COMWNICATIONS TO THE EDITOR
18%
'O
t
i
Vol. 69
lated on the weight of glycol, not on the glycolcopper complex. The magnitude of the optical rotations (1200') in claprammmium is striking. The sign and nitude of the rotations indicate that the form may be oriented as are the 2- and 3-hydroxyl groups of substituted methyl glycoside and the D - ( - ) - form as are the 3- and %-hydroxylgroups of substituted methyl glucoside. And such a condition is distinctly possible in view of the configurations which have been assigned to these two butanediols by M o d and Auernheimer.' Specific rotations for the appropriately substituted methyl glucosides in cuprammonium have been reported.* They were +M0 (436 mp) for methyl 2-methyl-/3-glucoside, and - 1008' (436 m p ) for methyl 4-methyl-B-glucoside.
~-21
TABLEI SPECrprC ROTATION OF 2,3-BUTANEDZOL S o l ~ a and t light mwcc L-(+)-forrn o-(-)-form
I
I
I
0.02
0.04
0.M
Water, Dline Water, Hg blue line (436 mp) Cuprammonium, Hg blue line
+ +
11.8' 20.6"
- 1200'
-
11.1" 19.2" +1200"
-
The samples of optically pure butanediols used in the investigation were supplied by Dr. Robert Fig. l.-Cor~ductancecurves in water at 25': (1) nhuadecylpyridonium iodate; (2) n-ochdecylpyridonium D. Coghill, formerly head of the fermentation division of the Northern Regional Research Laboiodate. ratory. W e the addition of methanol in suitable ( 1 ) S. A. Maell and A. H. Auanhdrncr, Tars Joaanu,, 64,79!4amounts to water solutions of certain paraffin- 796 (1944). (2) R. E. Reeves, 1. Bid. C h . .lW,49-S6 (1944). chain salts gives rise to a maximum in A, the SOUTI~ERN REGION&RESEARCH LABORATORY addition is not indispensable in,some instances, BURBAUOF AGRICULTURA~ AND INDUSTRIAL CHEXIS~RY nor is it sufficient to produce a maximum in others. A cnrcv~~iw RESEARCH . ADMINISTRATZON It is evident that the phenomenon is closely re- u. s. DEPARTMENT OF AGRICULTURE lated to the nature of the "gegenion." NEWORLEANS 19, LA. RICHARD E. REEVES Sufficient results have now been obtained to perRECEIVED APRXL 14,1947 mit of formulating a fairly general description of the electrical conductance of solutions of paraffinchain electrolptes in watq+xganic solvent mix- An ALBlJbUN FEUCTIOH ISOLATBD FROM HUMAH PLASbU AS A CRYSTALLIHE MERCURIC SALT tures; the details of .this work will be presented in Sir: the near future. Following the addition of mercuric chloride to GEORGE L. BROWN DEPARTYBNT OF CHEMISIRY PHILIPF.GRIBCEI~ a solution of human serum albumin, a fraction of BROWNU"8RSITY E. CKARLBS E v ~ n s the albumin crystallized. The best yield was ob~ O V I D B N CR. B ,I. CKARLES A. KRAUS tained when approximately one-third mole merRECEIVEDJUNE 12,1947 curic chloride per mole albumin was added to a 15% solution of Fraction V' or to human serum albumin crystallized with decanol,) in 15% C ~ M O ~ M - 2 , 3 - B U T A N E D I OCOM.€'LBxBs L ethanol at -5O, a t PH 5.2, I'/2 = 0.02. More sir: than half the senun albumin separated after In connection with a study of the properties of prolonged standing, or within a few days following cuprammoniurn-glucoside complexes the behavior seeding, in the form of rhombic or hexagonal of the optically active 2,3-tmtanediols in cupram- plates. Sparingly soluble in water, the crystals dissolved readily in 0.02 M sodium chloride and monium hydroxide solutibn has been observed. In Table I are given the specific rotations for could be recrystallized by the addition of ethanol. the D-(-)-and L-(+)-forms of the two butane(1) E. J. C o b , L. E. Strong, W. L. Hughes, Jr.. D. J. Mulford, diols in water (approx. 1% gl col concn.) and in J. N. Ashworth, M.Melin and H. L. Taylor, THIS JOUXNAL, U,469 cuprammonium. (approx. 0 . 8 6 ) . The rotations (ISM). (2) T h a r O ~ O ~ T ~ O which M , rill pruenUy he reported in full, were measured at 25'. The cuprammonium followed upon. and nre clacly relsted to, the methods for the cry.contained 15 g. of copper and 240 g. of ammonia tslliutlon of mrn dbamiru dencribel d r w h e r e in this iuue. Cohn, per liter. The rotations on this solvent are calcu- Hughannd W a r e ,(bid., eB, 1753 (1947).
