SU737403A1 - Method of preparing o,o-dialkyl-s-(alpha-methylvinyl)-dithiophosphates - Google Patents

Description

The invention relates to the field of chemistry of organophosphorus compounds, namely to a method for producing 0,0-dialkyl-B - (oL-methylvinyl) dithiophosphates of the general formula (s) (oB) j, where I is lower alkyl, which can be used as intermediates for the production of biologically active drugs, as well as a means to combat pests of agriculture. Substances of a similar structure are known, for example, O, O-dialkyl- $ -propargyl and O, 0-dialkip-S-allyl esters of dithiophosphoric acid, which have biological activity. These compounds are obtained by the interaction of the ammonium salts of O, O-dialkshiti (cosforc acids with propargyl chloride or bromide, as well as the interaction of the salts of dithioacid of phosphorus with allyl bromide in acetone solution {43 It is impossible to obtain the described methods O, O-dialkyl-5-di-methole di-methyl; ) - / schthiophosphates. It is known that when dialkyldithiophosphoric acid reacts with diketene at a temperature of 15 to 2 ° C, in addition to the main reaction product 0, Odialkyl-S-acetoacetyldationophosphate with an insignificant cake forms O, O-dialkyl-S- (cC- "tilvylnyl ) - etnophosphate 5} However, there is no physico-chemical characterization of 0, O-dialkyl-5- (pL-methylvinyl) dithiophosphates in the literature; the chain of the invention is an increase in yield of 0,0-dialkyl-S- (oC-methylvinyl) -dithiophosphates. This goal is achieved omicbt by the method of obtaining OjO-dialkyl 5- (dL methylvinyl) -dithiophosphates of formula 1, which consists in the fact that 05O-dialkshithiophosphoric acid under 3, .., 7 vertex is occupied with diketene in the presence of a base. The process can be carried out at a temperature of 15 to. The process is as follows. Equimope amounts of 0,0-diasyl dithiophosphoric acid and diketene are mixed in the presence of a base. The reaction mass is removed at room temperature (15–20 ° C) for 5–15 days and then heated for 1–2 hours at 100 ° C. Compounds of formula I are read by fractionation in vacuum. The anion exchanger AB- can be used as a base. 17-8, aniline, triethylamine or alcohol, youch metals, .-. The optimal conditions for the proposed process are: 1) the use of equilibrium amounts of the initial reagents. It was established experimentally that the yield of the target compounds depends little on the ratio of the starting components. Moreover, the presence of an excess of DITIO 1 SILTS leads to other directions of the reaction, which complicates the purification of the substance, 2) carrying out the method in a temperature range of 15-1 ° C. A stronger thermal effect leads to partial clearing of the reaction mixtures. However, heat treatment is necessary for the conversion of 0, O-dialkyl 5-adetoacetate-dithiophosphine to 0, O-dialkyl-S- (C1b.-metalvinsh1) -dithiophosphate; 3) the yield of compounds of formula 1 is increased if the reaction is carried out in the presence of a base, for example, Avovit AB-17-8; Proof of the structure of O, O-di-kil-5- (C1 methylvish) nsithiophosphates of formula I was carried out with. using elemental analysis of IR, NMR-IHj p-spectra. The purity of the compounds was controlled by spectral methods. In the IR spectrum X, absorption bands are observed (l): 540-560 (PS 660-665 (), 975-990, 1030-1О6 (DEW), I7O-1180 (ROAEK), 163O1640, ZO40-ZO70 (), B The NMR (31p) -spectra signals of nucleus 31 p are located. In the region from -85 to 8yid, which indicates the ditaphosphate structure, the structure of O, O-dialkyl - S (C1-mbsh11yshshsh) -dithiophosphates was confirmed by PMR- spectra,

Claims (4)

 - .. The PMR spectrum of 0,0-diisopropyl-5- (cimethylvinyl) -thiophosphate has the following characteristics (dmd): (CHj) CH-OR, 1.2 (doublet, 12Н1ц „bHz) -C (CHj) -C, a broadened peak due to slin-spine interaction with Drom P and vinn1y 1I with protons with a target. 2, O7 M.D. (ZN): CH-OR, 3.3-5 (seven quidisyterg lines, 1 N,% cts6 Gi). iniyl protons form a degenerate AV quadruplet in the region of 5.155, 22 m, d. (2H), The internal components of the inset member are melted into a doublet due to pin-spin interaction with the core, and the external components on the spectrum are 6 VIEWED, Example 1, Preparation 0, O- / shchetil5- (cC -M0gilvinyl) -dithiophosphate. A mixture of 20 g (0.1O7 g mol) O, a-dieth | ) osphoric acid, 9, OZ g (0.1O7 g mol) of diketene and 3 g of anion exchange resin AB-17-8 are kept at room temperature for 10 days. Then the anioEit is removed, the mixture is heated for 1 h at 10 ° C, and then it is fractionated under vacuum, 12.1 g (50%) 0, O-dieth-1 (5), dithiophoopate, T, kip, 81- 83 C (3 mm Hg, Art.) 1.51605 d | ° 1.1468, Found 8%: C 36.66: H 6.62, Calculated: C 37.17, H 6.63; "Ur 86 m, d, P r and m in p 2, Obtaining O, 0-ipropyl-5 - (° C-methylvin1)) yytyofosfata A mixture of 11.8 g (0.14 g) diketen and 21.4 g ( 0.1 g mol) OO-Diprrpaldithiophosphoric acid is kept at room temperature for two weeks, then heated for 1 h and fractionated in Vacuum using Widmer nozzle, 11.5 g (45%) 0.0 -dipropyl- 5 - (oC; methylWish) -dithiophosphate ,. t kip. 8 6-88 С (2.5 mm pT, CT), 5095, 1.0978; Found,%: C 42.45; H 7.24; R 12, O9, S l9 252 Drugs D: C 42.52, H 7.48, P 12.2 O: dp -87 ml. When the experiment was repeated in the presence of 3 g of anion exchanger, the yield of the target compound was 55%. acids, 5.9 g (0, O7 g mol) of diketene and 4 g of anion exchanger AB-17-8 were incubated for 5 days at KONfrnat temperature. Alionite was removed, the reaction mass was repeatedly fractionated under vacuum using a distillation apparatus. 10.7g (60%) O.O-diieopropyl-5 (cL-methylvinyl) -dithiophosphate, bp 85-86 ° C (2 mmHg) ,, 5026, dj ° 1.0833. Found %: C 42.57, H 7.31, R 12.3 ; Calculated,%: C 42.52: H 7.48; P 12.20 cGy -85 m. EXAMPLE 4, Preparation of O, 0-diisopropyl-5- (csC-methyl-1H1) -dithiophosphate, South About O-diisopropyl ester of 5-acetoxy-acetyldithiophosphoric acid is placed in an Arbuzov flask, 3 drops of a saturated alcoholic solution of sodium iopropylate are added and heated for 1 hour at 80-100 ° C. 0,0-diisopropy. 5 - (d methylvinyl) dithiophosphate, b.p. 6466 ° C (0.1 mmHg) 11 20 1.5045: in 1.0841. Found,%: P 12.40 .OPSa Calculated,%: P 12.20: or -86 ppm 10 g of O, O-diisopropyl ester of acetoxyacetyldithiophosphoric acid and O, 002-0, O05 g of mol of triethipamine are heated for 1 hour at 85 ° C and subjected to mono-film distillation, and then the mixture is fractionated under vacuum. The yield of the target compound is 6.4 g (75%) "Claim 1, Method of obtaining O O-dialkyl in (C {, methyl ethyl) dithiophosphates of the general formula CH ,, - 9-5PC9HOR1 CHj where R is the lowest alkqud by reacting 0 , 0 dialkvalidirphosphoric acid with diketes characterized in that in order to increase the yield of the target product, the process is carried out in the presence of a base,. 2, The method according to claim 1 of tl and h and torn, and so that the process is conducted at a temperature of from 15 to USSR, Source IOfs zmahaap taken into account during examination 1, the Federal Patent of Germany No. 1063148 ,, class. 12, 19/03, published 1060, 2. US patent number 2865SO1, cl. 424-219, opuvik, 1958. 3.Patesh- US№ 2906661, l, 424-219, publ., 1959 ,. 4. Zemlsky N. I. JDiyiuKOBa L, V. ivagea, non-volatile centered esters 0.0 diapquicitic acid, JFW, 196 5s 35, e 1481, 5 Author's certificate СХХ; R o no. 2629558/04, ft С FROM F 9/165, 19. (prototype).