Unlock instant, AI-driven research and patent intelligence for your innovation.

Catalyst use of triethylenediamine in catalyzing the reaction of aromatic aldehydes and nitrohydrocarbons to generate nitroaromatic alcohols

A technology of nitrohydrocarbon reaction and nitroaromatic alcohol, applied in the direction of physical/chemical process catalyst, organic compound/hydride/coordination complex catalyst, preparation of organic compound, etc., can solve the problem of nitroaromatic alcohol Problems such as amide compounds, to achieve the effect of high product yield, low price and high yield

Active Publication Date: 2017-05-10
XIHUA UNIV
View PDF1 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0032] There is also no report that nitroaromatic alcohols prepared by catalysis such as triethylenediamine are directly used for the preparation of amides without purification.

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Catalyst use of triethylenediamine in catalyzing the reaction of aromatic aldehydes and nitrohydrocarbons to generate nitroaromatic alcohols
  • Catalyst use of triethylenediamine in catalyzing the reaction of aromatic aldehydes and nitrohydrocarbons to generate nitroaromatic alcohols
  • Catalyst use of triethylenediamine in catalyzing the reaction of aromatic aldehydes and nitrohydrocarbons to generate nitroaromatic alcohols

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0093] Embodiment 1 The inventive method prepares nitroaromatic alcohol

[0094] The synthetic route is as follows:

[0095]

[0096] Add p-fluorobenzaldehyde (126mg, 1mmol), nitromethane (214μL, 4mmol) and triethylenediamine (110mg, 0.5mmol) into the reaction flask, add 2mL of acetonitrile and stir well, react at 0°C for 24 hours, reduce The solvent was distilled off under pressure, and silica gel column chromatography (PE:EA=10:1) gave 177.7 mg of a yellow oily product with a yield of 95%.

[0097] 1 H NMR (400MHz, CDCl 3), δ: 7.37-7.42(m, 2H), 7.09-7.06(m, 2H), 5.43-5.40(m, 1H), 4.51-4.58(dd, J=13.2, 9.8Hz, 2H), 3.17(d , J=3.8Hz, 1H). High-resolution mass spectrometry, the molecular formula is: C 8 h 8 FNO 3 +H + , Theoretical molecular weight: 186.0488, detected molecular weight: 186.0489.

Embodiment 2

[0098] Embodiment 2 The inventive method prepares nitroaromatic alcohol

[0099] The synthetic route is as follows:

[0100]

[0101] Add 2-thiophenecarbaldehyde (112mg, 1mmol), nitromethane (214μL, 4mmol) and triethylenediamine (110mg, 0.5mmol) into the reaction flask, add 2mL of acetonitrile and stir well, react at 0°C for 24 hours, reduce The solvent was distilled off under pressure, and silica gel column chromatography (PE:EA=10:1) gave 136.7 mg of a yellow oily product with a yield of 79%.

[0102] 1 H-NMR (300MHz, CDCl 3 ,d ppm) δ: 3.10(br s,1H),4.34(dd,J=3.6,13.2Hz,1H),4.56(dd,J=9.6,13.2Hz,1H),5.48(dd,J=9.6, 3.6Hz, 1H), 7.02 (t, J = 8.1Hz, 1H), 7.48 (d, J = 8.4Hz, 1H), 7.88 (d, J = 8.4Hz, 1H). High-resolution mass spectrometry, the molecular formula is: C 6 h 7 NO 3 S+H + , Theoretical molecular weight: 174.0225, detected molecular weight: 174.0230.

Embodiment 3

[0103] Embodiment 3 The inventive method prepares nitroaromatic alcohol

[0104] The synthetic route is as follows:

[0105]

[0106] Add p-tolualdehyde (120mg, 1mmol), nitromethane (214μL, 4mmol) and triethylenediamine (110mg, 0.5mmol) into the reaction flask, add 2mL of acetonitrile and stir well, react at 0°C for 24 hours, and reduce pressure The solvent was distilled off, and silica gel column chromatography (PE:EA=10:1) gave 161.1 mg of a yellow oily product with a yield of 89%.

[0107] 1 H-NMR (300MHz, CDCl 3 ,d ppm)δ: 2.37(s,3H),3.41(brs,1H),4.39(dd,J=3.9,13.2Hz,1H),4.63(dd,J=9.0,13.2Hz,1H),5.29( dd, J=9.0, 3.9 Hz, 1H), 7.29 (d, J=9.0 Hz, 2H), 7.45 (d, J=9.0 Hz, 2H). High-resolution mass spectrometry, the molecular formula is: C 9 h 11 NO 3 +H + , Theoretical molecular weight: 182.0817, detected molecular weight: 182.0821.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention discloses new application of triethylene diamine, potassium tert-butoxide, triethylamine, diethylamine or sodium ethoxide, specifically application as a catalyst in catalyzing reaction of aromatic aldehyde and nitro-hydrocarbon to generate nitryl aromatic alcohol. The catalyst involved in the invention is significantly different from the catalysts for preparation of nitryl aromatic alcohol in the prior art, and has the advantages of simple structure, convenience and easy availability, low price, and high product yield. Particularly, when triethylene diamine is adopted as the catalyst, the yield of nitryl aromatic alcohol preparation with triethylene diamine as the catalyst can reach more than 95%. The triethylene diamine catalyst has the advantages of simple operation, low cost and the like, and has good industrial application prospects.

Description

technical field [0001] The invention relates to the catalyst use of triethylenediamine, potassium tert-butoxide, triethylamine, diethylamine or sodium ethylate in catalyzing the reaction of aromatic aldehydes and nitrohydrocarbons to generate nitroaromatic alcohols. Background technique [0002] Nitroaromatic alcohol is an important raw material for the preparation of pharmaceutical intermediate amides, which is mainly prepared by aromatic aldehydes and nitrohydrocarbons under the action of catalysts. [0003] Claudio Palomo et al. (Eur.J.Org.Chem.2007, 2561–2574) reviewed the preparation methods of nitroaromatic alcohols. According to different catalysts, the preparation methods mainly include the following: [0004] (1) Using Hydroxynitrile lyase as a catalyst to catalyze the reaction between RCHO and nitrohydrocarbons, the reaction conditions: pH=7, room temperature, 48 hours, the yield is 25-77%; [0005] (2) by (molar ratio): La(OTf) 3 (1) / L-2(3) (the structure formul...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/02C07C205/16C07C201/12C07D333/16
Inventor 王周玉何涛艾文思蒋珍菊马小波徐志宏
Owner XIHUA UNIV