SU1250566A1 - 1,2lambda3,4lambda5-oxadiphospholanes and method of producing same - Google Patents

Abstract

1. 1, 2Д, 4, V-Oxadiphospholanes of the general formula 0. RO evh. Р () р-ok с-о. HI where I with R - C, H ,, R - CH, C H R - H or CH with R - iso-Cj H,, R-iso-CJH, or C.HS R, - H2. Production method 1,2, X 4A - -oxoxiphospholanes of the general formula O 2 () P-OR YAO d-0 RI 2 and ethoxy- 627. are 5 SbH, where at R - ,, R, - СН, С , H ,, R., v - H or CH, with R - iso-CjH, R, - iso-С. R, - H, consisting in that trialkylmethylene bisphosphonite is reacted with aldehyde or ketone at an equimolar ratio of reagents in the presence of anhydrous cesium fluoride as a catalyst, taken in an amount of 2-2.5 mol per 1 mole of the starting trialkylmethylene bisphosphonite and the process is carried out at room temperature in an inert gas atmosphere for 3–4 h. (LHG ate about 05 ty

Description

one

The invention relates to the chemistry of organophosphorus compounds, namely to a new type of phosphorus-oxygen-containing heterocycles with two phosphorus atoms of different valences — 1.2A, oxadiphospholanes of the general formula

About CH

P/

/

Ro-do

RI 1

, P when R - from S., H,

sn ,,

where with EG, H, R - CH, C, H5,, R - n or CH

- ieo-C, H or R-H and to the method of their preparation.

These compounds can be used as complexons and extractants of various metal cations, phosphorus-containing catalysts for stereo-directed synthesis of organic substances, for the preparation of organophosphorus polymers and as starting compounds for the synthesis of new types of organophosphorus compounds.

The purpose of the invention is to create a new, affordable method for producing 1,2,4-oxadiphospholanes, which have a fundamentally new structure, since they contain in the cycle a new communication fragment for phosphorus-containing heterocycles consisting of two phosphorus atoms of different valences separated by carbon atoms and oxygen.

All examples are carried out in an inert gas atmosphere. Cesium fluoride is calcined before the reaction and kept in an oil pump vacuum (5 h, 0.5 mm Hg). Spectra removed on the FT-80

C, Ratio

Diastereomers are determined by integrating the NMR spectra. The dominant isomers appear in the spectrum with.

Example 1. 2,4-diethoxy-4-α-OXO-5-ethyl-1,2,4-oxadiphospholane.

In a three-necked flask equipped with a stirrer, a reflux condenser and a dropping funnel, 4.6 g (0.02 mol) of triethylmethylene bisphosphonite, 6, C8 g (0.04 mol) of cesium fluoride and 1.2 g (0.02 mol) of propionic acid are placed. go aldehyde. After 10 min reaction 10

2505662

The mixture is heated to 30-35T. At the end of the exothermic reaction, the reaction mixture is stirred for another 2 hours at room temperature. Then 70 ml are added to the reaction mixture; absolute methylene chloride and stirred for 5-7 minutes Cesium fluoride is filtered off, methylene chloride is distilled off in vacuo, the residue is distilled.

The yield of 2.2 g (44%), so Kip. 95 C / 0.02 mm Hg v. /; dj 1.0760.

NMR spectrum p / 6, „, & p, ppm, /: 176.26 d. 62.00 d, J (Wed) 1.75 Hz; 176.05 d 61.80 d. J () 1.6 Hz; 173.16 d, 60.89 d, J (CP) L1.0 Hz; 171.90 d. 60.26 d, J (CP) 1.9 Hz; a mixture of caffeine diastereomers. The percentage of isomers in the mixture: 6: 3: 51: 40 Spectrum: - t / e. M 240;

P; 1.4680,

15

20

25

g tt / l p det -t 8

Calculated,%: C 40.00, H 7.55; R 25.79.

Found,%: C 40.35; H 7.68; R 25.43.

PRI mme R 2. 2,4-DIETOXI-4- -oxo-5-phenyl-1,2,4-oxadiphospholane.

The product is obtained according to the procedure described in Example 1, from 4.6 g 30 (0.02 mol) of triethylmethylene bisphosphonite, 6.04 g (0.04 mol) of cesium fluoride and 2.12 g (0.02 mol) of benzal - dehydrator with the release of 3.8 g (66%), b.p. Pb C (0.01 mmHg), p M.4951; 35 d: j.0794.

Spectrum (Br, „, 8р„ MD): 174.82 d, 58.16 d, J (СР) 1.5 Hz; 174. 19 d 57.90 d J (CP) P, 0 Hz; 171.53 d, 56,49 d, J (CP) 1.7 Hz; 40 170.56 d, 54.16 d, - J () 1.2 Hz; a mixture of caffeine diastereomers. The percentage of isomers in the mixture: 5.6: 9.4: 45: 40.

NMR spectrum 4 / S ,. Z.M.D./: 36. 79 w, 45 J () 74.9 Hz, J () 1.0 Hz; 35.24 dd, J () 67.5 Hz, J () 1.0 Hz; / 5s 5m.d. /: VO.Bbdd, J () 108.9 Hz, J (C) 14 Hz; 79.40 dd, J (P C) 100 Hz, J (C) 50 12.5 Hz.

Mass spectrum: you. 288,

Spn .ch r,.

55Calculated,%:

R 21.49.

Found,%: C P 21.12.

PRI me R 3. 2, A-diethoxy-4-oxo-5,5-dimethyl-1,2,4-oxadiphospholane.

The product is obtained according to the procedure of Example 1 from 4.6 g (0.02 mol) of triethylmethylene bisphosphonite, 6.04 g (0.04 mol) of cesium fluoride and 1.2 g (0.02 mol) of acetone with a yield of 3.4 g (70%), t. Kip. (0.01 mm),

1.4662, d 1.0860.

p go. NMR spectrum

 p / b ,, „, 6;„ ppm / 1

166.32 d., 61.65 d, J (P CP) 1.75 Hz, 164.89 d. 59.29 d, J () 2.9 Hz, a mixture of two diastereomers. The percentage of isomers in the mixture: 62:38.

Mass spectrum: ha / e 240 i M + M 240, g n p p

8 i "° 4 2

Calculated,%: C 40.00; H 7.55;

P 25.79.

Found,%: C 40.03; H 7.75; R 25.52.

EXAMPLE 4 2,4-diisopropoxy-4-oxo-5-isopropyl-1,2,4-oxa-diphospholane.

The product is obtained according to the method of Example 1 from 5.4 g (0.02 mol) of triiso-propylmethylene bisphosphonite, 7.54 g (0.05 mol) of cesium fluoride and 1.44 g (0.02 mol) of isobutyraldehyde with the yield 4..3 g (78%), 1.4568, d 1.0963, t. Kip. (0.01 mm Hg, Art.).

Spectrum Sp, ppm: 171.13 d, 60.78 d, J (CP) 2.15 Hz 170.97 d, 57.96 d, J () 5.05 Hz, 167.99 d, 57.09 d, J () 2 , 15 Hz, - 167.07 d. 56.27 d, J () 1.75 Hz, mixture of four parts of diastereomers. The percentage of isomers in the mixture: 14.3: 9.7: 41: 35.

Compiler L. Karunina Editor L. Avramenko Tehred N. Bonkalo Proofreader V. Booth

Order 4376/20 Circulation 343 Subscription

VNIIPI USSR State Committee

for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5

Production and printing company, Uzhgorod Project. four

ten

five

NMR spectrum C: / S, ppm /: 30.83 dd J () 69. l Hz, J () 7.2 Hz; 32.85 dd, J (P C) 69.0 Hz, 5 J () 3.5 Hz, / 8 5, ppm /: 75.83 dd, J () 111.8 Hz, J () 14.9 Hz; 76.08 dp ,, J (P С) 110.0 Hz, L () 13.6 Hz

Mass spectrum: t / at 282 m +, M „.„ 282, s „n, L

Vych: shlen,%: 46.81; H 8.57; R 21.95.

Found,%: C 46.56; H 8.29; R 21.47.

Example 5. 2,4-diisopropoxy-4-oxo-5-phenyl-1,2,4-oxadiphospholane. The product is obtained according to the procedure of Example 1 from 5.4 g (0.02 mol) of triisopropylmethylene bisphosphonite, 6.04 (0.04 mol) of cesium fluoride and 2.12 g (0.02 mol) of benzaldehyde with a yield of 3.8 g (60%), t. Kip. 127 ° C (0.01 mmHg), .5170, d 1.0718.

five

0

0

five

NMR spectrum P / Sp ,,,, Sp |

ppm /:

167.60d 56.95 d, J () - 1.0 Hz;

166.61d, 54.17 d, J () 1.2 Hz; a mixture of two diastereomers. The percentage of isomers in the mixture:

 65:35.

Spectrum I am - with: (L, 3, ppm): 31.07 dd, J () 71.53 Hz, J () i i1.0 Hz; 32.66 dd, J () 72.4 Hz, J () 1.0 Hz; (B 5, MD): 72.94 dd, J () 109.2 Hz, J () 17.9 Hz; 73.99 dd, J () 108.0 Hz, J () 0.0 Hz.

Calculated,%: C 53.17; H 7.01; P 19.59.

Found,%: C, 53.43; H 7.26; R 19.36.

s, n, p, p ,.

Claims (2)

1. 1, 2 ’, 4 / -Oxadiphospholane general formula SS EN? X ^hr -ok co-vv-v where with K - C ₇ H ₅ , K - CH _} , C ₇ H ₅ , C ₆ H ₅ K ₇ - H or C1C; with P - iso-C ₃ N _! , K-from-C ^ H, or C O _n By - H. v J? 2. The method of obtaining 1,2, λ ³ , 4), '-oxidiphospholanes of General formula 0 / ^CH \ noL- / ^app PTSH where with K - C ₇ H _b , K, .- CH ₅ , C _? H ₅ , C H, K, - N or sn · when K - iso-C ^ H ₇ , K, - iso-C ^ H ^ or C ₆ H ₅ K. _? - H, consisting in <£ that trialkylmethylenebisphosphonite is reacted with aldehyde or ketone at an equimolar ratio of reagents in the presence of anhydrous cesium fluoride as a catalyst, taken in an amount of 2-2.5 mol per 1 mol of the starting trialkylmethylenebisphosphonite and is carried out at room temperature in an inert gas atmosphere for 3-4 h δ and 1250566 one 1250566 2