SU290703A1 - Method of obtaining diethyleneimides of pyridilpyrazinylamidophosphoric acids - Google Patents

Description

(21) 1241531 / 23-04 (25) 1261299 / 23-04

(22) 16 .. 05.68

(46) 07.02.85, Bksh. № 5 (72) I.V. Sazonov, A.A. Kropacheza, Ie. Safonov, V.A. Chernov, I.B.Golubeva and S.M. Minakopa (71) All-Union Scientific Research Institute of Chemical Pharmaceutical Institute Sergo Ordzhonikidze

(53) 547.298.2..07 (088.8)

(54) METHOD FOR OBTAINING DIETHYLENYM WELLS

DERIVATIVES OF Pyridapin, PYRAZYNYLAMVOPHOSPHORNY MULOT.

(57) Method for preparing diethyl imidides of pyridyl pyrazinylamidophosphoric acid derivatives of general formula

 NC I

(Ng

where R (- H or CHj;

- H, halogen or nitro group;

R, 3 - H, nitro, halogen or

R,

methoxy group; X - N or CH,

characterized in that the dichlorohydrides of the derivatives of pyridylpyrazinyl amidophosphoric acids or their chlorohydrates of the general formula

T v 5

 T 0

Ri-4N-ANHP

where R, Rj, Rj and X have the indicated values,

is reacted with ethyleneimine in an organic solvent medium, for example benzene, in the presence of an organic base, for example, triethylamine, followed by imparting the target product with known techniques. This invention relates to the field of the preparation of compounds which can be used as insecticides or physiologically active substances. The method of producing diethylimide pyridyl-, pyrazinyl derivatives of phosphoric acids of the general formula H tYv / t Bi-j-KHP | N, l where RJ H or CH,. , halogen of Ioti ntrogruppa P, HifTporpynna, halogen or methoxy group, X - N or CH. The method is based on the fact that the dichlorohydrides of pyridylpyrazinylamidophosphoric acid derivatives or their chlorohydrates of the general formula B 2 RI JvHPx R j 5 RJ, R., and X have the indicated gdc are reacted with ethylene in an organic solvent, for example benzene, in the presence of an organic bases, for example, triethylamine, followed by isolating the target product TfjS.be-CTHbiMH. Example 1. Diethylene 5-chloropyrid-2-amido 1) osphoric acid. To 1 g (0.0228 mol) of ethyleneimnka and 2.3 g (0.0228 mol) of triethyla1 p1– 80 ml of benzene, 2.39 g (0.0144 mol) of dichlorohydrogen and 5-chloropyridyl- 2-am, of phosphoric acid, is then stirred for 0.5 h at the same temperature, 2 hours at and left until the next day. The precipitate is filtered, extracted twice with boiling ethyl acetate (2 x 80 br;), the benzo and ethyl acetate solutions are combined, I evaporated to obtain 2.32 g (78.8%) of diethylene: imide 5-chloro-nidryl-2-am1 hydrophobic acid. After crystallization from ethyl acetate m.p. 160-160,5 C. The substance is highly soluble in ethyl and methyl alcohol, chloroform, acetone, insoluble in water, ether. Found,%: C 42.19; H 4.99; C, 13.71; N 21.53; R 11.82. Cd H., Vnschsleno,%: C 41.79; H C 13.71; N 21.66; R 11.98. Example 2. Diethyleneimide 5-nitropyridyl-2-amidophosphoric acid. To a solution of 1.81 g (0.0422 mol) of ethylenimine and 4.3 g (0.0422 mol) of triethylamine in 80 MP of benzene, while stirring and cooling (3–10–3), was added 5.4 g (0.0211 mol) 5-nitropyridshl-2-amidophosphoric acid dichlorohydride. React; the ionic mass is stirred for 0.5 h at 10 ° C and stirred for 0.5 h at K 2 h at 20 ° C; then the precipitate is filtered off, dried, dispensed with 50 ml of water, the residue is filtered off, washed with another 5 MP of water and dried in a vacuum desiccator over P 0. Obtain 4.42 g (77.8%) of 5-nitro-phenyl enimide 5-nitro11 fmdil-2- amidophosphoric acid, after crystallization from methanol so pl. 167-167, with the introduction of a capillary at 162 ° C. The substance is soluble in chloroform, poorly in alcohol and acetone, insoluble in benzene, ether, water. Found,%: C 40.24; P 4.64; N 25.97; R 11.00. C g N N Oz R. Bmisleno,%: C 40.15; H 4.49; N 26.02; R 11.51. Example 3. Diethylene (3-nitropyridyl-2-amidophosphoric acid). 1C 1.45 g (0.0334 mol) of ethyleneimine and 3.4 g (0.0334 mol) of trietvlamine in 100 ml of benzene, while stirring and cooling (10 ° C), 4.27 g (0.0167 mol) of dichlorohydrin are added 3-nitropyridyl-2-amidophosphoric acid, then the reaction mass is stirred for 0.5 hours at 10 ° C and 3 hours at 20 ° C. The triethylamine hydrochloride is filtered, washed with benzene, the mother liquors are combined, they are taken to get 4.14 g ( 88.5%) 3-Shtiridil-2-amidophosphoric acid diethylenimide, after crystallization from ethyl acetate T.nji. 120-121.5 p. The substance is highly soluble in chloroform, alcohol, acetone, benzene, water, less soluble in ethyl acetate and ether. Found,%: C 40.25; II 4.70; N 25.76; R 11.80. . Calculated,%: C 40.15; And 4.49; N 26.02; R 11.51. Example 4. Ethylshgmgd 3,5-d ghlorpir11dnl-2-am1chosphosphoryic acid, K 0.73 g (0.169 mol) of ethylegatmin and 1.71 g (0.0169 mol) of tropethylamine in 80 ml of benzene with stirring and cooling () add 2.37 g (0.00846 mol) of dichloro anhydride - 3,5-dichlorg: iridyl-2-a до of phosphoric acid, then pereiIby 0.5 h at 10 ° C and 2 h at. The precipitate is filtered off, extracted with 8O ml of boiling ethnyl acetate, the mother liquors are combined, evaporated, and 2.23 g (90%) of diethylanimide 3,5-dnhlo-pyridyl-2-amidophosphoric acid is obtained, after crystallization from ethnacetate, t .pl. i41.5-142c. The substance is well soluble in alcohol, chloroform, worse in water, acetone, benzene, ethyl acetate, insoluble in ether and petroleum ether. Parshcheno,%: C 36.82; - And 3.8-1; C1 24.41; N 19.52; R 10.73. .. Calculated,%: C, 36.88; H 3.78; C1 24.19; N .19, 12; R 10.57. Example 5. Diethlet mid 6-methyl iridyl-2-amidophosphoric acid. To 1.43 g (0.0332 mol) of ethylsamin and 5.15 (0.0498 mol) of triethylamine in 70 g of benzene with stirring and cooling (10 ° C) are added. 4.34 g (0.0166 mol) of hydrochloride D11 chlorohydrin 6-methylpyridyl-2-amido}) of osphoric acid, then stirred for 0.5 h for 1 h at. 20 N is left until the next. The chlorohydrate of triethyla1P1 is filtered off, benzene, the uterine solutions are available, benzene is distilled off to give 3.21 g (83.3%) of diethyl and 6-methylpyridyl-2-amNo-4-sulphuric acid, m.p. 122.5-124.5 ° C (from ethyl acetate). The substance is dissolved, mo in water, alcohol, acetone, chloroform, insoluble in ether and petroleum ether. %: C 50.79; Ы 6,10; N 23.54; R 13.02. Sc, H, 5 .. Vnschleio,%: C 50.42; H 6.34; N 23.52; P 13.00. 34 Example 6. 5-iodopyridyl-2-amidophosphoric acid diethylenimide. To a solution of 0.63 g (0.01452 mol) of ethylene and 1.5 g (0.0143 mol) of triethylamine in 80 ml of benzene, while stirring and cooling to 8-10 ° C, 2.45 g (0.00726 mol a) 5-iodopyridyl-2-amidophosphorous acid acid dichlorohydride, then pereglegniniut 10 min at the same test, 1.5 h at 20 ° C and remain until next day. The precipitate is filtered off and extracted twice with about 80. "- in bales of nji. M with ethyldzgat, the mother liquors are combined, evaporated and semi-volga-from 2 g (78.1%) diethylene) 1m- {yes 5-1.yyear 11-1 -am1: dophosphoric acid, after crystallization from methanol t. 167.5-168, applying a capillary at. The substance is well soluble in chloroform, xyu in alcohol, poorly in water, acetone, benzel, acetylacetate; Found,%: C 3, 03; H 3 ,, 46; . 36.88: M 16.30; R 9.03. I .. Vagals,%: C 30; 87; 11 3.46; 1 36.25; N 16.00; R 8.85. Example 7. Diethylpyne. 5-bromo-6-methstiridyl-2-amidophosphate acid. To a solution of 0.8 g (0,0171 mol) of ethylene imip and 1.73 g (0,0171 mol) of triethylamine, about 80 mb of benzene, while firing of Sh1va PI-1 and cooling (), was added 2.6 g (0,00855 mol a) 5-bromo-6-1methyl-iiridpl-2 - amidophosphoric acid potassium dichlorohydrin, then 0.5 h intermittently at the same temperature and 2 hours at 20 C. Hydrochloride is hydrophilous; It is washed, washed with benzene, the mother liquors were combined; evaporated; 2.3 g (85%) of 5-bromo-6-met1 Shpyridyl-2-ami-2-dophosphoric acid were obtained; mp. 155-156,5.0 (from etlshatseta). The substance is soluble in alcohol, chloroform, benz le. plc :: o - in acetone, water, ethyl acetate-. Found,%: C 37.79; H 4.30; Br 24.97; N 17.64; P 9.6. C, ZP, VGM, OR. Vmsley,%: C, 37.87; H 4.45; Br 25.20; Ы 17.67; R 9.77. Example 8. Diethylenimide 3,5-dibromo-6-methylpyridyl-amidoose {) ortic acid. To a solution of 0.77 g (0.0197 mol) of ethyleneium and 1.82 g (0.0797 mol) of trinethlamine in 80 ml of benzene, with stirring and cooling, (8-10 ° C), add 3.42 (0.00896 mol a) 3.5 g-dibromo-6-methyl-pyridyl-4-amidophosphorus hydrochloride dichloride, then stir for 0.5 h while cooling and filtering for 3 h at 20 Tristilamine hydrochloride, washing with benzene5 mother liquors are combined. evaporated. And 3.41 g (9653%) of diethylenimide 3 J 5 - cybrom-6-met1-spirid1-1-a1 Shdofosfornoy acid, crystallized. ethyl acetate m.p. 132.5133,. The substance is soluble in chloroform rut, alcohol, benzene, and the solution o-1), t; 1 ij with s: J firm. MO In iodine,%: C 30.09; And 3.53; Paydemo 1A, 12; R 7.76, C ,, H ,,, Br .N.OP. „- 07 С 30,32; H 3.31; | 31; 1ЧКСЛЕО5 А. R 7.82. P P and. measures 9 Diethyle1a11-E-zh zaai1a.Ya5d, of phosphoric acid. K. Ras; BoiJy g (0.0133 mol) of ethyl lUuiHa-t 2 g (Os0198 mol) of dry acetone at a temperature of 3 100 mt dry acetone. 10–13c are added with reMciuiiBainni 1; 64 g (0.00658 mol) chloro Ili.npaTa of dichlorohydride pirazing.lamide After the unrepresented li: O Sf Or i OH SISL ABOUT. For 4 hours at 20 ° C, the hydrochloride of TJ rat tpI ethnula uina is filtered off, the mixture is treated with acetone, the mother liquor pi-i is taken up and evaporated. A small amount of this acetate (10 ml) is added to the residue, the mixture is filtered and the pyrazinilampdophosphoric phosphoric acid imide is crystallized from ethyl acetate. You; -. Od 0.87 g (65,, 5%), so pl. 137.5-139 C. The substance is soluble in water, alcohol, chloroform, moderately soluble in 1 benzene and 1 acetate. Found,%: C 42.9; H 5.54; N 31, 19; I 13.95, Cgiy-l OP. Calculated, X: C 42,66; H 5.37; N 31.10; R 13.76. IT P and Mer 10 Diethyl1 3, 3-di Syrompyrazyl-2-amidophosphorioioif KHcjTOTH. To a solution of 1–39 g (0.0322 mol) of ethnleny ina and 3.25 g of CO, 0322 mol) of trigctantine in 300 ml of bsol. At a temperature of 5.93 g (050161 mol) of dichlorapprade 3.5 are added with stirring - dibromopyrazinyl-2-ami-phosphoric acid, then stirred for 3 hours at and left until the next day. The precipitate is filtered off, 5 extracted with boiling gas and benzene twice in 80 ml, the mother liquors are combined and evaporated in vacuo to give 4.68 g (76%) of 3,5-dibrompyrazinyl-2-diethylenimide, of phosphoric acid, which is crystallized from ethyl acetate, t . 154 ° C (when introducing a capillary with .. The substance is soluble in. Chloroform, methyl alcohol, acetone, moderately soluble in benzene and ethyl acetate, soluble in water, ether. Found: C 25.24; H 2.71; Br 41, 27; N = 7.96; P 8.50. CgVr.NjOP. Vyisleno,%: C 25.08; And Br 41, 73; N 18.29; P 8.09, Example 11. Diethylesh-i-shd 3-chloropyrazinyl-2-amidophosphoric acid. To a solution of 0.78 g (0,0181 mol) of ethyleneimine and 1.83 g (0.181 mol) of tristilamine in 200 mp of benzene at 6-12 ° C, 2.23 g (0 , 00905 mol) of 3-chloropyrasiyl-2-azdophosphoric acid dichloride, and then stirred for 1.5 hours at the same The precipitate is filtered off, extracted with 80 ml of boiling benzene, the mother liquors are evaporated, evaporated to dryness, and 2.15 g (91.5%) of diethylene imide 3-chloropyrazinyl 2-amidophosphoric acid is obtained, crystallized from ethylacetate, mp. 138.5-139.5 C. The substance is dissolved in water, chloroform, methanol, insoluble in sulfur, moderately soluble in benzene, ethyl acetate. Found,%: C 36.95; n4.40: C1 13.90; N 27.40; R 11, 61, CgH ClNj-OP. Calculated,%: C 37.03; H 4.28; C1 13.65; N 27.39; R 11.93. Example 12. Diethylenimide-3-chl or-5,6-dimethyl-1-rasinil-2-amidophosphoric acid. To a solution of 0.85 g (0.0197 mol) of ethylenium a and 2 g (.0.01797 mol) of triethylamine in 1000 ml of benzene, 2.7 g (0.00985 mol) of 3-chlorohydrochloride dichlorohydride are added with stirring 5, 6-dimethylpyrazinyl-2-amidophosphoric acid, then stirred for another 2.5 hours at 10-15 ° C. The precipitate is filtered off, extracted with 80 ml of boiling benzene, the mother liquor is combined, evaporated to dryness, the residue is washed with ether and 2.3 g (81.2%) of 3-chloro-5,6-dimethylpyrazinyl-2-amidophosphonic acid diethylenimide are obtained. which crystallized from ethyl acetate, so pl. 1b4-165 C. The substance is soluble in water, chlorine form, methyl alcohol, moderately soluble in ethyl acetate, acetone, benzene, insoluble in ether. Found,%: C 41.49; H 5.36; C1 12.64; 24.38; R 10.70. C gHjjCl OP, Calc.,%: C 41.75; And 5.26 C1 12.32; 24.35; R 10.77. Example 13. Diethylenimide 5-bromo-3-methoxy-phasinyl-2-amvdophosphoric acid, To a solution of 0.41 g (0.00934 mol) of ethyl D1-min and 0.95 g (0.00934 mol) of triethyl in 150 ml of benzene at 150 ° С While stirring, 1.5 g (0.00467 mol) of 5-bromo-3-methoxy-pyrazinyl-2-a a-phosphoric acid dichloride was added with stirring, then stirred for 2 hours at 20 ° C. The triethe amine hydrochloride is filtered off, progressed with benzene, the mother liquors are combined, the benzene is distilled off, the residue is taken up in ether and 1.39 g (88.8%) of diethylene-5-bromo-3-meth-sipirazinyl-2- is obtained. amidophosphoric acid which crystallizes from ethyl acetate T.Sh1. 155-155 ,. 038 The substance is soluble in water, alcohol, chloroform, benzene, moderately soluble in ethyl acetate. Found,%: C 31.96; H 4.0; Br 23.74; P 9.30. CgH.ryOgP. Calculated,%: C 32.35; H 3.92; Br 23.92; R 9.26. Example 14. Diethylenimide 5-bromopyrazine-2-am1diphosphoric acid. To a solution of 1.17 g (0.0272 mol) of ethylenimine and 2.73 g (0.0272 mol) of triethylamine in 200 ml of benzene, 3.94 g (0.0136 mol) of dichloride anhydride was added at a temperature of 8–10 ° C with stirring. 5-bromopyrazyl-2-amidophosphoric acid, then 0.5 h stirring at the same temperature and 2 h at room temperature. The precipitate is filtered off and washed with benzene, and then extracted with boiling benzene (2x80 mp). The benzene, which had gone to the extra space, was distilled off, and 3.3 g (80%) of 5-bromopyrazsh-2-amide diethylene amide {) osphoric acid was obtained. WHICH is crystallized from methyl alcohol, so pl. 158.5-159 C (with decomposition). The substance is soluble in chloroform, moderately soluble in methyl and ethyl alcohol, poorly in benzene, ethyl acetate. Found,%: C 31.53; H 3.40; Br 26.23; N 22.34; R 10.02. CgH BrNjOP. Calculated,%: C, 31.58; H 3.67; W 26.28; N 23.03; R 10.19.

Claims (1)

A method of producing diethyleneimides through a single pyr and di-pyr-azi-nylamide phosphoric acid of the general formula where R (- H or CH ₃ ; R ₂ is H, halogen or nitro; R ₃ is H, a nitro group, a halogen or a methoxy group; X - N or CH, characterized in that the dichloro anhydrides of pyridylpyrazinylamidophosphoric acid derivatives or their hydrochlorides of the general formula I ^l ynrS C1 ₂ wherein R ^, R _2, R ₃ and X have the abovementioned meaning, are reacted with ethyleneimine in an organic solvent such as benzene, in the presence of an organic base, for example trietipamina, followed by isolation of the desired product by known methods.