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(S)-1-(2-hydroxyl-1-phenethyl)thiourea unilateral modified Fe-Anderson type heteropolyacid catalyst, preparation method and its application

A technology of heteropolyacid and phenethyl, applied in the field of Fe-Anderson type heteropolyacid catalyst and preparation, can solve the problems of expensive catalyst recycling and reuse, and achieves improved stereoselectivity, mild reaction conditions and high enantioselectivity. The effect of sex catalysis

Inactive Publication Date: 2017-03-22
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

While expecting to achieve high catalytic activity and high enantioselective catalysis, it can also solve the problems of expensive catalysts and recycling

Method used

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  • (S)-1-(2-hydroxyl-1-phenethyl)thiourea unilateral modified Fe-Anderson type heteropolyacid catalyst, preparation method and its application
  • (S)-1-(2-hydroxyl-1-phenethyl)thiourea unilateral modified Fe-Anderson type heteropolyacid catalyst, preparation method and its application
  • (S)-1-(2-hydroxyl-1-phenethyl)thiourea unilateral modified Fe-Anderson type heteropolyacid catalyst, preparation method and its application

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Experimental program
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Effect test

Embodiment 1

[0033] Fe-Anderson type heteropolyacid precursor (NH 4 ) 3 (H 2 O) 6 [FeMo 6 o 18 (OH) 6 ]·25H 2 Preparation of O

[0034] Take 15.9g (12.9mmol) ammonium molybdate and add it to 250ml deionized water, stir well to obtain a transparent liquid, then add concentrated hydrochloric acid dropwise to adjust the pH of the system to 2-4. Heat to boiling, slowly add 3.2g (9.3mmol) ferric sulfate solid, stir for 1h, a small amount of solid is produced, stop stirring, and suction filter while it is hot to obtain a brownish-red liquid, place it at room temperature, let it stand for 48h, recrystallize once, A white solid (NH 4 ) 3 (H 2 O) 6 [FeMo 6 o 18 (OH) 6 ]·25H 2 O, the yield is 80.3%.

[0035] Parent (NH 4 ) 3 (H 2 O) 6 [FeMo 6 o 18 (OH) 6 ]·25H 2 The infrared spectrum of O is as figure 2 shown.

Embodiment 2

[0037] Preparation of (S)-1-(2-hydroxy-1-phenylethyl)isothiocyanate

[0038] Add L-phenylglycinol (5mmol) to a dry reaction vessel, dissolve it with 20mL of alcohol, 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 0.7451 g (S)-1-(2-hydroxy-1-phenethyl)isothiocyanate. The yield was 91.3%.

[0039] The nuclear magnetic spectrum data of (S)-1-(2-hydroxyl-1-phenylethyl) isothiocyanate is as follows image 3 shown.

[0040] 1H NMR (501MHz, CDCl3) δ8.09(s, 1H), 7.28–7.01(m, 5H), 4.60(t, J=8.8Hz, 1H), 4.29(dt, J=14.1, 6.8Hz, 2H) ,2.86(t,J=7.5Hz,2H).

Embodiment 3

[0042] Preparation of Fe-Anderson Polyoxometalates Modified with One-side Amino Group

[0043] Take 1.5g (1mmol) parent (NH 4 ) 3 (H 2 O) 6 [FeMo 6 o 18 (OH) 6 ]·25H 2 O was dissolved in 10ml deionized water, and after stirring to obtain a light yellow solution, slowly added 0.2g (1.9mmol) trishydroxymethylaminomethane, heated to reflux, and after the reaction was carried out for 24h, 0.9g (3.0mmol) TBAB Add it into the reaction system, and immediately get a large amount of slightly yellow precipitate, that is, the crude product, and filter it with suction to get a light yellow liquid, and place it to get crystals, that is, Fe-Anderson polyacid [TBA] 3 {[NH 2 C(CH 2 O) 3 ]FeMo 6 o 18 (OH) 3}.

[0044] The infrared spectrum of the Fe-Anderson type polyoxometalate modified with one side amino group is as follows: Figure 4 shown.

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Abstract

The invention discloses a (S)-1-(2-hydroxyl-1-phenethyl)thiourea unilateral modified Fe-Anderson type heteropolyacid catalyst, a preparation method and its application. The method comprises the steps that under the acidic condition, ammonium molybdate reacts with ferric sulfate to generate a Fe-Anderson type heteropolyacid matrix; the obtained heteropolyacid matrix reacts with tris(hydroxymethyl)methyl aminomethane under the reflux condition to obtain amino unilateral modified Fe-Anderson type polyoxometallate; then, (S)-1-(2-hydroxyl-1-phenethyl)isothiocyanate is synthesized; at last, polyoxometallate is utilized for reacting with (S)-1-(2-hydroxyl-1-phenethyl)isothiocyanate to obtain a target compound. Accordingly, the preparation method is simple, the yield is high, the reaction condition is mild, and environmental friendliness is achieved; the catalyst is used for an oxidation coupling reaction of primary amine and is environmentally friendly, efficient and easy to recycle.

Description

technical field [0001] The present invention relates to the technical field of catalysis, especially the field of asymmetric selective catalysis, in particular to (S)-1-(2-hydroxyl-1-phenylethyl)thiourea unilaterally modified Fe-Anderson type heteropolyacid catalyst , preparation method and application thereof. Background technique [0002] Catalysis is the most promising and practical research direction in the application of polyoxometalates. Polyoxometallates combine the excellent properties of acid-base catalysts, redox catalysts, and metal oxide nanocatalysts, and are considered to be green multifunctional catalysts with wide applications. Since chiral polyoxometalates were successfully synthesized, people began to explore chiral polyacids in the field of asymmetric catalysis. Chiral polyoxometalates combine the excellent properties of polyacids and chiral materials. Its unique soluble mineral-like metal-oxide structure provides an ideal model for the theory of the or...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/16B01J27/19C07C249/02C07C251/24
CPCB01J31/34B01J27/19C07C249/02C07C251/24
Inventor 翟永彦余焓韩生何慧红李亮祝俊
Owner SHANGHAI INST OF TECH