N 0 I'ltS
Since only a small aniount of the pure coinpound was required, no attempt has been inadc to improve the methods which are described below. Experimental Part Stein corrections werc applied to tneltiiig 1) ~hich 'i were taken in melting poilit t u l w in l i i i heated copper block. 4-Nitro-N-ethyl-N-phenylbenzamide(I). -To the vigof anhydrous potaisiuin . of 4-nitrobenzoyl chloere was added ilowly ,it tooin temperature a solution of 20.0 g. of Eastinan KodaL After addition was comthirty minutes arid then ream of air. After thc yellow residue had beeii he'ited to about 70' SO thdt it txcame light orange in color and free N-ethylauiliue V ~ Ceii, odor, it wdz Lvashed Mith two LOO-inl. portions rochloric dcid and finally with large volume the filter. The crude air-dried product weighed $2.3 g. (yield 97%) arid melted a t 111-114". Material which had been twice rccrystallized from .it 119.5-12(~.5° and gar? thc following dnd1 .lnal. Calcd. for C,r,H140sA~-:C, 66.64; H , 3 . 2 2 , 1, 10.37, Found: C, 66.34; H, t ~ . ; 3 1 ; S , 10.46. 4-Amino-N-ethyl-N-phenylbenzamideI 11). -The reduction of (1) follol-ved essentially the procedure of "Organic S y n t h e s e ~ . " ~In it flask which waa fitted with a reflux condenser And a mercury-sealed stirrer, 20.0 g. of crude ( I ) ,20 ml. of 95c2 ethanol, 12 ml. of water and 18.0 g. of iron powder were mixed. After refluxing temprrature had beeii attained, i .3 ml. of 12 A' hydrochloric acid in 3.5 ml. of 95'3 ethanol was added gradually with vigorous stirring, and the refluxing and stirring were continued for three hour%. The acid tvaz neutralized with 0.7.5 g. of \odium hydroxide iii 20 nil of ethanol and the precipitated iron compounds were filtered from the warm solution with the help of a layer of filter aid. Reaction flask ,md filter cake were washed with two 50-ml. portions of !15qc ethanol. The product was isolated by cooling and then by concentration of the solution; the first two crops of white crystals weighed 9.6 g. and had a melting point of 161-162' which was not altered by recrystallization from ethanol. Further concentration and final dilution with water yieldedo 3.5 g. of less pure material of melting point 159.5-160.5 ; the total yield was 13.1 g. or 74wp. Analysis of the purer product gave these results. Anal. Calcd. for CltH&S:: C, 74.91; IT, 6.71; ?;, 11.93. Found: C, 75.11; H, 6.47; iX,11.76.
4-(N
.-
0 ) -N-ethyl-N-phenylbenzamide (111)
rhe eth (11) was carried out by means of acetaldehyde-ammonia in the presence of zinc and sulfuric acid according to the proccdure of G. Lockemann.' A 9.2-g. \ample of (II), 100 inl. of cthanol, 341) in1 of wnter, 38 g . of concd. sulfuric arid a i d 38 g. of Lint du\t w r e placed in n flask which was provided with a reflu\ coudenser and a n addition furinel Then 2 5 g . of freshly prepared acetaldehyde-ammonia in 80 nil. of wdter w'ds added to the refluxing solution in the course of forty minutes and re-
__-____
(2) Prepared essentially hy the method of "Organic Syntheses." Coll. Vol. I, 2nd ed Tohn iVAley- n n d Son,, Inc S e w S o r k , S- Y , 1941 p 394 Coll Vol 11 l o h n Wilev a n d Son, I n r Yen York Y F
Vol. 72
fluxing was continued for one hour. The solution was filtered, made alkaline with 120 ml. of 15 N ammonium hydroxide, and kept a t 5' for two days. The light tan crystalline precipitate was washed with three 50-ml. portions of 6 I\r ammonium hydroxide and a large quantity of water and was crystallized 5 times from ethanol and once from ethanol-water (approximately 1: 1). The final product weighed 1.0 g. (yield 10%) and melted a t 132.01:$2.5". Three grams of impure materinl were recovered from the mother liquors. Analysis of the purcr wnple yielded these results. .l?zal. Calcd. for CI;I-T~O C, 76.06; 11, 7.S3; X , 10.44; mol. wt.,268. Calcd. for C ~ J ~ I I Oithe N ~ diethylamino comptl.1 : C, 78 97; 13, 8.17; X , 9.45; mol. 296. Found: C , 7(i.l)3, 7 3 88; 13, 7 . 5 0 , 7.:- b,-i (19$!4!.
. . I
(21 The sample3 were puriticd a t the National Bureau of Standards the A.P.I. Research Project 6 on the "Analysis. purification, and prnperties of hydrocarbuns" under the siipervision of Frederick D. Rossini, from material supplied hy the following laborsttories: cis-2-pentene and tvans9-pentene, by the 4 . P . I . Research Project -15 on the "Synthesis and properties of hydrocarbons of low molecular weight" a t the Ohio State University, under supervision of Cecil E. Boord; 3-methyl-l-butene, by the Houdry Process Corporation through the courtesy of E. A. Smith. (21 Todd, Oliver and Muffman, Tars JOURNAL, 69, 1619 (1917). ( 4 I Waddington. Knowlton, Scott, Oliver, Todd, Hubhard, Smith - i t i l l l i ilTn1:811, i h i ! , 71, 7'17 !lLIi!>'i. by
NOTES
Sept., 1950
TABLEI VAPORPRESSURES IN -Water---B. p., OC.
&-2-Pentene-B. p.. oc. 9, calcd.
PO
4311
MM.
7Lrans-2-Pentene-B. p., ‘C. p , calcd.
-3-Methyl-l-butene-B. p., ‘ C . 9, calcd.
187.56 1.026 1.595 187.58 65 187.57 233.74 233.74 5.956 70 233.72 6.522 10.922 289.15 289.12 75 289.13 11.486 355.22 0.218 15.927 16.494 355.21 80 355.22 433.49 5.112 21.541 433.50 20.969 85 433.56 10.053 525.78 26,633 525.81 26.055 90 525.86 15.033 633.93 31,766 633.94 31,183 ,95 633.99 20,061 760.03 36,944 760.03 36.354 100 760.00 25.128 41,561 906.09 906.11 105 906.06 42.161 1074.7 30.245 1074.7 46,813 110 1074.6 47,423 1267,5 36.402 1268.1 52.100 115 1268 0 52.724 1489.2 40.602 1489.3 57.430 120 1‘489.1 58.070 1740.8 45 837 6 2 , 80:1 63.456 1740,8 123 1740.8 2025.7 51 189 68 211 68 882 ‘> c r ti do2*l im 2026, 0 a These values of thc pressures corresporidiiig to thc observed boiliiig teiriperatureb of water are from borne, Stimson arid Ginnings, J . Reseurch lVutl. Bzu. Staadards, 23, 261 (1939i. TABLEI1 CVNSrAXTS OI’ AT W I N E EQUATIONS AND POINTS A
us-2-Penteiie 6 87540 trans-2-Pentenc 6 90575 3-Methyl-1-butene 6 82618
B
SURMAL
c
BOILING N b P,OC
1069 466 230 786 36 94 1083 987 232 965 36 35 1013 474 236 816 20 06
The results of the measurements are presented in Table I. The data were fitted by least-squares adjustments to .\ntoine equations of the form, loglop = A - B (t C), where p is the vapor pressure in mm. and t is the temperature in “C. The constants of the equations so obtained and the normal boiling points of the compounds computed from these equations are listed in Table 11. Values of the vapor pressure calculated by means of the Antoine equations are given in Table I, columns 4, 6 and 8 for comparison with the experimental values in column 2 .
+
355.25 433.53 525 86 633 9‘4 760 00 906.00 1074 6 1268 1 1489 2 1740 7 202.5 9 tlic tables of
os-
the DoebnerY modification. Only iiiinor attciition has been given to condensations of vicinal polyketones with active-methylene compounds. Schmitt4 reported a condensation of inesoxalic ester with ethyl cyanoacetate and Sachs and coworkers; reported similar condensations of pentanetrione-2,3,4 with pentanedione-2,4, malonic ester and 9-nitrophenylacetonitrile. The latter compound was condensed also with l-(2’-methoxyphenyl)-butanetrione-1,2,3. In no case were structure proofs reported] the structures of the products being assumed, apparently, from analytical data alone. The present work was undertaken in order to study the condensations of active methylene cornpounds with 1,3-diphenylpropanetrione-1,”,3 (I), 0
0
0
the latter not having been studied in this manner. Malonic acid was employed as the principal methylene component for the twofold reason that it had not been condensed previously with vicinal tricarbonyl compounds and that structure studies The Chemistry of Vicinal Tricarbonyl Com- of any product would be facilitated by the prespounds. I. Condensation Reactions of 1,3- ence of the carboxyl functions. Structure studies were necessary to determine whether the carbon Diphenylpropanetrione-1,2,3 skeletons of the addenda were unchanged or had B Y DEXTERB . SHARPAND HENRYA. HOFFMAN undergone rearrangement in a manner similar to Perkin-Knoevenagel type condensations have that reported by Kohler and E r i c k s n 6 They been limited largely t o the use of aldehydes as car- isolated the benzoate of benzoin from the equibonyl components, although a few examples2 molar reaction of phenylmagnesium halide with I. appear in the literature in which simpIe ketones The two reactions would be comparable if it were have been used, most successfully by employing assumed that each involved an attack upon carbonyl carbon by the nucleophilic particles, (1) Abstracted in part from a thesis presented by Henry A. HoffTHERMODYNAMICS LABORATORY PETROLEUM EXPERIMENT STATIO\ BUREAUOF MINES BARTLESVILLE, OKLAHOMA RECEIVED APRIL13, 1950
man to the Graduate Faculty of Kansas State College in partial fulfillmeat of the requirements for the degree, Doctor of Philosophy, granted in January, 1950. Supported in part by a grant-in-aid from the Frederiak Gardner Cothell funds of Research Corporation. (2) Johnson, “Organic Reactiow,” Vol I. John Wiley and Sons, Inc., New York, N Y.,1942, p. 222
(3) (4) (5) ibid., Sachs (6)
Doebner, Be?., 55, 2140 (1900); 56, 1137 (1902). Schmitt, Compt. rend., 140, 1400 (1905). Sachs and Barschall, Be?., 84,3047 (1901); Saehs and Rohmer, 86, 3307 (1902); Sachs and Wolff, ibid., 56, 3221 (1903); and Herold, i b i d . , 40, 2714 (1907). Kohler and Erirkson, THISJ O U R N A L , 63, 2301 I I!l31).
