COMMUNICATIONS TO THE EDITOR
1600
VOl. s4
TABLE r
degradation products are listed in Table 11. These data show conclusively that phenylalanine can 70 % serve as a precursor of ring A and the benzylic carFraction Incorp. Dilutiona Incorp. Dilution bon atom in both the lycorine and belladine ring Chloroform-insystems but is unable to provide the CS-C~fragment soluble alkaloids 0.45 1.02 (ring C and the two-carbon side chain) in these Chloroformalkaloids. In agreement with our earlier results in 1.42 soluble alkaloids 0.95 formosissirna,2tyrosine can serve as the precursor Lycorine 0.095 5.46 X l o 3 0 . 1 1 1.55 X lo4 of the Ce-Cz unit, but not the CS-Cl unit of bellaBelladine 0.42 1 . 3 3 x 103 0.82 3 . 3 3 x 103 dine. Superficially, these findings are in conflict with a Specific activity of compound fed (pc./mM.) divided by the fact that in most Amaryllidaceae alkaloids ring specific activity of compound isolated. Phenylalanine fed
Tyrosine fed
s.
TABLE 11" Relative activity Phenylalanine Tyrosiue
Isolated and counted as
Fragment
I17
Belladine (IV) 1.00 1.00 Belladine niethiodide 0.96 0.95 X C1' N,N,N-Trimethylveratrj-lanlrrloniuiri iodide .92 . 00 C CI, C2 1-(p-Methoxypheny1)- 1,2-dibronioethanc .Ol .YY C CI, CZ l-(p-Methoxyphenyl)-1,2-ethanediol .O1 1.00 Formaldehyde (methone) 00 0.00 C CZ Anisaldehyde (octahydroxanthene) .Ol 0.98 Lycorine 1.00 4-(1,2-Dihydroxyethyl)-5,6-dihydro-5-rnethyl-8,9-1nethylenedioxyphenanthridine 0.99 111, cs Formaldehyde (methone) 0.00 .. 111, less CS 4-Carboxy-5-methyl-8,9-meth~.lenedioxyphenanthridinone 1.02 .. 111, Barium carbonate 0.00 .. 111, less Cq, C5 6-Methyl-8,9-methylenedioxyphenanthridinone 1.04 .. 111, less CqrC6 5-Methyl-8,9-methylenedioxy-6-phenylphenanthridiniuni perchlorate 0.95 111, c, Benzoic acid 0.97 .. a Samples werc counted i n a Packard Tri-carb Scintillation Counter in toluene or dioxane-naphthalene scintillator solutions.
Iv I\', Ring I\', Ring IV, Ring 111, Cl IV, Ring I11 I11
+ + + +
.
..
..
c*
..
incorporation of these amino acids in Nerine bowdenii, where a t least two alkaloid ring systems could be examined simultaneously. OCH,3
(o$oiH3 'A,
(7) D. R. McCalla and A. C. Seish, Cait. J . Biochcm. u r d Physioi.,
(&;C'H; A t B o
Bh7
0
('H30
BND
0
gm
CHjO
5
AMES,IOWA W. C. WILDMAN DEPARTMEST OF CHEMISTRY THEUNIVERSITY A . R . BATTERSBY BRISTOL,ENGLAXD S. W. BREUER RECEIVED OCTOBER 8, lY62
2
YHz
/
I),N-CH~ g2 \CH,
DOUBLE ADDITION OF A CARBENE TO AN ACETYLENE
Sit,:
111
,
CHEYISTRY
IOWA STATE UNIVERSITY OF SCIENCE A N D TECHNOLOGY
I1
& \ 'AI
37, DEPARTMENT 537 (1959). OF
0
H R I
(
A possesses a greater degree of hydroxylation than ring C. However, similar findings have been reported in the biosynthesis of the phenolic cinnamic acids related to lignin.' A more detailed study of the processes by which oxygen is introduced into the C6-C1 unit of these alkaloids is in progress.
.
aDDrODriafe dilution with inactive alkaloids. were "graAed by the described in a previous paper.6 The relative specific activities of pertinent
,,3, 2 0 ~. ,Q
(6) W. C . Wildman, H. M. Fales, R . J. Highet, S. W. Breuer and A. R.Battershy, Proc. Cheiia. SOL.,180 (1962).
(3) W. Mahler, Abstracts, 2nd International Symposium on Fluorine Chemistry, Estes Park, Colo., 1962, p. 90.
(1) R . Breslow, Organic Symposium, Bloomington, Indiana, June,
1_9:i;~ .
W. R.Moore, H. R . Ward and R. F. Merritt, J . A m . Chem. Soc., \-
--,.
Dcc. 3, 1962
4GO 1
CONDIUNICATIONS TO THE EDITOR
in 4 hours); b.p. 36', m.p. -66', absorption a t 1715 cm.-', mol. wt., observed, 259. The gem fluorines of IV are equivalent by n.m.r. I n ultraviolet light, chlorine adds to give the dichloro adduct as a solid cis-trans mixture. Anal. Calcd. for C&12Flo: c1, 21.32; F, 57.06. Found: C1,21.36; F, 56.72. 350' F3C CF3 In further demonstration of the structure, the I I bicyclobutane I1 reacts in the dark a t 200' to FzC=C--C=CFp F2 add chlorine across the diagonal bond. 111 IV A n a l . Calcd. for C&&Flo: c, 21.62; c1, 21.32; methyl)-3,3-difluorocyclopropene (I), b.p. 11', F, 57.06. Found: C, 2 1 . 3 i ; C1, 21.65; F, 57.04. m.p. -86', double bond absorption a t 1820 cni.-', F19 magnetic resonance shows this to be a cismol. wt. (vapor density), observed 212, calcd. trans mixture, different from the 1,2 isomers defor CjF8, 212. The cyclopropene I was chlorinated rived from the cyclobutene. The cis 1,3 isomer has in ultraviolet light to give 1,2-bis(trifluoromethyl)CF2 fluorines with coupling coril,2-dichloro-3,3-difluorocyclopropane as a 1: 5 cis- non-equivalent stants of 21 1 C.P.S. characteristic of c y c l o b ~ t a n e s . ~ trans mixture. The trans 1,3 isomer shows equivalent gem fluorines -1nal. Calcd. for CjCl2Fs: C, 21.20; C1, 25.08; as expected. F, 53.72; mol. wt., 283. Found: C, 21.76; C1, EXPLOSIVES DEPARTMENT 24.93; F, 54.09; mol. wt., 287. EXPERIMENTAL STATION WALTERMAHLER E. I. DU POXTDE NEMOURS AKD COMPAUY The cis-dichloro compound, isolated by gas WILMINGTON 98, DELAWARE chromatography, has m.p. -T2', 23 mm. vapor RECEIVED SEPTEMBER 10, 1962 pressure a t 0' and shows non-equivalent CF2 fluorines with coupling of l i 2 c.P.s., characteristic of RADIOSENSITIZED EXCHANGE OF cyclopropane^.^^^ The trans isomer has m.p. THE XENON DEUTERIUM ATOMS WITH METHANE -56', 27 mm. vapor pressure a t O 0 , and equivalent Sir, gem fluorines by n.m.r. In a recent paper' describing studies of the Difluorocarbene adds to the cyclopropene I a t 100' in the gas phase to give a 25% yield of 1,3- deuterium-methane exchange initiated by tritbis- (trifluoromethyl) - 2,2,4,4 - tetrafluorobicyclobu- ium @-rays, the absence of the abstraction retane (11), b.p. 39', m.p. - g o o , together with action (1) was reported. This surprising concluan 8% yield of 2,3-bis-(trifluoromethyl)-l, 1,4,4- sion is contradictory to what recently has been tetrafluorobutadiene (1111,b.p. 52', m.p. -91'. D CHd+HD CH, (1) A n a l . Calcd. for CeF,,,: C, 27.48; F, 72.52; thought to be a well-established and mol. wt., 262. Found for 11: C, 28.11; F, 72.50; is based mainly on the observations that no ethane mol. wt., 262. Found for 111: C, 27.82; F, was detected and that the only initial exchange 72.30; mol. wt., 263. product was CH,D. With evidence against (l), No band characteristic of unsaturation appears these authors' propose that the exchange proceeds in the infrared or Raman spectra of the bicyclo- via a non-abstraction mechanism (other than a high butane 11. The F19magnetic resonance spectrum activation energy inversion6), viz. D CHI +CH3D H (2) of the CF2 groups of the bicyclobutane in the first H + Dz +H D D approximation is of the type AB6 with a splitting (3) of 150 C.P.S. In detail, i t is A2B2'further compli- Moreover, temperature dependence studies of this cated by sevenfold multiplicity due to the equiva- exchange system' were found to be inconsistent lent CF3 groups. The pattern for the CF3 groups with the results of Berlie and Leroy,2 who found is a triplet of triplets. El = 4.5 kcal./mole and a steric factor of the The infrared spectrum of the butadiene I11 order of 10-j. shows absorption a t 1'750 and 1725 cm.-l, indicIn studies of the xenon radio-sensitized deuteative of two double bonds. The CF2 fluorines rium-methane exchange a t room temperature we are non-equivalent by n.m.r. with no detectable have obtained evidence consistent with LeRoy's spin-spin interaction with each other. contention3 that (1) occurs a t room temperature -4t 300' the bicyclobutane I1 slowly rearranges and above. Furthermore, our results are in to the butadiene I11 (20% conversion, 95% yield accord with the low values of E l and PI found by in 16 hours). At 350' the butadiene I11 cyclizes Berlie and LeRoy, with Whittle and Steacie's to 1,2 - bis - (trifluoromethyl) - 3,3,4,4 - tetra- estimate6 of E l = 7.8 kcal./mole and P1 to fluorocyclobutene (117) (15% conversion, 100% (1) R . F. Firestone, C. F. Lemr and G. J. Trudel, J . A m . C h e w . Soc., yield in 48 hours). This cyclobutene was prepared 84, 2279 (1962). independently by the cycloaddition of hexafluoro-2(2) M. J. Berlie and D. J. LeRoy, Can. J . Chem., 32, 650 (1954). (3) E . W. R . Steacie, "Atomic and Free Radical Reactions," 2nd butyne to tetrafluoroethylene a t 230' (3y0 yield
a-
+
+
+
+ +
-
(4) W. D. Phillips, J. Chem Phys , '26, 949 (1956). (5) E. G. Brame, Jr , unpublished observations. (6) J. A. Pople, W. G Schneider and H . J. Bernstein, "High Resolution Nuclear Magnetic Resonance," McGraw-Hill Book Co , Xew York, N. Y., 1959, p. 122 ( 7 ) I h z i ,1 146
Edition, Reinhold Publishing Corp., hTew York, h-,Y . , 1954, pp. 454455. (4) D. W. Coillet and G. h i . Harris, J . A m . Chem. SOL., 75, 1486 (1953). (5) E. Gorin, W. Kauzmann, J. Walter and H. Eyring, J . Chem. Phys., 7 , 633 (1939). (t?) E. Whittle and It. W. R . Steacie, .T. C ~ P I IZ'iiys., Z. 21, 998 ( I 9 . X ) .
