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Synthesis method and application of cage compounds

A clathrate compound and synthesis method technology, applied in the field of catalysis, can solve the problems of accelerating the oxidation rate of petroleum distillate, large amount of solvent medium, low yield of petroleum sulfoxide, etc., and achieve simple post-treatment process, simple preparation method, and product purity high effect

Inactive Publication Date: 2016-12-07
FUZHOU UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Patent (CN 105017100A) adopts H 2 o 2 As oxidizing agent, MnSO 4 It is used as a catalyst to catalyze the oxidation of crude oil sulfide into sulfoxide compounds. This oxidation system can accelerate the oxidation rate of petroleum fractions and can effectively avoid excessive oxidation, but the yield of petroleum sulfoxide obtained is low
Patent (CN 85100440A) used in acetic anhydride medium, at room temperature and N 2 Under protection, use 30% hydrogen peroxide as oxidant and concentrated sulfuric acid as catalyst to quantitatively oxidize alkyl (or aryl) sulfides to sulfoxides. The resulting sulfoxides have high yield and high purity, but the amount of solvent medium is large

Method used

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  • Synthesis method and application of cage compounds
  • Synthesis method and application of cage compounds

Examples

Experimental program
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Effect test

Embodiment 1

[0029] Example 1. Synthesis of Ni(II)-Salen(CHO) ligand with catalytic function

[0030] 1) Add 3.84 g of 5-bromo-3-tert-butyl salicylaldehyde and 0.45 g of ethylenediamine to a 100 mL three-necked flask in sequence, then add 70 mL of ethanol, and react at 70 °C for 24 h under the protection of an inert gas. After cooling to 15 °C, the reaction solution was concentrated to 20 mL by rotary evaporator at 40 °C, and then allowed to stand at -30 °C for 3 h, suction filtered with a Buchner funnel, and the filter cake was washed with 10 mL ice ethanol After 5 passes, the filter cake was collected to obtain 3.46 g of the Salen(Br) ligand, with a yield of 86%. 1 H NMR (CDCl 3 , 400MHz) δ(ppm): 1.41[s, 18 H, C(CH 3 ) 3 ], 3.94(s, 4H), 7.20(s, 2H), 7.37(s, 2H), 8.29(d, J=1.6 Hz, 2H), 13.82(s, 2H, OH);

[0031] 2) Add 3.0 g Salen(Br) ligand, 1.53 g Ni(OAc) to a 100 mL three-necked flask in sequence 2 4H 2 O and 60mL chloroform / methanol (1:1, v:v) solution, and then reacted at 85 °C...

Embodiment 2

[0033] Embodiment 2. Synthesis of Ni(II)-Salen(CHO) ligand with catalytic function

[0034] 1) Add 3.84 g of 5-bromo-3-tert-butyl salicylaldehyde and 0.45 g of ethylenediamine to a 250 mL three-necked flask in sequence, then add 150 mL of ethanol, and react at 100 °C for 12 h under the protection of an inert gas. After cooling to 30 °C, the reaction solution was concentrated to 10 mL by rotary evaporator at 70 °C, then allowed to stand at -5 °C for 5 h, suction filtered with a Buchner funnel, and the filter cake was washed with 20 mL of ice ethanol for 3 After several times, the filter cake was collected to obtain 3.37 g of Salen(Br) ligand, the yield of which was 84%. 1 H NMR (CDCl 3 , 400MHz) δ(ppm): 1.43[s, 18 H, C(CH 3 ) 3 ], 3.92(s, 4H), 7.18(s, 2H), 7.35(s, 2H), 8.29(d, J=1.6 Hz, 2H), 13.80(s, 2H, OH);

[0035] 2) Add 3.0 g of Salen(Br) ligand and 1.50 g of NiCl to a 100 mL three-necked flask in sequence 2 ·6H 2 O and 60 mL of dichloromethane / methanol (1:1, v:v) so...

Embodiment 3

[0037] Example 3. Synthesis of cage compounds

[0038] Dissolve 200 mg Ni(II)-Salen(CHO) in tetrahydrofuran, add 13.8 μL tris(2-aminoethyl)amine under nitrogen atmosphere, heat and reflux for 8 h, and remove the solvent by rotary evaporation after the reaction is complete, the obtained solid After washing with methanol and drying in vacuo, 178 mg of the clathrate compound was obtained with a yield of 81%, and its single crystal was obtained by recrystallization. High resolution mass spectrometry (HR-MS, ESI): [C 126 h 138 N 10 o 6 Ni] + m / z calculated: 2120.9075; experimental: 2120.8988.

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Abstract

The invention discloses a synthesis method and application of cage compounds. The cage compounds is Schiff base compounds prepared by carrying out amine-aldehyde condensation on a didentate Ni(II) Salen-(R1-R1) ligand and tridentate tri(2-R2-ethyl)amines. The Ni(II) Salen-(R1-R1) ligand is prepared by the following steps: carrying out reaction on brominated salicylaldehyde and ethylenediamine to synthesize a Salen ligand, adding a nickelous salt to carrying out coordination so as to obtain a Ni(II) Salen catalyst, and finally, adding p-formacyl phenylboronic acid to carry out coupling. The obtained cage compounds can be used for catalyzing the oxidization of thioanisole, ethyl phenyl sulfide, dibutyl sulfide, dibenzyl sulfide and other thioethers at higher activity and selectivity to generate sulfoxide products.

Description

technical field [0001] The invention belongs to the technical field of catalysis, and in particular relates to a synthesis method of a three-dimensional cage compound and its application in catalyzing the oxidation of sulfide to sulfoxide. Background technique [0002] As an important intermediate, sulfoxide compounds are widely used in fine chemical industry, medicine, pesticide, synthetic fiber, plastic, printing and dyeing, rare metal extractant, organic synthesis and other industries. Synthetic sulfoxide is usually obtained by oxidizing sulfoxide, but during the oxidation process, sulfoxide can be further oxidized into sulfone, which will affect the yield and purity of sulfoxide. For example, the Chinese patent (CN 102070498A) uses 98% concentrated sulfuric acid as a catalyst, saturated ketone or hydroxylamine as a cocatalyst, and 30% hydrogen peroxide as an oxidant to catalyze the oxidation of sulfides to sulfoxide products, and the yield of oxidized aromatic hydrocarbo...

Claims

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Application Information

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IPC IPC(8): C07C249/02C07C251/24B01J31/22C07C315/02C07C317/14C07C317/04C07C317/22
CPCB01J31/2217B01J2231/70B01J2531/0213B01J2531/0241B01J2531/847C07C249/02C07C315/02C07C251/24C07C317/14C07C317/04C07C317/22
Inventor 鲍晓军白正帅徐霜霜岳源源
Owner FUZHOU UNIVERSITY
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