3 150
COMMUNICATIONS TO THE EDITOR
Vol. 69
143-145’ (lit.,J m, p. 146-147’) and was readily converted by copper chromite reduction to quinolizidine which was identified as before. Details of the synthesis of quinolizidine and various derivatives will be reported in a subsequent publication,
phenyl)-24rnidazolidone, m. p. 128-130’ (Anal. Calcd. for C24H2403N2:C, 74-20; H, 6.23. Found: C, 74.54; H, 6.39). This compound was heated for forty-eight hours a t 120’ with ca. 4 N aqueous ethanolic sodium hydroxide. After extraction with ether, 72% of 3,4-dibenzyloxyphenyl-N2-methyl-ethylenediaminewas isolated (3) Orhiai, Tsuda and Yokoyama, Bcr., 68, 2291 (1935). as dihydrochloride, m. p. 184-155’ (Anal. DEPARTMENT OF CHEMISTRY C, 63.44; H , 6.48. UNIVERSITY OF ROCHESTER V. BOEKELHEIDECalcd. for C23H2a02Nz.2HC1: ROCHESTER, NEWYORK S. ROTHCHILDFound: C, 63.65; H, 6.46). The latter, by palRECEIVED NOVEMBER 14, 1947 ladium catalyzed hydrogenation, gave 91% of 3,4 - dihydroxyphenyl - N2 - methyl - cthylenediamine dihydrochloride (C 111), m. p. 202-203’ DIAMINES. I. THE SYNTHESIS OF AMINO (Anal. Calcd. for C9H140~N2.2HC1:C, 42.36; ANALOGS OF ADRENALINE. ARTERENOL AND H, 6.32. Found: C, 42.55; H, 6.49). EPHEDRINE The dihydrochlorides of C (IV), m. p. ca. 245’ Sir: (dec.) (Anal. Calcd. for CsHl2O2N2.2HC1 : C, Diamines C (R and R’ = H or CHI) wherein 39.85; H, 5.85. Found: C, 40.09; H, 5.71), the alcoholic hydroxy group of arylalkanolamines, such as adreaaline, arterenol and ephedrine, is re- and of C (V), m. p. ca. 249’ (dec.) (Anal. Calcd. placed by an amino group (111, I V and v ) have for CloHI6N2.3HCl:C, 50.64; H, 7.65. Found: attracted interest,’ but only I2and 113have been C, 50.69; H, 7.82) were obtained from B (IV) and B (V) by acid hydrolysis. described adequately. Recently Funke and Bovet Diamines of type C are sympathomimetics of reported that a group of diamines including I and IV are ~ympathomirnetics.~Methods of prepara- relatively low toxicity. When administered intration, physical and chemical properties of the new venously in dogs and cats I11 and I V showed one-tenth of the pressor activity of adrenaline, I diamines wese not reported. only 1/900. I V is therefore more potent than it Prior to that, we had investigated numerous cy,B-diamines. Thus, a-aminoketones ArCOCH- appears from published data.* As a bronchodila(NHR)R’ were cyclized to imidazolones (A) tor I11 was ten times stronger than 117. LABORATORIES R. DUSCHINSKY which, .due t’o labilization of the double bond by RESEARCH ROCHE,INC. L. A. DOLAN aryl,5 could be selectively hydrogenated to HOFFMANN-LA NUTLEY, NEWJERSEY L. 0. RANDALL imidazolidones (B) . Hydrolysis (for the adrenaG. LEHMANN line analog after protective benzylation) afforded RECEIVED KOVEMBER 18, 1947 r\
L.
HN
I
NR
I - - 1
HdCO‘NR
I
- I
NH2
NHR
I
A r b C R ’ ArCH-CHR’ ArCH-CHR’ B C A I, Ar = Ph; fz = R‘ = H.-11, Ar = Ph; R = H; R’ = CHa.-111, Ar = 3,4-(HO)&!sHs; R = CHI; R’ = H.-IV, Ar = 3,4-(HO)*CbH3; R = R’ = H.-V, Ar = Ph; R z= R’ CHa.
RAMAN SPECTRUM AND NORMAL MODES OF VIBRATION OF BUTADIENE-1.2’
Sir:
We have recently redetermined the Raman spectrum of butadiene-1,2 in an effort to improve the assignment of the normal modes of vibration. A very pure sample of butadiene-1,2 was obtained from the Cryogenic Laboratory of this College. Refluxing adrenalone hydrochloride with 2 This sample is identical with the one used in obmoles of potassium cyanate in water and neutraliz- taining the thermodynamic properties of this ing with hydrochloric acid gave almost 100% of A molecule.2 The Raman spectrum was obtained (111), m. p. 276-277’ (Anal. Calcd. fer CloHlo- in two different spectrograph^,^^^ up to 2000 cm.-’ 03Nz: C, 58.25; H, 4.89. Found: C, 58.14; H, shifts. The spectrum obtained generally agrees 5.02). Hydrogenation in acetic acid with pal- with the previous one of Bourguel and Piaux5; ladium charcoal a t 3 atm. pressure yielded almost there were, however, a few important differences, 100% of R (111), m. p. 167-169’ (Anal. which warrant a reassignment. The polarizations Calcd. for C10H1203N2: C, 57.68; H, 5.81. of the strong lines were also obtained and were Found: C, 57.85; H, 5.93). Benzylations of B useful guides in making the new assignment. (111) gave 9CI7, of l-methyl-4-(3,4-dibenzyloxy- The following assignment has been made for the normal modes of vibration of butadiene-1’2. (1) Review by Nartung, Ind. Eng. Chem., 37, 128 (1945). (2) Peist and Amstein, Bcr., 88, 425,3172 (1895). (1) The work described in this communication was carried out (3) Jaeger and van Dijk, Proc. Acad. Sci. Amsterdam, 44, 26 (1941). (4) Punke and Bovet, Compt. rend. SOC.biol., 141, 327 (1947). I and IV a p p e u t o have equal preasor activity. (6) Cf. Duschinciky and Dolan, TEISJOUI~NAL, 67, 2079 (1945); “E. C. Barell-Jubilee Volame,” Bade, 1948, p. 164. (6) Cf.Suter and Ruddy, Tau JOWBNAL, 66,747 (1944).
under Contract N60nr-269 Task Order V between the office of Naval Research and the Pennsylvania State College. (2) Aston and Szasz, THIS JOURNAL, 69, 3108 (1947). (3) Rank and Wiegand, J . Opl. SOC.Am., 36, 325 (1946). (4) Rank. Scott and Fenske, I n d . En& Chcm., Anal. E d . , 14. 816 (1942). (6) Bourguel and Piaux, Bull. soc. shim., 61, 1041 (1932).
COMMUNICATIONS TO THE EDITOR
Dec., 1947
Symmetry class'
Frequency
A' A' A' A' A' A" A" A' A! A" A' A" A' A'
C-C stretching C=C stretching Skeleton angle change in plane Skeleton angle change out of plane ==CHI torsion CHI internal angle change
CH2 internal angle change CH, wagging (rocking) CHIIwagging (rocking)
T, OK.
230
65.26 64.87
* 0.30
0.24
0.88
0.2
842 1327 2870 2910 2931 2954 2993 3061
10
0.40
5 3 2
dP 0.26
phenylsulfonic acid was removed from the ether by appropriate extractions. The ether was evaporated, the residue dissolved in 0.5 ml. of ammoni-
This assignment leads to the following improved agreement between the calculated and experimental entropies : So Calculated So Experimenl all
0.11 0.37
7 0.2 10 (broad) 5 0.9 0.5 5 1 5
858' 1102
CH stretching
Polarization
Intensity
10
876 1072 1961 210 555 322 523 1374 1439 1462 1391' 1003 1132
A" A" A'
CH bending
3151
250
These calculal.ed entropies were obtained using a value of 1900 cal./mole for the potential barrier hindering the rotation of the methyl group-in fair agreement with a value predicted from other considerations. We wish to thank Dr. N. Sheppard for helpful discussions. (6) Lines observed in the infrared spectrum only. Infrared data obtained from American Petroleum Institute Research Project 44. Catalog of Infrared Spectrograms, Serial No. 41. (7) Notation according to Herzberg, "Infrared and Raman Spectra," D Van Noslrand Co., New York, N. Y., 1945, p. 105.
G.J. Szasz DEPARTMENT OF PHYSICS J. s. MCCARTNEY CHEMISrRY AND PHYSICS D. H. RANK PENNSYLVANIA STATECOLLEGE STATE COLLEGE, PENNSYLVANIA RECEIVED SEPTEMBER 26, 1947
290
273.25
66.65 66.58 * 0 . 1 7
68.21 68.40 * 0 . 1 4
69.45 69.39 t 0 . 1 8
acal alcohol, and an aliquot, equivalent to 1-7 micrograms of protein placed as a transverse line on Whatman No. 1 paper, 2 X 57 cm. The chromatogram was developed with n-pentanol saturated with 2 N ammonia. 600 450 U
9 300
3 150
SCHOOL OF
PAPER CHROMATOGRAPHY APPLIED TO THE ISOTOPIC DERIVATIVE METHOD OF ANALYSIS
5
15 25 Strip number. Fig. 1.
35
45
The diagram shows counts of successive 5-mm. strips of a chromatogram prepared from a mixture We have described a.method of analysis of simulating silk hydrolysates. Total counts in a amino acids in t'he form of isotopic, p-1131-phenyl resolved band divided by C,, counts per mole of sulfonyl (pipsyl) derivatives.' The estimation of isotopic reagent, gives equivalents of amino acid. these derivatives using paper chromatography is Recoveries were: glutamic acid 104%, serine 91%, glycine 1 0 0 ~ o ,alanine 100%. The ostensible reported here. One mg. of amino acids in 0.6 ml. of 0.3 M pipsylglycine was eluted and identified by adding sodium bicarbonate was shaken at 100' with 9 mg pipsylglycine carrier and demonstrating unof 1131-pipsylchloride. After acidification, de- changed isotope concentration after purification. rivatives were extracted with ether, the aqueous Analyses indicated 41y0 of silk nitrogen in glycine. Estimations may be made independent of comlayer evaporated, sodium bicarbonate added, and the procedure repeated twice. Residual p-iodo- plete resolution of bands by adding indicators (either unlabelled derivative or derivative labelled (1) Kerton, Udcnfriend end Canaan. THISJOURNAL, e8, 1390 with a second isotope) before chromatography, (lQ46).
Sir:
