COMMUNICATIONS TO THE EDITOR
Nov., 1951
5511
by Domnin3 in his presumed synthesis of cyclooctyne always seems to have afforded mixtures of cy-
through silica gel: micro b.p. 177-178' (740 mm.), 1.4891, P o d 0.8979. ( A d . Calcd. for C9Hl4: C,-88.45; H, 11.55. Found: r-----CHOH co NHaNHz.Hz0 rC=NNH* C, 88.24; E, 11.64). Quan--f (CHzh 1 (CHz)s I titative reduction in acetic L C=NNH2 acid using Adams catalyst 55% 73 % 65 % from dmethyl m.p. 121-123' dec. required 102Oj, of two sebacate molar equivalents of hy[Ol NazSOI, HgO, drogen. Hydration with KOH (alc.) in benzene sulfuric acid and mercuric sulfate in acetic acid gave cvclononanone, identified ai its semicarbazone (m.p. 179-180°). Mixed melting clic acetylenes and isomeric allenes when applied to point with an authentic specimen showed no depresthe nine- and ten-membered carbon rings. Thus, sion. Infrared spectrum of cyclononyne (Fig. 1) for example, dehydrohalogenation of l-chlorocyclo- showed characteristic absorption for C s C a t 4.54 p. nonene or dehalogepation of 1-bromo-2-chlorocyI 1 clodecene gave a mixture of CsHle and CloHle hydrocarbons, respectively, which upon ozonolysis yielded a mixture of suberic and azelaic acids or a mixture of azelaic and sebacic acids. Further, the infrared spectrum of the C10H16 hydrocarbon mixture showed a very weak absorption a t 4.55 p (C=C stretching) and a much stronger absorption a t 5.16 , , , , , , , , , ,j p (C=C=C stretching). However, we have obtained the cyclic C9 and Claacetylenes employing a modification of a method developed by Curtius for synthesizing diary1 acetyl e n e ~ . The ~ method as applied to the nine- and tenmembered carbocycles is illustrated by the synthesis of cyclodecyne from sebacoin. The cyclic acetylenes (C, and C1J as first isolated I , , , , J 3 4 5 6 7 8 9 10 11 12 13 14 15 were found to contain small amounts of carbonyl Yare I m g t h , P. compounds and saturated hydrocarbons but they were not contaminated with allenes or other unsat- Fig. 1.-Upper curve infrared spectrum of cyclodecyne; lower curve infrared spectrum of cyclononyne. urated hydrocarbons. Final purification of the two acetylenes was achieved by chromatography Further concerning these two cyclic acetthrough silica gel. Their purification was followed ylenes and details the related cyclic cis- and trans-olefins by means of infrared absorption spectra, refractive will be presented as soon as possible in regular arindex measurements, and by quantitative catalytic ticles. hydrogenation. A. T. BLOMQUIST Cyclodecyne was purified by chromatographing THEBAKERLABORATORY . ROBERT E. BURGE.TR. LIANGHUANGLIU through silica gel: b.p. 203-204' (740 mm.), %'OD OF CHEMISTRY UNIVERSITY JAMESC. BOHRER 1.4903, dZo40.8975 (Anal. Calcd. for Cl0H16: CORNELL NEWYORK ARTHURC. SUCSY C, 88.16; H, 11.84. Found: C, 88.30, 88.06; ITHACA, JOHN KLEIS H, 11.78, 11.98). Quantitative reduction in acetic RECEIVED SEPTEMBER 14, 1951 acid using hdams catalyst required 99-100% of two molar equivalents of hydrogen. Ozonolysis gave only sebacic acid (37%), m.p. 126-129' after Sir : A NEW TOTAL SYNTHESIS OF ESTRONE recrystallization and the mixed melting point with We wish to announce a novel and relatively short an authentic specimen of sebacic acid (m.p. 129131') was 126-129'. The ozonolysis product was total synthesis of estrone in which the rings are also characterized as sebacic acid by conversion to formed in the sequence A, C, B, D starting from the bis-p-toluidide, m.p. 198-200' (cor.). Hydra- anisole (as ring A).l The scheme is stereospecific, tion of the acetylene with sulfuric acid and mercuric except for one step which a t the present stage of desulfate in acetic acid gave cyclodecanone, isolated velopment, nevertheless, proceeds so as to give the as its semicarbazone, m.p. 203.5-205.5' (cot.). A correct stereoisomer as the only crystallizable prodmixed melting point with an authentic specimen uct in 36% yield. The tribasic acid I (R = H) was produced as showed no depression. The infrared spectrum of previously described,2 by reduction of the product the unsaturated hydrocarbon (Fig. 1) showed char(1) This method was conceived prior to 1946 as an alternative to the acteristic absorption for C=C a t 4.53 p. of Johnson, Jones and Schneider (ref. 2); see also the M.S. Cyclononyne was purified by chromatographing approach thesis of W. P. Schneider, University of Wisconsin, 1946. A similar ap' -
v
u,
0
,
(3) N. A. Domnin, J Gcn. Chem ( U S S E ), 8, 851 (1938): Chcm. Abs., 88, 1282 (1939) Curtius , and K. Thun, J , (4) T. Curtius, Bar, 11,2161 (1889). I? Prakt Chrm , [2J44,1BR (1891)
3
,
0
,
proach has been suggested independently by J. Dutta and D . K. Banerjee, Science and Cttllurc, 14, 408 (1947). (2) W, S. Johnson, A. R. Jones and W, P. Schneider, THISJOURNAL, 72,2396 (1860); m i atoo b,I,. Turner, ibid , 78, 1284 (1961).
CO?JRITJhYC.\TIONS TO TIIE
Rood I
I1
CHx A ---COOCHJ
H
EDITOR
Yol. 73
steps involve no stereochemical problems. Partial saponification and homologation by the Arndt-Eistert reaction afforded, as previously d e ~ c r i b e d , ~ homomarrianolic acid methyl ether, m.p. 224.2225.8', undepressed on admixture with authentic material.6 Cyclization of the dibasic acid yielded dl-estrone methyl ether, m.p. 143.2-144.2', undepressed on admixture with an authentic specimen.8 The demethylation and resolution of this product have already been d e ~ c r i b e d . ~ , ~ (6) W. S. Johnson, D. K. Banerjee, W. P. Schneider and C. D ( h t s c h e , THISJ O U R N A L , 72, 1426 (1950).
LABORATORY OF ORGANIC CHEMISTRY VSIVERSITY OF \\'~scossrx WILLIAM S. JOHNSOS ;\[ADISON fi, JvIS. ROBERT G. CHRISTIANSES RECEIVED AuGusr 7, 1951
VARIATION OF ELECTRIC DIPOLE MOMENT WITH BOND LENGTH
Sir:
~/;:....\,,coocH~
I
CH,O/
vv 0
I \.
from the Stobbe condensation of diethyl succinate with ethyl y-anisoylbutyrate (prepared v i a the Friedel-Crafts reaction of glutaric anhydride with anisole). Dieckmann cyclization of the trimethyl ester I (R = CHs) and methylation in situ gave the keto diester I1 (R = CHI), m.p. 95-95.5', which was crystallized directly from the reaction mixture in 36% yield. Reformatsky reaction of I1 (K = CHa) with methyl bromoacetate gave a mixture of a lactone Anal. Calcd. for C21H260i: (m.p. 112.5-113'; C, 64.60; H, 6.71. Found: C, 64.67; H, 6.75) and hydroxy ester (n1.p. 101.3-101.9'; Anal. Calcd. for C z ~ H ~ o O C,~ :6'2.54; H, 7.16. Found: C, 62.63; H, 7.27), which was not separated but treated directly with formic acid (to lactonize the hydroxy ester) followed by dilute sodium hydroxide which converted the mixture of isomeric lactones into essentially one form of the unsaturated mono acid 111, m.p. 121-122'; Anal. Calcd. for Cz1H2607: C, 64.60; H, 6.i1. Found: C, 64.92; H, 6.78. Cyclization of 111 by the inverse FriedelCrafts method3 gave a single keto diester IV, m.p. 147.8-148.4'; Anal. Calcd. for Cz1H2406: C, 67.72; H, 6.50. Found: C, 68.02; H, 6.91. Hydrogenolysis of the keto group over palladium catalyst promoted by perchloric acidJ yielded a single unsaturated diester IV (methylene in place of keto group), m.p. 112-112.2' (perhaps the same as Anner and Miescher's5 isomer m.p. 113-115'), which on further hydrogenation in neutral medium gave practically exclusively, racemic dimethyl marrianolate methyl ether, i n p . 99.5-100' (reportedI6 95At this stage all four of the asymmetric 96'). centers have beeti introduced, and the subsequent (3) W S. Johnlwn and I€. J Glenn, THISJOURNAL, 71,1092 (1949). (4) The method of Kindlef. see K W Roqennlund and E Karq, H e r , 78, 18.50 (1942) (br c . h r r p r n n r t h' htggllfh-t.~
i ~ li h oc l n
ACIO, li,,z17R 1 1 ~ 8 3 ,
-1quantity of importance for the understandin: of absorption intensities in the infrared is E , the derivative of the electric dipole moment of a bond with respect to the bond length, evaluated at the equilibrium internuclear distance.l Bartholoom@ has estimated E for HC1, HBr and H I from absorption intensities; experimental difficulties make the values thus obtained somewhat uncertain. Recently a new point of view as to the origin of electric dipole moments in molecules has been publi~hed.~ I t seems worth while to consider the variation of electric dipole moment with internuclear distance from the new point of view. According to equation (9) of the paper just mentioned, with accompanying discussion, a bond moment may be considered as arising from an internal field, E , of the form
where the symbols have the same significance as previously. The bond moment is then given by the product of this field and the longitudinal polarizability, bl, so that (2)
Consider first
This term we claim to be effectively zero or negligible compared to the other term composing c ; the reason for this is as follows. As was pointed out in the previous paper,3 the quantity E is a small difference of two large quantities. Neglecting this small difference, we find Z,/Ra3
z
ZL,lRt,2
(4)
for two atoms a and b; hence Z I R 2must be approximately the same for different atoms. It therefore seems reasonable to assume that this quantity is approximately constant for the same atom when a (1) L. Pauling and E. B. Wilson, Jr , "Introduction to Quantum Mechanics," 3.IcOrdn-Hill Book Co., In:., New York, N Y., 1935, pp. 309-810. (2) E. Bartholome. Z . Ohvrik. . Chcm.. B23. 131 (1933). (3) R. P. Smith, T ,Kee, J I, M w e e , and XI. Byring, T H IJ~O I I R N A ~ , 7 8 , 2203 /IP:1).
