NOTES
May, 1945
881
which reproduces their results with considerable accuracy in this range. However, their equation gives values which are too low when extrapolated to the higher temperature range reported here, as shown in the third column of Table I. Consequently, an equation was derived which fits the data in the range 0 4 O o within our limit of error. Log Pmm. = - (2018.37/T) - 6.0303 log T 24.91300
correspond to 1.3-1.5% of the weight of the original leaves. After one recrystallization this crude wax had an acid number of 49.0, a saponification number of 79.3 and a melting range of 222230'. Several componentswere isolated from this wax as described below. Ursolic Acid.-Saponification by ethanolic potassium hydroxide yielded an acid fraction, representing 43% of the original wax. This was (1) The deviations of the observed values from those purified by the method of Sand04 to yield a macalculated by means of this equation are shown terial identical with ursolic acid, as shown by the in the fourth column of the table. The heat of melting point (285'), X-ray powder patterns of vaporization calculated by means of this equa- the acid and of its sodium salt, and the optical ~ sodium salt protion with suitable corrections2 was found to be properties of the p y s t a l ~ . The duced the sharper ditrrsction pattern; since this 5720 cal./mole at the normal boiling point, pattern has not been published, 276.03'R., as compared with the calorimetric spacings and relative intensities ofthed interplanar d o n are value2 of 5482. cal/mole. presented in Table I. The value found a t the ice-point may be compared with other values in the literature. Wiberg TAEILE I and Siitterlin' report 681 mm., Simon and Huter' X-RAYPOWDBR PATTERN OF SODIUM URSOLATB find avalueof 679.1(calcd.), Thompson and LinnAnal. Calculated for CtcHaOCO&I: C, 78.87; H, ett6 680 mm. The average is within our limit of 10.60, neut. equiv., 465. Found: C, 78.94, 78.76; H, 10.44, 10.64; neut. equiv., 460. error, equation (1) giving a value of 679 mm. Interplnoar Intensity Interplanar .Intensity, The authors wish to thank the Physics Departspocinp. A. 1/11 spacing, A. 1/11 ment of Indiana University who loaned a cathe14.6 0.50 2.83 0.04 tometer and to express their appreciation for a 10.3 03 2.71 .08 grant from the Graduate School Fund of Indiana .50 2.63 .05 9.2 University. 7.6
+
(3) E.Wiberg and W. Sntterlin, Z. Eleklrochcm., 41, 151 (1935). (4) A. Simon and J. Huter, ibid., U , 28 (1935). (5) H. W.Thompson and J. W. Linnett, Trans. Faraday Soc., 81, 681 (1936).
CHEMISTRY DEPARTMENT INDIANAUNIVERSITY RECEIVED OC~OBBR 2, 1944 BLOOMINGTON, INDIANA FROM EASTERN REO~ONAL RESEARCH LABORATORY,~ PHILADELPHIA, PENNSYLVANIA]
[CONTRIBUTION
Ursolic Acid and Paraan Hydrocarbons from Cryptostegia Leavese BY JONATHAN W. WHITE,JR.,
AND
F. R. SENTI
6.90 6.49 5.96 5.68 5.17 5.01 4.82 4.61 4.49 4.18 3.88 3.75 3.52 3.37 3.24 3.17 3.06 2.92
.03 1.00 0.50
.50 .bo
08 .18 .13 .14 .12 .10 .07 (13 .09 .06 .03 *
.
2 :54 2.42 2.35 2.28 2.23 2.18 2.13 2.10 2.05 2.00 1.98 1 95 1.91 1.87 1.79 1.71 1.66 1.59
.04
.05 .04 .04 .03 .04 .Ol .04 .03
.01 .02 .03 01
.
.01
.Ol During an investigation of methods for the re.Ol covery of rubber from the leaves of Cryfitostegia .06 .Ol grundifira, a brief study of some of the constit.04 .01 uents of the leaf-cuticle wax was made. A fer06 mentation pretreatment for rubber recovery resulted in a leaf fraction consisting of all the epiUrsolic acid has previously been reported to be a dermis, veins, and latex ducts, and representing constituent in the skin of several fruits and of about 18% of the original leaf weight.* From such leaves as Arbutus uncdo, Epigaea asiatica, this leaf fraction was isolated ursolic acid and a and mistletoe.' mixture of n - p a r a Cze,Ca and CSShydrocarbons. (4) C. E.Sando, J . Bid. Chcm.. BO, 477 (1931). The leaf fraction was exhaustively extracted (5) The &etala ace blades which show biaxial positive interferenct with hot acetone. When the extract was cooled figures with 2B approximately 130°. The index a. c r w w k of the to room temperature a voluminous crystalline blades, mu 1.6Sl; 6, alongthe blades, w85 1.561; and 7 , perpendicuto the blades, wna undetermined. These values a n i n agree= precipitate farmed, repFesenting 7.1-8.2% of the lar with thosp reported by Sando.4 weight of the material extracted. This would ment (6) K. S. M-kley, S. B. Hendricks and C. E. Sando, J . Biol. (1) One of the laboratories of the Bureau of Agri<ural and Industrial Chemistry. Agricultural R-h Administration. United States Departmenr of Agriculture. (2) Natural Rubber from Domestic Sources, Paper. (3) J. Naghski. J. W. White, Jr., 9. R. Hoover and J. J. Willamnn, bprcu.
Chm., 111, 133 (1935): K. S. Markley and C. E. Snndo.'ibid., l l * , 641 (1937); W.A. Nealey, Weslnn C a n w and Packer, 88, No. 12, 22 (1941); A. h n n , AHi ZV Conn. Nor. chin. pura applicafa (1932) 696 (LUI); K. Fujii, N. Shimpd. and T. s.pH,J . P k w m . SOC.Japan, 68, 660 (1935); E. I. v.p Itallie, Pharm. Weekblad, W, 824 (1981).
n-Paraffin Hydrocarbons.-From the neutral fraction after saponification a waxy product was isolated which, after a thirty-minute treatment in concentrated sulfuric acid at 120°, was crystallized from a mixture (1:1) of Skellysolve B and 95% ethanol. Its physical properties and long spacing (dwl) are shown in Table I1 under total hydrocarbons. A combustion analysis of this sample shows C, 85.1170, H, 14.91%. This indicates a paraan hydrocarbon, but the limits of error of the analysis do not permit a disor mixtures tinction between c & ~and CSSHSS corresponding to this range of composition. Accordingly, the product was fractionally crystallized by cooling after another sulfuric acid treatment (in which no darkening was observed). Three fractions were obtained. They are shown as fractions 1, 2, and 3 in Table I1 in the order of increasing solubility in the Skellysolve B-ethanol solution, and hence shorter chain length. The best photographs of the paraffins were obtained with filtered Cu radiation, using a 10-mil collimating system and a sample-to-film distance of I O TABLE I1 PHYSICAL PROPERTIES OF HYDROCARBON MIXTURES Sample
First transition point, heating, " C .
M. p., "C.
Fddl''
c 3 1
+
20% Con" Fraction2 95% Cai 5% Caaa 90% e31 5% Caa 5% G O Fraction3 80% Cat
+ + +
+ 20%Czoa
CsaHes. The crystal spacing 43.1 A. is slightly larger than that (42.8 A.) given by the mixture, indicating that the content of CaHm in this fraction is somewhat greater than 207& The melting point and crystal spacing of fraction 2 are in fair agreement with those of a mixture containing 95% CalHM and 5% CwHm, but the low transition point of this fraction indicates the presence of a small percentage of CWHW.Chibnal17 lists data for a mixture of 90% C~IHM, 5% CaHm, and 5% GHw, and in fair accord with the data for fraction 2. The data for fraction 3 are consistent with those for a mixture of about 80% Ca& and 20% CzsHw. The melting point and crystal spacing of a 50-50 mixture of CmHw and G H w would be close to the values observed for this fraction, but binary mixtures of paraffins Mering in chaih length by four or more carbon atoms crystallize in two phases,s each phase giving a separate dwl value. However, only one phase was observed in each of the fractions. Acknowledgment.-Acknowledgment is made of the cobperation of C. L. Ogg, who made the microanalyses. PHILADELPHIA, PA.
RECEIVED DECEMBER 9,1944
Crystal spacing
awl,A.
Total hydrocarbons 61 7 68 3-68.8.68.3 43.0 Fraction 1 G l 9-62.5 68.8-69.4 68.6 43.1 80%
Vol. 67
NEWCOMPOUNDS
982
NEW COMPOUNDS
62 0 68.8 .. 42.8 61.0-61 6 67.9-68.5 68.3 42.2
Some Polymethylenediamine1~* Incidental to another problem, a series of diamines of the general formula H*N(CHz),NR* has been prepared by the following reactions:
62 0-62.2 67.9-68.0
,cooGH, /CHrOH (CHds --j (CHdz + kOOGHs \CH~OH
67.4 42.0
61.0 67.8 . About 42.0 59.7-60 0 67.0-67.5 67.0 41.4
60.0-60.5 66.6-66.8 66.0 41.5 CaiHsc" 62 0-62.5 67.G67.8 67.3 41.55 a A. C. Chibnall, S. H. Piper, A. Pollard, E. F. Williams and P. N. Sahai, Biockm. J., 28, 2189 (1934). S. H. Piper, A. C. Chibnall, S. J..Hopkins, A. Pollard, J. A. B. Smith and E. F. Williams, z b d . , 25,2072 (1931).
Chibnall, et d.,1examined the cuticle constituents of a large number of plants and found that all paraf6ns present contained an odd number of carbon atoms. We et h i s to be true for the paraliins of cryptostegia leaf wax and accordingly have compared our data with those given by Pipe9 and Chibnall' for the odd-parailh hydrocarbons. The data for fraction 1 agree fairly well with the data for a mixture of 80% CaHw and 20% (7) A. C. Chibnall, S. B. Piper, A. Pollard. E. F. Williams and P. N. S a w Biochrm. J . , 1B,2189 (1934). (8) S. H.piper, A. C. Chibnall, S. J. fIopkin8, A. Pollard. J. A. B. W t h and E.F. Willinma. BioChm. J . , 88,2073 (1831).
/CHnBr+ (CHdr \CH2Br
@:; >
-
N--CHt(CHn).CHrBr
@~-c~z(cHn)sCHARi
----t
HtNCHt(CHd&Hm Ethyl adipate, ethyl sebacate and ethyl ruberate were reduced to the corresponding polymethylene glycols either with sddium and n-butyl alcohol*or by catalytic reduction with copper chromium oxide.4 Yields by both methods were 80-86q. The polymethylene &bromides were prepared from thi g1yd.s by the action of dry hydrogen bromide.' The 1-dialkylaminopolymethylene p h t l d h i d e s were prepared from the polymethylene &bromides axtd potas(1) The work docribcd In thb paper waa dom under a COlrtRct recoQmended by f8c Cooh Medial R a n u c h batrean the O f h e of Sdentiec Research and Development a d t h e U-ty of
Mlwouri. (2) M1crarruly.a by L& M8y and Froncea Mur. M b o e h d d Laboratory, Columbia Univmity. (3) "Organic Synthesm," COIL Vol. 11, p. 154 (1943). (4) Ref. S, p. W. (5) "Organic Spnthaa." VOL
w. p. m.
