(s)-1-(1-hydroxyethyl-1-isopropyl) thiourea-modified cr-anderson type heteropolyacid catalyst, preparation method and application thereof

A technology of isopropyl and hydroxyethyl, which is applied in the preparation of hydroxyl addition, catalytic reaction, chemical instruments and methods, etc., can solve the problems of high dosage, low catalyst activity, and difficulty in recycling, etc. High enantioselectivity and environmentally friendly effect

Active Publication Date: 2018-04-13
上海元革新材料科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

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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  • (s)-1-(1-hydroxyethyl-1-isopropyl) thiourea-modified cr-anderson type heteropolyacid catalyst, preparation method and application thereof
  • (s)-1-(1-hydroxyethyl-1-isopropyl) thiourea-modified cr-anderson type heteropolyacid catalyst, preparation method and application thereof
  • (s)-1-(1-hydroxyethyl-1-isopropyl) thiourea-modified cr-anderson type heteropolyacid catalyst, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Cr-Anderson type heteropolyacid precursor (NH 4 ) 3 [Cr(OH) 6 Mo 6 o 18 ] preparation

[0032] 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%.

[0033] Parent (NH 4 ) 3 [Cr(OH) 6 Mo 6 o 18 ] The infrared spectrum of image 3 shown.

Embodiment 2

[0035] Preparation of (S)-1-(1-hydroxyethyl-1-isopropyl)isothiocyanate

[0036] Add (R)-(+)-1-(2-naphthyl)ethylamine (0.8562g, 5mmol) into a dry reaction vessel, dissolve it in 20mL of 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 0.8448 g (R)-1-(2-(naphthyl)ethyl)isothiocyanate. The yield was 79.6%.

[0037] The nuclear magnetic spectrum of (S)-1-(1-hydroxyethyl-1-isopropyl) isothiocyanate is as follows Figure 4 As shown, the specific data are as follows:

[0038] 1 H NMR (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,1...

Embodiment 3

[0040] Preparation of Cr-Anderson Polyoxometalates Modified with One-side Amino Group

[0041] 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 a hydrothermal kettle, heat it to 140°C, and react for 24 hours, then add 4.83g of tetrabutylammonium bromide into the above solution at 85°C, a large amount of pink precipitates are produced, which is the crude product. Filter to get a red liquid, place it to get crystals, which is the organic one-side amino modified Cr-Anderson polyacid [TBA] 3 {[NH 2 C(CH 2 O) 3 ]CrMo 6 o 18 (OH) 3}.

[0042] 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 a Cr-Anderson type heteropolyacid catalyst modified by (S)-1-(1-ethoxyl-1-isopropyl) thiourea, and a preparation method and application thereof. The preparation method comprises the following steps: firstly, reacting ammonium molybdate and chromic nitrate to generate Cr-Anderson type heteropolyacid (NH4)3[Cr(OH)6Mo6O18], and then carrying out hydrothermal reaction on Cr-Anderson type heteropolyacid (NH4)3[Cr(OH)6Mo6O18] and tris(hydroxymethyl) aminomethane, thereby obtaining organic unilateral amino-modified polyoxometallate; then with L-valinol as a raw material, synthesizing (S)-1-(1-ethoxyl-1-isopropyl) isothiocyanate; and finally, reacting (S)-1-(1-ethoxyl-1-isopropyl) isothiocyanate and organic unilateral amino-modified polyoxometallate to obtain the target catalyst. The preparation process has mild and environmental-friendly conditions; and the obtained catalyst has the advantages of high catalytic activity, high enantioselectivity and recoverability.

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 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 f...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/12C07C29/03C07C33/26C07C41/26C07C43/23C07C33/46
CPCB01J31/12B01J2231/32C07C29/03C07C41/26C07C33/26C07C43/23C07C33/46
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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