Several epoxy difunctional hybrid alkylene‐silicone telomers with different silicone characters and organic spacers (linkers) were prepared via the platinum‐catalyzed polyhydrosilylation of α,ω‐dihydrosiloxanes and α,ω‐dienes. Thereafter, the resulting SiH‐terminated prepolymers were terminally functionalized with 4‐vinyl‐1,2‐epoxycyclohexane or allyl glycidyl ether. In the presence of a lipophilic cationic photoinitiator, the terminally epoxy‐functionalized hybrid alkylene–silicone telomers were photopolymerized to give crosslinked, soft, elastomeric, and transparent films. The progress of the photoinitiated cationic ring‐opening epoxide polymerizations was monitored using optical pyrometry. Potential applications for these novel photocurable epoxy‐functional telomers are as modifiers for UV curable coatings, printing inks, adhesives, and release coatings. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Es wird uber Darstellungsmethoden, Eigenschaften, 1R-und 1H-NMR-Spektren der diamagnetischen, sublimierbaren Monophosphin -cyclopentadienyl-carbonyl -Komplexe C S H~V ( C O )~P H~ und CsH5Mn(CO)zPH3 sowie der Monophosphin-carbonyl-Komplexe Cr(C0)5PH3, Mo(CO)sPH3 W(C0)5PH3 und Fe(C0)4PH3 berichtet. Die Massenspektren der Verbindungen werden angegeben und diskutiert.Vor einiger Zeit isolierten wir die ersten Cyclopentadienyl-carbonyl-phosphinund Carbonyl-phosphin-Komplexe von Ubergangsmetallen2). Nachfolgend sei nunmehr ausfiihrlicher iiber Darstellung und Eigenschaften von CSHSV(CO)~PH~, C5HsMn(CO)zPH3, Cr(CO)SPH3, Mo(CO)sPH3, W(C0)5PH3 und Fe(C0)4PH3, den ersten bekannt gewordenen Vertretern dieser neuen Klasse von Verbindungen, berichtet.Bei der Umsetzung von Methylmethoxycarben-pentacarbonyl-chrom(0) mit PH3 hatten wir die Bildung von Methylphosphinocarben-pentacarbonyl-chrom(0) erhofft, falls sich PH3 analog NH3 verhielt, das nach (1) p C H 3 p H 2 (CO),Cr =C,Cr(C0)4(PH3)2 1 reagiert3). Statt dessen war gelbes, recht bestandiges Bis-phosphin-tetracarbonylchrom(0) (1) entstanden. Als offensichtlich iiberraschend gut zur dx-dx-Ruckbindung geeigneter Ligand hatte PH3 also einen CO-Liganden und den gesamten Carbenrest substituiert, wahrend NH3 nur dessen OCH3-Gruppe zu aminolysieren vermag. Wir haben uber das cis-konfigurierte 1 sowie dessen Mo-und W-Homologe, die un-

OR' ( a ) , R = CH3, R1 = H (b), R = CH3, R1 = COCH3 (c)> R = CH3, R1 = Tetrahydropyran-2-yl ( e ) , R = C2H5, R1 = COCH3 i f ) , R = C2H5, R1 = Tetrahydropyran-2-yl (d), R = C2H5, R' = H 190-In spite of numerous experiments directed toward this aim 131, no simple and productive technique has hitherto been found.For our investigations we chose the route ( I ) +(5) via the 5.1Op-methylene steroids (4) [41. For the success of this pathway it was essential t o reduce 3-oxo-5(10)-estrenes ( I ) (which are readily obtainable by Birch reduction and subsequent enolether cleavage of steroids having an aromatic ring A) stereospecifically to 3P-hydroxy-5(10)-estrenes (2). This reduction gives only 15-20% yields when carried out with complex metal hydrides, hydrogen in the presence of a platinum catalyst, or according t o the Meerwein-Ponndorf method; the main products are 3cr-hydroxy-5(1O)-estrenes [4C, 51. A total yield of only about 30% is also obtained in the conversion of ( I ) into (2) by epimerization of 3a-hydroxy-5(10)-estrenes [5aJ or via 5,l Op-epoxy steroids [4cl.We have now found that 3-oxo-5 (10)-estrenes ( l a ) -( I f ) [IR: v = 1710 cm-1 (C=O), NMRI6J: 6 = 2.45 (intensity = 4, WI/, = 4 Hz) (H-1 and H-2). 2.75 (intensity = 2, W I / , = 5 Hz) (H-4)] 171 can be converted into the corresponding 3phydroxy compounds (2a)-(Zf) [NMR: 6 = 3.90-4.20 (H-3); with (2c) and ( 2 f ) this signal partly overlaps with that of the O C H 2 group of the tetrahydropyranyl ether] 171 in 65-90% yield by catalytic hydrogenation if highly active Raney nickel is used as catalyst and the reaction is performed under a hydrogen pressure as close t o 200 atm as possible. Compounds (Zb), ( 2 c ) , (Zej, and ( 2 f ) can, according to Simmons-Smith [*I, be converted into the 5$,19-cycloandrostanes (36). (3~). (3e). and (3f), respectively [IR: v = 3050 cm-1 (cyclopropane), N M R : 6 = 0.40 (cyclopropane)] in yields of up to 90% by refluxing with diiodomethane and zinc-copper couple [91 in ether/l,2-dimethoxyethane for 2 h. Jones oxidation[lol of the products with chromic acid in acetone smoothly affords the 3-ketones (46). (4c), (4e), and (4f) [IR: v = 1705 cm-1 (C=O), 3050 cm-1 (cyclopropane), N M R : 8 = 0.48 (cyclopropane), 2.52 (singlet, intensity = 2) (H-4)] [7J, which are isomerized o n treatment with concentrated hydrochloric acid in glacial acetic acid (2:3) for 10 min at 70 "C [3b, 3C,4CI. Mixtures of 17p-hydroxy and 17F-acetoxy steroids may then be isolated which can be hydrolyzed to the testosterones (5a) or (5d), or acetylated t o the testosterone acetates (5b) or (5e) [UV: €240 = 16500; IR: v = 1670 cm-1 (C=O), 1615cm-1 (C-C); NMR: 6 = 1.20 (CH3-10), 5.70 (H-4)] ["I. The yield of the reaction (4) +(5) again amounts to up t o 90%.

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