The Crystal and Molecular Structure of 4-Aza-5-oxo-tricyclo[4.4.0.03,8]decane (Aza-twistanone)

Die kristalline Struktur von Aza-twistanon wurde durch eine Röntgenstruktur-analyse untersucht. Die Kristalle gehören zur monoklinen Raumgruppe P21/n mit den Zelldimensionen a = 6,662(6), b = 13,36(2), c = 8,606(9) Å, = 98,97(2)°, V = 757 Å3, Z = 4. Die Struktur wurde mit Direktmethoden gelöst und bis zu R = 0,035 verfeinert (mittlere (c) = 0,003 Å3).Die cis-Amidgruppe ist relativ stark deformiert und hat einen Torsionswinkel C -C -N-C von 14,5(4)° (Deformation aus der Ebene c = 5,0(5)° und N = 13,5(4,0)°). Die gegenüberliegende äthylenbrücke weist einen Torsionswinkel von 25,1(5)° auf. Die entsprechenden Winkel in Twistan betragen je 20°. Das tricyclische Gerüst von Aza-twistanon hat approximative.

Ethyl 6-chloro-2-[(2-chloro-7,8-dimethylquinolin-3-yl)methoxy]-4-phenylquino line-3-carboxylate

In the title compound, C30H24Cl2N2O3, the two quinoline ring systems are almost planar [maximum deviations = 0.029 (2) and 0.018 (3) angstrom] and the dihedral angle between them is 4.17 (8)degrees. The dihedral angle between the phenyl ring and its attached quinoline ring is 69.06 (13)degrees. The packing is stabilized by C-H center dot center dot center dot O, C-H center dot center dot center dot N, weak pi-pi stacking [centroid-centroid distances = 3.7985 (16) and 3.7662(17) angstrom] and C-H center dot center dot center dot pi interactions.

Synthesis Of (+/-)-2-Isopropyl-5,6-Dimethylbicyclo[3.2.1]Oct-6-En-8-One

Methanolic hydrogen chloride cyclization of the triketone 8, prepared from the Mannich base 7 and 2-methylcyclopentane-1,3-dione, gives ketones 9 and 10. NaBH4 reduction of 9 followed by Grignard reaction with CH3MgI affords the diol 12. Catalytic hydrogenation of 12 followed by PCC oxidation yields the ketoalcohol 13. Dehydration of 13 with SOCl2/pyridine results in a 1:1 mixture of the endo-14 and exo-15 olefins, separated by chromatography.

Stereospecific construction of multiple contiguous quaternary carbons. Total synthesis of (±)-cis,anti,cis-1,8,12,12-tetramethyl-4-oxatricyclo[6.4.0.02,6]dodecan-3-ol, a thapsane isolated from Thapsia villosa var minor

The details of the first total synthesis of a natural thapsane lg containing three contiguous quaternary carbon atoms, starting from cyclogeraniol (9) '5 described. The Claisen rearrangement of 9 with methoxypropene in the presence of a catalytic amount of propionic acid produced ketone 10. Rhodium acetate-catalyzed intramolecular cyclopropanation of a-diazo-&keto ester 12, obtained from 10 via 8-keto ester 8, furnished cyclopropyl keto ester 7. Lithium in liquid ammonia reductive cleavage of cyclopropyl compound 7 gave a 1:l mixture of hydrindanone 6 and keto1 13. Wittig methylenation of 6 furnished ester 21. Epoxidation of 21, followed by BF3-OEt2-catalyzed rearrangement of epoxide 23 afforded hemiacetal 25. Treatment of hemiacetal 25 with triethylsilane in trifluoroacetic acid furnished lactone 22, a degradation product of various thapsanes. Finally, DIBAH reduction of lactone 22 generated the thapsane

Direct conversion of 13-beta-alkylgonatetraenes into 13-beta-alkylgon-4-en-3-ones

Birch reduction of 8,9-didehydroestradiol-17 beta 3-methyl ether 1 or 9(11)-didehydroestradiol-17 beta 3-methyl ether 2 followed by acid hydrolysis results in a mixture of 19-nortestosterone 8 and 19-nor-9 beta, 10 alpha-testosterone 9 in varying amounts. However, reduction of their acetates with sodium or lithium, tert-butyl alcohol in liquid ammonia and in the presence of aniline affords exclusively 19-nortestosterone. Similarly, 18a-homo-19-nortestosterone 12 is prepared from the acetate of 18a-homoestradiol-17 beta 3-methyl ether, 10.

Organometallic chemistry of diphosphazanes .13. Palladium complexes of unsymmetrical diphosphazanes Ph(2)PN(Pr-i)PYY'

Unsymmetrical diphosphazanes Ph(2)PN(Pr-i)PYY' [YY' = O2C12H8 (L(1)), O2C20H12 (L(2)); Y = Ph and Y' = OC6H4Br-4 (L(3)), OC(6)H(4)Me-4 (L(4)), OC(6)H(3)Me(2)-3,5 (L(5)), N(2)C(3)HMe(2)-3,5 (L(6))] react with cis-[PdCl2(COD)] (COD = cycloocta-1,5-diene) giving the chelate complexes of the type cis-[PdCl2{eta(2)-Ph(2)PN(Pr-i)PYY'}] [YY' = O2C12H8 (1), O2C20H12 (2), Y = Ph and Y' = OC6H4Br-4 (3), OC(6)H(4)Me-4 (4), OC(6)H(3)Me(2)-3,5 (5), N(2)C(3)HMe(2)-3,5 (6)]. The P-N bond in 3 and 5 undergoes a facile cleavage in methanol solution to give cis-[PdCl2{eta(1)Ph(2)P(OMe)}{eta(1)-PhP(NHPri)(Y')}] [Y' = OC6H4Br-4 (7), OC(6)H(3)Me(2)-3,5 (8)]. Reactions of Pd-2(dba)(3) . CHCl3 (dba = dibenzylideneacetone) with the diphosphazanes Ph(2)PN(Pr-i)PPhY' [Y' = OC(6)H(4)Me-4 (L(4)), N(2)C(3)HMe(2)-3,5 (L(6)), N2C3H3 (L(7))] in the presence of MeI yields cis-[PdI2{eta(2)-Ph(2)PN(Pr-i)PPhMe}] (9); the P-O or P-N(pyrazolyl) bond of the starting ligands is cleaved and a p-C(Me) bond is formed. An analogous oxidative addition reaction in the presence of Ph(2)PN(Pr-i)PPh(2) (L(8)) yields cis-[PdI(Me)(eta(2)-L(8))] (10) and cis-[PdI2(eta 2-L(8))] (11). The structures of 8 and 9 have been determined by X-ray diffraction. Copyright (C) 1996 Elsevier Science Ltd

Di- and tri-metallic complexes containing two bridging cyclodiphosphazane ligands: the crystal structure of [MO2(CO)8{µ-cis-[PhNP(OC6H4Me-p)]2}2]

The reactions of the mononuclear cyclodiphosphazane complexes, cis-[Mo(CO)(4){cis-[PhNP(OR)](2)}(2)] with [Mo(CO)(4)(nbd)] (nbd = norbornadiene). [Mo(CO)(4)(NHC5H10)(2)] or [MCl(2)(cod)] (cod = cycloocta-1,5-diene) afforded the homobimetallic complexes; [Mo-2(CO)(8){mu-cis-[PhNP(OR)](2)}(2)] (R = C(5)H(4)Me-p 5 or CH2CF3 6) or the heterobimetallic complexes. [Mo-2(CO)(8){mu-cis-[PhNP(OE)](2)}(2)MCl(2)] (R = C(6)H(4)Me-p; M = Pd 7 or Pt 8). In all the above complexes, the two metal moieties are bridged by two cyclodiphosphazane ligands. The reactions of the mononuclear complexes, cis-[M(CO)(4)(A){cis-[PhNP(OC(6)H(4)Me-p)](2)}] with (M'Cl-2(cod)] afforded the trinuclear complexes, cis-[M'Cl-2[M(CO)(4)(A){cis-[PhNP(OC(6)H(4)Me-p)](2)}](2)] (M' = Pd, M = Mo, A = P(OMe)(3) 10; M' = Pt, M = Mo. A = P(OMe)(3) 11; M' = Pd. M = W. A = NHC5H10 12; M' = Pt, M = W. A = NHC5H10 13). The structure of the complex 5 has been determined by single-crystal X-ray crystallography.

Rearrangement approaches to sesquiterpenes containing multiple contiguous quaternary carbon atoms. Total synthesis of (+/-)-myltayl-8(12)-ene and (+/-)-6-epijunicedranol

Details of the first total syntheses of the sesquiterpenes myltayl-8(12)-ene and 6-epijunicedran-8-ol are described. The aldehyde 13, obtained by Claisen rearrangement of cyclogeraniol, was transformed into the dienones 12 and 18. Boron trifluoride-diethyl ether mediated cyclization and rearrangement transformed the dienones 12 and 18 into the tricyclic ketones 16 and 17, efficiently creating three and four contiguous quaternary carbon atoms, respectively. Wittig methylenation of 16 furnished (+/-)-myltayl-8(12)-ene (11), whereas reduction of the ketone 17 furnished (+/-)-6-epijunicedranol (23).

Structure of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecyl 1,10-ditosylate by X-ray crystallography and F-19-NMR spectroscopy

2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecyl 1,10-ditosylate and its precursors were synthesized and characterized by H-1- and F-19-NMR spectroscopic methods and X-ray crystallography. These compounds are building blocks for the syntheses of the surfactants containing polyperfluoromethylene spacer. The molecule has extended all-trans conformation with molecular symmetry (1) over bar (C-i). There is a reasonably strong C-H ... O interaction in the crystal and there are two F ... F intermolecular contact distances less than the sum of van der Waals radii. (C) 1999 Elsevier Science B.V. All rights reserved.

Self-assembly of Ru-4 and Ru-8 assemblies by coordination using organometallic Ru(II)(2) precursors: Synthesis, characterization and properties

Coordination-driven self-assembly of binuclear half-sandwich p-cymene ruthenium(II) complexes [Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1a) or [Ru-2(mu-eta(4)-N,N'-diphenyloxamidato)(MeOH)(2)(eta(6)-p-cymene)(2)]( O3SCF3)(2) (1b) separately with an imidazole-based tetratopic donor L in methanol affords two tetranuclear metallamacrocycles 2a and 2b, respectively. Conversely, the similar combination of L with 2,5-dihydroxy-1,4-benzoquinonato (dhbq) bridged binuclear complex [Ru-2(mu-eta(C6H2O4)-C-4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1c) in 1:2 molar ratio resulted in an octanuclear macrocyclic cage 2c. All the self-assembled macrocycles 2a-2c were isolated as their triflate salts in high yields and were characterized fully by multinuclear (H-1, C-13 and F-19) NMR, infrared (IR) and electrospray ionization mass spectrometry (ESIMS). In addition, the molecular structure of macrocycle 2a was established unequivocally by single-crystal X-ray diffraction analysis and adopts a tetranuclear rectangular geometry with the dimensions of 5.53 angstrom x 12.39 angstrom. Furthermore, the photo-and electrochemical properties of these newly synthesized assemblies have been studied by using UV-vis absorption and cyclic voltammetry analysis.

An 8-to-1 bit 1-MS/s SAR ADC With VGA and Integrated Data Compression for Neural Recording

Low power consumption per channel and data rate minimization are two key challenges which need to be addressed in future generations of neural recording systems (NRS). Power consumption can be reduced by avoiding unnecessary processing whereas data rate is greatly decreased by sending spike time-stamps along with spike features as opposed to raw digitized data. Dynamic range in NRS can vary with time due to change in electrode-neuron distance or background noise, which demands adaptability. An analog-to-digital converter (ADC) is one of the most important blocks in a NRS. This paper presents an 8-bit SAR ADC in 0.13-mu m CMOS technology along with input and reference buffer. A novel energy efficient digital-to-analog converter switching scheme is proposed, which consumes 37% less energy than the present state-of-the-art. The use of a ping-pong input sampling scheme is emphasized for multichannel input to alleviate the bandwidth requirement of the input buffer. To reduce the data rate, the A/D process is only enabled through the in-built background noise rejection logic to ensure that the noise is not processed. The ADC resolution can be adjusted from 8 to 1 bit in 1-bit step based on the input dynamic range. The ADC consumes 8.8 mu W from 1 V supply at 1 MS/s speed. It achieves effective number of bits of 7.7 bits and FoM of 42.3 fJ/conversion-step.

Diurnal and seasonal variation of mixing ratio and delta C-13 of air CO2 observed at an urban station Bangalore, India

We present here observations on diurnal and seasonal variation of mixing ratio and delta C-13 of air CO2, from an urban station-Bangalore (BLR), India, monitored between October 2008 and December 2011. On a diurnal scale, higher mixing ratio with depleted delta C-13 of air CO2 was found for the samples collected during early morning compared to the samples collected during late afternoon. On a seasonal scale, mixing ratio was found to be higher for dry summer months (April-May) and lower for southwest monsoon months (June-July). The maximum enrichment in delta C-13 of air CO2 (-8.04 +/- 0.02aEuro degrees) was seen in October, then delta C-13 started depleting and maximum depletion (-9.31 +/- 0.07aEuro degrees) was observed during dry summer months. Immediately after that an increasing trend in delta C-13 was monitored coincidental with the advancement of southwest monsoon months and maximum enrichment was seen again in October. Although a similar pattern in seasonal variation was observed for the three consecutive years, the dry summer months of 2011 captured distinctly lower amplitude in both the mixing ratio and delta C-13 of air CO2 compared to the dry summer months of 2009 and 2010. This was explained with reduced biomass burning and increased productivity associated with prominent La Nina condition. While compared with the observations from the nearest coastal and open ocean stations-Cabo de Rama (CRI) and Seychelles (SEY), BLR being located within an urban region captured higher amplitude of seasonal variation. The average delta C-13 value of the end member source CO2 was identified based on both diurnal and seasonal scale variation. The delta C-13 value of source CO2 (-24.9 +/- 3aEuro degrees) determined based on diurnal variation was found to differ drastically from the source value (-14.6 +/- 0.7aEuro degrees) identified based on seasonal scale variation. The source CO2 identified based on diurnal variation incorporated both early morning and late afternoon sample; whereas, the source CO2 identified based on seasonal variation included only afternoon samples. Thus, it is evident from the study that sampling timing is one of the important factors while characterizing the composition of end member source CO2 for a particular station. The difference in delta C-13 value of source CO2 obtained based on both diurnal and seasonal variation might be due to possible contribution from cement industry along with fossil fuel / biomass burning as predominant sources for the station along with differential meteorological conditions prevailed.