V O L U M E 2 2 , N O . 7, J U L Y 1950 Table I.
Analytical a n d Crystallographic D a t a of S u l f a n i l a m i d e Derivatives
Compound Benzvlidene sulfanilamide o-Chiorobenzylidene sulfanilamide p-Chlorobenzylidene Sulfanilamide Cinnamvlidene sulfanilamide 3.4-Dimbthoxybenzylidene sulfanilanude 2.4-Dimethoxybenzylidene sulfanilaniiiie Furfurylidene sulfanilamide o-Hydroxybenzylidene sulfanilamide p-Hydroxybenzylidene sulfanilamide p-Methoxybenzylidene sulfanilamide m-Methylbenzylidene sulfanilamide o-Nitrobsnzylidene sulfanilamide m-Nitrobenzvlidene sulfanilamide p-Sitrobenz;lidene s~dfanilamide Cinchonidine sulfanilamide HzSO, Quinine sulfanilamide HrSO, Quinine sulfanilamide l’/z HtSO’ Glucoseanil sulfanilamide Mannoseanil sulfanilamide a ¶ ,
b
951
Melting Point Block,
Nitrogen Calcd., Found,
%
O C .
188 180 186 216 193 19’7. 196 211 204 200 201 183 170 175 183 209 186 211 202
10.16 9.02 9.52 9.79 8.75 8.75 11.20 10.14 10.14 9.66 10.22 13.77 13.77 13.77 8.80 8.41 8.71 8.38 8.38
%
10.73,10.70 9.68, 9.60 9.52, 9.46 9.68, 9.64 8.85, 8.71 8.72, 8.80 11.12,11.07 10.07,10.02 10.20,10.25 9.69, 9.80 10.05,10.11 13.77.13.65 13.73,13.68 13.79,13.75 8.75, 8.67 8.40, 8.35 8.84, 8.86 8.28, 8.20 8.22. 8.28
Opti- ElonSign
ga-
tion
Refractive Indexes a t 25 %_ Alpha Beta Gamma 1.494 1.676 >1.703 > 1.703‘ 1.514 >1.703 1.655 >1.703 1.486 > 1.703” >1.703 1.528 1.521 1.605 > 1.703 1.674 > I 703 1.655 > 1.703 1.651 1.493 > I .703 1.680 1.482 >1.703 1.666 1.512 1.645 >1.703 1.498 1 661 1,492 >1.703 1.690 21 703 1.476 1 676 1,574 > 1 . 70x >1.703n 21.70: 1.524 1 5Y.i > 1 b71h 1.507 1,657 1.596 1.668 1.618 1.574 >1.703 1 569 1 574 >1.6766 1.581 1 615 1 636
Axial Disper-
sion r > v r > u r > c
Sone
v > r
r>r r > o
None Sone r > u None None None hione None r 2 v None r > u r > 7,
Crystal System Monoclinic AM~noclinic Monoclinic Monoclinic Monoclinic Monoclinic hlonoclinic Monoclinic Monoclinic Monoclinic i\tonociinic Orthorhombic Orthorhombic Orthorhombic hfonoclinic Monoclinic Monoclinic Monoclinic Monoclinic
is only a small amount above 1.703.
Crystals dissolve in oil above recorded refractive index.
No dispersion No pleochroism Alpha, 1.505 Beta, 1.639 Gamma, >1.85
B. Anhydrous Monoclinic Phase. This stable phase, as Watanabe (19)found, predominates in commercial preparations. Most desirable crystals for microscopic studies were obtained by hastening crystallization from hot acetone solution. These crystals appear to be orthorhombic between crossed Nicols, but are definitely monoclinic. The same phase, but different habit, was obtained from methanol. Crystals from the latter solution do not appear orthorhombic. Goniometric measurements and refractive indexes proved, as pointed out by Watanabe, that the crystals from acetone and methanol were the same phase. System, monoclinic Sign, positive Common orientation, E t a Elongation, negative Dispersion axial, slight, c > r No pleochroism Alpha, 1.555 Beta, 1.672 Gamma, > 1.85 Keenan
( 4 ) reports for this phase the following: System, ? Alpha, 1.570 Beta (ni), 1.677 Gamma, > 1.733
C. Anhydrous Monoclinic Phase. This stable phase is obtained upon crystallization from hot n-propyl or n-butyl alcohol, from chloroform, or from water on long standing. No transformation of phase C was evident after one year’s standing. System, monoclinic Sign, positive No dispersion KO pleochroism Common orientation, centered E t a Elongation, positive ( E t a ) Alpha, 1.547 Beta, 1.633 Gamma, >1.85 The data for this phase correspond to those found in this laboratory by White (IS). Van Zyp (11) reported different habits of sulfanilamide which he considered to be the same phase. Watanabe (12)reported x-ray and goniometric studies of three phases. Williams and Maresh (14) reported no quantitative data or optical-crystallographic propert,ies in isolating five phases of sulfanilamide By using ten different organic solvents and water, two anhydroua phases of sulfanilamide and the monohydrate were isolated. A complete correlation between the results obtained in this
laboratory and the results reported by Watanabe, Van Zyp, and Williams and Maresh was not possible. SUMMARY
Fourteen Schiff bases, three cinchona alkaloid addition products, and two anils with sugars of the sulfanilamide have been prepared and analyzed, and their optical-crystallographic properties have been reported. Sulfanilamide has been recrystallized from different solvents and analyzed, and the optical-crystallographic properties have been reported for three distinct phases. &4method of identification of sulfanilamide making use of the optical-crystallographic data of the Schiff base with p-chlorobenzaldehyde and the quinine bisulfate addition product has been suggested. LITERATURE CITED
(1) Assoc. Official Agr. Chemists, “Official and Tentative Methods of Analysis,” 3rd ed., 1930. (2) Gray, W. H., Buttle, G. A. H., and Stephenson, D., Biochem. J . 31,724(1937). (3)Hultquist, M. E.,Poe, C. F., and Witt, K . F., J . .4m. Chem. Soc., 67,588 (1945). (4) Keenan, G. L.,J. Assoc. Ofic.Agr. Chemists, 27, 153 (1944). (5) Kienle, R. H., and Sayward, J. M., J . Am. Chem. SOC.,64,2464 (1942). (6) Larsen, Junius, Witt, N. F., and Poe, C. F., Mikrochemie, 34,1 (1948). (7) Poe, C. F., and Dewey, B. T., J . Am. Pharm. Assoc., 25, 419 (1936). (8) Poe, C. F.,and Sellers, J. E., J . Am. Chem. SOC.,54,249 (1932). (9)Poe, C. F.,and Swisher, C. A.,Zbid., 57,748 (1935). Powell, H. )VI,, Rose, C. L.,and Bibbina, F. E., J. (10) Stuart, E.H., Am. Pharm. Assoc., 28, 90 (1939). . 75,585 (1938). (11) Van Zyp, C., P h a ~ m Weekblad, (12)Watanabe, A,, Naturwissenschaften, 29, 116 (1941). (13)White, B. J., Univ. Colo. Studies, 26,104 (1941). (14)Williams, E. F.,and Maresh, C., Abstracts of Papers, 104th Meeting, AM.CHEM.SOC.,Buffalo, N.Y., Sept. 7 to 11, 1942, p. 2L. (15) Yalowitz, M.L., J . Assoc. Ofic. AUT.Chemists, 21, 351 (1938). RECEIVEDAugust 15, 1949.
Correction I n the article on ‘(Stable High-Frequency Oscillator-Type Titrimeter” [Anderson, Kermit, Bettis, E. s.,and Revinson, David, ANAL.CHEM., 22,743 (1950)], the professional connection of the authors should have been given as Fairchild Engine and Airplane Corporation, K’EPA Division, Oak Ridge, Tenn.
