Preparation method of large-steric-hindrance alkyl substituted phosphite diester

A phosphinic acid diester and large steric hindrance technology, which is applied in chemical instruments and methods, compounds of Group 5/15 elements of the periodic table, organic chemistry, etc., can solve the problems that waste will pollute the environment and have little improvement. , to achieve the effect of easy operation and good theoretical research value

Active Publication Date: 2020-03-27
WENZHOU UNIVERSITY
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Problems solved by technology

Although the use of alcohols instead of halogenated hydrocarbons has certain advantages, there are still key shortcomings in these methods that have not been overcome. For example, these methods are limited to primary alcohols and are not suitable for large sterically hindered secondary alcohols and tertiary alcohols. ZnBr

Method used

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  • Preparation method of large-steric-hindrance alkyl substituted phosphite diester
  • Preparation method of large-steric-hindrance alkyl substituted phosphite diester
  • Preparation method of large-steric-hindrance alkyl substituted phosphite diester

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Synthesis of (diphenyl)methylphosphonite diethyl from benzhydryl alcohol and triethyl phosphite

[0026]

[0027] Add benzhydryl alcohol (0.0921g, 0.5mmol) in the tubular reactor, replace nitrogen three times, add triethyl phosphite (0.1715ml, 2.0equiv.), TMSOTf (0.0181ml, 20mol%) under the protection of nitrogen, Then react at 100°C for 24h under stirring. After the complete reaction was monitored by TLC, the product was separated and purified by column chromatography, and the separation yield was 82%. 1 H NMR (500MHz, CDCl 3 )δ7.53 (d, J = 7.0Hz, 4H), 7.29 (t, J = 7.0Hz, 4H), 7.25–7.17 (m, 2H), 4.43 (d, J = 25.0Hz, 1H), 4.12– 3.67(m,4H),1.09(t,J=6.9Hz,6H). 13 C NMR (126MHz, CDCl 3 )δ136.90(d, J=5.2Hz), 129.47(d, J=8.0Hz), 128.56, 127.11(d, J=1.6Hz), 62.62(d, J=7.0Hz), 51.35(d, J =138.2Hz), 16.22(d, J=5.8Hz). 31 P NMR (202MHz, CDCl 3 )δ25.10.

Embodiment 2

[0029] Synthesis of Diethyl (2-Methyldiphenyl)methylphosphonite from 2-Methylbenzhydryl Alcohol and Triethyl Phosphite

[0030]

[0031] Add 2-methylbenzhydrin (0.0991g, 0.5mmol) into the tubular reactor, replace the nitrogen three times, add triethyl phosphite (0.1715ml, 2.0equiv.), TMSOTf (0.0181ml, 20mol%), and then reacted at 100°C for 24h under stirring. After the complete reaction was monitored by TLC, the product was separated and purified by column chromatography, and the separation yield was 87%. 1 H NMR (500MHz, CDCl 3 )δ7.96(d, J=7.5Hz,1H),7.47(d,J=6.9Hz,2H),7.31–7.07(m,6H),4.67(d,J=26.0Hz,1H),4.04– 3.73(m,4H),2.32(s,3H),1.10(dt,J=17.0,7.0Hz,6H). 13 C NMR (126MHz, CDCl 3 )δ136.43(s), 136.37(d, J=6.9Hz), 135.34(d, J=3.8Hz), 130.61, 129.80(d, J=7.5Hz), 129.50(d, J=5.3Hz), 128.43, 127.12, 126.97, 126.20, 62.57(dd, J=15.9, 7.0Hz), 46.69(d, J=139.4Hz), 19.99, 16.23(t, J=5.1Hz). 31 P NMR (202MHz, CDCl 3 )δ25.95.

Embodiment 3

[0033] Synthesis of Diethyl (4-Methyldiphenyl)methylphosphonite from 4-Methylbenzhydryl Alcohol and Triethyl Phosphite

[0034]

[0035]Add 4-methylbenzhydrin (0.0991g, 0.5mmol) into the tubular reactor, replace the nitrogen three times, add triethyl phosphite (0.1715ml, 2.0equiv.), TMSOTf (0.0181ml, 20mol%), and then reacted at 100°C for 24h under stirring. After the completion of the reaction was monitored by TLC, the product was separated and purified by column chromatography, and the separation yield was 85%. 1 H NMR (500MHz, CDCl 3 )δ7.51(d, J=7.7Hz, 2H), 7.41(d, J=6.8Hz, 2H), 7.29(t, J=7.6Hz, 2H), 7.21(t, J=7.3Hz, 1H) ,7.11(d,J=7.9Hz,2H),4.39(d,J=25.1Hz,1H),4.03–3.76(m,4H),2.29(s,3H),1.11(q,J=7.2Hz, 6H). 13 C NMR (126MHz, CDCl 3 )δ137.15(d, J=5.0Hz), 136.69(d, J=2.0Hz), 133.87(d, J=5.2Hz), 129.45, 129.37(d, J=4.8Hz), 129.28(d, J = 2.8Hz), 128.52, 127.02 (d, J = 1.7Hz), 62.57 (dd, J = 6.9, 1.7Hz), 50.93 (d, J = 138.2Hz), 21.00, 16.24 (dd, J = 5.6, 3.3 Hz). 31 P...

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Abstract

The invention discloses a preparation method of large-steric-hindrance alkyl substituted phosphite diester, and relates to a novel method for preparing the large-steric-hindrance alkyl substituted phosphite diester compound which is difficult to synthesize by a known method through direct reaction of large-steric-hindrance alcohols and triphosphite by using trifluoromethanesulfonic acid trimethylsilyl ester as a catalyst. Therefore, the method can be a breakthrough for synthesizing the large-steric-hindrance alkyl substituted phosphite diester compound by an Arbuzov method, and is an improvedArbuzov method with high universality due to the fact that the method is also suitable for common primary alcohol raw materials. Specifically, according to the method, stable and low-toxicity large-steric-hindrance alcohols are used as raw materials; the method has the advantages of simple reaction conditions, easy operation and no need of a solvent, no transition metal is contained in the catalyst, the product has no transition metal residual hidden trouble, the byproduct is micromolecular alcohols such as ethanol, and almost no toxicity exists, so the method is a green synthesis method of large-steric-hindrance alkyl substituted diphosphite, and has good research value and synthesis application prospect.

Description

technical field [0001] The invention belongs to the technical field of organic chemical synthesis, and in particular relates to a green product which directly reacts bulky hindered alcohols and phosphite triesters under the catalysis of trimethylsilyl trifluoromethanesulfonate to prepare bulky hindered alkyl-substituted phosphonites. resolve resolution. Background technique [0002] Organophosphorus compounds containing C-P(O) bonds have extensive and important applications in the fields of medicine and agriculture, as well as in organic synthesis and catalysis. [0003] The famous Arbuzov (Arbuzov) reaction, through the reaction of halogenated alkanes and phosphite triesters under high temperature heating to generate C-P (O) compounds, is an important classic method for the synthesis of organic phosphonite derivatives, in the laboratory and It is widely used in the industry to manufacture various organic phosphine compounds. But the shortcoming of this reaction is also ob...

Claims

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Application Information

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IPC IPC(8): C07F9/40
CPCC07F9/40
Inventor 徐清周婷婷韩立彪
Owner WENZHOU UNIVERSITY
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