Dialkyl(aryl)-cis-2-(2-hydroxyaryl)-2-alkyl(aryl)ethenylphosphine oxides and method of obtaining them

FIELD: chemistry.

SUBSTANCE: invention can be used for separating rare-earth and coloured metals and pertains to new phosphorous-containing complex-forming phosphine oxides with general formula (I) and methods of obtaining them: , where R1 = H, R2 = Ph, R3 = R4 = Ph, Me, Et, Pr, CH2Ph, 2-MeO-C6H4, C8H17; R1 = 4-Me, R2 = Ph, R3 = R4 = Ph, CH2Ph, 2-MeO-C6H4; R1 = H, R2 = 1-naphthyl, R3 = R4 = Ph, CH2Ph, 2-MeO-C6H4; R1=H,R2 = Bu,R3 = R4 = Ph; R1 = H, R2 = Ph, R3 = cyclo-C6H11, R4 = Et, Ph. The method of obtaining phosphine oxides (I) involves reaction in a medium of an organic solvent of chlorophosphorinine oxides with formula (II) with corresponding Grignard reagents, hydrolysis of the reaction mixture and separation of target compounds.

EFFECT: obtaining new phosphorous-containing complex-forming compounds with formula (I).

18 ex, 1 tbl

 

The invention relates to the chemistry of organophosphorus compounds, namely to new phosphine oxides of General formula (I)

where R1=N, R2=Ph, R3=R4=Ph, Me, Et, Pr, CH2Ph, 2-MeO-C6H4C8H17(1-7);

R1=4-Me, R2=Ph, R3=R4=Ph, CH2Ph, 2-MeO-C6H4(8-10);

R1=H, R2=1-naphthyl, R3=R4=Ph, CH2Ph, 2-MeO-C6H4(11-13);

R1=H, R2=Bu, R3=R4=Ph (14);

R1=H, R2=Ph, R3=cyclo-C6H11, R4=Et, Ph (15-16),

and the way they are received.

It is known that the oxides have a high extraction (complexing properties with respect to the ions of rare earth and non-ferrous metals and are often the starting compounds to obtain phosphines, which in turn are used as ligands in metal-complex catalysis ([1] Phosphine Oxides, Sulphides, Selenides and Tellurides, Vol.2, The Chemistry of Organophosphorus Compounds. Ed. by Frank R.Hartley. John Wiley & Sons - 1992, 664 p; [2] M.G. de Bolster. Phosphoryl Coordination Chemistry: The Period 1975-1981. In: Topics in Phosphorus Chemistry. Ed. By M.Grayson, E.J.Griffith. J.Wiley & Sons, 1983. N.-Y., Chichester, Brisbane, Toronto, Singapore. Vol.11. P.69-295).

The compounds of formula (I) can be used as a starting compound in chemistry to obtain phosphines with a hydroxyl group in the fourth position of one of the radicals as legendofkatboi-type metal complex catalysis, and as a neutral chelating ligands for the extraction of rare earth and non-ferrous metals.

Known conventional trialkyl(aryl)phosphine oxides of the formula R3P=O, the method of obtaining of which lies in the interaction of Grignard reagents with phosphorus oxychloride in diethyl ether or tetrahydrofuran ([3] U.S. patent No. 3338701, publ. 29.08.1967 g), however, this method is applicable only for simple symmetric phosphine oxides.

Also known is a method of obtaining a simple symmetric phosphine oxides of phosphorus oxychloride and Grignard reagents in the mixture of the hydrocarbon - ether or tetrahydrofuran ([4] the United Kingdom patent No. 1376028, publ. 04.12.1974 g).

Known unsymmetrical phosphine oxides of the formula R′R2P=O and (R′)2RP=O, which are offered in a mixture of phosphorus oxychloride, two alkylchloride R′Cl RCl, and metal magnesium ([5] RF patent №2032691, publ. 10.04.1995 g). The process is carried out in a mixture of hydrocarbons with tetrahydrofuran, in this part of the solvent is distilled before the hydrolysis step.

It is also known that asymmetric phosphine oxides can be obtained by the reaction of O,O-dialkylated(aryl)phosphonates and O-alkyldimethyl(diaryl)Phosphinates with Grignard reagents ([6] H.R.Hays, D.J.Peterson. in Organic Phosphorus Compounds. Ed. by G.M.Kosolapoff, L.Maier. Wiley-Intersci., N.-Y., L., Sydney, Toronto. 1972. Vol.III. P.341-500).

Structural analogs of compounds (I) are phospho the new acid of the following structure:

which is produced by hydrolysis derivatives of 4-aryl-2,5,6,7,8-pentachlorbenzene[e]-1,2-oxaphosphorin-2-oxide ([7] Wefering, Athaullah, AlN, Ihalainen, Rev, Aiginoglu, Abjorensen, Casabella, Resason, Valery Morozov. Joh. 2002, T, VIP, S-1888; [8] Wefering, Casanova, Aiginoglu, Namatanai, Fax, Casabella, Resason. Zhur.org.chem., 2002, V.38, VIP, S-1239). Complexing properties of these acids has not been studied (not identified).

The target phosphine oxides (I) can be obtained by the above methods, as Grignard reagents containing as an additional functional substituent hydroxyl group, the literature is not known.

The authors have not found substances, such synthesized compounds (I), in the scientific and patent literature.

Object of the present invention are new phosphine oxides, expanding Arsenal of known extractants (complexing funds), and to develop a method of their synthesis.

The technical result is the new dialkyl(aryl)-CIS-2-(2-hydroxyaryl)-2-alkyl(aryl)attilmopiremi formula (I) and the way they are received, allowing to obtain these compounds with the release of not less than 80%.

The technical result is achieved by the claimed method for production of dialkyl(aryl)-CIS-2-(2-hydroxyaryl)-2-alkyl(aryl)is daniltchenko formula (I), having complexing properties through the interaction of a six-membered heterocyclic derivatives of phosphorus - substituted in benzoflavone 4-aryl(alkyl)-2-chlorobenzo[e]-1,2-oxaphosphorin-2-oxide (II) (hereinafter "chlorostannate") magnetogenesis compounds (Grignard reagents) (scheme 1).

R1=H, R2=Ph, R3=R4=Ph (1), Me (2), Et (3), Pr (4), Ch2Ph, (5) 2MeO-C6H4(6), C8H17(7);

R1=4-ME, R2=Ph, R3=R4=Ph (8), CH2Ph (9), 2MeO-C6H4(10);

R1=H, R2=1-naphthyl, R3=R4=Ph (11), CH2Ph (12), 2MeO-C6H4(13);

R1=H, R2=Bu, R3=R4=Ph (14);

R1=H, R2=Ph, R3=cyclo-C6H11, R4=Et (15), Ph (16).

Scheme 1.

The method includes processing chlorostannate (II) with a Grignard reagent R3MgX (X=Cl, Br, I) (R4=R3=the above primary alkyl, benzyl or aryl) in a molar ratio of 1÷(2.0-2.6) or initial processing cyclohexylmaleimide (R3=cyclo-C6H11) in a molar ratio of 1÷(1.2-1.4) and the subsequent processing of another Grignard reagent R4MgBr (R4=Ph, Et) in a molar ratio of 1:(1.2-1.4). The target compound (I) further isolated after treatment of the reaction mixture with water or with water, acidified Sol is Oh acid (pH 3-6) well-known techniques: the separation of the aqueous and organic phases, distillation of the organic solvent (a mixture of benzene and ether, or THF, or isooctane) or filtering drop-down sediment. Then, the obtained compound (yield 80%to 95%, the content of the basic substance is not less than 95%) is dried in air or in vacuum (0.1-12 mm Hg).

Source chlorostannate (II) are both available compounds which can be retrieved easily from pentachloride phosphorus, corresponding pyrocatechin and aryl - or alkylation (methods of their synthesis are described in: [9] Wefering, Aiginoglu, Ihalainen, Athaullah, Rev, AlN, Casabella, Resason, Namatanai, Averianov. Joh. 1998, T, 9, S-1509; [10] Wefering, AlN, Annorexia, Athaullah, Namatanai, Abjorensen, Ihalainen, Resason, Aiginoglu. Joh. 2004, T, VIP, S-1972; [11] Wefering, Annorexia, AlN, Athaullah, Namatanai, Resason, Ihalainen, Aiginoglu. Joh. 2006, T, Issue 3, S-432).

The inventive method of producing phosphine oxides (I) excludes the formation of a mixture of compounds obtained by using the methods described in the patent [5] and in [6, 7].

The method is illustrated by the following examples.

Example 1. A solution of 30 g (0.0965 mol) of chlorostannate (IIa) in 20 ml of benzene was added dropwise with stirring in a stream of argon to phenylmagnesium prepared from 5.1 g (0.2125 mole) of Mg is 22.4 ml (33.4 g, 0.2125 mole) of bromine benzol in 150 ml of diethyl ether using the standard method ([12] preparative organic chemistry. Translation edited Nsswitch. Ed. "Chemistry", Moscow-Leningrad, 1964. 907). The resulting reaction mass was heated at boiling ether for 30 minutes, then cooled and neutralized with a solution of 18 ml of concentrated hydrochloric acid in 100 ml of distilled water with vigorous stirring and boiling ether. The solution was stirred 30 min until reaching room temperature. This was accompanied by the formation of a precipitate, which was filtered and washed with 20-30 ml of ether, and dried in air or in a vacuum of 12 mm Hg Obtained 36 g (87%) of 2-(2-hydroxy-5-chlorophenyl)-2-phenylethylhydroperoxide (1) (taking into account the additional amount of sediment deposited from the filtrate after removal of the ether and benzene), TPL 185-186°C. Found, %: C 72.65, H 4.91, P 7.29. With26H20ClO2R. Calculated, %: C 72.47, H 4.64, P 7.20. An NMR spectrum31P{1N} (36.46 MHz, CDCl3): δP22.6 ppm IR spectrum, cm-1: 431, 455, 511, 525, 543, 592, 630, 639, 665, 693, 720, 728, 739, 767, 812, 836, 893, 922, 933, 945, 977, 999, 1030, 1069, 1114, 1172, 1216, 1262, 1289, 1313, 1330, 1376, 1418, 1436, 1446, 1465, 1496, 1558, 1586, 1655, 1686, 1812, 1864, 1890, 1910, 1958, 2588, 2730, 2783, 2856, 2926, 3062, 3631, 3651, 3677. An NMR spectrum1H (600 MHz, DMSO-D6, 45°, δ ppm, J Hz): 9.17 sh. (HE, 1H), 7.70 sh. m (N12, 4H), 7.49 ush. m (N142N,3JHC13CH14 7.1), 7.40 ush. m (N137N8N9-11, 5H), 6.33 ush. with (N5, 1H), 7.03 (N3, 1H,2JPCH3 20.5).

Example 2. To the Grignard reagent, obtained by the standard technique of 2.2 g (0.0924 mol) of magnesium and 5.75 ml (13.1 g, 0.0924 mol) of iodomethane in 100 ml of diethyl ether, was added dropwise a solution of 13.8 g (0.0444 mol) of chlorostannate (IIa) in 25 ml of benzene. After adding a solution of the reaction mass was heated with vigorous stirring for 30 min (this happened stratification). After cooling to room temperature the reaction mass was neutralized with vigorous stirring and boiling ether 30 ml of water and then 8 ml of hydrochloric acid. The organic layer was separated, added 2-4 ml of acetone and the resulting homogeneous organic layer was besieged by dilution with water. Selected 13.0 g (96%) of 2-(2-hydroxy-5-chlorophenyl)-2-phenylethylhydroperoxide (2) in the form of a light brown powder, TPL 172-175°C. Found, %: C 62.37, H 5.49, P 10.55. C16H16ClO2P. Calculated, %: C 62.64, H 5.22, P 10.11. An NMR spectrum31P{1N} (36.46 MHz, CDCl3): δP37.0 ppm IR spectrum, cm-1: 422, 452, 534, 567, 637, 694, 759, 819, 879, 910, 940, 954, 1031, 1114, 1138, 1221, 1284, 1303, 1334, 1377, 1409, 1464, 1496, 1573, 1587, 1604, 2582, 2683, 2854, 2924, 3380. An NMR spectrum1H (600 MHz, DMSO-D6that δ ppm, J Hz): 1.24 d (CH3, 6H,2JPCH13.1), 6.56 (N3, 1H,2 JPCH3 16.2), 6.83 d (N8, 1H,3JH7CCH8 8.6), 7.08 (N5, 1H,4JH7CCH5 2.6), 7.21 D. D. (N7, 1H,3JH8CCH7 8.7,4JH5CCCH7 2.6), 7.24-7.28 (m6H3, 5H), 9.76 USS (HE, 1H).

Example 3. To the Grignard reagent obtained by the standard method of 0.43 g (0.0179 mole) of magnesium, 1.44 ml (2.8 g, 0.0179 mol) of iodata in 20 ml of diethyl ether, was added dropwise a solution of 2.5 g (0.0080 mole) of chlorostannate (IIa) in 10 ml of benzene and heated at boiling 0.5 h the Solution was cooled and hydrolyzed in 30 ml of water and 2.3 ml of hydrochloric acid. Organic and aqueous layers were filtered and separated. Then the solvents were released, the solidified residue greenish color again washed with hydrochloric acid (15 ml 10% solution), was separated from the leaching solution by decantation and then dried under vacuum. Received 2.52 g (94%) of 2-(2-hydroxy-5-chlorophenyl)-2-generateelectricity (3) in the form of a brown powder, TPL 75-77°C. Found, %: C at 64.29; H 6.12, P 9.41. C18H20ClO2P. Calculated, %: C 64.57, H 5.98, P 9.27. An NMR spectrum31P{1N} (36.46 MHz, CDCLQ: δP47.5 ppm IR spectrum, cm-1: 450, 505, 532, 583, 632, 653, 677, 693, 727, 743, 763, 823, 850, 887, 916, 941, 975, 991, 1036, 1119, 1187, 1218, 1235, 1284, 1332, 1377, 1414, 1460, 1495, 1569, 1586, 1601, 1812, 1876, 1959, 2588, 2687, 2856, 2930. An NMR spectrum1H (600 MHz, CDCl3that δ ppm, J Hz): 1.09 D. T. (CH3, 6H,3JPCCH17.6,sup> 3JHCCH7.5), 1.64-1.70 m (RSN2, 4H, AB-part of the spectrum AVMH3,3JH(X)CCH(A)7.5,3JH(X)CCH(B)7.5), 6.32 (RSN3, 1H,2JPCH18.1), 6.92 (N5, 1H,4JHCCCH2.6), 7.05 d (N8, 1H,3JHCCH8.7), 7.19 D. D. (N7, 1H,3JHCCH8.7,4JHCCCH2.6), 7.26 ush. m (N92N,3JHCCH7.5-7.7), 7.31 ush. m (N102N,3JHCCH7.5-7.7,3JHCCH7.1), 7.33 m (N11, 1H,3JHCCH7.1), 8.57 sh. (HE, 1H).

Example 4. To the Grignard reagent obtained by the standard method of 0.8 g (0.0333 mol) of magnesium, 3.25 ml (5.67 g, 0.0333 mol) of 1-jumprope in 20 ml of diethyl ether, was added dropwise a solution of 5.2 g (0.0167 mole) of chlorostannate (IIa) in 15 ml of benzene and heated at boiling 0.5 hours While the reaction mass has acquired a dark brown color. The solution was cooled and hydrolyzed in 40 ml of water and 2 ml of HCl, the resulting layers were separated. In the organic layer will drop a yellow precipitate, which was filtered, washed with acetone and dried in a vacuum of 12 mm Hg Obtained 4.7 g (81%) of 2-(2-hydroxy-5-chlorophenyl)-2-phenylethylhydroperoxide (4), TPL 143-145°C. Found, %: C 66.20, H 6.15, P 8.81, Cl 9.87. C20H24ClO2P. Calculated, %: C 66.21, H 6.62, P 8.55, Cl 9.79. Mass spectrum (here and below are listed the most common isotopes), m/z: 364, 362 [M], 347, 345 [M-HE], 329, 327, 321, 319, 305, 304, 302, 294, 284, 275, 265, 22, 261, 259, 230, 228, 194, 166, 165, 139, 135, 134, 119, 106, 92, 78, 64, 41, 27. An NMR spectrum31P{1N} (162.0 MHz, DMSO-D6): δP37.8 ppm IR spectrum, cm-1: 420, 464, 488, 533, 592, 637, 691, 717, 763, 817, 851, 889, 943, 1033, 1078, 1112, 1155, 1205, 1236, 1251, 1277, 1341, 1378, 1406, 1462, 1493. 1570, 1588, 1605, 1772, 1878, 1967, 2728, 2923, 3210. An NMR spectrum1H (250 MHz, DMCO-D6that δ ppm, J Hz): 0.92 t (CH3, 6H,3JHCCH7.2), 1.47 m (CH2, 4H,3JHCCH7.2-7.5), 1.58-1.65 m (RSN2, 4H,2JPCH214.9,3JHCCH7.0-7.4), 6.46 (N3, 1H,2JPCH16.3); 6.88 (N8, 1H,3JH7CCCH8 8.7); 7.11 (N5, 1H,4JH7CCCH5 2.7); 7.36 D. D. (N7, 1H,3JH8CCH7 8.7,4JH5CCCH7 2.7), 7.28 and 7.32 two m (C6H5).

Example 5. To the Grignard reagent obtained by the standard method of 0.81 g (0.0338 mole) of magnesium, 3.9 ml (4.28 g, 0.0338 mol) benzylchloride in 40 ml of diethyl ether, was added dropwise a solution of 4.5 g (0.0145 mole) of chlorostannate (IIa) in 20 ml of benzene. This was accompanied by the formation of a white precipitate. The reaction mixture was heated for 30 min, then cooled and treated with stirring with a solution of hydrochloric acid (10 ml) in 30 ml of water. Precipitated from the organic layer, the residue was filtered off, washed with a small amount of acetone and dried under vacuum (65°s, 12 mm Hg). Received 6 g (90.5%) of 2-(2-hydroxy-5-chlorophenyl)-2-generatedigitsresponse is a (5), TPL 210-211°C. Found, %: C 72.91; H 5.38, P 6.92, Cl 7.78. With28H24ClO2R. Calculated, %: C 73.28, H 5.23, P 6.76, Cl 7.74. The mass spectrum of the compound, m/z: 460, 459, 458 [M]+•, 443, 442, 441 [M-HCl], 433, 423, 422, 401, 377, 370, 369, 368, 367, 366, 349, 321, 320, 319, 304, 303, 301, 289, 285, 277, 275, 230, 229, 228, 166, 165, 139, 121, 91 [PhCH2], 65. An NMR spectrum31P{1N} (162.0 MHz, DMSO-D6): δP29.1 ppm, IR spectrum, cm-1: 449, 481, 487, 559, 575, 586, 636, 700, 721. 753, 780, 794, 821, 832, 864, 888, 915, 938, 973, 991, 1001, 1030, 1067, 1108, 1128, 1162, 1199, 1236, 1258, 1286, 1335, 1377, 1409, 1455, 1495, 1570, 1600, 1772, 1817, 1904, 1960, 2595, 2722, 2772, 2922, 3421. An NMR spectrum1H (600 MHz, DMSO-D6, 40°, δ ppm, J Hz): 3.06 ush. d (CH2, 4H,2JPCH14.6), 6.42 (N3, 1H,2JPCH20.5); 6.49 (N5, 1H,4JH7CCCH5 2.6), 6.81 d (N8, 1H,3JH7CCH8 8.7), 7.15 D. D. (N7, 1H,3JH8CCH7 8.7,4JH5CCCH7 2.6), 7.34 and two 7.15 m (3C6H5, 15H).

Example 6. To the Grignard reagent obtained by the standard method of 0.92 g (0.0383 mol) of magnesium, 4.74 ml (7.16 g, 0.0383 mol) of ortho-bromoanisole in 20 ml of tetrahydrofuran, was added dropwise a solution of 5 g (0.0161 mol) of chlorostannate (IIa) in 10 ml of benzene. After the addition the reaction mass was heated at the boil for 0.5 hours in a day was a partial sediment. The precipitate was filtered, washed with water, acidified with hydrochloric acid, and then with clean water. The filtrate of the individual also was treated with water (pH 3.0-4.0), formed when this precipitate was separated. Precipitates were combined and dried in air and then in vacuo (65°With 18 mm Hg). Received 6 g (76%) of 2-(2-hydroxy-5-chlorophenyl)-2-phenylethenyl-bis(2-methoxyphenyl)phosphine oxide (6), TPL 218 to 221°C. Found, %: C 68.77; H 5.14, Cl 7.44, P 6.12. C28H24ClO4P. Calculated, %: C 68.50, H 4.89, Cl 7.24, P 6.32. An NMR spectrum31P{1N} (162.0 MHz, DMSO-D6): δP16.1 ppm IR spectrum, cm-1: 406, 498, 551, 581, 633, 696, 727, 755, 803, 817, 846, 888, 945, 1021, 1045, 1072, 1088, 1111, 1126, 1148, 1248, 1277, 1377, 1414, 1432, 1462, 1477, 1576, 1590, 1958, 1722, 2854, 2924. An NMR spectrum1H (600 MHz, DMSO-D6, 45°, δ ppm, J Hz): 3.67 (och3, 6N), 6.52 (N8, 1H,3JH7CCH8 8.7), 6.93 (N5, 1H,4JH7CCCH5 2.4), 6.92 and 6.93 two ears. d (N12, 2H,3JH13CCH12 8.7-8.8), 6.98 d (RSN3, 1H,2JPCH3 19.5), 6.99 D. D. (N7, 1H,3JH8CCH7 8.6,4JH5CCCH7 2.4), 7.03 ush. D. D. (N142N,3JHCCH8.0,3JHCCH6.0), 7.20 m (N92N,3JHCCH7.8), 7.27-7.31 m (N10N11N13, 5H), 7.47 ush. D. D. (N15, 2H,3JPCCH15 7.4-7.7,3JHCCH15 7.4-7.7).

Example 7. To 3.5 g (0.1458 mol) of magnesium shavings, pre-activated crystalline iodine in 60 ml of isooctane under stirring in argon atmosphere was added dropwise 26.43 ml (at 35.02 is, 0.1458 mole) of 1-iodooctane. To the obtained after boiling (30 minutes) the solution was bury a solution of 18 g (0.0579 mol) of chlorostannate (IIa) in 20 ml of benzene. Observed the formation of a white emulsion which was heated at boiling for 40 minutes, then cooled and treated with a solution of hydrochloric acid (10 ml) in 30 ml of water. Isooctanol-benzene layer was separated, the solvent was removed by distillation in a vacuum of 12 mm Hg, the Residue was dried under vacuum (100°C, 0.1 mm Hg). Received 27.9 g (96%) of 2-(2-hydroxy-5-chlorophenyl)-2-generateelectricity (7) as a greenish oil. Found, %: C 71.22, N 9.07, P 6.27. C30H44ClO2P. Calculated, %: C 71.64, H 8.76, P 6.17. Mass spectrum, m/z: 502 [M]+•, 467 [M-Cl], 389 [M-C8H17], 276 [M-2C8H17], 229 [M-PO(C8H17)2], 228 [M-PO(C8H17)2-N]. An NMR spectrum31P{1N} (162.0 MHz, DMSO-D6): δP40.8 ppm IR spectrum, cm-1: 409, 472, 536, 567, 634, 671, 697, 724, 762, 822, 848, 885, 945, 1031, 1112, 1136, 1223, 1282, 1335, 1378, 1411, 1445, 1467, 1493, 1572, 1591, 1958, 2855, 2926, 2955, 3059.

Example 8. To a solution of phenylmagnesium obtained from 1.49 g (0.0621 mol) of magnesium and 6.53 ml (9.75 g, 0.0621 mol) of bromine benzol in 90 ml of ether was added with stirring dropwise a solution of 8 g (0.0246 mole) of chlorostannate (IIb) in 20 ml of benzene, so that the mixture is evenly boiling. The resulting reaction mass was heated at boiling for another 0.5 h, then cooled and when paramesh is the so called added 20 ml of water, then a solution of 10 ml of concentrated hydrochloric acid in 20 ml of water. This was accompanied by the formation of a white precipitate. The reaction mixture was stirred until reaching room temperature and then was filtered. The precipitate was dried first in air and then in vacuum of 0.1 mm Hg(80°). Selected 9.13 g (83.7%) of 2-(2-hydroxy-4-methyl-5-chlorophenyl)-2-phenylethylhydroperoxide (8), TPL 194-197°C. Found, %: C 73.02, H 5.13, P 6.73. With27H22ClO2R. Calculated, %: C at 72.89; H 4.95, P 6.97. An NMR spectrum31P{1N} (162.0 MHz, DMSO-D6): δP17.3 ppm IR spectrum, cm-1: 507, 522, 554, 593, 614, 693, 722, 739, 748, 768, 818, 838, 870, 889, 999, 1028, 1071, 1097, 1119, 1131, 1159, 1221, 1259, 1308, 1337, 1409, 1461, 1562, 1586, 1612, 1956, 2727, 2854, 2924, 3055, 3396. An NMR spectrum1H (600 MHz, CDCl3, 25°C δ ppm, J Hz): 6.95 d (N3, 1H,2JPCH3 18.8), 6.40 (N5, 1H), 6.95 (N8, 1H), 7.39, 7.65 7.45 and three m (C6H5, 15 NM), 9.40 (HE, 1H).

Example 9. To the Grignard reagent, obtained by the standard technique of 1.3 g (0.0542 mol) of magnesium, 6.24 ml (6.86 g, 0.0542 mol) benzylchloride in 90 ml of diethyl ether are added through an addition funnel with compensator was added dropwise a solution of 6.7 g (0.0206 mol) of chlorostannate (IIb) in 20 ml of benzene. The reaction mass was heated at boiling for another 0.5 hours, then cooled to room temperature and treated with distilled water, then with a solution of 10 ml conc. salt sour the s in 20 ml of water. Falling in this white precipitate was filtered and dried under vacuum (12 mm Hg, 100°). Selected 9.36 g (92%) dibenzyl-2-(2-hydroxy-4-methyl-5-chlorophenyl)-2-generateresponse (9) with TPL 169-172°C. Found, %: C 73.44; H 5.77, P 6.24. With29H26ClO2R. Calculated, %: C 73.65, H 5.50, P 6.56. The mass spectrum of the compound, m/z: 472 [M]+·., 381 [M-CH2Ph], 290 [M-2CH2Ph], 243 [M-PO(CH2Ph)2], 230 [M-PO(CH2Ph)2CH], 202, 183, 91 [CH2Ph]. An NMR spectrum31P{1N} (162.0 MHz, DMSO-D6): δP29.5 ppm IR spectrum, cm-1: 481, 488, 536, 588, 603, 699, 723, 735, 756, 795, 821, 834, 863, 886, 914, 929, 1005, 1031, 1067, 1128, 1161, 1180, 1199, 1235, 1257, 1338, 1377, 1455, 1495, 1569, 1587, 1601, 1958, 2725, 2855, 2923, 3364. An NMR spectrum1H (600 MHz, CDCl3, 25°C δ ppm, J Hz): 6.29 (N3, 1H,2JPCH3 21.4), 6.78 (N5, 1H), 7.04 (N8, 1H), 7.12-7.39 m (N10-12N15-17, 15 NM), 2.29 (CH3, 3H).

Example 10. To the Grignard reagent obtained by the standard method of 1.45 g (0.0604 mol) of magnesium, 7.48 ml (11.30 g, 0.0604 mol) of ortho-bromoanisole in 100 ml of diethyl ether, was added dropwise a solution of 7.8 g (0.0240 mol) of chlorostannate (IIb) in 50 ml of benzene. The reaction mass was heated at boiling for another 0.5 hours, then cooled to room temperature and treated with distilled water, then with a solution of 10 ml conc. hydrochloric acid in 20 ml of water. Thus was obtained a viscous white butter-like PR the product, which was separated from the acidic aqueous solution, washed with distilled water and dried under vacuum (12 mm Hg, 100°). Selected 10.77 g (89%) of 2-(2-hydroxy-4-methyl-5-chlorophenyl)-2-phenyl-bis(2-methoxyphenyl)phosphine oxide (10) with TPL 207-210°C. Found, %: C 69.17, H 5.33, P 6.24. With29H26ClO4R. Calculated, %: C 68.98, H 5.15, P 6.14. An NMR spectrum31P{1N} (162.0 MHz, DMSO-D6): δP16.4 ppm IR spectrum, cm-1: 499, 552, 592, 696, 722, 754, 803, 885, 1022, 1045, 1073, 1088, 1126, 1148, 1247, 1277, 1377, 1402, 1462, 1575, 1590, 1712, 1959, 2723, 2853, 2923, 3364. An NMR spectrum1H (600 MHz, CDCl3that δ ppm, J Hz): 2.12 (CH3, 3H), 3.67 (och3, 6N), 6.47 (N8, 1H), 6.92-6.94 m (N12, 2H), 6.93 (N5, 1H), 6.95 (RSN3, 1H, 2JPCH3 20.5), 7.02 ush. m (N14, 2H), 7.03 m (N10N11N13, 5H), 7.21 ush. d (N92N,2JH10CCH9 7.8-8.0), 7.46 ush. D. D. (N152N,3JHCCH7.0-7.2,3JPCCH7.0-7.2).

Example 11. To the Grignard reagent obtained from 0.8 g (0.0333 mol) of magnesium and 3.50 ml (5.23 g, 0.0333 mol) of bromine benzol in 50 ml of diethyl ether, with stirring in a stream of argon was added dropwise a solution of 5 g (0.0138 mole) of chlorostannate (IIc) in 10 ml of benzene. The reaction mass was heated at the boil for 0.5 h, cooled to room temperature and treated with distilled water, a solution of 5 ml of concentrated hydrochloric acid in 20 ml of water is, then again with water. The resulting yellow precipitate was filtered and dried in a vacuum of 12 mm Hg (100°). Selected 6.45 g (97%) of 2-(2-hydroxy-5-chlorophenyl)-2-naphthas-1-laterdeveloped (11), TPL 173-175°C. Found, %: C 75.11, H 4.77, P 6.23. C30H22ClO2P. Calculated, %: C 74.92, H 4.58, P 6.45. An NMR spectrum31P{1N} (162.0 MHz, DMSO-D6): δP16.8 ppm IR spectrum, cm-1: 409, 433, 506, 532, 546, 589, 627, 643, 694, 720, 747, 780, 800, 829, 889, 929, 970, 998, 1018, 1070, 1098, 1117, 1162, 1233, 1284, 1377, 1418, 1439, 1463, 1495, 1587, 2723, 2853, 2923, 3374. An NMR spectrum1H (600 MHz, DMSO-D6, 45°, δ ppm, J Hz): 6.49 (N8, 1H,3JH7CCH8 8.7), 6.70 (N3, 1H,2JPCH3 20.6), 6.96 D. D. (N7, 1H,3JH8CCH7 8.7,4JH5CCCH7 2.4), 7.20 d (N5, 1H,4JH7CCCH5 2.4), 7.38 (N9, 1H,3JHCCH7.0), 7.42-7.44 and 7.46-7.47 two m (N10N13N14N17N18, N), 7.75 D. D. (N16, 4H,3JPCCH11.4,3JHCCH7.6), 7.87 (N15, 1H,3JHCCH8.1), 7.91 D. D. (N12, 1H,3JHCCH6.2,4JHCCCH3.2), 8.17 D. D. (N11, 1H,3JHCCH6.1,4JHCCCH3.2), 9.71 (HE, 1H).

Example 12. To the Grignard reagent obtained from 0.8 g (0.0333 mol) magnie and 3.86 ml (4.22 g, 0.0333 mol) of benzylchloride in 20 ml of diethyl ether with stirring in a stream and the rut was added dropwise a solution of 5 g (0.0138 mole) of chlorostannate (IIc) in 10 ml of benzene. Next, the resulting reaction mass was treated as in example 11. Selected 6.62 g (94%) of 2-(2-hydroxy-5-chlorophenyl)-2-(naphthas-1-yl)ethenylbenzene-phosphine oxide (12), TPL 178-181°C. Found, %: C 75.34, H 5.47, P 6.29. C32H26ClO2P. Calculated, %: C 75.52, H 5.11, P 6.10. An NMR spectrum31P{1N} (162.0 MHz, DMSO-D6): δP30.8 ppm IR spectrum, cm-1: 417, 454, 479, 504, 538, 582, 620, 640, 683, 699, 720, 745, 783, 798, 815, 842, 863, 883, 911, 930, 957, 1019, 1031, 1069, 1118, 1153, 1198, 1229, 1283, 1342, 1377, 1411, 1455, 1495, 1586, 1601, 1710, 1825, 1884, 1958, 2717, 2921, 3030, 3441. An NMR spectrum1H (600 MHz, DMSO-D6, 45°, δ ppm, J Hz): 3.27 and 3.33 two m (CH2, 4H,2JH(A)CH(B)13.5-14.0,2JPCH(B)13.5-14.0,2JPCH(A)15.2), 6.12 (N3, 1H,2JPCH3 22.8), 6.59 (N5, 1H,4JH7CCCH5 2.7), 6.79 (N8, 1H,3JH7CCH8 8.7), 7.12 D. D. (N7, 1H,3JH8CCH7 8.7,4JH5CCCH7 2.7), 7.17 D. D. (N9, 1H,3JHCCH7.1,4JHCCCH0.9), 7.30-7.35 m (N16-18, 10H), 7.44 D. D. (N10, 1H,3JHCCH7.2,3JHCCH8.1), 7.46 7.50 and two m (N13and N142N;3JHCCH8.2,3JHCCH6.8,4JHCCCH1.4;3JHCCH8.2,3JHCCH6.8,4JHCCCH1.2), 7.85 ush. d (N15, 1H,3JHCCH8.3), and 7.93 7.91 two ears. d (N11and N122N,3JHCCH7.3-8.7), 10.01 ush. (HE, 1H).

Example 13. To the Grignard reagent obtained from 0.8 g (0.0333 mol) of magnesium and 4.12 ml (6.23 g, 0.0333 mol) of ortho-bromoanisole in 50 ml of diethyl ether with stirring in a stream of argon was added dropwise a solution of 5 g (0.0138 mole) of chlorostannate (IIc) in 10 ml of benzene. Then the reaction mass was treated as described in example 11. Selected 6.59 g (88%) of 2-(2-hydroxy-5-chlorophenyl)-2-naphthas-1-retinyl-bis(2-labels-Setenil)phosphine oxide (13), TPL 145-148°C. Found, %: 71.12, H 5.19, P 6.07. C32H26ClO4P. Calculated, %: C 71.04, H 4.81, P 5.73. An NMR spectrum31P{1N} (162.0 MHz, DMSO-D6): δP21.9 ppm IR spectrum, cm-1: 406, 430, 498, 514, 554, 580, 639, 685, 723, 757, 801, 824, 885, 1020, 1044, 1073, 1115, 1140, 1165, 1247, 1278, 1377, 1413, 1462, 1589, 1638, 2722, 2854, 2923, 3391. An NMR spectrum1H (600 MHz, CDCl3, 25°, δ ppm, J Hz): 3.76 (och3, 6N), 6.15 (N5, 1H,4JHCCCH2.5), 6.78 D. D. (N7, 1H,3JH8CCH7 8.9,4JH5CCCH7 2.5), 6.80 ush. d (N16, 2H,3JHCCH7.6), 6.83 D. D. (N182N,3JHCCH8.0,3JHCCH5.8), 6.98 (N3, 1H,2JPCH3 19.5), 7.25 ush. d (N9, 1H,3JHCCH6.9), 7.71 (N15, 1H,3JH14CCH15 8.3), 7.73 m (N11, 1H), 8.22 m (N12, 1H), 7.31-7.34 and 7.36-7.38 two m (N10N13N14N17N19, 7H).

Example 14. To the Grignard reagent derived from 1. g (0.0750 mol) of magnesium and 7.9 ml (11.9 g, 0.0750 mol) of bromine benzol in 100 ml of diethyl ether, with stirring in a stream of argon was added dropwise a solution of 10 g (0.0344 mole) of chlorostannate (IId) in 10 ml of benzene. The reaction mixture was heated at the boil for 0.5 h, then cooled to room temperature and treated with water as described in example 11. From the organic layer by distillation solvents were removed, the remaining glassy substance, 2-butyl-2-(2-hydroxy-5-chlorophenyl)ethenylpyridine (14), dried in a vacuum of 12 mm Hg (100°C)yield 12 g (85%). Found, %: C 70.24, H 6.13, P 7.73. With24H24ClO2R. Calculated, %: C 70.16, H 5.85, P 7.55. Mass spectrum, m/z: 410 [M]+•, 290 [M-Ph-C3H7], 277 [M-Ph-C4H9], 202 [Ph2RO], 153 [M-Ph2PO4H9], 152 [M-Ph2PO4H9-N], 77 [Ph]. An NMR spectrum31P{1H} (162.0 MHz, DMSO-D6): δP19.7 ppm IR spectrum, cm-1: 405, 436, 456, 512, 539, 605, 641, 695, 719, 738, 782, 822, 879, 906, 998, 1027, 1071, 1099, 1120, 1156, 1236, 1278, 1378, 1412, 1437, 1489, 1496, 1592, 1817, 1892, 1959, 2247, 2721, 2870, 2929, 2956, 3058. An NMR spectrum1H (600 MHz, DMSO-D6that δ ppm, J Hz): 0.88 t (N12,3JHCCH7.2), 1.35 m (N11), 1.42 m (N10), 2.53 m (N9), 6.44 ush. d (N8,3JHCCH8.7), 6.47 d (RSN3,2JPCH21.9), 6.88 ush. with (N5), 7.34 m (N7N14), 7.45 m (N15), 7.61 m (N13).

Example 15. actor 1.83 g (0.0057 mole) of chlorostannate (IIa) in 15 ml of benzene was added dropwise through the addition funnel with stirring in a stream of argon to cyclohexylmaleimide, made from 0.17 g of Mg (0.0069 mole) and 0.84 ml (1.12 g, 0.0069 mol) of cyclohexylamine in 30 ml of diethyl ether using the standard method. The reaction mixture was heated at boiling for 1 h, then cooled to room temperature. To the resulting reaction mass (an NMR spectrum31P{1N}, 36.46 MHz, CDCl3that δP36.5 ppm) was added dropwise a solution of Grignard reagent prepared from 0.18 g (0.0069 mole) of magnesium and 0.51 ml (0.753 g, 0.0069 mol) of brometane in 30 ml of diethyl ether. The reaction mass was heated at the boil for 6 hours, cooled to room temperature and treated with distilled water, a solution of 3 ml of concentrated hydrochloric acid in 10 ml of water, then again with water. The resulting white precipitate was filtered and dried in a vacuum of 12 mm Hg (100°). Selected 2.16 g (96%) of 2-phenyl-2-(2-hydroxy-5-chlorophenyl)ethinylcyclohexylcarbamate (15), TPL 85-87°C. Found, %: C 67.95; N, 6.74; Cl 9.12; 8.23; P 7.97. With22H26PO2Cl. Calculated, %: C 67.95; N, 6.74; Cl 9.12; 8.23; P 7.97. An NMR spectrum31P{1N} (162.0 MHz, DMSO-D6): δP50.5 ppm IR spectrum, cm-1: 536, 634, 695, 724, 768, 823, 889, 942, 1004, 1030, 1111, 1214, 1280, 1377, 1410, 1462, 1494, 1571, 1588, 2595, 2721, 2854, 2924, 3374. An NMR spectrum1H (600 MHz, CDCl3, 25°C δ ppm, J Hz): 1.12 D. T. (CH3, 3H),3JPCCH17.3,3JHCCCH7.4), 1.21, 1.26, 1.35, 1.68-1.71, 1.83 and 1.93 six m (C6H11, RSN 2, 13H), 6.30 (N3, 1H,2JPCH18.8), 6.89 (N5, 1H,4JH7CCCH5 2.4), 7.17 m (N8And-part of the spectrum of AB, 1H,3JH7CCH8 8.7), 7.20 m (N7In the spectrum of AB, 1H,3JH8CCH8 8.7,4JH5CCCH7 2.4), 7.27 m (N9, 2H), 7.32 m (N102N,3JHCCH7.0-7.7), 7.36 m (N11, 1H,3JHCCH7.0-7.4), 7.78 o.sh. (HE, 1H).

Example 16. A solution of 3.0 g (0.01 mole) of chlorostannate (IIa) in 10 ml of benzene was added dropwise with stirring in a stream of argon to cyclohexylmaleimide made with 0.33 g of Mg (0.014 mole) and 1.43 ml (1.91 g, 0.014 mol) of cyclohexylamine in 30 ml of diethyl ether using the standard method. The reaction mixture was heated at boiling for 1 h, then cooled to room temperature. To the resulting reaction mass (an NMR spectrum31P{1N}, 36.46 MHz δP36.5 ppm) was added dropwise a solution of Grignard reagent prepared from 0.34 g (0.0142 mol) of magnesium and 1.49 ml (2.23 g, 0.0142 mol) of bromine benzol in 20 ml of diethyl ether. The reaction mass was heated at the boil for 6 hours, cooled to room temperature and treated with distilled water, a solution of 3 ml of concentrated hydrochloric acid in 10 ml of water, then again with water. The resulting white precipitate was filtered and dried in a vacuum of 12 mm Hg (100°). You is Elena 3.6 g (85.3%) of 2-(2-hydroxy-5-chlorophenyl)-2-phenylethylhydroperoxide (16), TPL 196-198°C. Found, %: 68.6, H 7.03, P 7.65. C26H26ClO2P. Calculated, %: C 68.57, H 7.00, P 7.69. An NMR spectrum31P{1N} (162.0 MHz, DMSO-D6): δP29.4 ppm, IR spectrum, cm-1: 505, 527, 553, 591, 631, 689, 665, 694, 736, 768, 808, 833, 852, 888, 917, 999, 1030, 1073, 1112, 1173, 1216, 1259, 1288, 1377, 1417, 1461, 1497, 1561, 1586, 2728, 2854, 2922, 3056, 3386. Mass spectrum, m/z: 436 [M]+•, 419 [M IT], 401 [M-Cl], 353 [M-C6H11], 229 [M-POPh(C6H11)], 228 [M-POPh(C6H11)-N], 208 [POPh(C6H11)], 83 [C6H11]. An NMR spectrum1H (600 MHz, CDCl3, 25°C δ ppm, J Hz): 7.44 m (N12); 7.30-7.35 m (N9-11N13N14); 6.99 and 7.01 two m (N7N8AB-range,2JH(A)CCH(B)8.7); 6.83 ush. d (RSN3,2JPCH3 20.2), 6.32 ush. with (N5); 2.13 ush. m (RSN); 1.19 ush. m, 1.30 ush. m, 1.70 ush. m, 1.78 ush. m, 1.88 ush. m (C6H11, 10H).

The problem of extraction of rare earth and non-ferrous metals is extremely important due to their great importance in engineering and other fields. While Arsenal phosphorus-containing complexing funds (extractants), which are still used for the separation of lanthanides, small (mostly trialkyl(aryl)phosphine oxides, trialkylphosphine and dialkylphosphate). A distinctive feature of the proposed structure of the phosphine oxides (I) is the presence of one of R is dikalov atenilol fragment, containing 2-hydroxy-aryl Deputy located in the CIS-configuration relative to phosphoric part, which makes these compounds chelating character, i.e. the ability to complexation. The following are examples of solvent extraction of gadolinium in the water - chloroform some representatives of phosphine oxides (I) (compounds 1, 2, 5, 10), confirming their high extractive properties.

General methodology for extraction. To 5 ml of the aqueous solution of Gd(NO3)3(With=1·10-3mol/l) and picric acid (HPic, C=6·10-4mol/l) was added 5 ml of a chloroform solution of phosphine oxide(1, 2, 5, 10) (C=6.5·10-4÷9.2·10-3mol/l). A two-phase system was stirred in a closed flask on a magnetic stirrer for 1.5 h, and then left for 24 h in a dark place. After extraction the concentration of Gd(Pic)3in the aqueous phase was determined spectrophotometrically by the method according to the intensity of peak electronic absorption picrate ion in 353.40 nm ([13] Keeled, G.M.Lein, P.Stuckler, T.Kaneda, D.J.Cram, J. Am. Chem. Soc., 1979, 101, №13, 3553, [14] R.C.Helgeson, G.R.Weisman, J.L.Toner, T.L.Tarnowski, Y.Chao, J.M.Mayer, D.J.Cram, J. Am. Chem. Soc., 1979, 101, №17, 4928). Electronic absorption spectra were recorded on the device "Perkin Lambda 35" using cuvettes with a thickness l=10 mm, the Degree of extraction (EPic) was calculated according to the formula: EPic=100%·(1-a/a0), where a0and As optical density before and after extraction, respectively.

Data on the degree of extraction of Gd(Pic)3from water into chloroform, depending on the concentration of phosphine oxides (1, 2, 5, 10) as extractants are presented in the table.

The values of the degrees of extraction Gd(Pic)3from water into chloroform, depending on the concentration of the extractant
The concentration of the extractantE %
the extractant 1the extractant 2the extractant 5the extractant 10
055.05.05.0
6.5·10-41010.59.1
9·10-41112.48.511.7
2.7·10-31721.214.130.3
4.6·10-32130.520.547.3
6.4·10-32438.526.558.1
9.2·10-33047.840.068.1

Found that when the concentration is of extragent (phosphine oxide) > 9.2·10-3in the two-phase extraction system precipitation, representing a complex of gadolinium ion with phosphine oxide.

The allocation of the complex Gd(III) extractant (1). To 100 ml of an aqueous solution of Gd(NO3)3(With=1·10-3mol/l) and picric acid (HPic, C=6·10-4mol/l) was added 100 ml of a chloroform solution of the phosphine oxide (1) (C=6.4·10-2mol/l). A two-phase system was stirred in a closed flask on a magnetic stirrer for 1.5 h, and then left for 24 h in a dark place. The aqueous solution was centrifuged, precipitated precipitate was separated and dried. On the basis of elemental analysis of precipitated sludge complex Gd(III) with an extractant (1) was determined its composition - Gd(Pic)3(H2O)3(1)3. Found, %: C 50.62; N, 4.31; N, 5.76; P 4.67; Gd 6.92. Calculated, %: 52.69; N, 3.32; N, 5.76; P 4.25; Gd 7.19.

Experimental data show that the obtained phosphine oxides exhibit good extraction properties due to the complexing solvent extraction ion is Gd(III) in the water-chloroform. They form with the ion gadolinium complexes in a molar ratio of Gd(III): ligand =1:3, which are soluble in chloroform in a concentration range of ligand from 6.5·10-4to 9.2·10-3mol/l At concentrations of ligand (phosphine oxide) above 9.2·10-3mol/l in a two-phase system under the conditions of extraction watching what I precipitation, that facilitates the forming of complexes from the solution.

Thus, an effective way to generate new connections - dialkyl(aryl)-CIS-(2-hydroxyaryl)-2-alkyl(aryl)etinilestradiol with good complexing properties, alkylation chlorostannate Grignard reagents.

1. Dialkyl(aryl)-CIS-2-(2-hydroxyaryl)-2-alkyl(aryl)attilmopiremi General formula (I)

where R1=N, R2=Ph, R3=R4=Ph, Me, Et, Pr, CH2Ph, 2-MeO-C6H4C8H17;

R1=4-Me, R2=Ph, R3=R4=Ph, CH2Ph, 2-MeO-C6H4;

R1=H, R2=1-naphthyl, R3=R4=Ph; CH2Ph;

R1=H, R2=Bu, R3=R4=Ph;

R1=H, R2=Ph, R3=cyclo-C6H11, R4=Et, Ph.

2. A method of obtaining a dialkyl(aryl)-CIS-2-(2-hydroxyaryl)-2-alkyl-(aryl)ethinylestradiol (I) according to claim 1, including:

interaction in the environment of organic solvent by heating chlorostannate formula (II)

with a Grignard reagent R3MgX (X=Cl, Br, I) in a molar ratio of 1-(1,2-1,4), subsequent processing by another Grignard reagent R3MgX (X=Cl, Br, I) in the same molar ratio,

and when R3=R4processing the weave of the compounds (II) produce a Grignard reagent in a molar ratio of 1-(2,0-2,6),

hydrolysis of the reaction mixture with water or an aqueous solution of hydrochloric acid and identification of target compounds by known methods.

3. The method according to claim 2, characterized by the fact that as an organic solvent, a mixture of benzene and ether, or THF, or isooctane.



 

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EFFECT: obtaining of new biologically active substances.

184 cl, 52 tbl, 62 ex

FIELD: chemical technology.

SUBSTANCE: invention describes a method for synthesis of pentaerythritol diphosphites with the high content of spiro-isomer. Pentaerythritol diphosphites are synthesized by a successive re-esterification method in the presence of monophosphite, and then in the presence of substituted phenol or other alcohol, and wherein indicated reactions of re-esterification are carried out under conditions of controlled temperature and pressure. The reaction conditions provide to synthesize intermediate derivative and final pentaerythritol diphosphite with the high content of spiro-isomer and the high total yield of diphosphites.

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The invention relates to organic chemistry, chemistry of physiologically active compounds and may find application in biomedical research

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to an intermediate compound, i. e. tert.-butyl-(E)-(6-{2-[4-(4-fluorophenyl)-6-isopropyl-2-[methyl(methylsulfonyl)amino]-pyrimidine-5-yl}-(4R,6S)-2,2-dimethyl[1,3]dioxane-4-yl]acetate that can be used in synthesis of compound of the formula (IV)

eliciting inhibitory effect on activity of HMG-CoA-reductase and, therefore, can be used for preparing pharmaceutical agents for treatment, for example, hypercholesterolemia, hyperproteinemia and atherosclerosis. Also, invention relates to a method for preparing indicated intermediate compound by reaction of the new parent compound - diphenyl-[4-(4-fluorophenyl)-6-isopropyl-2-[methyl(methylsulfonyl)amino]pyrimidine-5-ylmethyl]phosphine oxide with tert.-butyl-2-[(4R,6S)-6-formyl-2,2-dimethyl-1,3-dioxane-4-yl]acetate in the presence of a strong base in simple ether or aromatic solvents or their mixtures at temperature in the range from -200C to -900C. Also, invention relates to a method for preparing of compound of the formula (IV) wherein R1 means hydrogen atom or pharmaceutically acceptable cation and to a method for preparing intermediate compounds of the formula (VI):

wherein each P1 and P2 represents independently (C1-C4)-alkyl or group:

and wherein P3 represents (C1-C8)-alkyl. Applying new intermediate compounds and proposed methods provide enhancing quality and yield of compounds.

EFFECT: improved preparing methods.

9 cl, 1 tbl, 8 ex

The invention relates to a new method of obtaining perphosphate lithium General formula (I), where a = 1, 2, 3, 4, or 5, b = 0 or 1, C = 0, 1, 2 or 3, d = 0, 1, 2 or 3; e = 1, 2, 3, or 4, provided that the sum of a+e = 6, the sum of b+c+d = 3, and b and C are not simultaneously denote 0, provided the ligands (CHbFc(CF3)d) can be different, and monochlor - or fluorine-, dichloro - or debtor, chlortetracycline, hormone, HARDI-, Hartry or chlortetracycline, formano, Ferdi-, fortri or fortetracycline or cryptomonadales subjected to electrochemical fluorination in an inert solvent, the resulting mixture of products if necessary, divide by distillation at various fluorinated products and the fluorinated alkylphosphine, put in an aprotic, polar solvent at from -35 to 60oWith interaction with lithium fluoride

The invention relates to a molecular complex compound consisting of mono - or bestinformation the compounds of formula (I), where R1and R2denote independently of each other C1-C12-alkyl, unsubstituted or substituted one to four times C1-C8the alkyl and/or C1-C8-alkoxyl phenyl or the group fulfills I TS cor3; R3is unsubstituted or substituted one to four times C1-C8the alkyl and/or C1-C8-alkoxyl phenyl, and-hydroxyketones the compounds of formula (II), where R11and R12denote independently of each other C1-C6-alkyl, or R11and R12together with the carbon atom to which they are linked, represent cyclohexenone ring; R13- HE; R14- hydrogen

The invention relates to besatisfied, compositions based on these photoinitiators and coating methods

The invention relates to new biologically active compound, specifically to the dichloride 2-[5-(2-methylpyridyl]ethyl, bis{2-[5-(2 - methylpyridine)] ethyl}of phosphoryla (I) of the formula I

MeCCHMeCH2CHP=0

possessing antibacterial activity

The invention relates to mono - and dieselpowered, and to their use as photoinitiators the photopolymerization compounds Ethylenediamine

-diphenylphosphinoethyl, n-2-hydroxy(2-nitroxy)-3,5 - dibromopropylether showing neurotropic activity" target="_blank">

The invention relates to new chemical compounds, namely, N-substituted the hydrazones: N-definiltey - ylacetic, N-2-hydroxy-(I) and N-2-nitroxy (II)-3,5-dibromoindigotin formula

(C6H5)CHNHN=CHwhere X=HE(I), ONa(II) showing neurotropic activity

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to an intermediate compound, i. e. tert.-butyl-(E)-(6-{2-[4-(4-fluorophenyl)-6-isopropyl-2-[methyl(methylsulfonyl)amino]-pyrimidine-5-yl}-(4R,6S)-2,2-dimethyl[1,3]dioxane-4-yl]acetate that can be used in synthesis of compound of the formula (IV)

eliciting inhibitory effect on activity of HMG-CoA-reductase and, therefore, can be used for preparing pharmaceutical agents for treatment, for example, hypercholesterolemia, hyperproteinemia and atherosclerosis. Also, invention relates to a method for preparing indicated intermediate compound by reaction of the new parent compound - diphenyl-[4-(4-fluorophenyl)-6-isopropyl-2-[methyl(methylsulfonyl)amino]pyrimidine-5-ylmethyl]phosphine oxide with tert.-butyl-2-[(4R,6S)-6-formyl-2,2-dimethyl-1,3-dioxane-4-yl]acetate in the presence of a strong base in simple ether or aromatic solvents or their mixtures at temperature in the range from -200C to -900C. Also, invention relates to a method for preparing of compound of the formula (IV) wherein R1 means hydrogen atom or pharmaceutically acceptable cation and to a method for preparing intermediate compounds of the formula (VI):

wherein each P1 and P2 represents independently (C1-C4)-alkyl or group:

and wherein P3 represents (C1-C8)-alkyl. Applying new intermediate compounds and proposed methods provide enhancing quality and yield of compounds.

EFFECT: improved preparing methods.

9 cl, 1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention can be used for separating rare-earth and coloured metals and pertains to new phosphorous-containing complex-forming phosphine oxides with general formula (I) and methods of obtaining them: , where R1 = H, R2 = Ph, R3 = R4 = Ph, Me, Et, Pr, CH2Ph, 2-MeO-C6H4, C8H17; R1 = 4-Me, R2 = Ph, R3 = R4 = Ph, CH2Ph, 2-MeO-C6H4; R1 = H, R2 = 1-naphthyl, R3 = R4 = Ph, CH2Ph, 2-MeO-C6H4; R1=H,R2 = Bu,R3 = R4 = Ph; R1 = H, R2 = Ph, R3 = cyclo-C6H11, R4 = Et, Ph. The method of obtaining phosphine oxides (I) involves reaction in a medium of an organic solvent of chlorophosphorinine oxides with formula (II) with corresponding Grignard reagents, hydrolysis of the reaction mixture and separation of target compounds.

EFFECT: obtaining new phosphorous-containing complex-forming compounds with formula (I).

18 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to phosphine oxides, which can be used as quelating agents for extraction of lantanides from acid water solutions, and can be applied for ecological monitoring of sewage waters in regions of processing and burial of radioactive wastes. Efficient extraction of lanthanum, gadolinium and lutetium from highly-acid water solutions by method of temperature-induced phase separation is achieved by application of phosphine oxides of general formula , where: R1=C4H9, R2=C6H5, R=C6H13, R2=C6H5, R1=C8H17, R2=C6H5, R1=C6H5, R2=C4H9 as quelating agents.

EFFECT: elaboration of novel efficient extractants of lanthanides.

2 cl, 5 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing antipyrenes of general formula (I) R = Et, Pr, C6H13, CH2Ph, Ph, 2-CH3OC6H4. The method involves reacting 3,3,5-trimethyl-2-chloro-1,2-oxaphospholene-2-oxide with an organomagnesium compound (Grignard reagent) RMgX (X = Br, I) in a medium of organic solvent in molar ratio 1 : (2.0-2.6) while stirring for 0.5 to 2 hours, hydrolysis of the reaction mass with an aqueous solution of hydrochloric acid, separation of the organic phase and extraction of desired compounds from the organic phase using known methods.

EFFECT: design of a new method of producing antipyrenes.

2 cl, 8 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to a method for photochemical hardening thick-layered ethylene-unsaturated systems of light-emitting diode light sources. The invention describes a method of hardening ethylene-unsaturated polymerisable compounds to obtain coatings, external resinous layers or adhesives with cross-sectional thickness greater than approximately 0.25 mm, which involves addition of at least one acylphosphine oxide photoinitator to the said compounds and illumination of the obtained mixture with light from a light-emitting diode.

EFFECT: good surface hardening and good hardening in the mass without formation of surface wrinkles in case of thick cross sections.

15 cl, 3 ex

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