2746
DANIEL
s. TRIFAN AND LOUISNICHOLAS
methyl ether of phenylferrocenylmethanol (111, R = CHs) was obtained, m.p. 111-112". Anal. Calcd. for C18H180Fe: C, 70.59; H , 5.88; active H, 0.0. Found: C, 70.26; H, 5.20; active H, 0.0. The infrared spectrum showed absorption of aliphatic C-H a t 2880,2930 and 2970, phenyl absorption a t 1492 and 1559, absorption of unsubstituted ferrocene rings a t 1104 and very strong ether absorption a t 1063 cm.-'. Isopropyl Ether of Phenylferrocenylmethanol (111, R = i-Pr-).-Benzoylferrocene (1 g.) was reduced by the method of Meerwein-Ponndorf-Verley." The hydrolyzed reaction mixture was extracted with benzene, the solvent removed and the mixture extracted with Skellysolve B and chromatographed on alumina with methanol. I n addition to a small amount of the methyl ether of phenylferrocenylmethanol, there was isolated 0.35 g . (33%) of yellow crystals of the isopropyl ether, m.p. 74-75'. Anal. Calcd. for CPOHdlFe: C, 72.07; H, 6.31. Found: C, 71.24; H, 6.81. The infrared spectrum showed absorption in the aliphatic C-H region a t 2880, 2930 and 2970, phenyl absorption a t 1492, 1540 and 1559, absorption of unsubstituted ferrocene rings a t 1104 and very strong ether absorption a t 1063 cm.-'. Like the carbinol and the methyl ether, the isopropyl ether is soluble in concentrated hydrochloric acid. Reduction of Monobenzoylferrocene by Sodium.-To 0.25 g. of monobenzoylferrocene in 3 ml. of benzene was added 2.5 g. of 5y0 sodium amalgam. The mixture was (17) A. L. Wilds, "Organic Reactions," Vol. 11, John Wiley and Sons, Inc., New York, N . Y., 1944, p. 178.
[CONTRIBUTION FROM
THE PLASTICS
VOl. 79
refluxed 2 hr., poured into water and filtered. The organic layer was washed, dried and chromatographed on alumina. Evaporation of solvent from the eluted yellow band, just preceding the large red band of unreacted monobenzoylferrocene, left 35 mg. of orange yellow powder, 150-170" dec. (180-185' red droplets). This substance is believed to be phenyldiferrocenylmethanol(IX). Infrared absorption was found a t 3520 (OH), 1492 and 1600 (phenyl) and 1107 cm.-' (ferrocenyl). Anal. Calcd. for C2,11s,0Fe2: C, 68.05; H, 5.04; active H, 0.21. Found: C, 68.44; H,5.11; activeH, 0.36. This compound was dissolved in 95% ethanol by refluxing for 15 min. Excess zinc dust was added, then alternately, small amounts of hydrochloric acid and zinc dust till most of the color was gone from the solution. The niixture was filtered, washed, dried, extracted with benzene and the solvent evaporated. The residue was extracted with henxane and chromatographed on alumina in that solvent, yielding a yellow solid with an infrared spectrum identical to that of phenyldiferrocenylmethane (VI). A 30-mg. sample of the hydroxy compound was refluxed with methanol for 7.5 hr. Evaporation of the methanol yielded crystals which were purified by chromatography on alumina. The resulting product 28 mg., m.p. 158' dec., is presumably the methyl ether of IX. Its infrared spectra showed peaks a t 2920, 2820, 1554, 1494, 1106 and a high absorption, indicative of ethers, a t 1076 cm.-'. Anal. Calcd. for C28Hs60Fe2: C, 65.55; H, 5.31. Found: C, 69.41; H, 5.59. BROOKLYN 1. N. Y.
LABORATORY, P R I N C E T O N UNIVERSITY]
Reductive Cleavage of Ferrocene' BY DANIELS. TRIFAN AND LOUISNICHOLAS RECEIVED JULY 25, 1956 In contrast to the extreme resistance of ferrocene to catalytic reduction, this aromatic ring system is reduced readily by lithium in ethylamine with cleavage of the molecule to metallic iron and cyclopentadiene. The reaction of lithium with ferrocene in ethylamine is very rapid and may be stopped after several minutes with good conversion. Qualitative experiments have ascertained that other metal-amine, ammonia combinations also similarly reduce ferrocene.
No method has yet been described for a mild controlled degradation of the ferrocene ring system (bis-cyclopentadienyl iron, Fe(CsH&) suitable for structure assignments for isomeric substituted ferrocenes. I n this investigation a convenient degradation procedure was sought which would effect cleavage of the ferrocene molecule into its component parts and permit separate examination of each of the resulting 5-carbon rings. The catalytic hydrogenation route to dearomatization and collapse of the ferrocene molecule appears to be unsuccessful. The resistance of ferrocene to catalytic hydrogenation over platinum has been reported by Woodward, Rosenblum and Whiting.2 Our own attempts to hydrogenate ferrocene using the more active 5% rhodium-onalumina in acetic acid for periods up to several weeks have given similar negative results. Under these same conditions benzene is completely hy-
drogenated in 5 minutes. Fischera also has reported failure to hydrogenate ferrocene with Raney nickel in alcohol a t 150' and 150 atmosphere^.^ As a means of transferring an electron to the ferrocene nucleus to dearomatize the molecule, the use of alkali metals was investigated. Lithium does not attack ferrocene in refluxing ether, benzene or toluene, although attack does occur a t ca. 200" in mineral oil with formation of metallic iron. I n contrast to these slow heterogeneous reactions, however, rapid cleavage of the ferrocene molecule into metallic iron and cyclopentadiene is obtained by use of lithium in ethylamine, the amine functioning as solvent for lithium atoms. This reducing system has been investigated by Benkeser and co-workers in connection with benzenoid aromatic compounds.6
(3) E. 0.Fischer. Angcw. Chcm., 67, 475 (1955). (4) ADDEDIN PROOF.-we have recently noted the interesting publication of A. N. Nesmeyanov, E.G. Perevalova, R.V. Golovnya, T. V. Nikitina and N. A. Simukova, Isvest. Akad. Nauk S.S.S.R., (1) This research was supported jointly by the Army, N a v y and Air Force under Signal Corps Contract No. DA-36-039SC-42633. Ofdcl. khim. Nauk, 749 (1966),in which these investigators report the first successful catalytic hydrogenation of ferrocene and several of its Most of this material was submitted in preliminary form in August, derivatives using Raney nickel at 265-345O and 200-280 atmospheres. 1955,and presented before the Division of Organic Chemistry, 130th (5) (a) R. A. Benkeser, R. E. Robinson, D. A. Sauve and 0. H. National Meeting of the American Chemical Society, Atlantic City. Thomas, THISJOURNAL, 76, 631 (1954); 77, 3230 (1955); (b) R. A. N. J., September, 1956. Bsnkeser, C. Arnold, R.F. Lambert and 0. H. Thomas, i b i d . , 77, 6042 (2) R. B. Woodward, M. Rosenblum and M. C. Whiting, T H I S (1855). JOURNAL, 74, 3458 (1952).
June 5 , 1957
REDUCTIVE CLEAVAGE OF FERROCENE
274 7
therefore determined by solution in dilute sulfuric acid and titration of ferrous ion. I n a semiquantitative run designed to verify the elemental state of the initial iron product, the volume of hydrogen produced from the acidification of the reaction mixture corresponded roughly to that calculated from the amount of ferrocene reduced? The finely divided iron obtained from a single run with sodium-ethylamine was pyrophoric and more reactive than that from lithium-ethylamine, probably because of a larger amount of adsorbed hydrogen in the former case due to the more rapid rate of hydrogen evolution. The cleavage reaction proceeds by attack of lithium on carbon with transfer of an electron. Attack on the ferrocene aromatic system has difTABLEI ferent consequences from the parallel attack on QUALITATNERATESOF REDUCTION OF FERROCENE benzenoid aromatic systems. I n the latter case Metal Amine Description of initial reaction the n-electrons are displaced to give resonanceLi Ethylamine Vigorous reaction, black iron stabilized negative ion free radicals,Ke.g., I, with Gradual appearance of black iron; Na Ethylamine no consequent molecular rupture.
A series of qualitative experiments summarized in Table I has been carried out to indicate the generality of ferrocene reduction by other alkali and alkaline earth metal-amine, ammonia combinations. The progress of the reaction was followed by the rate of reflux and the appearance of black metallic iron. Rates are substantially lower with sodium than with lithium, and lower in n-hexylamine than in ethylamine. Calcium-amine combinations give no reaction. In liquid ammonia, however, reductions with calcium, lithium and sodium are all vigorous. The lithium-ethylamine combination appears to be the most convenient and has therefore been selected for use in quantitative studies.
Ca Mg Li Na Ca Li Na Ca Mg
much slower than Li Ethylamine No reaction No reaction Ethylamine n-Hexylamine Gradual appearance of black iron: slower than Na-ethylamine %-Hexylamine Some darkening only after ca. 0.5 hr. n-Hexylamine No reaction even at b.p. Liq. NH, Vigorous reaction, black iron Liq. NHI Vigorous reaction, black iron Liq. NH, Very vigorous reaction, black iron Liq. NHI No reaction
When these results are compared with data on the reaction of sodium with various aromatic hydrocarbons, i t may be estimated that in the series of aromatic compounds of increasing electron affinity: benzene
