SU547453A1 - Method for preparing 2-thio1,2-oxa-phosphol-3-ene derivatives - Google Patents

Description

one

This invention relates to the chemistry of organophosphorous compounds with a C-P bond. A new method for the preparation of derivatives, 2-oxa-phosphol-3- "on a common formula

n

-Hal

-g

j b

p / fi / R

X

ei

where NaE is chlorine and bipromine;

R and R - the same or different lower

alkyg 1.

A known method for producing thiophosphonic acid halides by reacting phosphorus pentachloride with alkyl vinyl ethers, followed by treating the resulting adduct with hydrogen sulfide ij.

There is also known a method for producing 2-thio-1,2-oxa-phosphol-4-ene derivatives by reacting a mixture of trihalide phosphorus and et, B-unsaturated ketone with hydrogen sulfide at room temperature 2J. However, the compounds of this formula, their preparation method and properties are not described in the literature.

The aim of the invention is to obtain derivatives of 2-thio-1,2-oxaphosphol-3-ene, which can be used as intermediates for the preparation of flotation agents, insecticides or lubricants.

The proposed method for the preparation of 2-thio-1,2-oxaphosphol-3-ene derivatives is concluded in that 3-alkyl-1, 2-alkadienphosphonic acid dichloride is reacted with chlorine or bromine in an inert organic solvent at 0-25 ° C followed by treatment of the reaction mixture with hydrogen sulfide.

The composition and structure of the products obtained are proved by spectroscopic methods and elemental analysis data.

The method is simple, the initial reagents are available.

Example 1. 2,4-Dichloro-2-thio-5,5-dimethyl-1, 2-oxaphosphol-3-ene.

Claims (2)

To a stirred solution of 9.25 g (0.05 mol) of 3-methyl-1,2-butadienephosphonic acid dichloride anhydride in 5 O ml of benzene, chloroform, or tetrachloride add L-3.55 g a solution of 0.05 mol of chlorine mixed with inert raaoi 1: 2 (nitrogen or argon) is bubbled in the same solvent or under the same conditions. Then, when cooled with ode, a small amount of hydrogen sulfide TROC is passed into the solution, compared to equimolecular, the solvent is distilled off and the target product is distilled under vacuum, yield 16.4 g (72%), bp 72–730 ° C / 1 mm; npl, 5441: 1, dj ° l, 0203, Spec. tr NMR: d- 6.50, d 1.73, () 33.5 Hz J K-spectrum, cm-: 1583 () Found,%: C 27.32; 27.55; H 3.31; 3 , 52; se 32.45 j 32.55; 5 14.42; 14.49; P 13.89; l4, O7. N ce ce = sample; Calculated,%: C 27.6 O; H 3, 32 , 68; S 14.78; R 14.27. Example 2. 4-Bromo-2-chloro-2 yew-5, 5-dimethyl-1,2-oxaphosphol-3-ene. To a solution of 18.5 g ( 0.1 mol) of 3-methyl-1,2-butadiene phosphonic acid dichloride in 1OO ml of carbon tetrachloride, chloroform or benzene with stirring add 16 g (0.1 mol) of bromine or a solution of 16 g of bromine in 20 ml of the same solvent. Light yellow crystals fall out. Then, hydrogen sulfide is bubbled through the suspension until the precipitate is completely dissolved, the solvent is distilled off and the target product is distilled in a vacuum, yield 15 g (b5%) kip. 93-94 ° C / 1.5 mm Hg; m.p. 75-76-С (from hexane). . 1.70 (NMR spectrum:., 6.70,.,., P - 67.8 (NdRO) MD, 35.5 Hz IR spectrum, 1573 (C-C). Found: C 22 , 85; 2 3.18; And 2.32; 2.41; C1 + B 43.2b; 43.75; 6 12.06; 12.12; R 11.57; 11.74. С-Н- WU CiOSP Calculated,%: C 22.91H, 2.67; Cf + Br, 44.14; 512.26; R, 11.87. Example 3. 2,4-Dichloro-2-thio-5-methyl-5-ethyl -1,2-oxaphosphol-3-ene. To a stirred solution of 9.95 g (0.05 mol) of 3-methyl-1 dichlorohydride, D-pentadienylphosphonic acid in 5O ml of carbon tetrachloride, add a solution of 3.55 g ( 0, O5 mol) of chlorine in 5O of the same solvent at 5-10-C. Then, at the same temperature, a small excess of hydrogen sulfide is passed into the solution compared to equimolecules The solvent is distilled off and the target product is distilled under vacuum, yield 9.8 g (85%), bp 78 .., T / 1.5418; d, 2 ° C / 1 mm Hg. , I.JJ. 22-240 ° C. NMR spectrum: S 6.5O, CH2 (fp-85.4, 0.87, ... -CH ISRO) 1585 (СБС), 3107 IR spectrum, cm (СН ), 702 (R 5). Found,%: C 31.38; 31.50; H 3.49 j 3.63; CI AOR, 75; 31.02 $ 13.53; 13.91 P 17.17; 13 , 50. Calculated,%: C 31.17; H 3.9O-C 30.73; S 13.85; R 13.42. Example 4. 2,4-Dichloro-2-thio.-5-. -megyl-5-isopropyl-1,2-oxafooofol-3-ene, To a stirred solution of 6.39 g (0, 03 mol) of 3,4-dimethyl- | -1, 2-pentadiene-phosphonic acid dichlorohydride in 50 mc of carbon tetrachloride A solution of 2.13 g (O, OZ mol) of chlorine in 30 ml of the same solvent was added at O-ICPC. Then, at the same temperature, a small excess of hydrogen sulfide is passed into the solution compared to equimolecular one, the solvent is distilled off and the target product is distilled in vacuum, yield 5.2 g (70.6%), b.p. 72 74 ° C / 1 mm Hg, so pl. 34-36 ° C. NMR spectrum: 6.38, (Y (j ((j) 1.58, 2.03, (CHg) (P -89.7 (H3DD) ppm: 1.08, O, 88, J cmcHj, "- f 1586), 31O7 IR spectrum, cm (CH "), 703 (Prg5). Found,%: C 34.03; 34.47; H 4.19, 4.28; Ci 28.53; 28., S 12.87; 12.99; P 12.68; 12.89. Calculated,%: C 34.28; H 4.49; C 28.98; S 13.06; P 12.65. derivatization of 2-tis -1, 2-oxa-phosphol-3-yne of the general formula -CHt) where 6 is chlorine or bromine; R and R are the same or different lower alkyls. 547453 b6 the fact that, dichloran-Sources of information, taken in the 3-alkyl vvvngyridride - 1,2-alkadienphosphonium in the examination: New acid is subjected to the interaction of D. Purdela, R. Valchanu, Chemistry with chlorine or bromine in the cf. &. -organic compounds of phosphorus, M., Chem. de inert organic solution-j 1972, p. 416. bodies at 0-25 ° С with the subsequent processing 2. PackageGFRG№1003750, class12о 24 which reaction mixture with hydrogen sulfide.