J. Chem. Eng. Data 1989, 34, 368-370
368
Aminolysis of Para-Substituted Benzalacetophenones El-Sayed M. E. Mansour," Samir K. El-Sadany, Ahmed A. Kassem, and Hamdy A. Maksoud Chemistry Department, Faculty of Science, Alexandria University, Alexandria, Egypt
The nucieophlilc addition of prlmary aromatic amines on para-substituted benzeiacetophenoneswas studied in ethanoilc solution. The formed adducts were assigned to be &arylamIno+3-( para-substituted phenyi)propiophenones, and their structures were contlnned by elemental analysls and spectroscopic methods.
The nucleophilic attack on carbon-carbon double bonds has been the subject of numerous investigations that were summarized in review articles (1-3). a$-Unsaturated ketones with addition compounds of heterocyclic amines such as piperazine, morpholine, and piperidine have been described by Pollard and others (4-6). Similar addition compounds with aromatic amines instead of heterocyclic amines have now been prepared.
I
Y where X = H, CI, Br, CH,, or OCH, and Y = H, CI, CH,, OCH,. or NO,
Procedure The a,&unsaturated ketone (0.2 mol) prepared as previously described (7-9) was dissolved in a minimum amount of boiling methanol under reflux. As soon as the substance completely dissolved, the corresponding anhydrous aromatic amine (0.2 1 mol) was added and the solution refluxed for 10 h. The use of an excess of amine tended to make the addition more complete and obviated much difficulty in the recrystallization process. The addition product separated after standing in an icebox for several hours. I t was filtered, washed with small amount of alcohol to remove untreated amine, airdried, and recrystallized from alcohol three times before being subjected to analysis. The yield of the crude product was almost quantitative. The resulting addition products are listed in Table I. They are all stable under ordinary conditions. Similar to the pipera-
Table I. Physical Data XCsH,CHCH,COCeHS
I
NHCeHIY
X compd no. IIa H IIb H IIC H IId H IIe H IIIa CH3 IIIb CH3 C1 IVa IVb CI Va Br Vb Br OCH3 VIa VIb OCH3 VIC OCH, VId OCH3 VIe OCH3
Y formula C,,H,.NO H CH3 OCH3 C1 NO2 NO2 C1 H
c1
H NOz H CH, OCH, NOz C1
mp, "C yield, % 161 159 139 167 172 192 186 235 155 238 136 173 151 182 166 148
75 86 67 80 88 70
74 90 89 83 72 68 78 63 87 77
zine addition products, but like the addition products of piperidine and morpholine which were reported by Georgy and Schwyzer (6),they are decomposed by heating with water, yielding the corresponding starting amine and the a,@-unsaturatedketones. Similarly, dilute hydrochloric acid decomposes them into the hydrochloride of the corresponding amine and the unsaturated ketone, respectively. The structure of the ,above-mentioned amino ketones are established by the elemental analysis and their spectral data. Elemental analyses were in excellent agreement with those calculated. The I R spectra showed bands assigned to N-H at 3400-3600 cm-' and C=O at 1650 cm-'-acid. The mass spectra of the produced amino ketones were studied. The relative intensities of the most prominent peaks in their fragmentation patterns are recorded in Table 11.
Reghtry No. IIa, 742-43-8; IIb, 37904-94-2; IIc. 802-49-3; IId, 94864-08-1; IIe, 804-20-6; IIIa. 95006-21-6; IIIb, 100410-41-1; IVa, 119948334: IVb, 11994644-4; Va, 11994645-5; Vb, 11994646-8; VIa, 802-48-2; VIb, 119946-37-7; VIc, 119948-36-8; VId, 119948-39-9; VIe, 961 7 1-57-2; PhNH,, 62-53-3; p-MeCeH,NH,, 106-49-0; p-MeOC,H,NH, 104-94-9; p-CICeH,NHg, 106-47-8; P - O ~ N C ~ H ~ N100-01-6; H~, PhCW CHCOPh, 94-41-7; p-MeC,H,CH=CHCOPh, 4224-87-7; p-CIC,H,CH= CHCOPh, 956-04-7; p -BrC,H,CH=CHCOPh, 1774-66-9; p MeOC,H,CH=CHCOPh, 959-33-1.
0021-9568/89/1734-0368$01.50/00 1989 American Chemical Society
Journal of Chemical and Engineering Data, Vol. 34, No. 3, 1989 389
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Literature Cited Patai, s.; Rapporot, 2. I n The Chemlstry of Alkenes; Patai, S., Ed.; Intersclence: New York, 1964; pp 469-583. Rapporot, 2.; Ladkani, D. Chem. Scr. 1974, 5 , 124-133. Schreiber, B.; Martinek, H.; Wolschann, P.; Schuster, P. J. Am. Chem. SOC. 1978, 101, 4708. (a) Stewart, V.; Pollard, C. B. J. Am. Chem. SOC. 1938, 58, 1980. (b) Stewart, V.; Pollard, C. B. J. Am. Chem. SOC. 1937, 5 9 , 2006. (c) Stewart, V.; Pollard, C. B. J. Am. Chem. SOC. 1937, 5 9 , 2702.
(5) (6) (7) (8) (9)
Cromwell, N. H.; Bruch, J. S. J. Am. Chem. SOC. 1944, 66, 872. Georgi, A.; Schwyzer, B. J. Rakt. Chem. 1912, 86, 273-276. Hanzluk, V.; Bianchl, S. Ber. Msch. Chem. a s . 1899. 32. 2282. Weitz, E.; Schefer, A. Ber. Msch. CY”. Qes. 1921, 5 4 , 2338. Davey, W.; Gwilt, J. R. J. Chem. Soc.1957, 1008.
Received for review May 9, 1988. Revised November 17, 1988. Accepted Januaw 30, 1989.
