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150was added. The aqueous layer was extracted with CH2CI, (3 X 5 mL), and combined CH2C12 layers were washed with 5% aqueous NaHCO, ( I x 10 mL) and H 2 0 (1 X 10 mL), then dried, filtered, and concentrated. Chromatography (9.9:O.l CHCI,/MeOH) afforded 24 (0.019 g, 68%): mp 169-171 OC (EtOAc/ether); IR (CHCI,) ,958,914 cm-I; 'H NMR (60 (s, 6 H), 1.37 (s, 3 H); MS calcd for C14H,,03 (M+-S02Me) 233.1178, found 233.1 155. Procedure for the Conversion of Mercapto Adducts 15 and 20 into Methylthio Adducts 16 and 21, Respectively. Diazabicyclo[5.4.0]undecene (DBU) (1 9 pL, 0.123 mmol) and CH31 (0.1 mL, 1.6 mmol) were added to a solution of the mercapto adduct (0.021 g, 0.0616 mmol) in anhydrous benzene (IO mL). The reaction mixture was stirred for 2 days, then washed with 1 N HCI (3 X IO mL) and H 2 0 ( I X IO mL), dried, filtered, and concentrated to give the corresponding thiomethyl adduct (0.022 g, quantitative yield).Conversion of Amino Adduct 29 into syn-N-Acetylamino Adduct 30. Acetic anhydride (0.5 mL) and pyridine (0.5 mL) were added to a solution of 29 (0.023 g, 0.071 mmol) in CH2C12 (7 mL). The solution was stirred for 23 h, then toluene was added, and the solution was concentrated to give 30 (0.026 g, quantitative yield).Preparation of 0-Acetyl Adduct 28. (Dimethy1amino)pyridine (DMAP) (0.025 g, 0.202 mmol) and acetic anhydride (0.2 mL, 2.0 mmol) were added to a solution of the hydroxy adduct 27 (0.046 g, 0.184 mmol) in anhydrous benzene (8 mL). The solution was refluxed for 3.5 days. Additional 4-(dimethy1amino)pyridine (0.045 g) and acetic anhydride (0.2 mL) were added, and refluxing was continued for 2 more days. TLC showed that the reaction was still incomplete; however, the solution wsa allowed to cool, diluted to 5 mL with EtOAc, washed with 5% (v/v) HCI ( 1 X IO mL) and brine (1 X IO mL), dried, filtered, and concentrated. Chromatography (8:2 petroleum ether/EtOAc) yielded 28 (0.030 g, 52%): mp 136-138 OC (ether); IR (CHCI,)

New Prussian Blue (PB) films were prepared by being cast from colloidal PB dispersions in an organic solvent containing cationic surfactants. The electrochromic behaviors of the cast PB films are similar to those of electrodeposited PB films. However, the cyclic voltammetries of both the PB films were quite different from each other. To make the difference clear, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and X-ray photospectroscopy (XPS) were used in measurements of these films grown on Pt and indium tin oxide electrodes. The EDX results for fresh PB films indicated that cast films contain K+ ions, suggesting a soluble-form PB, KFe[Fe(CN)6], while electrodeposited films do not, suggesting an insoluble-form PB, Fe4[Fe(CN)6]3. The transient spectral observations indicated the participation of a unique electrochemically active iron(III) site in the reductive cycles of a cast film, although the participation of a plural electrochemically active iron(III) sites was proposed for an electrodeposited film. After a repeated cyclic scan a cast PB film maintained its unique active site, while an electrodeposited film had plural sites comprising both a soluble and an insoluble form of PB.

Asymmetric Reduction of Benzoylformic Ester to Methyl Mandelate ( S )or (R)-18. GeneralProcedure for 20-50-mg Scale. An ampule (2 mL) containing magnesium perchlorate (Mg(CIO,),-l .5 H 2 0 , 1 .O equiv) sealed with a small rubber septum was evacuated and flushed with argon several times. Methyl benzoylformate (1 .O equiv) was injected via syringe, followed by a solution of the 1,4-dihydropyridine (1.0 equiv) in freshly distilled acetonitrile (1 mL). The ampule was kept in the dark and the reduction allowed to proceed for 5-10 days monitored by TLC. After this period, water (100-200 pL) was added, and the reaction mixture was concentrated in vacuo. The residue was triturated with boiling chloroform (2-3 mL) and the relative yield of methyl mandelate 18, as a chloroform solution, was determined by using capillary GC." The chloroform solution was concentrated to about 0.1 mL, and the alcohol 18 was isolated via preparative TLC using 20% ethyl acetatehexanes as the eluent. Extraction of the silica gel bands, with ethyl acetate, gave methyl mandelate after filtration through a millipore filter, and concentration gave the crystalline alcohol 18. After dissolving this material in 1.0 mL of methanol, the specific rotation of the sample was measured, followed by determination of the accurate concentration of 18 in the alcohol using HPLC calibration.'* Pyridinium Salt 20. Isolation of the pyridinium salt 20 was achieved during the preparative TLC by extraction of the base-line silica gel layers with ethyl acetate (5 mL). Filtration and concentration gave the orange salt 20 (40-50% recovery): 'H N M R (CD,CN) 6 9.08 (br s, 1 H, 6-H), 8.79 (br s, 1 H, 2-H), 7.60-7.40 (m, 5 H, C6H5), 5.77 (s, 2 H, CH2C6Hj). 4.82 (d, J = 5.2 Hz, 2 H, CHIOH), 4.68 (br s, OH), 4.42 Abstract:A novel c y c l o p h a n e , 2,2,20,20-tetramethyI-1 1,29-dinitro-7,15,25,33-tetraoxaheptacyclo-[32.2.2.23~6.216~19.221~24.19~13.127~3'] hexatetraconta-3,5,9(44),10,~2,16,18,21,23,27(39),28,30,34,36,37,40,42,45-octadecaene ( l ) , was synthesized by the reaction of 3,5-bis(bromomethyl)nitrobenzene (2) with bisphenol A (3). Both stepwise 2:2 cyclization of 2 and 3 via U-shaped precursor 4 and direct 2:2 cyclization of 2 and 3 were performed under several reaction conditions.With the coexistence of benzene in the reaction solvent, relatively high yield of 1 was achieved even without operation under high dilution conditions. This can be explained in term of a "template" effect of benzene in the cyclization step. The cyclophane