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phonium salts which can undergo further decomposition to tetracovalent phosphorus compounds. Experimental SectionMaterials. The starting phosphines were prepared by standard techniques or purchased when possible. Their 1H and 31P nmr spectra agreed with literature values.Reactions. Equimolar quantities (ca. 5 X mol of the phosphine and diethyl peroxide) were allowed to react in methylene chloride. Usually the reactants were cooled to at least 0" before mixing. The reactions were monitored by 1H and 31P nmr spectroscopy. In those studies in which other solvents were used the methylene chloride was evaporated at room temperature in cucuo and the residue was dissolved in the appropriate solvent. Benzoic acid was added to each reaction mixture and the formation of ethyl benzoate was demonstrated by glpc.formed by exchange. Once again the compound 19 is quite unstable and it decomposes readily to tetracovalent phosphorus compounds.The relative instability of the compounds with amino nitrogen bonded to phosphorus is not unexpected. Amino nitrogen can stabilize a positive charge on phosphorus and therefore enhance dissociation to phos-Abstract: Solvolysis of trianisylvinyl chloride (1-CI) and bromide (1-Br) and of l-anisyl-2,2-diphenylvinyl bromide (7) in 80% ethanol follows a first-order course in the substrate, is independent of the concentration of added sodium hydroxide, and is only slightly dependent on that of added p-toluenethiolate ion. The solvolysis of 1-Br is 1.75 times faster than that of a-bromo-p-methoxystyrene, excluding the addition-elimination mechanism. The similar rates for 1-Br and 7 point to the absence of P-aryl participation. The Grunwald-Winstein nz values of 0.34-0.53 and the kl-B,/kl.CI value of 58 at 120" are discussed in terms of intermediate vinylic cations in the solvolysis. The reactivity difference between a-bromostyrene and a-phenylethyl bromide is entirely due to activation energy difference. Vinylic and saturated cations are compared.inylic cations were studied very little until recent V years. Lately, they were suggested as intermediates in electrophilic additions to allenes and acetylenes (eq l),* in the deamination of vinylamine~,~ or in the reaction of 2-oxazolidones in basic solution4 or vinyltriazenes in acidic solution5 (eq 2). Ions with contributing vinylic cation structures were observed by nmr,6 and solvolysis products of acetylenic sulfonates ( I ) Presented in part at

The solvolysis of a-chloro-(3) and a-bromo-4-methoxystyrene (4) in 80% EtOH gives 4-methoxyacetophenone and 4-methoxyphenylacetylene and is mechanistically SN1. The solvolysis is enhanced by two P-methyl substituents ; the Winstein-Grunwald rn values are 0.76-1 -00 at 25 " C and k1(4)/k1(3) = 54. In the acetolysis of compounds (3) and (4). 4'-methoxyacetophenone is formed, k1(4)/k1(3) = 0.46-456. k1(80% EtOH)/k,(AcOH) = 0.13 for (3) and 15 for (4). kUcOH/klAcoD = 1.94 for (3) and 1.45 for (4), and deuterium is not incorporated in the unchanged (3) and ( 4). The hydrolysis of a-acetoxy-4-methoxystyrene and the addition of AcOH to 4-methoxyphenylacetylene and 4-methoxystyrene in AcOH are faster than the solvolyses of ( 3) and ( 4).These data suggest that the acetolysis of the chlorostyrene (3) is by concomitant S , 1 and electrophilic additionelimination (Adx-€) routes, while that of ( 4) is mainly SN1. The competition between the two routes is discussed.IT has been shown that Sxl solvolysis of vinyl halides may compete both with substitution by nucleophilic addition-elimination 3 y 4 and with E2 eliminati0n.l9~ An additional route, electrophilic addition-elimination [equation (l)] rather than the s N 1 route [equation (2)] was suggested for the solvolysis of 4-amino-a-bromostyrene in 80% EtOH. Although it is now clear that the S N ~ route prevails for this compound,8 the electrophilic addition-elimination route (designated here AdE-E) was observed in another system9 and should be considered especially in solvolysis in acidic media. Criteria for distinguishing between the two mechanisms were suggested 10 and we planned to study some of them with a-halogenostyrenes, a system in which presumably both routes can operate. ArCX=CH, ___t ArCXMe +H+ + +Nu--HX ArCX(Nu)Me -ArC(Nu)=CH, (1) -x-+ +Nu-ArCX=CH, ___t ArC=CH, ___t(2) ArC(Nu)=CH, (2)

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Abstract. Physical properties (roughness, gloss, mechanical, surface topography and adhesive) of a bioadhesive film for the transdermal delivery of drugs and its interactions with a skin model surface were studied. Roughness is a measurement of the small-scale variations in the height of a physical surface. No significant differences in Ra between the "x" and "y" dimensions for both the skin model and patch were detected, due to uniformity in their production. Scanning electron microscope pictures showed small particles projected from the film. Those particles resulted in increasing roughness and surface area. For the patch, gloss values measured at 20°were 6.0±0.9 and at 60°, 32.2±2.2 gloss units, respectively, indicating a semi-gloss material. Concerning the mechanical properties, the tensile strength of the film resulted four-to sevenfold greater than the peel force from the model skin used, indicating the suitability of the film for skin application. The adhesion to skin model depended on the amount of water used for film application and on the elapsed time between film application and removal. Finally, the model skin that was invented by Charkoudian can be used as an alternative to costly and highly variable human skin substrates since it possesses human topography.

variable temperature probes. Probe temperatures were calibrated before use. TMS and CFCfi in a capillary were used for proton and fluorine references, respectively. Carbon-13 spectra were obtained by the INDOR method described previously.16Preparation of Ions.-Solutions of ions were prepared as described previously in this series, with concentrations and conditions given in text.

Das oestrogen stark wirksame 1,2,10 ,Il-Tetrahydro-5,14-dioxy-chrysen3) tragt die funktionellen Gruppen an den beiden endstandigen Ringen des Chrysen-Geriistes in den Stellungen 5 und 14. Der gleichen Gruppe von Chrysen-Derivaten kann das D-Homo-dihydro-testosteron4), eines der kraftigsten Androgene, welches nach der beim Chrysen iiblichen Numerierung Sauerstoff -Funktionen in Stellung 4 und 14 besitzt, zugeordnet werden. Es erschicn deshalb von Interesse auch Verbindungen dieser Reihe mit Sauerstoffatomen in Stellung 4 . und 13 her~ustellen~) uncl auf ihre biologisehe Wirksamkeit zu priifen.Als Ansgangsmaterialien fiir die Synthese von hydrierten Derivaten des 4,13-Dioxychrysens benotigten wir grossere Mengen 1-Keto-5-methoxy-tetralin und ,5-o-Anisyl-iithylhromid. Es war naheliegend, fiir die Herstellung des 1-Keto-6-methoxy-tetralins eine Reaktionsfolge zu wahlen, bei welcher das p-o-Anisyl-lthylbromid, bzw.der /?-o-Anisyl-athylalkohol ein Zwischenprotlukt darstellt. I m experimentellen Teil werden fiir die Bereitung der letzteren Verbindung sowie ihres p-Toluolsulfonsaure-esters aus technischem o-Anisidin genaue Arbeitsvorschriften angegeben. Die Herstellung des p-o-Anisyl-athylchlorids6) wurde wesentlich vereinfacht. Die Cyclisierung der sowohl aus ,$-o-Anisyl-Bthylchlorid, als auch aus dem entsprechenden Bromid und Tosylester mittels Malonester-Synthese hergestellten y-o-Anisyl-butterslure mit Phosphoroxychlorid wurde noch J . Lockett und W . P. Short7) durchgefiihrt.Eine weitere be queme Hers tellungsweise f iir das 1 -Ke t o -5 -methoxy-tetralin besteht in der partiellen katalytischen Hydrierung des 175-Dioxynaphthalins zum 1, 5-Dio~ytetralin~) (I) und Osydation des daraus gewonnenen Monomethyllthers (1%) mit Chromsaure. 113. Mitt. Heiv. 28, 618 (1945).

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