Dec., 1047
COMMUNICATIONS TO TIIE EDITOR
For comparative purposes the melting points of some related compounds were redetermined. p-Phenylphenacyl chloride, reported t o melt at 122-123°,2 was obtained after many recrystallizations from ethanol as colorless Calcd. for Cl~HIIOCl: needles melting sharply a t 129.0'. C1, 15.42. Found': C1, 15.40; 15.16. The melting points of the p-phenylphenacyl halides decrease consequently from the chloride t o the bromide, m. p. 127.0°,3 and iodide as in the series of the phenacyl halides. Phenacyl chloride, reported as melting a t 52-55°,4 54°,6 56.5°,457-58'; 58-59 O8 and 59O,O was prepared according to the procedure of Korten and Schollsb; treated in ethanol with active charcoal, crystallized from alcohol, distilled and finally recrystallized from carbon tetrachloride, it melts sharply a t 56.5'. (2) A. Ccillet, Bu!l. soc. chim., [3] 17,510 (1897); S.L. Silver and A . Lowy, T H I S JOURNAL, 66, 2430 (1934). (3) Crystallized first many times from ethanol (m. p. 125') and then twice from carbon tetrachloride. Reported melting points are 125.5', N. L. Drake and J. Bronitsky, THISJOURNAL, 62, 3719 (1930), and 126-12;'", B. R. Carpenter and E. E . Turner, J . Chcm. SOL.,869 ( 1 9 3 4 ) . (4) Ch. f t . Gibson, J. D . A. johnson and D . C. Vining, Rcc. trau. ckim., 49,1006 (1930). (5) N. Puschin and K . S. Hrustanivic, Ber., 71, 798 (1938). ( 6 ) A. P . J. IIooE;eveen, Rec. Irau. chim., 5 0 , 669 (1931). (7) A. Collet, Bull. sac. ckim., [3] 17, 506 (1897). (8) (a) W. Staedd. Bcr., 10, 1830 (1877); (b) H.Korten and R . :Scholl,i b i d . , 34, 190.2 (1901); (c) D.A. Clibbens and M. Nierenstein, I . Ckcm. Soc., 107, .I492 (1915). (9) F. TGtin, i b i d . , 97, 2500 (1910).
3149
Phenacyl iodide, reported to melt a t 28,1° 2 9 . E ~ 3 0and ~~ 30'12, was apparently never crystallized from a solvent, evidently being considered too soluble in common solvents for this purp0se.1~ We obtained it in 95.4% yield by mixing solutions of phenacyl bromide and sodium iodide in dry acetone. The precipitate of sodium bromide, immediately formed, was separated and washed with dry acetone. The acetone solutions, quickly evaporated a t room temperature, left as residue a reddish oil which was extracted with ether. The ethereal solutions, decolorized with sodium thiosulfate, dried with anhydrous sodium sulfate and quickly evaporated gave an oil that, poured over ice, crystallized immediately. This crude product treated with active charcoal in ethanol was recrystallized from very dilute alcohol using the following technique: The product is dissolved in a small amount of slightly heated ethanol, small pieces of ice added and the flask kept in ice water; the substance separates in crystalline form. By repeating this process a few times the phenacyl i o d i p was obtained in colorless crvstals meltina shardv a t 34.4 Anal. Calcd. for &H,OII I, 51.58. Found': I, 51.68,51.81.
.
(10) (11) (12) (13)
A. Lucas, Bcr., 32, 601 (1899). A. Collet, Comgt. rcnd., 1x8, 312 (1899). J. U.Nef, Ann., 308, 294 (1899). C. Paal and H. Stern, Ber., 32, 532 (1899).
DEPARTAMENTO DE QUfMICA DA HEINRICH RHEINBOLDT FACULDADE DE FILOSOFIA, CIQNCIAS E LETRAS MADELEINE PERRIER UNIV.S l o PAULO,BRAZIL RECEIVED MARCH1, 1947
1COMMUNICATIONS T O T H E E D I T O R QUINOLIZIDINE
diethyl di-(P-(2-pyridyl)-ethyl) -malonate. Anal. Calcd. for C~3H32018N~:C, 47.77; H, 3.89. Recently it became of interest to us to find a Found: C, 47.95; H, 3.77. Catalytic reduction of diethyl /3-(2-pyridyl)simple and convenient method of preparing quinolizidine (norlupinane) and various related ethylmalonate using copper chromite as catalyst compounds. It was found that diethyl /3-(2- a t 250' gave a 65% yield of quinolizidine; b.. p. 1.4796. The quinolizidine pyridyl) -ethyl malonate, prepared by the Michael 84' at 21 mm.2; n20a2~ addition of diethyl malonate to 2-vinylpyridine, was identified through formation of its picrate2; methiodide,2 dec. 309-311' could be hydrogenated directly to quinolizidine in m. p. 198-199'; (Anal. Calcd. for CloH20NI: C, 42.71; H, 7.17. 65% yield. The addition of various nucleophilic reagents to Found: C, 42.50; H, 7.09); and hydrochloride, 2-vinylpyridine was recently reported to THIS indefinite m. p. (Anal. Calcd. for CsHlsNCl: C,61.53; H, 10.32. Found: C,61.20; H, 10.01). JOURNAL in an interesting article by Doering and Wei1.l Our experiments on the addition of di- Catalytic reduction of diethyl &(2-pyridyl)-ethylethyl malona1.e to 2-vinylpyridine, which were malonate using Raney Ni a t 140' gave 3-carbethcarried out independently and prior to their pub- oxy-4-ketoquinolizidine in 90% yield; b. p. 149' lication, are in1 good agreement with their results. at 0.15 mm. Anal. Calcd. for C12H1903N: When 2-vinylpyridine was treated with an excess C, 63.97; H, 8.50; N, 6.22. Found: C, 63.92 of diethyl malonate, there was obtained yields of H, 8.47; N, 5.97. The structure of the 342 t o 4370 of diethyl /3-(2-pyridyl)-ethylmalonate ; carbethoxy-4-ketoquinolizidine was established b. p. 162-164' a t 2 mm. Anal. Calcd. for by its conversion, via hydrolysis and decarboxylaCI4Hl9O4N:C, 63.38; H, 7.22; N, 5.28. Found: tion, to 4-ketoquinolizidine (a-norlupinone). The C, 63.35; H, 7.26; hi, 5.27. When diethyl 4-ketoquinolizidine formed a hydrochloride, m. p. malonate and 2-vinylppridine were employed in (2) The following physical constants have been recorded for equivalent amounts, the major product was a quinolizidine and its derivatives. Prelog and Bozicevic (Ber., 12, 1103 (1939)) give b. p. 69-70' at 11 mm.; picrate, m. p. 196'; high-boiling viscous oil whose composition as indi- methiodide, dec. 333". Clemo, Ramage and Raper ( J . Chcm. Soc., cated by analysis of the picrate, is presumed to be 2959 (1932)) give b. p. 72' at 16 mm.; picrate 194'; methiodide,
Sir :
(1) W. E. Doering and R . A. N. Weil, Tms (1947).
JOLI~HAL. 69,
2461
dec. 335'. Galinovsky and Stern (Bey., 16, 1034 (1943)) give 70' at 10 mm.; picrate, m. p. 199-20O0; and methicdide, dec. 333'.
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).
