Preparation and application of DMAP hydrochloride as catalyst of recoverable acylation reaction

A technology of hydrochloride and acylation is applied in the field of preparation and application of DMAP hydrochloride as a recyclable acylation catalyst, which can solve the problems of inapplicability of acylation reagents and damage to the structure.

Active Publication Date: 2015-03-18
NANKAI UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, they are not suitable for strongly acidic acylating reagents such as acid chlorides. Since the reaction will release strong acids such as hydrogen chloride, the catalyst may form new salts with strong acids and destroy the original structure.

Method used

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  • Preparation and application of DMAP hydrochloride as catalyst of recoverable acylation reaction
  • Preparation and application of DMAP hydrochloride as catalyst of recoverable acylation reaction
  • Preparation and application of DMAP hydrochloride as catalyst of recoverable acylation reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Embodiment 1: the synthesis of DMAP hydrochloride:

[0019] Add 30 mL of toluene and 5.0 g (40.9 mmol) of DMAP into a 100 mL round-bottomed flask, and stir it electromagnetically to dissolve it. 2.92 g (80 mmol) of dry HCl gas was introduced into the system, and a white solid precipitated out of the system immediately. React at room temperature for 1 h, filter with suction, and dry in vacuo to obtain 6.28 g of white solid, yield 96.9%, melting point: 220—221°C. 1 H NMR (400MHz, CDC13) δ15.45(br, 1H), 8.14(t, J=6.8Hz, 2H), 6.78(d, J=6.8Hz, 2H), 3.27(s, 6H). 13 C NMR (100MHz, CDCl 3 )δ138.6, 106.8, 40.3.

Embodiment 2

[0020] Embodiment 2: the pivaloylation reaction of 1-cyano cyclohexanol:

[0021] Add 2.50 g (20 mmol) of 1-cyanocyclohexanol, 0.16 g (1 mmol) of DMAP hydrochloride and 2.64 g (22 mmol) of pivaloyl chloride into a 10 mL single-necked bottle. Control the reaction temperature to 110° C., react for 4 hours, and cool the reaction system to room temperature. Add 20 mL of n-hexane to the reaction system, filter and recover the catalyst, dry it in vacuum and put it into the next cycle. The filtrate was washed with 20mL water, 20mL saturated sodium bicarbonate, 15mL saturated brine, MgSO 4 Drying, precipitation under reduced pressure, and flash column chromatography yielded 3.97 g of a colorless oily product, with a yield of 95.0%. 1 H NMR (400MHz, CDCl 3 ( s, 9H).

Embodiment 3

[0022] Embodiment 3: the benzoylation reaction of o-nitrophenol:

[0023] Add 2.78g (20mmol) of o-nitrophenol, 20mL of toluene, 0.16g (1mmol) of DMAP hydrochloride and 4.52g (22mmol) of benzoic anhydride in a 50mL single-necked bottle. Control the reaction temperature to 60° C., react for 4 hours, and cool the reaction system to room temperature. Add 20 mL of n-hexane to the reaction system, filter and recover the catalyst, dry it in vacuum and put it into the next cycle. The filtrate was washed with 20mL water, 20mL saturated sodium bicarbonate, 15mL saturated brine, MgSO 4 Drying, desolvation under reduced pressure, and flash column chromatography yielded 4.67 g of the product as a pale yellow oil, with a yield of 96.1%. 1 H NMR (400MHz, CDCl 3 )δ8.25—8.18 (m, 2H), 8.16 (dd, J=8.0, 1.6Hz, 1H), 7.75—7.66 (m, 2H), 7.54 (t, J=7.6Hz, 2H), 7.48—7.43 (m, 1H), 7.43—7.37 (m, 1H).

[0024] The following acylation products can be synthesized by the same method, see Table 1 and Ta...

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Abstract

The present invention relates to an application of dimethylaminopyridine (DMAP) hydrochloride serving as recyclable catalyst in an acylation reaction (as represented by equation I). The application comprises: dissolving DMAP into a nonpolar solvent, aerating with dry hydrogen chloride gas, and filtrating the solution to obtain DMAP hydrochloride; adding a catalytic amount of DMAP hydrochloride to inert alcohol, phenol and amine under a solvent-free or organic solvent condition, and completely reacting with an acylation reagent at 0-130 ℃; adding a nonpolar solvent, and filtrating the recyclable catalyst, that is, the DMAP hydrochloride; and conducting washing, caustic scrubbing, liquid separation and organic phase drying on the filtrate, and evaporating and removing the solvent to obtain the acylated product. The recycled DMAP hydrochloride can be used in the next catalytic cycle.

Description

technical field [0001] The present invention relates to the preparation and application of DMAP hydrochloride as a recyclable acylation catalyst. Background technique [0002] DMAP is a commonly used catalyst for acylation reactions, and its loading and recovery have been extensively reported. Its main method has: DMAP loads in polymer material, obtains soluble DMAP derivative, but is difficult to realize the recovery of catalyst (see literature: 1.Price, K.E.; Mason, B.P.; Bogdan, A.R.; et al.J. Am.Chem.Soc.2006, 128, 10376—10377.2.Liang, C.O.; Helms, B.; Hawker, C.J.; et al.Chem.Commun2003, 2524—2525.); Silica gel and polymer-loaded heterogeneous DMAP catalyst, but its catalytic activity is often greatly reduced (see literature: 1.Chen, H.-T.; Huh, S.; Wiench, J.W.; et al.J.Am.Chem.Soc. .Yuang, J.-H.; Shi, M.Adv.Synth.Catal.2003, 345,953—955.3.Corma, A.; Garcia, H.; Leyva, A.Chem.Commun 2003,2806—2807.) . In recent years, new polymer-loaded highly active and easily rec...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C255/46C07C253/30C07C205/43C07C201/12C07C67/08C07C67/14C07C69/63C07C69/78C07C69/14C07C69/157C07C69/757C07C69/67C07D311/52C07D215/22C07C233/92C07C231/02C07D213/64C07D233/90B01J31/02C07D213/74
CPCC07C231/08C07D311/52C07C2103/74C07D213/74C07C205/43C07D215/22C07C201/12C07C269/04B01J31/02C07C233/92C07C253/30C07C67/14C07C67/08C07D213/64C07C231/02C07C2101/14C07C255/46C07D233/90Y02P20/584B01J31/0239B01J31/0244C07C2601/14C07C2603/74C07C271/44C07C69/63C07C69/78C07C69/14C07C69/157C07C69/75C07C69/704C07C69/24
Inventor 汪清民刘智慧马巧巧姜育田季玉祥赵卫东
Owner NANKAI UNIV
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