The method of obtaining s-triphenylcarbinol esters of dealkylation and tetrathiofulvalene acids

 

(57) Abstract:

Usage: in the chemistry of organophosphorus compounds. The essence: gaining S-triphenylcarbinol esters of linear dealkylation and tetrathiofulvalene acids f-ly I (RX)2P(S)GePh3where R is lower alkyl; X Is O, S, are the reaction tetratetracontane with triphenyl(isobutyric)Hermanni f-crystals RXGePh3where R and X are described above, when 20 - 80oWith subsequent isolation of the target products by the known methods (extraction, distillation).

The invention relates to the chemistry of phosphorus - organic compounds, and in particular to a new method of obtaining S-triphenylcarbinol esters of dealkylation and tetrathiofulvalene acids of General formula (I)

(RX)SGePh3where R is lower alkyl; X is 0, s

Trialkylsilyl and Staniloae analogues of the proposed S-triphenylcarbinol esters of dealkylation and tetrathiofulvalene acids have been used as a tick and insecticide, and also can be used as intermediates for the targeted synthesis of analogues of such insecticide as metasystox, time, leibold, parathion, etc., (U.S. Patent N 3992425 (1970), Inventions abroad, 1977, vol.4, N 6, U.S. Patent N 4588114, Rehim. By esters of dealkylation and tetrathiofulvalene acid is not described in the chemical and patent literature. The literature describes only the method of obtaining S-triethyl-, tributyl and triphenylcarbinol cyclic ethers dithiophosphoric acids containing alkylene deputies (CME2CME2CH2CME2CH2Snresn2CME2), the interaction of the ammonium salts of cyclic alkylenediamine acids with trialkyl and triphenylarsine by boiling in a solution of benzene (Rao R. J. Organogermanium (IV) 0,0-Alkaline Dithiophosphates. //Phsphorus, Sulf. Silic, 1990, Vol. 53, NO. 1-4, PP. 203-209)

RSHNH3+RGeCl 4 RSGeR + NH4Cl

where R=CME2CME2CH2CME2CH2Snresn2CME2;

R Et, Bu, Ph

According to the literature method ammonium salt of 2,3-dimethylethylenediamine acid is treated with triethylaluminum in benzene solution by boiling. The formed ammonium chloride is filtered off, the distillation residue receive 73% of the S-triethylsilyl-O-2,3 - dimethylallylpyrophosphate.

The disadvantages of this process are the use of solvent (benzene), conducting the reaction when heated (bath temperature up to 100aboutC), which requires additional costs of materials and energy, the formation of inseparable of fine sediment (x including the need to prior inaccessible cyclic alkylenediamine acids based on teratological and diols when heated to 80-90about(Stage 1) with the imminent release of toxic and polluting of hydrogen sulfide and the formation of by-products (trithiolane acids and their esters, trialkyltin and tetrathionate). The hydrogen sulfide dissolved in cyclic alkylenediamine acids, pollutes them. (Hoffmann H. Becke-Goehring H. Phosphorus Sulfides.//Topics in Phosphorus Chemistry, 1976, Vol. 8, PP. 193-271; Pat. USA 3328360 (1962-1967). Polymers containing phosphorus/Rozanski A. Miller H. N. H. Horowitz H//C. A. 1968, Vol. 68, N 2, 3 568f

P4S10+ 4 R 4 RSH + 2 H2S

where R2CME2CH2CME2CH2Snresn2CME2.

Also in the described method requires a pre-processing of the received cyclic alkylenediamine acids ammonia with formation of the corresponding ammonium salts alkylenediamine acids (Hoffmann H. Becke-Goehring H. Phosphorus Sulfides.//Topics in Phosphorus Chemistry. 1976, Vol.8, PP, 193-271).

RSH + NH3___ RSHNH3< / BR>
where R2CME2CH2CME2CH2Snresn2CME2.

However, in the calculation of the three-stage method for synthesis of S-trialkyl and triphenylene-Oh, Oh-alkylenediamines based on tetratetracontane, their outputs are significantly lower than in the proposed method of obtaining S-triphenylcarbinol EPE is AI diodes tetratetracontane (stage 1) will reach 75% in the calculation of the original teratological, and outputs ammonium salts alkylenediamine acids 58% (stage 2), and the final S-triethylsilyl-O,O-2,3-dimethylallylpyrophosphate 73% (stage 3). Thus the total yield ammonium salts alkylenediamine acids in stages 1 and 2 is only 43% and the target S-triethylsilyl-O-2,3 - dimethylallylpyrophosphate three stages in the calculation of the original teratological not exceed 31%

The objective of the invention is to create a new simpler way of obtaining new S-triphenylcarbinol esters of linear dealkylation and tetrathiofulvalene acids with good yields and purity of the target product.

The task was solved by the described method of obtaining S-triphenylcarbinol esters of dealkylation and tetrathiofulvalene acids, namely, that teratological subjected to interaction with germaniyorganicescoe compounds, which are used triphenyl(etaxi) and triphenyl(isobutyric)Teutons at 20-80aboutWith subsequent isolation of the target products by the known methods (extraction, distillation).

The reaction proceeds according to the following scheme:

P4S10+ 8RXGePh3___ 4 (RX)SGePh3+ 2 (Ph3Ge)2S

where R ness the keel and triphenylcarbinol cyclic ethers alkylenediamine acids proposed method for the synthesis of S-triphenylcarbinol esters of linear cyclic alkalinity and tetrathiofulvalene acids are those as phosphorus compounds containing the group P(S)S-, are used directly teratological that reduces the synthesis of target products, simplifies the process, makes it possible to avoid the undesirable formation of hydrogen sulfide increases the purity of the products; as germaniyorganicescoe derived using alkoxides and allylmercaptan triphenylamine, the reaction is carried out at 20-80aboutC.

The structure of the obtained compounds is confirmed by IR, NMR1H and31R spectroscopy, mass spectrometry and elemental analysis.

The target products are formed from the outputs (64-69%). The invention is illustrated by the following examples.

P R I m e R 1. O,o-Diethyl-S-triphenylpyridinium (1).

A mixture of 0.4 g (0.90 mmol) of tetratetracontane and 2.5 g (7.2 mmol) of triphenyl(ethoxy)Herman stirred at 20aboutC for 6 hours the Mixture is vacuum at 0.02 mm RT.article 2 h at 40aboutC. the Residue is extracted with anhydrous hexane and benzene. Hexane and benzene extracts vaccum at 0.02 mm RT. Art. 1 h at 40aboutC. In the remainder of 1.24 g (69%) o,O-diethyl-S-triphenylphosphate with so pl. 98aboutC.

An NMR spectrum31P (Bruker MSL-400, 162 MHz, WITH6H, M. D. J, Hz): 0,92 (T, 6N, CH2OH,3Jn-n7,0); 3,75 (D. K. 4H, SNO,3Jn-n7,0,3JR-n15,5); 6,93-of 7.60 (m, 15 NM, C)

IR-spectrum (UR-20, the suspension in vaseline oil, KBr, , cm-1): 3072 Wed, 3055 cf (=C-H, Ar); 2960 sq, 2932 Wed, 2870 cf (CH3as, s), (CH2, as, s); 1590 SL, 1490 cf (C=C, Ar); 700 cp (P=S), (PS2as); 546 cp, cp 516 (P-S), (PS2s), 465 c (GePh3as); 428 c, 415 c, 405 c (Ge-S). Mass spectrum (Hitachi M-80-B, PI, 70 eV): m/z (IRel,): 491 (M)+(5%), 306 (M-2EtO-PS2)+(100) (HEE, 100 eV), m/z (IRel,): 412 [M+H-Ph/+(63), 381 [M+H-Ph-S/+(22), 259 (M+H-3Ph/+(5).

Found, C 54,88; H 5,40; Ge Br15.15; P 6,67; S 13,31.

C22H25GeO2PS2.

Calculated C 54,02; H 5,17; Ge 14,85; P 6,34; S 13,08.

P R I m m e R 2. S,S'-Di-ISO-butyl-S ' -triphenyltetrazolium (2).

A mixture of 0.9 g (2.0 mmol) of tetratetracontane and 6.8 g (16.3 mmol) of triphenyl(from-butylthio)Herman stirred at 80aboutC for 0.5 hours, the Mixture is vacuum at 0.02 mm RT.article when 40aboutWith over 2 hours Of residue on film evaporator allocate 3.0 g (64%) S,S'-di-isobutyl-S-triphenylmethylchloride (2) at a temperature of thermocouple 200about(0,002 mm RT.cent.).

An NMR spectrum31P (Bruker MSL-400, 162 MHz, WITH6H6,p, M. D.): 83,5. Range PMR (Varian T-66,5); the 1.44 to 1.76 (m, 2H, SNSN2); and 2.26 (doctor d, 4H, CH3SP,3Jn-n6,5,3JR-n13,0); 6,80-of 7.70 (m, 15 NM, (C).

IR-spectrum (UR-20, liquid film, KBr, , cm-1): 3073 cp, 3057 cp, 3030 SL, 3015 sq, (=C-H, Ar); 2967 cp, 2930 SL, 2888 CL (CH3as, s), (CH2as, s); 1590 SL, 1490 cf (C=C, Ar), 1390 SL, 1370 SL /(CH3)2With the heme s/; 705 O. S. W (P=S), (PS2as), 565 cp, cp 535 (P-S), (PS2s), 468 cp. W (GePh3as), 417 SL (Ge-S).

Found, C 55,36; H 5,72; Ge 13,00; P 5,98; S 21,73.

C26H33GePS4< / BR>
Calculated C 54,09; H 5,78; Ge 12,59; P Lower Than The 5.37; S 22,17.

Also highlighted 0.5 g (19%) of bis(triphenylmethyl)sulfide with so pl. 137-140aboutC.

Range PMR (Bruker WM-250, 250 MHz, C6D6, , M. D.): 6,98-the 7.65 (m, N, C).

IR-spectrum (UR-20, the suspension in vaseline oil, KBr, , cm-1): 480 c (GePh3as).

Found, C 67,46; H 4,34; Ge 22,25; S 5,70.

C36H30Ge2S.

Calculated C 67,56; H 4,74; Ge 22,70; S 5,00.

Thus, the inventive method provides for the achievement of this goal.

The advantages of the proposed method are:

the achievement of high yields of the target products (64-69%),

the method allows us to simplify the process, to minimize the stage of synthesis of the finite S-triphenylcarbinol esters of diti and titrate is in a single phase, because excluded the stage of obtaining ditio and tetrathiofulvalene acids, ammonium salts;

the method allows to increase the purity of the target products by eliminating the formation of hydrogen sulfide and fine crystalline salts and other by-products;

mild reaction conditions, reduce the cost of energy in the claimed method.

The METHOD of OBTAINING S-TRIPHENYLCARBINOL ESTERS of DEALKYLATION AND TETRATHIOFULVALENE ACIDS of General formula

< / BR>
where R is lower alkyl;

X IS O, S,

the interaction of tetratetracontane with alkoxy - or allylmercaptan triphenylamine General formula

RXGe(C6H5)3,

where R and X have the above values,

at 20 80oWith subsequent isolation of the target product.

 

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