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 - N 2 - 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 t o 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).
