136
ALVIN S. WHEELER.
ican whiskey, but had the taste of spirits, and little difference could be noted between the two-year old sample and the eight-year old. The judgment of So. 2623 was that it was a good flavored whiskey, b u t with very light body. No. 2689 was pronounced a good flavored whiskey. Nos. 2625 and 2627, the samples aged in uncharred packages, were both called immature whiskey, even when the eight-year old sample was tested. Iiut this judgment was based on a comparison with those aged in charred packages. On that basis the eight-year old sample was thought to be about I t o 2 years old. This shows what a marked effect the storage in charred wood has upon the flavor of the whiskey.
Conclusions. There are important relationships among the acids, esters, color, and solids in a properly aged whiskey, which will differentiate it from artificial mixtures and from young spirit. 2 . All of the constituents are undergoing changes as the aging process proceeds, and it is evident that the matured whiskey is the result of these combined changes. 3. The amount of higher alcohols increases in the matured whiskey only in proportion to the concentration. 4. Acids and esters reach an equilibrium, which is maintained after about three or four years. 5 . The characteristic aroma of -American whiskey is derived almost entirely from the charred package in which it is aged. 6. The rye whiskies show a higher content of solids, acids, esters, etc., than do the Bourbon whiskies, hut this is explained by the fact t h a t heated warehouses are almost universally used for the niaturing of rye whiskies, and unheated warehouses for the niaturing of Bourbon whiskies. j . The improvement in flavor of whiskies in charred packages after the fourth year is due largely t o concentration. 8. The oily appearance of a matured whiskey is due t o material extracted froin the charred package, as this appearance is almost lacking in whiskies aged in uncharred wood. 9. The “ b o d y ” of a whiskey, so-called, is due largely t o the solids extracted froin the wood. I.
[COSTRIBCTION FROM THE CHEMICAL
L.IBORATORY OF
THE UXIVERSITY OF NORTH
CAROLISA.]
THE CONDENSATION OF CHLORAL WITH PRIMARY AROMATIC AMINES. 11. B Y A L V I N S. W H E E L E R Keceived October 21. 1907.
.I number of condensation products of chloral with primary aromatic
PRIMARY AROMATIC AMINES.
I37
amines have already been described. The first mention of such a reaction is probably that of Maurnend,' who hoped t o obtain indigotin by the action of chloral ( 2 mols.) upon aniline (3 mols.). His product was a brownish black uncrystallizablc substance containing no chlorine. Schiff and AmatoZ first described a condensation product of chloral ( I mol.) and anilinr ( 2 mol>.) with thc formula CCl,CH(SHC,H,),. In the same year Wallach3 described this compound. Later,4 he gave a full dewription of the products obtained from aniline, p-toluidiue, and a sample of xylidine boiling at 2 I 2-2 16'. Eibner, studied the condensation of chloral with p-nitraniline, m-chloraniline, p-chloraniline, and I ,2,4-dichloraniline and showed that I ,2,4,6-trichloraniline and 2,6-dichlor-4-nitraniline do not react. Wheeler and Wellera prepared the 0- and m-nitraniline compounds and Wheeler and Daniels' showed that only addition products could be obtained with the naphthylamines. Niementowski and Orzechowskis found that one molecule of chloral condensed with one molecule of anthranilic acid but later@obtained the expected diphenamine compound. Finally Rughrimer'o describes the compounds with 0- and p-phenylenediamine and I ,2,4- and I ,~,4-toluvlenediamine. He also states thdt only addition products are oht,iined with the naphthvlamines. The chloral diphenamine compounds vary considerably in stability. Most of them may be kept for years. They possess great crystallizing power. Their behavior toward alkalies is variable. The aniline derivative is decomposed by alcoholic potash into aniline, chloroform and I'henyl cyanide according t o Wallach. The p-nitraniline derivative, on the other hand, is converted into a hydroxy compound, one chlorine atom being replaced by a hydroxyl group according to Wheeler and Glenn." They are not stable in the presence of strong mineral acids, which split them so as t o re-form the amine. Eibner has shown that boiling acetic anhydride and benzoyl chloride give the acetyl or benzoyl derivative of the original amine. Finally, the writer has found that all of them react with great readiness with bromine in the cold. There is a substitution of one hydrogen atom in those which have been analyzed. This substitution probably occurs in the methylene group of the chloral residue. Ber., 3, 246 (1870). a
Gazz. chim. ita]., I, 376 (1871). Ber., 4, 668.
* Ann., '73, 274. Ibid, 302, 335. This Journal, 24, 1063.
J. Elisha Mitchell Sci Soc., 22, 90 (1906). Ber., 28, 2812.
Ibid., 35, 3898. l o Ibid., 39, 1653. l 1 J. Elisha Mitchell Sci. SOC, 19,63 (1903).
138
ALVIN S.
WHEELER.
Chloral and p-Bromnniliiae. 7'rzchlorethylidenedi-p-bromphenamine, CCl,CI-I(NHErC,H,),. With c. w. nlILLER.--Ten grams of p-bromaniline were dissolved in j o cc. benzene and 8 grams chloral ( 1 . 2 grams required by theory) in I O cc. benzene were added. The mixture was concentrated one-half on t h e water bath and cooled. Aiwhite flocculent precipitate came down, giving a melting-point of 13j '. On further evaporation a second and much larger crop was obtained, showing a meltingpoint of I 19'. By several recrystallizations from benzene the meltingpoint was raised t o 140'. The yield was very high. Analysis: calculated for C,,H,,N,Cl,Br,, C 35.15, €I 2.34, ?T j.93, C1 Br 56.24; found, C 35.03, E-I 2.46, S 6.38, C1 - PJr 5j.58. Trichlorethylidenedi-p-bromphena tnine consists of fine colorless needles, melting at 140' and decomposing a t 2 0 j ' . It is extremely soluble in alcohol, acetone, glacial acetic acid and hot benzene. It is sparingly soluble in cold benzene and insoluble in ligroin. I t is readily purified by using a mixture of benzene and ligroin. I t is not decomposed by boiling water b u t is split by boiling concentrated hydrochloric acid with the regeneration of p-bromaniline. -1 bromine derivative is easily obtained b y adding bromine t o a glacial acetic acid solution. The product, consisting of colorless plates, melts a t 203 ' after several recrystallizations from glacial acetic acid. Deterniinations of carbon, hydrogen and nitrogen give very satisfactory figurcs for a nionobroni compound. Chlorine gives a similar reaction. The product, ci ystallizing in long colorless needles, melts a t 93' after reciystallization froin glacial acetic acid. A study of the constitution of these halogen derivatives is under way. Chloral and o-Aitisidznc. 7 ' ~ ichlovctii31idened 1-o-1tietltoxyplteizamane, CCl,CH(NHOCH,C,H,),. With w. s. DICKSON.-TWOmolecules ( I 2.3 grams) of o-anisidine were dissolved in j o cc. benzene and one molecule (7.3 grams) of chloral was added. After warming a short time on the steani bath ;L small quantity of colorless needles deposited. These decomposed a t about 2 I j' and weighed 0.95 gram. On concentration of the filtrate in a desiccator a mass of fern-like crystals was obtained mixed with a thick liquid. Xfter filtering, the crystals were pressed on a porous tile. The product w . white, ~ melted a t 1 1 2 - 1 1 4 ' and weighed 9.7 grams. On recrystallizing from benzene the melting-point was raised t o I Z I'. The thick liquid finally solidified, considerably increasing the 1 ield. Analysis : calculated for C,,H1,O2YLLClJ, C1 28.3j, N 7 . 4 7 , found, C1 2 8 . 3 5 , N 7.30. Trichlorethylideriedi-o-riietho~yi~h~n;Lx~,inc crystallize< from ligroin or benzene in magnificent ihombohedra. one-half inch or t l i O X long, with a slight yellow color. It is ca4lv soluble in cold ben7t.n~arid carbon tetrachloride and in hot glacial acetic acid. I t is slightly soluble in cold ligroin and fairly soluble in hot liqroin. It crystallizes from alcohol in long slender prisms. One hundred cc'. of boiling alcohol will dissolve ap-
+
PRIMARY AROMATIC AMINES.
I39
proximately 7 grams and a t 25' about 2.5 grams. It is insoluble in and unchanged by boiling water. When boiled in concentrated hydrochloric acid the odor of chloral could be detected in the vapors. A bromine derivative is readily obtained by adding bromine t o a concentrated glacial acetic acid solution. The product crystallizes in clusters of needles which decompose a t about 230'. This compound is being further investigated. Chloral and p-Anisidine. Trichlorethylidenedi-p-methoxyfhenamina, CCl,CH(NHOCH,C,H,),.-To a solution of I 2.3 grams of p-anisidine in 2 0 cc. of benzene (a nearly saturated solution) is added 7 . 3 grams of chloral. The solution turns t o a dark red color a t once, much heat is developed and a deposition of 0.22 gram of small colorless crystals occurs. These decompose a t about 215' a s in the case with o-anisidine. After filtering, the reaction mixture is boiled fifteen minutes and then allowed t o stand several hours. An abundant crystalline precipitate formed. After filtering and pressing on a clay plate, the product melted a t 115' and weighed 10.5 grams. A further yield was obtained from the motherliquor. Purification by means of the mixed solvent, benzene and ligroin, raised the melting-point t o I IS-120'. tlnalysis: calculated for C,BH,,O,N,CI,, C1 28.35; found, 28.41. The para compound crystallizes from ligroin in brilliant scales, showing a strong pink color i n the mass. It nielts a t 118-120' and decomposes a t 158'. I t is fairly soluble in cold benzene, alcohol and ether. I t is readilv soluble in glacial acetic acid, hot benzene and hot alcohol. The alcoholic solution einits a most disagreeable odor and on spontaneous evaporation t o dryness a jet black crystalline mass remains. On treatment with bromine in glacial acetic acid solution a crystalline product is obtained which blackens a t about 198~. This compound is being studied further. Chloral and Anthranilic Acid.-The product obtained in this case depends upon the proportions used. One molecule of chloral will condense with one or two molecules of anthranilic acid with the elimination of one molecule of water. The two products have been described by Niemeritowski but his method yields a mixture and since we wish t o prepare the compounds in order t o study their bromine derivatives we have improved upon his method.' Trichlorethylidene-o-aminobenzoic .4cid (Chloral-anthranilic Acid) , CC1,CH :NC,H,COOH. With W. S. DICKSON.-Five grams of anthranilic acid were dissolved in 40 cc. of boiling benzene (a saturated solution) and 5.5 grams chloral in IO ccI benzene were added. The weights are in the proportion of one molecule t o one molecule. The mixture was boiled Since writing the above, larger quantities of the mono-compound have been prepared in benzene solution and a small amount of the di-compound has been isolated from the product.
* 40
A L V I S S. Jj'HEELER.
under a reflux condenser for three hours, filtercd from a sinall precipitate and cooled. X crystalline deposit, \:eigliing. ,j grams and melting a t 148-1 I ', separated. 'I'he cr!,stals were large elongated tables occurring in clusters. 1:roni the filtrate was obtaiiwd 3 grams of niaterial, melting at 1-15--I5'. '. Se\-cral recrystallizations ironi l)erizciic* raised t h e 1Tielting-point t o I jzO. Sieiiitnto\i-ski a n d ( ) r z r ~ h o w s k i1xep;ired ' this coiripound without t h e use of ail!. alvc.111. 'I'hc!. useti ;in t x c % of chlordl and got stt\-eral bJ,-prodticts. \i.e li;iv(a tried their riicthotl 1)ut have employed theoretical proportions. I ~ \ . C > Iso I i v c ~~ L >thi. I s a i w 1 ,!.-prodttcts. The mortar was placed i i i ;i block oi ice and t h e prt\.iousl!. cooled substances rapidl!. stirred togetlicr. 'I'lie i l i i s t Lin: liiluefictl t h e n rapidly liccamc. vu!. hard. This proc!tict (lecoinposcd a t itbout I 2 : ', after two hours on icc a t I 2;' m c l Lifter three hours niov a t rooiii teiiilxtrature at 118'. I t \vas then rublxd 111) witli ;L little water and filtercd. 'I'ht deconiposition point row t o I3,5", So\\ , taking advaiitagc of the marked differcncc in solubility i n I)eiizeiic. of t h e iiioiio- ant1 di-cornpounds (not observed 1)~.Nieineiitowski) t lie erystdliiic' I I I ~ S S ,weighing 8 . 2 granis, was extracted ivit 11 4,i cc. boiling I)cnzcne. 1;roni the extract therc separated a niass of colorless needles, weighing 3.7 grams aiid melting at i4g-I 5 2 consisting therefore of the nearly pure mono-compound. 0 1 1 evaporating the filtrate a residue \vas o1)tainr.d. weighing 1.3 grams and melting a t 1 6 0 ' ~ ;I fair quality of thc tli-c'onil)ound. second extraction was madc. with 35 cc'. of boiliiig 1)tnzeiie. On cooliug. this yielded a. product weighing 0.8 grani and melting :it 162" a i i d ;i rc.siduc melting a t 1 5 7 ' after evaporation. 'l'here still rc,tiiaincd a i l inso1ul)lc residue:, (lark purple in color. 'I'hesc. results ;m in ii:arketl contrast to thosc ol)tained h y our method of boiling in beiizc~ne,lor \w gvt practically only t h e mono-compound and coiisequcntly ;I niuch larger !ield. \17c further identified t h c niono-conil)ouiid 1.)). :i cliloriiic. tl
