2172
L. CHAS.RAIPORD AND STEWART E. HAZLET
When @l/dN, is tending to attain zero as the first degree of Nz, then at NZ = 0, b&/dN2 differs from zero, as it is to be seen from equation (1) (Fig. 1 ) . 2 This is one of the two cases pointed out by Lewis and Randall. When d&/bNz is tending to attain zero as the higher degree of Nz, then dgs,/bNz is likewise tending to attain zero, but the left part of the equation (1) has for its limit zero (Fig. 2). Figures 1 and 2 correspond t o such partial molal quantities, as for instance the volume (or heat capacity or heat content). According to Fig. 1 in the infinitely dilute solution only the partial molal volume of the solvent is constant. According to NI = 1 Fig. 2 in the infinitely dilute Fig. 3. solution the partial molal volumes both of the solvent and solute remain constant. Hence it is natural to turn to such a case, when this constancy extends into the (2) Figure 1 correspond? to Fig 7 of I x x i s snrl Randall.
1701. 57
field of finite concentrations (Fig. 3 ) . As the temperature is rising, i. e., when the abnormality of the solutions is decreasing, it may be expected that the trend will be from Fig. 1 via Fig. 2 to Fig. 3. The partial molal volumes for the system waterethyl alcohol‘ (apparently for the temperature 20-25’) calgl culated by Lewis and Randall correspond to Fig. 1. The calculations made by us of the partial molal volumes for g 40’ are given in Fig. 2 . With a further rise of temperature it is likely that we shall arrive a t Fig. 3. When d&’bNz is approaching zero as Nz in a degree below one, then a t Nz = 0, bjj2/bNz is infinite (Fig. 4). The partial molal volumes of the system water-strong electrolyte3 correspond to this NI = 1 case. Fig. 4. The third case when a t NZ = 0, b&/bN2 and b&/bN2 are infinite, is apparently of no practical value.
L
-1
(3) Redlich and Rosenfeld. Z Eleklrocham , 37, 705 (1031).
Moscow, U. S. S. R.
RECEIVEDMAY27, 1935
[CONTRIBUTION FROM THE LABORATORY OF ORGANIC CHEMISTRY O F THE STATE UNIVERSITY OF IOWA]
Amides Obtained from Benzenesulfinic Acid BY L. CHAS.RAIFORD AND STEWART E. HAZLET A large number of aryl sulfinic acids have been prepared’ but few of them have been converted into the corresponding acid chlorides, while the behavior of the latter toward amino compounds has received very little attention. Hilditch and Smiles2 obtained benzenesulfinyl chloride in rectangular plates that melted a t 38’. Braun and Kaisers may have obtained this product as a solid, but they recorded no melting point. Although they used specially purified starting material, Whalen and Jones4 could not duplicate (1) Gattermann, Be?., SP, 1136 (1899); Knoevenagel and Kenner, i b i d . , 41, 3315 (1908);Claasz, Ann., 880, 303 (1911). (2) Hilditch and Smiles, Bcr., 41, 4115 (1908); J . Chem. Soc., 97, 2585 (1910). ( 3 ) Braun and Kaiser, Bey., 66, 552 (1923). (4) Whalen and Jones, THISJOURNAL, 47, 1355 (1925).
Hilditch and Smiles’ results, and they did not obtain crystals when they followed Braun and Kaiser’s directions. Their product was an oil with a boiling range of 85-90’ a t 3 to 4 mm. In the present work, the purpose of which was to test further the action of benzenesulfinyl chloride on amino compounds, the “crude” acid chloride was obtained in nearly quantitative yield by treatment of benzenesulfinic acid5 with thionyl chloride a t room temperature. Distillation, when successful, gave about 83% of a yellow oil a t 8085’ and 2 mm. Often rapid and violent decomposition of material took place. Comparison of products obtained by the action of “crude” chlo(5) Prepared as directed by Gattermann, ‘‘Praxis des organischen Chemikers,” 18th Auflage, Walter de Gruyter, Berlin, 1923, p 268.
s o v . , 1935
AMIDESOBTAINEDFROM BENZENESULFINIC ACID
ride and distilled material showed that little purification was accomplished by distillation. With the exceptions noted below the sulfinamides listed were obtained by treatment of two molecular proportions of the required amine, dissolved in about three volumes of dry ether,
2173
with 1.25 proportions of "crude" benzenesuhyl chloride in two volumes of ether, with continuous agitation a t 0'. The solid that separated was shaken with water to remove amine salt, the residue, if any, was mixed with the ether filtrate and from this the amide was isolated. Analytical
TABLEI AMIDESFROM BENZENESULFINIC ACID Starting material
o-Chloroanilineb m.-Chloroanilineb p-Chloroaniline o-Bromoaniline' m-Bromoaniline p-Bromoaniline o-Toluidine m-Toluidine p-Toluidineb o-Anisidine'
Yield," % '
Crystal formd
70" Very poor 78 2OC 19 47 29 44 56O Very poor
Tan Plates" Lavendar Pink' Lavendare Pinke Needles' Yellow plates Purple
Poor 89 29 26 Very poor' 26 Highh Very poori Very poork
Formula
hi. p.. o c .
Cubes" Purpleg
107-108 106 155.5 108-1 10 112-114 150.5 124-125 102-103 100-101 113 shrinks 108-113 133-134 131 114-115 183 143-144 100- 104 165 6 206 165-166
Analyses, yo nitrogen Calcd. Found
5.58 CinHioONClS 5.58 CuHioONClS CizHioONClS 5.58 4.73 C12HloONBrS CBHIOONR~S 4.73 C I ~ H ~ O O N B ~ 4S. 7 3 6.06 CisHiaONS 6.06 Ci3Hi30NS 6.06 CiaHi30NS 5.67 CisHia02NS
5.40 5.85 5.53 4.46 4.68 4.67 5.99 5.96 5.94 3.63
5.67 5.57 CiaHi30nNS 5,67 5.60 CisHisOzNS 4,84 4.85 CISHISOPNS Yellow 10.14 10.38 CisHnOsNzS Tan rods" 5.25 5.14 CieHisONS Rodse 6.06 5.79 CiaHiaONS J 4.78 4.72 CieHiiONS 4.28 3.89 CisHi40NClS Yellow plates Pink 4.28 4.05 CiUHi4ONClS The amide was ether soluble, and was obtained from Unless otherwise noted, yields represent purified material. When no crystal form Represents crude product. the filtrate after removal of the amine hydrochloride by filtration. is specified, the substance is amorphous; no entry indicates colorless. e Crystallized from dilute alcohol. When not Largely hydrolyzed designated, a chloroform-ligroin (SO-SO0) mixture was used. Crystallized from methanol. Amide was separated from amine salt by shaking with a mixture of chloroform and water. during recrystallization. Reaction Prepared in pyridine solution. Treatment of chloroform solution with ligroin precipitated the amide. Reaction seemed complete in half an hour. mixture stood overnight before being worked up. m-Anisidineb p- Anisidine p-Aminobenzoic ethyl ester 2-Methyl-5-nitroaniline @-Naphthylamine Benzylamine 4-Aminodiphenyl 2-Amino-4'-chlorodiphenyli 4-Amino-4'-chlorodiphenyl'
'
'
TABLE I1 ANILIDESOF BENZENESULFONIC ACID Starting material
o-Bromoaniline m-Bromoaniline o-Toluidine m-Anisidine p-Aminobenzoic ethyl ester 2-Methyl-5-nitroaniline 4-Arninodiphenyl 2-Amino-4'-chlorodiphenyl 4-Amino-4'-chlorodiphenyl
Yield, %
72c 69' 97" Nearly quant." Nearly quant." 88f 67l 74f Nearly quant.l
Crystal form
Needles" Plates Laven. plates Needles Plates Cubes Needles Prisms Powder'
M. p.,
oc.
130-131 117.5-1 18.5 122-123 82.5-83.5 183.5-184 1i5-1ifje 147-148 136-138 145-143.5
'
Formula
Analyses, yo nitrogen Calcd. Found
Cl~Hlo02NBrS CllHlo02NBrS CisHisOoNS' CisHiaOaNS CisHisOaNS CisHizO*NzS CieHibOnNS CieHi40zNClS Ci8H1402NClS
4.48 4.48
4.47 4.51
5.32 4.59 9.61 4.53 4.07 4.07
5.26 4.46 9 . 51d 4.52 3.97 4.04
..
..
Chloroform-ligroin (60-80°). Morgan and a crystallized from alcohol; in other cases dilute alcohol was used. Mcklethwait [ J . Chem. SQC.,89, 1294 (1906)] found 172" and satisfactory analysis for a product obtained by boiling a toluene solution of the amine and acid chloride for three hours, evaporating the mixture to dryness, extracting the residue with sodium carbonate solution and precipitating the amide by acid. No yield was given. In the present work heating, Deterether solution of the reactants, followed by standing, gave no change. Pyridine was then used as a solvent. The reaction carried out in mination made by semimicro Dumas method. e Reaction carried out in ether solution. Previously obtained and analyzed by Hinsberg [ A n n . , 265, 184 (1891)l who recorded no yield. It was prepyridine. A mixture of the two pared in the present work for comparison with the sulfhamide of the same base, in. p. 124-125'. melted at 85-95'.
Lours F. FIESERAND ARNOLDM. SELIGMAN
2174
data for these products are given in Table I. were prepared. For purposes of comparison of physical prop- Table 11. erties a number of corresponding sulfonamides IOWA CITY, IOWA
[CONTRIBUTION FROM THE CHEMICAL
VOl. 57
Data for them are given in RECEIVED MARCH23, 1935
LABORATORY OF HARVARD UNIVERSITYJ
Cholanthrene and Related Hydrocarbons BY LOUISF. FIESER AND ARNOLDM. SELIGMAN The synthesis of cholanthrene by three differ- genic activity than might have been expected ent methods has been reported recently by Cook on the basis of the available data.4 and his associates.' We have found that the Another hydrocarbon having the cholanthrene modified Elbs synthesis2 provides still another ring system was obtained very easily starting with route to this interesting hydrocarbon. The ke- fluoranthene (VI) from coal tar. By the methtone I11 was prepared from the known 4-bromo- ods of Fittig and LiepmannJ6modified in some dehydrindone-1 (I)3 as indicated, and on pyrolysis tails, fluorene-l-carboxylic acid can be prepared in any desired quantity by the oxidation of fluoranthene, followed by the reduction of the resulting keto acid VII. 1-(a-Naphthoy1)-fluorene (VIII) was obtained from a-naphthylmagrlesium + CO-CH2 I
-
CH2 CH
I1
CHrCHz I11
there was obtained a hydrocarbon corresponding to the description1 of cholanthrene, IV. From
bromide and fluorene-1-carboxylic acid chloride, and on pyrolysis it yielded the hydrocarbon IX. C!H&H,
IV
V
the ketone resulting from the reaction of the Grignard compound of I1 with P-naphthoyl chloride, the isomeric hydrocarbon V was obtained. Dr. M. J. Shear has observed that crystalline cholanthrene injected subcutaneously in mice produced effects similar to those obtained with methylcholanthrene and in approximately the same time. The hydrocarbon induced ulcerations beginning with the fortieth day and the first tumor, noted on the sixty-second day, took successfully on transplantation. From these preliminary results it appears that a methyl group at CZO is of less influence in determining the carcino(1) Cook, Haslewood and Robinson, J . Chem. SOL, 667 (1935); Cook and Haslewood, {bid., 767,770 (1935). (2) Fieser and Seligman, THISJOURNAL, 67,942 (1935). (3) Miersch, Ber., 81, 2110 (1892); Mayer, Phipps, Ruppert and Schmitt, ibid., 61, 1966 (1928).
To indicate the relationship to the carcinogenically active parent hydrocarbon, this substance may be called 15,16-ben~dehydrocliolanthrene.~ The Friedel and Crafts reaction of the above acid chloride with naphthalene was investigated, with rather unexpected results. The condensation proceeded poorly in carbon bisulfide, probably because of the sparing solubility of the com(4) Cook and co-workers, Proc. Roy. Sac. (London), B111, 455, 454 (1932);B117,318 (1935). (5) Fittig and Liepmann, Ann., 8 0 , 1 (1879). (6) Fieser and Seligman, THISJOURNAL, 67, 1377 (1935).
