacid catalyst , preparation method and application thereof. 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 fo...

Claims

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Application Information

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IPC IPC(8): B01J31/16C07C33/26C07C33/46C07C29/48C07C43/23C07C41/26
CPCY02P20/584B01J31/0228B01J27/188B01J2231/70C07C29/48C07C41/26C07C33/26C07C33/46C07C43/23
Inventor 余焓戴国勇茹诗翟永彦韩生
Owner 上海元革新材料科技有限公司
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