The method of obtaining diethylarsine esters diisobutylaluminum acid


C07F9/72 - Aliphatic compounds

 

(57) Abstract:

Usage: in the chemistry of organophosphorus compounds. The inventive method of obtaining diethylarsine esters diisobutylaluminum acid of the formula (I) (i - BuS)2P(S)SAsEt2the reaction tetratetracontane with isobutyl ether diethylthiocarbamate acid i-BuSAsEt2at 20oWith the presence of benzene, followed by separation of the target product known techniques (distillation). The invention relates to a new method of obtaining a new connection, which may find application as a fungicide or insecticide.

The invention relates to the chemistry of organophosphorus compounds, namely to a new way of getting dietilammonieva ether diisobutylaluminum acid of the formula (I)

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O, O-Dialkyldithiophosphate arsenic possess physiological activity (fungicidal and insecticidal activity) (Perry C. A.// Gazz. 1959, -Vol., 89. -P. 1315. -Rehim. - 1960.-22460. Patent Germany N 1022048 (1958). - Chem. Abstr. -1960. -20055. Shvetsova-Shilovsky K. D., Melnikov N. N., Andreev E. I., Bokarev L. P., Sapozhnikov Y. N.// AH, -1961.-so 31. -S. 845; Melnikov N. N., Shvetsova-Shilovsky K. D., Malutin B. E., Andreev E. I., Gar K. A., Gorbachev K. A., Warsaw S. P., Kofman L. P.-Ed.mon. (With the implemented diethylaminoethyl ether diisobutylaluminum acid is not described in the chemical and patent literature.

The literature describes a method for O,O-diethyldithiophosphate 5-carboxyl-5,10-dihydrophenazine (1) and (2) the interaction of the potassium salt Diethyldithiophosphoric acid 5-acetyl (or 5-benzoyl-5,10-dihydrofinasteride boiling in the medium of anhydrous acetone dithiophosphoric acid 5-acetyl (or 5-benzoyl-5,10-dihydrofinasteride by boiling in a solution of acetone (chudaeva N. A., Kamei, H., Manakov K. A. Synthesis of some arsenic - and armatocereus derivatives O,O-dialkyldithiophosphoric acids.// Zhur.General.chemistry, 1966, T. 36, N 11. S. 1994-1999).

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where (1) R = MeO (90%);

(2) R = Ph (92%).

The disadvantages of the described method are carrying out reactions when heated (bath temperature up to 75oC), which requires additional costs of materials and energy, the formation of difficult-fine precipitate (potassium chloride). The disadvantages of this method is also a multi-stage synthesis of target products, including the necessity of obtaining the prior O,O-Diethyldithiophosphoric acid based on teratological and ethanol by heating to 80-90oC (stage I) with the imminent release of gaseous toxic hydrogen sulfide and the formation of by-product is dithiophosphoric acid, they pollute it (Hoffman 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 N. H., Horowitz, H. H.// C. A., 1968, Vol 68, No. 2, 3568f).

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In addition, in the described method requires a pre-processing O, O-dialkyldithiophosphoric acid potassium with formation of the corresponding potassium salts of O,O-dialkyldithiophosphoric acids (H. Hoffman, Becke-Goehking H. , Phosphorus Sulfides. // Topics in Phosphorus Chemistry. 1976, Vol.8. pp. 193-271) (stage II).

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Output Diethyldithiophosphoric acid is 76,5% in the calculation of the original teratological (stage I), the output of the potassium salt Diethyldithiophosphoric acid up to 70% per Diethyldithiophosphoric acid (stage II), and outputs the target 5-acetyl - 5-benzoyl-5,10-Digi gropedasain-10-S-(O,O-diethyldithiophosphate) (1) and (2) is 90% and 92%, respectively, in the calculation of the potassium salt Diethyldithiophosphoric acid (stage II). Thus, the output of the potassium salt Diethyldithiophosphoric acid is 53,6% in terms of the initial tetratetracontane on both stages I and II, and the total outputs 5-acetyl - 5-benzoyl-5,10-dihydrophenazine-10-S-(O, O-diethyldithiophosphate) (1) and (2) do not exceed 48,2 and 48.0%, respectively, in three stages I, II and III in the calculation of Shoba get dietilammonieva ether diisobutylaluminum acid in good yield and purity of the target product.

The task was solved by the described method of obtaining dietilammonieva ether diisobutylaluminum acid, which consists in the fact that teratological subjected to interaction with mishacollins connection, which used isobutyl ether diethylaminoethoxy acid, followed by separation of the target product known examples (distillation).

The reaction proceeds according to the following scheme:

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Distinctive features from those described in the literature method for the synthesis of 5-acetyl - 5-benzoyl-5,10-dihydrophenazine-10-S-(O,O-diethyldithiophosphate the proposed method to obtain dietilammonieva ether diisobutylaluminum acids are those that compounds of phosphorus containing group is 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 michalkaronski derived using isobutyl ether diethylaminoethoxy acid, the reaction is carried out at 20oC in the environment of benzene.

The structure of the obtained compounds is confirmed by the data of IR, brasaetsa exit 77%. The invention is illustrated by the following example.

S,S'-Diisobutyl-S"-diethylaminoacetate.

To a solution of 4.8 g (21.6 mmol) of isobutyl ether diethylthiocarbamate acid in 5 ml of anhydrous benzene at 20oC under stirring add portions of 1.2 g (2.7 mmole) of tetratetracontane. The mixture is stirred for 2 h at 20oC and vacuum for 2 h at 0.06 mm RT.article when 40-50oC. the balance on the device for molecular-film distillation allocate 3.4 g (77%) S,S'-Diisobutyl-S-Diethylenetriamine when the temperature of thermocouple 130oC (0.07 mm RT.cent.), p20D1,5901.

An NMR spectrum31P (Bruker CXP-100, 36,5 MHz, C6H6,p, M. D.): 92.4. Range PMR (Varian T-60, 60 MHz, C6D6internal standard (Me3Si)2O , M. D., J, Hz): 0,80 (g, 12H, CH3CHCH2S3JH-H7.0); 1.02 (t, 6H, CH3CH2AS,3JH-H7.0); 1.58 (K, 4H, CH3CH2S3JH-H7.0); 1,68 is 2.10 (m, 2H, CH3CHCH2S); 2.84 (D. D., 4H, CH3CHCH2S3JH-H7.0,3JP-H15.0). IR-spectrum (Fourier transform infrared spectrometer Bruker IFS 113, the liquid film , cm-1), 2959 O. S., 2926, 2869 (CH3AS,S), (CH2AS, S); 1453 cf (CH3AS, S, (CH2AS, S), 1409 Wed, 1386 cf / (CH3)2C hem S/; 680 O. S.)+(10); 241 (M-ASEt2)+(56); 152 (M-Bu-S-SASEt2)+(100); (HEE, 100 eV), m/z (IRel,%): 185 (M+H-BuSASEt2)+(31); 269 (M+H - 2SD)+(91).

Found,%: C 35.80; H, 6.90; AS 18.77; P 7.44; S 31.42; C12H28AP4.

Calculated,%: C 35.46; H 6.96; AS 18.45; P 7.63; S 31.49.

Thus, the claimed method provides the achievement of this goal.

The advantages of the proposed method are:

achievement of output target product (77%) in comparison with the known in the literature;

the method allows us to simplify the process of synthesis of the final dietilammonieva ether diisobutylaluminum acid proceeding directly from industrially available tetratetracontane, because it excluded the stage Diethyldithiophosphoric acid and its potassium salt;

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

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

The method of obtaining diethylarsine esters diisobutylaluminum acid formula

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characterized in that teratological subject ot the With subsequent isolation of the target product.

 

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