May, 16-12 analysis to be at least 99.0%. The metals were melted in small iron crucibles 0.75 inch in diameter and 2.25 inches high, which were turned from a low carbon steel rod. Tests have shown that very little iron is dissolved by either of these metals in the liquid state if the duration of contact is kept at a minimum. The crucibles containing the alloys were heated in a F'yrex glass tube in an atmosphere of argon by means of a high frequency furnace. Thorough mixing was assured by use of a pure iron wire stirrer which was oscillated with a solenoid at the top of the tube. After cooling the iron crucible was removed from the alloy by turning i t off on a lathe. During this process the alloy was bathed in a stream of dry oil to protect it from the action of the atmosphere. The samples for analysis were prepared by rolling the alloys, under oil, into thin sheets from which were cut narrow strips for the X-ray examination. All alloys of the serics crystallized with a facecentcrcd cubic type o f lattice. 6.1
5.9
4
.-
E
d
6.7
0
1227
NOTES
20 40 Go 80 Atomic per cent. of strontium. Fig. 1.
Dimorphism of Amylcaine Hydrochloride BY HENRVR. KKEIDERA N D AUEL R .
~ , ~ E N O ~ I
During the investigation' of the chemical and physical properties of amylcaine hydrochloride (mono-n-amylaminoethyl-p-aminobenmate hydrochloride), a local anesthetic used for dental and medical purposes,*two aystalline forms (rectangular plates, melting at 153.5'. and rods, melting at 176') were obtained. The absence of alcohol of crystallization and water of hydration was demonstrated by a negative Zeisel ethoxyl determination and by the fact that no loss in weight was observed when the crystals were heated above the melting point, although the lower melting form was transfonned into the higher melting form under these conditions. Therefore, a dimorphic habit was indicated. Experimental Rectangular Plate Form (Fig. l).-Two grams ol conimcreially available aniglcainc hydrochloride was diswlvrd in 25 cc. ofhot wmcr. thr solution wulcd to r o o i i i temperature and the resultant crystals wcre filtered. washed with cold ethanol and dried in vacuuln over sulluric acid; melting point 151.5' (cor.). \\'hcn kept at thc melting point, thc liquid solidified spontaneously or UI>OII rratching the microscope slide. yirlding thc highcr melting lorn. Anal. Calcd. for C I ~ H & S ~ I I C I : X, 9.77; CI. 12.86. F0""d: N,9.5; CI. 12.4.
100
The results of the X-ray analysis are summarized in the table and shown graphically in the figure. At.%%
m in A. Dmdty
0
10.28 31.37 51.80 80.W 100 5.847 6 . ~ 8 0 n.07~ 5 . ~ 0 5.627 5.720 2.578 I . M ~ 1 . n ~ 1.n3n 2.180 2.41n
It is obvious that the values of a0 vary directly with the strontium content. Although no thermal analysis has been reported for this system, it is quite apparent from the above results that calcium and strontium form a continuous series of solid solutions at room temperature. Acknowledgment.-The author wishes to acknowledge the kindness of Prof. G. L.Clark of the University of Illinois, in whose laboratory the preliminary study of this problem was conducted. RBCBIVBD MARCH6.1842
Fig. I.-Amyleaine hydrochloride, rectangular plate form. m. p. 153.5' ( X 100). Between crowd nicols the crystals appeared as dongated plates with a relatively high hirelringence. They exhihitcd positivc elongation and parallel extinction. In convergent polarired light hiaxial figurer were common. with the acute hiwtrix and masionally an optic axis in the field of vier. Rc/rorlin indicts (determined by immersion in organic liquids): (I 1.510; 6 1.582; v > 1.855 (all *0.002). Rod Form (Fig. 2).-A saturated solution of ninylcaine hydrochloride in hoiling namyl alcohol WBS moled slowly in a water-hnth to %lo. h n ~ thick. , hexagonal rods were
-
-
(I1 J . An. Hd.A i m . . 116, Zmxl (1841). (a) s.D.h t d h ."d w. P. whitmom. TWSJOU*NAL. 1*,2z80 (1937).
Vol. 64
NOTES
I:ig. 2.-Amylrainr
hydrochloride. hexagonal rod form. n,. I>. I i t i ' ( X 100).
Between e r a s ~ dnicols Ihc crystals appeared as lung miwith hexagonal cros~section cxhibiting negative elongation. sharp, parallel rxtinctian and relatively low hirefrim gence. In ronvergcnt polarirrd light partial uuiavial ligures were observed. indicating particles with faces parallel to the optic axis. When Ihe crystals were CNShcd. ir. regular angular fragments were obtained. An masionnl particle did not extinguish sharply whcn the stage was rc. volved and in convfrgent polarired light exhibited a par. tial uniaxial figure. The optical rharartcr was negativc. Rcfrocliir indircr: w = I..%Y?; e * 1 . 5 3 (-0.002). Pseudomorphic Habit (Fig. :$).-When thc lower melting farm was kept at trmpcmtures j u s t hrlow the melting point. the crystals Iwcame opaque and showed no tcndency to melt a t the l o w r tcmprrature but melted sharply a t 176'. This transformation conhl be follawcd readily hy the rhangc to B lowrr birefringence during the heating. .
Fig. :$.-Amylcaine
hyclrwhloride. pseudomorphic habit. tn. I). l i f i " ( X 1tX)).
dihydroxycholanic acid by the elimination of the keto group of 3(u),I1-dihydroxy-12-ketocholanic acid by the treatment with hydrazine hydrate and scdium ethylate at 200". They obtained a compound having presumably two oxygen atoms less than the starting material. We have obtained from this reaction a compound melting with decomposition at 1.76' with the empirical formula C*,H,oOs (11). 'The reduction of .7(a),ll-dihydroxy-l2-ketocholanic acid (I) to R(a),ll.l2-trihydroxycholanic acid (11) is shown by the analysis and relative ease of its oxidation with chromic anhydride and subsequent Clcmmensen reduction to neo-lithobilianic acid (111). Similarly neo-lithobilianic acid was obtained by the action of sodium ethylate and hydrazine hydrate on 1I-hydroxy-12-ketocholanir acid, followed by oxidation of the resulting dihydroxy compound. Reduction to the dihydroxy compund was the major product of bath hydrazine reactions. In addition we have oxidized directly 11hydroxy-l2-ketocliolanicacid to neo-lithobilianic acid. This product was not reported by Barnett and Reichstein' who oxidized the methyl ester of 11-hydroxy-12-ketocholanicacid under very mild conditions and obtained 1 I,l2-diketocholanic acid. The reduction of a carbonyl to a carbinol group with hydrazine and alkoxide is not without analogy in the literature, for Marker and Lawson' succeeded exclusively in converting pregnan20(a)-oI-3-one to pregnanediol-.7(~),20(ar)by the Wolff-Kishner method. Later Dutcher and Wintersteiner' in their investigation of this method of reduction of steroidal ketones showed in several cases that the conversion to a carbinol would take place in preference to the complete reduction to a methylene group. We thank Parke, Davis and Company for their assistance. Experimental Part
Sterols.
CXL.1.
3(a),11,12-Trihydroxycholc Acid'
RY RUSSELLE. MARKBR.ANTHONYC. SHAFXA,RLWN
M.JomstHARRYhf. CROOKS,J R . . EMERSON
L.
AND
WITTIIECKRR
We have repeated the work of Longwell and Wintersteinerl who attempted to prepare 3(a),II(I) oridmi mnuwript miv-! jllnr 27. in4 I. i?l 1.onrrcll and \\'inlcnl.icwr. Twr Jovmrrt..
el, ZlXl
I1,12-DihydroxycholaoicAcid.-A mirture of I g. 01 11hydraxy-12-ketocholanic acid, 5 ce. of 85% hydrazine hydrate. and 1.8 g. of sodium in fXl cc. of absolute ethanol was heated in B sealed tube for twelve hours at 200'. The product was diluted with water and extracted with ether. The aqueous layer was acidified and extracted with ether. The ether extract w a s washed with water. dried and evaporated. The product was crystallized from ether- .(a)
and Reich.itein. HI~.. Chim. Arln. Xn. 826 11938). .ad Larwn, TnxaJovln*~. el, 062 11830). ( 5 ) Vutrbn mnd Wint-leincr. ibid., 61, 1082 (1030). R-dt
(4) Mark-
11940l.
