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

A technology of heteropolyacid and phenethyl, applied in the field of catalytic chemistry, can solve the problems of low catalyst activity, high dosage, difficult recycling and the like, and achieve the effects of high catalytic activity, high enantioselectivity and environmental friendliness

Active Publication Date: 2016-08-17
上海元革新材料科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The invention solves the technical problems of the existing chiral organic small molecule catalysts with low activity, high

Method used

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

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Cr-Anderson type heteropolyacid precursor (NH 4 ) 3 [Cr(OH) 6 Mo 6 o 18 ] preparation

[0036] Take 7.41g (6mmol) of ammonium molybdate and add it to 20mL of deionized water, stir well to obtain a clear liquid, then add concentrated nitric acid dropwise, and adjust the pH of the system to 4~5. Heat to boiling, maintain strong stirring, and start to slowly add 1.66 g (7 mmol) chromium nitrate solid, stir until a large amount of pink solid is produced, stop stirring, and let stand for 15-30 minutes. Suction filtration to obtain 5.26 g of pink crystalline solid material with a yield of 82%.

[0037] Parent (NH 4 ) 3 [Cr(OH) 6 Mo 6 o 18 ] for the infrared spectrum image 3 .

Embodiment 2

[0039] Preparation of (S)-1-(1-phenylethyl)isothiocyanate

[0040] Add (S)-(+)-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%.

[0041] The NMR spectrum of (S)-1-(1-phenylethyl)isothiocyanate is shown in Figure 4 . The specific data are as follows:

[0042] 1 H NMR (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

[0044] Preparation of Cr-Anderson Polyoxometalates Modified with One-side Amino Group

[0045] The above-obtained Anderson matrix (NH 4 ) 3 [Cr(OH) 6 Mo 6 o 18 ] 1.071g (1mmol) was dissolved in 10mL deionized water to obtain a light red clear liquid, and then 0.402g (3mmol) of trishydroxyaminomethane was slowly added. Then add the above system into the hydrothermal kettle and heat it to 140°C in the hydrothermal kettle. After 24 hours of reaction, add 4.83g of tetrabutylammonium bromide to the solution dissolved as above at 85°C, resulting in a large amount of pink The precipitate is the crude product, and the red liquid can be obtained by suction filtration, and the crystal is obtained after standing, which is the Cr-Anderson type polyacid [TBA] modified by organic one-sided amino group 3 {[CH 2 NH 2 C(CH 2 O) 3 ]CrMo 6 o 18 (OH) 3}.

[0046] The infrared spectrum of the Cr-Anderson type polyoxometalate modified with one side amino group is as follows: Figure 5...

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Abstract

The invention discloses an (S)-1-(1-phenethyl) thiourea-modified Cr-Anderson heteropolyacid catalyst, and a preparation method and an application thereof. The method comprises the following steps: firstly, reacting ammonium molybdate and chromic nitrate to generate Cr-Anderson heteropolyacid (NH4)3[Cr(OH)6Mo6O18]; carrying out hydrothermal reaction on the Cr-Anderson heteropolyacid and tris(hydroxymethyl)aminomethane in a hydrothermal kettle to obtain an organic unilateral amino-modified polyoxometallate; and with (S)-(+)-1-phenylethylamine as a raw material, synthesizing (R)-1-(1-phenethyl) isothiocyanic acid; and finally reacting (R)-1-(1-phenethyl) isothiocyanic acid and the organic unilateral amino-modified polyoxometallate to obtain the target heteropolyacid catalyst. The preparation method is simple; and the obtained heteropolyacid catalyst is applied to asymmetric dihydroxylation of olefin, is friendly to environment, can be recycled, has high enantioselectivity and high catalytic activity 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 (S)-1-(1-phenylethyl)thiourea-modified Cr-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 form an active ...

Claims

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Application Information

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IPC IPC(8): B01J31/16B01J27/19C07C29/48C07C33/26C07C33/46C07C41/26C07C43/23C07B53/00
CPCB01J27/19B01J31/0249B01J31/34B01J2231/70C07B53/00C07B2200/07C07C29/48C07C41/26C07C33/26C07C33/46C07C43/23
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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