March, 1945
COMMUNICATIONS TO THB: EDITOR
503
Isobutylation of I with isobutyl bromide gave (Methylphosphonium chloride is an unstable com65% of ethyl cr-carbethoxy-a-cyano-y-methyl-pound of high volatility a t room temperature.*) pentanoate (11, R = isobutyl), m. p. 120' The conclusion drawn from these data, that tri(calcd. N, 12.35. Found: N, 11.97). Hydrolysis methylphosphine is a considerably stronger base with hydrochloric acid gave 79% of dl-leucine, than dimethylphosphine, was verified by a competition experiment. Thus, a mixture of 14.0 cc. ni. p. 278'. WINTHROPCHEMICAL COMPANY NOELF. ALBERTSON of each of the two phosphines and of hydrogen RENSSELAER, NEW YORK €3. F. TULLAR chloride yielded 13.9 cc. of uncombined phosphine which analyzed for 95% dimethylphosphine. RECEIVED FEBRUARY 19,1945 Although supplementary data involving other reference acids are desirable and are being proBSTRAIN AND BASE STRENGTH cured, i t is evident from these data that the Sir: strength of the phosphine bases (measured with The .peculiar behavior of the methylamines-an hydrogen chloride) increases regularly with the increase in base strength from ammonia to number of methyl groups. This verification of methylamine, a further increase to dimethyl- prediction is strong support for the B-strain hyamine, followed by a marked decrease to tri- pothesis. Certainly, no other simple explanation tnethylamine-has been ascribed to B-strain.' for the markedly different behavior of'the methylIn the trimethylamine molecule B-strain results amines and the methylphosphines is now availfrom the steric requirements of the three methyl able. groups crowded about the small nitrogen atom. There is good reason to believe that B-strain is I t is postulated that these requirements are met also an important factor in the carbon compounds by a spreading of the C-N-C bond angle to a and can account for many of the peculiar reactions value greater than the tetrahedral angle. The of tertiary butyl and related highly branched deniolecule therefore resists the addition of the acid rivatives. This point will be developed in subseto the free electron pair which would teiid to re- quent publications. duce the bond angle to the tetrahedral value. The assistance afforded by two grants from the Trimethylamine thus behaves as a much weaker Penrose Fund of the American Philosophical base than i t otherwise would. Society is gratefully acknowledged. Electron diffraction data reveal that the DEPARTMENT OF CHEMISTRY C-P-C bond angle in trimethylphosphine2 is WAYNEUNIVERSITY 100 * 4O. B-strain must therefore be absent. DETROIT1, MICHIGAN HERBERT C. BROWN Consequently, the strength of the phosphine RECEIVED FEBRUARY 1, 1945 bases should increase regularly with the number ON THE BIOGENESIS OF NORNICOTINE AND ANABASINE1
. I t % possible to estimate from published data Sir: the relative strengths of the phosphine bases. Phosphine does not react with hydrochloric aci'd. Methylphosphine is absorbed by concentrated hydrochloric acid, but dilution decomposes the salt and liberates the free base. Neither dimethylphosphine nor trimethylphosphine may be liberated from its salts in this way-addition of alkali is nece~sary.~I t is thus evident that methylphosphine is a stronger base than phosphinc itself, and that both dimethyl- and trimethylpliosphine are stronger than the monomethyl derivative. However, no decision can be reached on the critical point-the relative strength of dimethyl- and trinicthylphosphine. Accordingly, the hydrochlorides of these two bases were prepared and their relative strength determined. r)iinethylphosphoniuiii chloride is a white crystalline solid of inoderate volatility, exhibiting saturation,pressures of 1.3 mm. and 46 mm. a t 25 and 75' respectively. Trimethylphosphonium chloride is much less volatile. Its saturation pressure is but 0.4 mm. a t 75' and 14 mm. a t 120'. ( I ) Brown. Bartholomar and Taylor, Tnrs J O I I R N A L . 66, 435 (10-14). (2) Springall ani1 HrocLway. i h i d , 6 0 , !l!lfj (l!l:W). (3) I i , t f r n n n n , B e r . , 4. 604 (1871).
The localization of the nicotine synthetic mechanism in the root of the tobacco plant (Nicotiana tubacum) has been established earlier by the use of reciprocal grafts and of sterile excised root cultures.2 Similar experiments recently performed in this Laboratory have shown that nornicotine in Nicotiana glutinosa and in N . glauca is formed only in the leaves and a t the expense of nicotine translocated from the roots. Specifically, i t has been found that N . glutinosa leaves do not carry out total alkaloid synthesis, for these leaves contain none of the three major tobacco alkaloids when grown on tomato roots. Conversely, N . glutinosa roots produce not nornicotine but nicotine, for only nicotine is present in tomato shoots grown on N . glutinosa roots. In this respect the root systems of N . tubacum and N . glutinosa arc equivalent and have been experimentally interchanged without resulting marked changes in the alkaloid composition of the leaves. It is concluded, therefore, that the leaves of N . glutinosa contain a mechanism capable of convert(1) This work was supported in part by the Rockefeller Founda-
tion. (2) Daw.wn. A m . J . Botany. PS, 66 (1942); 18, 813 (1942).
ing nicotiiie
t i ) iiornicotilie probably hy transnit~thylatioii. .Yicoiiciizu glurmz cont:~iiisprincipnlly anabasine. \\-lien grafted to *V.tnbncunz roots:' or when liyliritlizctl with the Ixtter spccies4 the leaves have 1)een rel)ortetl ti) contain predominaiitly anaba.;iiic. ICe1)etitiori oi these experiments in this !:ilxir:ttory has tliscloscd that thc supposed anaba.;iiic (IC tlic grafts a i i t l of thc hybrids is actually : t iiiisture oi ;iii:ibasine anti nornicotiiici with iisu:iliy niore ~ioriiicoti~ie than aiiabasiix, 'lhe tlificult sc.par:ition o f xiabasine from norriicotinc i r i iiiistures of the two was acconiplished by re1)vatecl fracti(ma1 crystallizativns of the picrates a i i t i of the methylated picrates after removal of iiicotine by the mcthod of Smith and '1'0 show that the iiornicotine present in the leaves t ~ these i plants actually arose in situ and at the ~.;l)enst: ~i nicotine translocated froin the roots, .\-.gla LICU scions were grafted to S.tubucunz roots. After a period of growth, a tornato scion was ::rafted to the apes of each LV,gluricu scion. Ultiinately, these three-tiered plants were examined for alkaloids. The s.glaucu scions contained one px-t of iiicotine to fifty parts of mixed anabasine ant1 iiornicotine, while the tomato scions ~ 0 1 1 taincd only nicotine. It is now clear that the replacement of the methyl group of nicotine in the plant leaf by the hydrogen :~toniof nornicotine accounts for tlie inw . u e in secondary arniiie content (previously :tt.txibutcd to anabasine4) of such graft combina1.ioiis a i i d ficnetic:ii iiybrids. It f c ) l l o ~ sthat esq)ineiit oi hybrids beI"'ctLiti(J11S' iJf t h e (le\ . ghiiica that would t i t , I1 :T. f(Zb(LCZLII2 alld iuitablr. for the ci)Iiiniercial cstr:ictitrti oi' :tii:ilx-.iiie are without justificatioii. (JI \,
Schmuck, Kostrrfi a n d 1iorozilin;r. Cc~m$!. rrriil orcril
S. ( I ) o k Z ~ i d y J25, , 477
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RESOLUTION OF 9-HYDROXYFLUORENE-LCARBOXYLIC ACID
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