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Phosphorus chiral important intermediate preparation method

An intermediate and chiral technology, applied in chemical instruments and methods, compounds of Group 5/15 elements of the periodic table, organic chemistry, etc., can solve the problem of inability to industrially apply naphthalene lithium reagents, industrialization is difficult, and no reaction is given Steps and yields, etc., to achieve the effect of simple operation, short process route, simple reagents and reactions

Active Publication Date: 2018-08-17
SHANGHAI JIAO TONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] In 2000, Imamoto et al reported the method (Journal of Organic Chemistry, 2000, 65 (6), 2000, 2000, 2000, 2000, 65 (6), 1877-1880), where the cleavage of the C-S bond requires the use of naphthalenelithium reagents that cannot be applied industrially
In 2002, Imamoto etc. reported the method (Bulletin of the Chemical Society of Japan, 2002,75 (6), 1359-1365) directly reacting with borane tert-butylphosphine as a starting material, wherein Tert-butylphosphine is a very difficult and dangerous raw material, so the industrialization of this route is also very difficult
In 2009, O'Brien et al. mentioned in their reported article the method for the synthesis of borane methyl tert-butylphosphine hydrogen by reduction and reboration after the reaction of tert-butyl phosphine dichloride and methyl Grignard reagent, but No specific reaction steps and yields are given. Since methyl Grignard reagent can react with two C-Cl bonds on tert-butylphosphine dichloride, there are problems of reaction selectivity and separation and purification in this method.

Method used

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Examples

Experimental program
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Effect test

Embodiment 1

[0031] Embodiment 1, the synthesis of tert-butylphosphine dichloride (I)

[0032] In a dry 100mL single-necked flask, slowly dropwise add phosphorus trichloride (40mL, 0.46mol, 2.5eq) to a solution of tert-butylmagnesium chloride in tetrahydrofuran (1.0M, 180mL, 0.18mol), and react at room temperature for 24 hours , and filtered under nitrogen protection to obtain the target product as a white solid. The yield was 51%.

[0033] 1 H NMR (400MHz, CDCl 3 ): δ (ppm) = 1.23 (d, J PH =14.8Hz,9H,C(CH 3 ) 3 ); 31 P NMR (162MHz, CDCl 3 ): δ (ppm) = 200.0 (s); 13 C NMR (100MHz, CDCl 3 ): δ (ppm) = 24.4 (CH 3 ),23.8(d,J PC =20.9Hz, C(CH 3 ) 3 ).

Embodiment 2

[0034] Embodiment 2, the synthesis of ethyl tert-butylphosphonite (II)

[0035] In a dry 250mL one-necked flask, a tetrahydrofuran solution (75mL) of tert-butylphosphine dichloride (10.8g, 67.9mmol) was added, and absolute ethanol (25mL, 427.9mmol, 6.3eq) was added dropwise. After reacting at room temperature for 12 hours, distillation gave the target product as a colorless oil with a yield of 84%.

[0036] 1 H NMR (400MHz, CDCl 3 ): δ (ppm) = 6.71 (d, J PH =514.4Hz,1H,PH),4.24-4.02(m,2H,OCH 2 ),1.34(t,J HH =7.2Hz,3H,CH2 CH 3 ),1.11(t,J PH =17.6Hz,9H,C(CH 3 ) 3 ).

Embodiment 3

[0037] Embodiment 3, the synthesis of ethyl tert-butylphosphonite (II)

[0038] A toluene solution (20 mL) of tert-butylphosphine dichloride (5.4 g, 34.0 mmol) was added to a dry 150 mL one-necked bottle, and absolute ethanol (15 mL, 256.7 mmol, 7.5 eq) was added dropwise. After reacting at 0° C. for 24 hours, distillation gave the target product as a colorless oil with a yield of 72%.

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Abstract

The invention discloses a phosphorus chiral important intermediate preparation method, which comprises: carrying out a substitution reaction on phosphorus trichloride and tert-butyl magnesium chlorideto obtain tert-butyl phosphine dichloride I; carrying out an esterification reaction on the tert-butyl phosphine dichloride I and ethanol to obtain tert-butyl ethyl phosphite II; carrying out a methylation reaction on the tert-butyl ethyl phosphite II under the action of a methyl Grignard reagent methyl magnesium iodide to generate methyl tert-butyl phosphine oxide III; and obtaining a methyl tert-butyl phosphine hydrogen compound VI protected with borane through a borane reduction one-pot method. According to the present invention, the method has advantages of low-cost and easily-available raw material, short route, simple operation and good atomic economy, and provides the simple and easy-performing route for the preparation of the borane methyl tert-butyl phosphine hydrogen.

Description

technical field [0001] The invention belongs to the fields of pesticides and chemicals, and in particular relates to a preparation method of an important phosphorus chiral intermediate, that is, a preparation method of borane methyl tert-butylphosphine hydrogen. Background technique [0002] Borane methyl tert-butyl phosphine hydrogen is a compound of methyl tert-butyl phosphine hydrogen protected by borane. The pure product (racemate) is a white, crystalline solid that is easy to sublime. After resolution, two optically pure isomers can be obtained, that is, boranemethyl tert-butylphosphine hydrogen in two configurations of R and S. In 2000, as an important intermediate for the synthesis of phosphine chiral bisphosphine ligands, it was developed and reported for the first time by Imamoto et al. (Journal of Organic Chemistry, 2000, 65(6), 1877-1880). The phosphine chiral bisphosphorus ligand containing the methyl tert-butylphosphine structure in the structure can efficientl...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/50
CPCC07F9/5009C07F9/5068
Inventor 张万斌张振锋刘洋
Owner SHANGHAI JIAO TONG UNIV
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