SU1234399A1 - Method of producing azomethineimines - Google Patents

Description

(21) 3806694 / 23-04

(22) 10/29/84

(46) 05/30/86. Bksh. Number 20

(71) LSU them. A.A. Zhdanova

(72) L.L. Motherland, J.V. Mitrofanov and I.K. Korobitsyna

(53) 547.792.5 (088.8) (56) The chemistry of Doublebonded Functional Groups. - Ed. S. Patai Interscience, Nev-York, 1977, Supp.A. Part 1, ch. 6, p. 369-532.

Korobitsina, I.K., Khalikova, AV, Rodina, L.L., Shusherina, N.P. 4-Phenyl-1, 2, 4-triazolin-3,5-dione in organic synthesis.-CHC, 1983, No. 2, p.147

Wamhoff N., Wald K. Zur Photolyse und Therraolyse von 4-Apyl-l, 2,4-trizolip-3, 5-dionen. - Chem. Her., 110, .1699 (1977).

Korobitsina I.K., Rodina L.L., Lorkina A.V.-ZHOH, 1981, No. 17, p. 2021.

Attenburrov J., Cameron A., Evans R., Hems V., Jansen A., Chapman J., Walker T. A synthesis of vitamin A from cyclohexanon. - J. Chem. Soc., 1952, 1094.

Rodina L.L., Lorkina N.V., Korobitsina I.K. Azomethins based on 4-phenyl-1, 2,4-triazolin-3, 5-dione and aryl-substituted diazamethanes. - ZHOH, 1982, No. 18, l. 9, p. 1991 (54) (57) 1. METHOD FOR OBTAINING AZOMETHYNMINES OF GENERAL FORMULA

YAGN

Y4.

where R is phenyl or tolyl

radical;

R is phenyl, unsubstituted or substituted by an alkyl residue with C L nitro group, fluorine,

by reacting the diazo compound with a substituted 1,2,4-triazolin-3, 5-dione in an organic solvent medium, characterized in that, in order to increase the yield and expand the assortment of the target product, the pentane solution of the diazo compound of the formula

H - CHN,

where N. has the above values,

obtained by the interaction of the aryl aldehyde of the formula

,

where H has the indicated values,

with hydrazine hydrate in pentane, followed by treatment of the reaction mass activated with manganese oxide, is reacted with a solution of a substituted 1,2,4-triazolin-3, 5-dione of the general formula

Rrn

v

where H is as defined above, in absolute ether. The invention relates to methods for the synthesis of azomethine amines of general formula A,. where r is. phenyl or tolilnyy radical; R, 2 is phenyl, unsubstituted or substituted by an alkyl residue with a nitro group or fluorine, and can be used in organic synthesis. The purpose of the invention is to increase the output and the expansion of the target product range. Example 1. Preparation of 3,5-dioxo-A-phenyl-1-phenylmethyltetrahydro-H-1, 2,4-triazole (R, R ,,) To a solution of 5 mmol of benzaldehyde in 50 ml of pentane is added while cooling (bath temperature 0 ° C) 8 mmol of hydrazine hydrate; The reaction mixture is vigorously stirred for 1 hour, after which the pentane layer is separated and 2 g of activated manganese dioxide is added to it. Further stirring of the reaction mixture is carried out in the dark at room temperature. After 1 h, the mixture is filtered, the solvent is partially (up to a volume of 20 ml) evaporated in vacuo. An orange solution of DNA compound is obtained, the IR spectrum of which contains an intense absorption band (s)., 2070 cm K solution 88 mg (0.5 mmol) 4-phenyl-1, 2,4-triazolin-3,5-dione in 15m absolute ether, a solution of the resulting diazo compound is added dropwise. The precipitate formed is filtered off and washed with absolute ether (five times 10 ml each time). The output of azomethine imine 79%, so pl.152 153 ° C. C, 67.56; And 4 Found, N 16.09. 45,, N, 0 ,. Vrchsleno,%: C 67.92; And 4.15; N 15.85. IR (1.5% solution in CHCl), 940 (61); 1035 (32); 1100 (20); 1210 (71); 1260 (70); 1350 (23); 1435 (71); 1515 (61); 1610 (36); 1730 (83); 1790 (39); 3020 (48); 3060 (58). 992 Example 2. Preparation of 3,5-dioxo-4-phenyl-1- (4-nitrophenyl) -methyl methyl tetrahydro-1H-1, 2,4-triazole (R n-NO-C, H,). And, R, To a solution of 175 ml (1 mmol) of 4-phenyl-1, 2,4-triazolin-3,5-dione in 30 ml of absolute ether, a solution (1 mmol) of 4-nitrophenyl diazomethane in 15 ml is added dropwise with stirring pentane, the resulting and: 3 of the hydrazone p-nitrobenzialdehyde as in Example 1. The precipitate formed is filtered off and washed five times with absolute ether. The yield of azomethine imine (m.p. I18-i20 ° G (with decomp.). Found: C 58.05; H 3.27; N 18.00., Vych ° sleno,%: C 58.07 ; H 3.25; N 18.06. IR spectrum (1.5% solution in CHCij), cm: 960 (10); 1020 (17); 1070 (17); 1110 (19); 1135 ( 13); 1290 (12); 1315 pl. (17); 1347 (55); 1415 (47); 1398 (34); 1530 (29); 1596 (20); 1720 (82); 1780 (27); 3030 (12). SnSR UV spectrum /, nm (): 275 (13000); 333 (8780); 434 (9560). Example 3. Preparation of 3,5-dioxo-4-phenyl-1- (4-fluorophenyl a) methyltetrahydro-1H-1, 2,4-triazole (R, en, R, nF-CJI). To a solution of 5 mmol of 4-fluorobenzaphidehyde in 50 ml of pentane is added with cooling and stirring (bath temperature) 8 mmol of hydrazine hydrate The process is conducted at room temperature. 2 g of activated manganese dioxide was added to the reaction solution, after 1 h the mixture was filtered and the resulting pentane solution was added to 88 mg (0.5 mmol) of 4-phenyl-1,2,4-triazolin-3, 5-dione in 15 ml of absolute ether. The precipitate formed is filtered off and washed with five portions of absolute ether (. on 10 ml). 95 mg of bright yellow powdered azomethine imine (1c) (68%) are obtained, m.p. 112-114 ° C. Found,%: C 62.96; H 3.60; N 15.08. C H N O O F. IR spectrum (1.5% solution in: 940 (14); 1035 (12); 1080 (I); 1150 (18); 1170 (34); 1210 (31); 1260 (41); 1430 (65); 1515 (60); 1610 (30); 1730 (86); 1790 (34); 3060 (24); 3080 (19). UV-D spectrum, nm (): 324 (3210); 411 (. Example 4. Preparation of 3,5-d oxo-4-phenyl-1- (2-fluorophenyl) methyl tetrahydro-1H-1,2,4-triazole (R,; R 0- FC H, -). Mixing 5 mmol of 2-fluorobenzal dehydrate in 50 ml of pentane and 8 mmol of hydrazine hydrate when hydrated to 0 ° and stirring gives hydrazine fluoride benzaldehyde. 1 hour, the mixture is filtered and obtained n pentane solution was added to 85 ml (0.5 mmol) of 4-phenyl-1,2,4-tr azoline-3,5-dione dissolved in 15 ml of absolute ether. The precipitate was filtered off and washed five times with absolute ether (10 m each. 99 mg of azomethine imine in the form of bright yellow silky crystals (68%), m.p. 143-145 ° C, are found. Found: C, 62.24; H, 4.03; N, 14.81. Calculated,%: C 63.62; H 3.53; N 14.84. JK-spectrum (1.5% solution in CHCL), cm-910 (18); 950 (22); 1040 (31); 1080 (62); 1110 (18); 1170 (30); 1210 (40); 1270 (48); 1425 (60); 1510 (68); 1600 (28); 1730 (86); 1790 (46); 3040 (19); 3080 (16). UV spectrum L, nm (e): 270 (3330); 413 (7330). Example 5. Preparation of 3,5-d oxo-4-phenyl-1- (4-dimethylaminophenyl) methyltetrahydro-1H-1,2,4-triazole (R, CJI; R., P- (CH3) NC Mixing 5 mmol of aldehyde dissolved in 50 ml of pentane and 8 mmo of hydrazine hydrate under OC are prepared with hydrazine 4-dimethylbenzaldehyde 2 g of active manganese dioxide is added to the reaction mixture to oxidize the hydrazone at room temperature. 99 mg of an orange-red powder of azomethimine (69%) were isolated, mp 195-196 C. Found: C: 66.28; H 5.34; 18.23. N DT, 0. Calculated,%: C 66.22; H 5.23; 18.17. N IR spectrum (1%) solution in CHCl3), cm-940 (51); 950 (29); 1080 (62); 1090 (52); 1160 (50); 1117 (56); 1210 (40); 1260 (42); 1280 (35 ); 1340 (27); 1380 (80); 1410 (50); 1510 (58); 1540 (56); 1590 (75); 1610 (67); 1710 (69); 1730 (65); 1790 (32 ); 3020 (31). UV spectrum, nm (): 277 (6620); 351 (4450); 488 (31450). Example 6. Preparation of 3,5-dioxo-4-feng. L-1 - (4 -ortophenyl) -methyltetrahydro-1H-1, 2,4-triazole (RR nFC Hj. A dot was added to a solution of 5 mmol of 4-fluorobenzaldehyde in 75 ml of pentane with cooling (bath temperature 0 ° C) and stirring 8 mmol of hydrazine hydrate. Then, at 20 ° C, 2 g of activated manganese dioxide is added, after I h the mixture is filtered and the pentane solution is added to 0.5 mmol of 4-phenyl-1,2,4-triazolin-. -3,5-dione in 25 ml of absolute ether. The precipitate is filtered off and washed with absolute ether. 95 mg (68%) of bright yellow azomethine imine, m.p. 112-114C. Example 7. Obtaining 3,5-DIOXO-4-P-tolyl-T- (4-nitrophenyl) methyltetrahydro-1H-1, 2,4-triazole (R, p-CH ,,, R., --n -NO C Hj. Mmol 4-p-tolyl To a 1 -1, 2,4-triazolin-3,5-dione solution in 30 ml of absolute ether was added dropwise with stirring a solution (X1 mmol) of 4-nitrophenyldiazomethane in 15 ml pentane, obtained from p-nitrobenzaldehyde analogously to example 1. The precipitated precipitate is filtered off, washed five times with absolute ether. The yield of azomethine imine is 94% (at the source 4-P-TOLYL-1,2,4-triazolin-3,5-dione), mp 167.5-169 ° C (with diff.) Found,%: C 59.36; H 3.81; N 17.89. Calculated,%: C 59.26; H 3.73; N 17.28.

tyltetrahydro-lU-1,2,4-triazole (R 0-CH C H, R H).

To a solution of 1 mmol of A-0-tolyl, 2,4-triazolin-3,5-dione in 30 ml of absolute ether, a solution {ii 1 mmol) of 4-nitrophenyl diazomethane in 15 ml of pentane prepared from -nitrobenzaldehyde is similar to Example 1. The precipitated precipitate is filtered, washed five times with absolute ether.

The output of azomethine imine 90% (on the original 4-0-tolyl-1,2,4-triazolin-3, 5-dione), so pl. 153-154С (with diff.).

Found,%: C 59.52; H 3.75; N 17.03.

Calculated,%: C 59.26; H 3.73; N 17.28.

Example 9 (comparative), To the full solution of I mmol 4-phenyl-1, 2,4-triazolin-3, 5-dione in 30 ml of absolute ether, a solution of 1.2 mmol phenyldiazomethane in 15 ml of absolute ether is added dropwise to complete decolouration of the reaction solution. At the same time, nitrogen evolution and precipitation of a colorless amorphous precipitate are observed — an oligomer which is filtered and re-precipitated from chloroform by the addition of hexane (mp. 124-126 ° C, mol. weight 500).

IR spectrum (, 385): SWR (18); 1080 (14); 1140- (26); 1170 square (26); 1230 (52), 1260 square (38); 1320 square (20); 1360 (38), 1390 (40); 1420 (60); 1505 (62); 1600 (25); 1730 (90); 1780 (38); 2860 (5); 2900 square (12); 3030 (14); 3080 square (18)-.

Found,%: C 67.49; And 4.44; N 15.79.

(C. “..) n Calculated,% C 67.90; H 4.18;

N 15.83.

Example 10 (comparative). To a saturated solution of 1 mmol of 4-feNSh1-1, 2,4-triazolin-3, 5-dione in 30 ml of absolute ether is added dropwise a solution of 1 mmol of azobenzyl in 15 ml of absolute ether. When this occurs, the release of nitrogen, discoloration of the solution and the precipitation of a colorless precipitate, which is filtered and re-precipitated from chloroform by adding hexane (mp. 130135 C, mol., Weight 500).

IR (CHC, 394fA): 940 (15) 1050 (39); 1120 square (20); 1150 (23); 1210 square (27); 1260 (38); 1330 (15); 1390 (39); 1430 (45); 1450 square (20); 1490 pl, (19); 1510 (35); 1610 (24); 1740 (71); 1790 square (nineteen); 2860 square (Ii); 2900 (19); 2930 (20); 2980 (33); 3030 square (29); 3080 square /18).

Example 11 (comparative). To a solution of 1 mmol of phenyl-o (-naphthyl diazomethane in 25 ml of absolute ethyl alcohol, 1 mmol of 4-phenyl-1, 2,4-triazolin-3,5-dione is added in the form of a powder without solvent. A rapid nitrogen separation is observed, gradual dissolution of the precipitate and color change through the sylvite to colorless. According to TLC (eluent: ether - hexane 1: 1, the interaction products are phenyl-c-naphthyl tone and 4-phenylurazole (first blue iodine staining).