SU1754721A1 - Method of ethoxycarbonylmethylene-di-tert-butyl-(n-alkyl-n-phenylamino) -phosphoranes synthesis - Google Patents

Abstract

The invention relates to organophosphorus substances, in particular, the preparation of ethoxycarbonylmethylene-di-tert-butyl (M-methyl (or ethyl or mzopropyl) -M-phenylamino} phosphorans, intermediates for organic synthesis. Class Synthesis is carried out by the reaction of ztoxyethynyl di-tert-butylphosphorane with phenylazide and the corresponding alkyl alcohol at room temperature under an inert gas atmosphere.% yield; mp; ° C; gross f-a: 51) 79; C2H34PM02, b) 49; not; CigHazNOzP, c) 100; oil: C21NzeRN02. This method allows, under mild conditions, without long time spending, to obtain target substances in high yield.

Description

This invention relates to the chemistry of organophosphorus compounds with a P – C bond, namely, to a new method for the preparation of ethoxycarbonylmethylene di-tert-butyl (M-alkyl-N-phenylamino) phosphorus of the general formula:

(tert-StsN9 P CH-C 0,, g

s, nL ° C H (I)

where R is methyl, ethyl or iso-propyl.

Compounds (I) are not described in the literature. They are new compounds and can be used as intermediates in organic and organophosphorus synthesis for the production of new types of organophosphorus complexes and extractants, as well as for the stereoselective synthesis of organic compounds by the Wittig reaction,

The purpose of the invention is to develop an accessible process for the preparation of ethoxycarbonylmethylene di-tert-butyl-alkylenephenyl amino-phosphoranes.

The objective is achieved by a process for the preparation of compounds of formula (I), which consists in reacting ethoxyethylenyl-di-tert-butylphosphine with phenylazide and alcohol at room temperature under an inert gas atmosphere.

The proposed method in the literature is not described. The preparation of the ylides of formula (I) is unexpected, since it is known that the phosphorus (IV) substituted hemiacetals polyamine ketenes, as well as other various e / J-alkoxyvinylphosphoric compounds, are not subjected to alkylotropic migration with the formation of phosphors.

but

4 GO

New in the proposed method is the detected -1,5-alkylotropic migration from the oxygen atom to the nitrogen atom, which is easy for even spatially obstructed groups and is regiospecific.

The proposed method allows to obtain the target products under mild conditions with high yields. The starting materials for the synthesis of phosphoranes (I) are readily available. The proposed method is simple and does not require a lengthy investment of time and complex instrumentation.

Ethoxycarbonylmethylene di-tert-butyl - - {M-alkyl-G-phenylamino-5-phosphorans are colorless crystals that are air-resistant.

The proposed process can be represented by the following scheme:

G NLS and

(Tpev-C jPC-COCjHs + CgHsNi + ROHrr С С 5

- UHSN R

.6nsn

(tr "t-StsN9 R. CH-S

C6H5-N-R

The structure of the synthesized compounds was confirmed by NMR, 13C, 31P - spectroscopy,

PRI me R 1. Preparation of ethoxycarbonylmethylene di-tert-butyl (M-ethyl-N-phenylamino} -phosphorane.

A solution of 1.8 g (0.015 mol) of phenylazide in 5 ml of ethanol is added dropwise to a solution of 3.21 g (0.015 mol) of coxyethyl-di-tert-butylphosphine in 15 ml of ethanol. After 0.5 h, the excess alcohol is distilled off in vacuo to give 5.3 g (quant.) Of an oily product with 5 p 85.3 ppm, which is ethoxycarbonylmethylene di-tert-butyl (M -ethyl-1M phenylamino) - phosphorane of 90-95% spectral purity by 31P NMR. Extraction of the product with hexane, followed by recrystallization from hexane, allows to obtain this compound as white crystals with a yield of 2.7 g (51%), m.p. 79 ° C.

PMR spectrum (, 5, M A-): 1-20 d. 3JPH 14.3 Hz (CH3 to t); 2.04 d. 2JpH 6 Hz, 1.98 d., 19 Hz (P-CH-); 4.24 square meters (Shg a C2H50); 0.30 t. (CH3 in CrHyO) 4.0 pent. 3JHH 3JPH 7.1 Hz (CH2 in CzHsN-CeHs); 1.27 t. (CH3 in C2H5NCeH5); 6.95 d., 7.20 t., 6.84 t. (SbH5).

NMR13S spectrum (SDS1d, ppm): 28.03 (CH3 Vtr-C4H9); 37.11 d., 1Jcp 71 Hz (C Thu. Per t-C4H9); 26.48 d., 1Jcp 122.8 Hz (P-CH-);

166 18 (CO); 59.51 (CH2 in C2H50); 14.82 (CH3 in CaHsO); 62.82 d. 3JCp 8.6 Hz (CH2 in C2H5M); 16.37 d. 4JCP 6.8 Hz (CH3 in C2H5N); 153.31, 2Jcp2.4 Hz, 123.11, 128.23; 120.05 (C6H5). Found,%: C 68.01; H 9.87; N 3.78; R

8.49.

C20P34PN02

Calculated,%: C 68.35; H 9.75; N 3.98; R 8.81.

Lrimer2, Preparation of ethoxycarbonylmethylene dm-tert-butyl (M-methyl-M-phenylamino) -phosphorane,

To a solution of 1.46 g (0.0068 mol) of ethoxyethinyl-di-tert-butylphosphine in 10 ml of methanol, a solution of 0.8 g (0.0068 mol) of phenylazide in 5 ml of methanol is added dropwise with stirring. After 0.5 h, the excess alcohol is distilled off in vacuo, yielding 2.3 g (if) of ethoxycarboxymethylene-di-tert-butyl (M-methyl-M-phenylamino) -phosphorane with 5 p 88.3 ppm 90-95% spectral purity by NMR31P. Extraction of the product with hexane and subsequent recrystallization from hexane allows to obtain the target

product in the form of crystals with a yield of 1.15 g (49%).

PMR spectrum (, 5, m d.): 0.98 d., 3JpH

14.3 Hz (CH 3 in tert.-SlNd); 1.8 d., LRN 19 Hz, 2.0 d. Vrn 22 Hz (P-CH-); 4.45 sq. M. (CH2 in

C2H50); 1.23 t. (CH3 in C2H50); 3.48 d., 3JPH

.1.4 Hz (CH3 in SNZM): 7.27 d., 7.32 t., 6.93 t. (CbH5).

NMR 13C (a, b, ppm): 27.93 (CH 3 in Tper-C / iHg), 37.30 d „1JCP 70.2 Hz (C

four in tert-C / iHg); 24.56 d., 1JcP 124.8 Hz (P-CH-); 59.44 (СНа in С2Н50); 15.10 (CH3 in C2H50); 54.16 d., 3JPC 8.3 Hz (CH 3 in CH 3 N); 123.44; 128.67; 120.39 (C6H5).

Found,%: C 67.51; H 9.70; P 8,89

С1эНз2М02Р

Calculated,%: C 67.63; H 9.56; R 9.18. PRI me R 3. Preparation of ethoxycarbonyl-m8-thylene-di-tert-butyl (M-isopropyl-M-fe-ylamino) -phosphorine

To a solution of 0.86 g (0.004 mol) of ethoxyethylenyl-di-tert-butyl phosphine in 10 ml of isopropyl alcohol, 0.48 g (0.004 mol) of phenylzide in 2 ml of isopropanol is added dropwise with stirring. After 0.5 s

excess alcohol is distilled off in vacuum; 1.46 g (amount) of ethoxycarbonylmethylene-di-tert-butyl (M-isopropyl-M-phenylamino) - phosphorane of 90-95% spectral purity is obtained in NMR P as an oil p 81.3

ppm (Sat)

PMR spectrum (, Dm.d.): 1.09 d. 3JPH 14.4 Hz (CH3 in t-C Ho), 2.39 d, 2JpH 14.7 Hz (); 4.48 square meters. (CH2 in C2H50); 1.3 t. (CH3 in C2Hs); 4.65 m., 3JHH3JpH 9.8 Hz (CH in

ISO-SzN); 1.15 d. (CH3 to iso-SzN M); 7.20 d., 7.30 t., 6.92 t (CbN $).

Nuclear Magnetic Resonance Spectrum (Sat, d, ppm): 28.5 (CH 3 in tert-C 4 H 9); 36, 48d, SSR 72.4 Hz (from Thurs. to tert-SzNe); 28.6 d. Jcp 122.2 Hz (); 59.87 (CH in CrH50); 15.34 (CH3 in C2H50); 69.88 ".;; JCP 8.7 HZ {CH in iso-CsHyN); 24.37 d., JCP 3.8 Hz (CH3 in iso-C3H7N); 165.13 (C-0); 154.35, Jcp 2.3 Hz, 123.67; 128.69; 120.53 (C6H3).

Claims (1)

The invention The method of obtaining ethoxycarbonylmethylene-di-tert-butyl (N-anKHn-N- t) eHHflaMM-but) -phosphorane of the general formula (tert-C4H912P CH-С C6H5-N-R , 0 OC2HS where R is methyl, ethyl or iso-propyl, comprising ethoxyethinyl-di-tert-butylphosphine reacting with phenylazide and an alcohol of the formula ROH, where R has the indicated values, at room temperature in atmospheric gas.