Soluble fullerene-based n-channel organic thin-film transistors printed by using a polydimethylsiloxane stamp.

A polydimethylsiloxane stamp was applied for the first time to the fabrication of n-channel thin-film transistors based on soluble small molecule organic semiconducting materials. The stamping method was found to facilitate film transfer onto a gate insulator surface irrespective of its surface free energy. We used [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) and C(60)-fused N-methylpyrrolidine-meta-dodecyl phenyl (C60MC12) as n-channel materials. The stamped thin-film transistors of C60MC12 achieved a high electron mobility of 0.39 cm(2)/(V s) and a current on-off ratio of 1 × 10(7). The mobility of the stamped C60MC12 thin-film transistors did not depend much on the surface free energy of the SiO(2) gate insulator with and without surface treatment using a silane-coupling reagent. In particular, the stamped C60MC12 thin-film transistor exhibited a relatively high mobility of 0.1 cm(2)/(V s) on a high energy surface of untreated SiO(2). In addition, a complementary inverter composed of an n-channel and a p-channel stamped thin-film transistor was demonstrated for the first time, which exhibits a maximum gain of 63 at a supply voltage of 50 V.

Intramolecular Cyclizations of o-Acylbenzyllithiums. Formation of Benzocyclobuten-1-ol Derivatives and Their Thermal Isomerization.

The formation of benzocyclobutenol derivatives by intramolecular cyclizations of o-acylbenzyllithiums is described. Treatment of o-(trialkylsilylmethyl)phenyl ketones with lithium diisopropylamide (LDA) followed by quenching of the resulting benzylic carbanions with chlorotrialkylsilane resulted in stereoselective formation of the corresponding 1-trialkylsiloxy-2-(trialkylsilyl)benzocyclobutenes in good yields. Subsequently, o-acyl-m-methoxybenzyllithiums were found to work well in cyclization to benzocyclobuten-1-ol derivatives. The reaction of 2-benzoyl-3,4,5-trimethoxybenzyllithium, generated in situ by deprotonation of 6-methyl-2,3,4-trimethoxybenzophenone with LDA, with chlorotrimethylsilane afforded the corresponding 1-(trimethylsiloxy)benzocyclobutene. Cyclization of 2-pivaloyl-3-methoxybenzyllithiums, generated in situ from tert-butyl 2-methyl-6-methoxyphenyl ketones upon deprotonation with LDA, proceeded spontaneously even at -78 degrees C to give the corresponding benzocyclobuten-1-ols. We also describe the results of thermal isomerization of these 1-trimethylsiloxy-2-(trialkylsilyl)benzocyclobutenes.

Efficient Synthesis of 1-Amino-2-naphthalenecarboxylic Acid Derivatives via a Sequential Michael Addition/Enolate-Nitrile Coupling Route and Its Application to Facile Preparation of 9-Amino Analogues of Arylnaphthofuranone Lignans.

The reaction of 2-(alpha-lithioalkyl)benzonitriles, generated in situ by treatment of 2-alkylbenzonitriles with LDA in diglyme, with alpha,beta-unsaturated carboxylates and nitriles produced 1-amino-3,4-dihydro-2-naphthalenecarboxylates and carbonitriles in 54-98% yields through Michael addition of the lithio nitriles to alpha,beta-unsaturated carboxylic acid derivatives, followed by zinc iodide-promoted intramolecular enolate-nitrile coupling of the resulting enolate intermediates. The dihydronaphthalenecarboxylic acid derivatives were converted to the corresponding 1-amino-2-naphthalenecarboxylic acid derivatives in 43-99% yields on dehydrogenation with palladium on activated carbon in refluxing p-cymene. Subsequently, we showed that, by using a similar reaction sequence, 9-amino analogues of arylnaphthofuranone lignan derivatives {9-amino-4-arylnaphtho[2,3-c]furan-1(3H)-ones} could also be prepared from 2-(arylmethyl)benzonitriles and furan-2(5H)-one in good overall yields (59-61%).

Reactions of Vinyl Sulfoxides with Magnesium Amides. One-Pot Synthesis of Symmetrical and Unsymmetrical beta-(Dialkylamino) Dithioacetals.

Vinyl sulfoxides (PhSOCR(1)=CHR(2): R(1) = H, Me, or Ph; R(2) = H or Me) were treated with (dialkylamino)magnesium reagents, generated in situ from the reaction of EtMgBr with secondary amines (R(3)R(4)NH: R(3) = Et, i-Pr, or Bn; R(4) = Me, Et, or i-Pr) in refluxing Et(2)O for 1 h, and stirring at room-temperature overnight gave the corresponding symmetrical beta-(dialkylamino) dithioacetals [(PhS)(2)CR(1)CHR(2)NR(3)R(4)] in 24-84% yields. When the (diethylamino)magnesium reagent was treated with appropriate thiols (RSH; R = p-ClC(6)H(4) or Bn) prior to the interaction with phenyl vinyl sulfoxide, the corresponding unsymmetrical beta-(diethylamino) dithioacetals [(PhS)(RS)CHCH(2)NEt(2)] were produced in 63-67% yields.