Potassamide induced in situ benzylation of 5,6-dihydroisoquinolines: Structure of novel products

Potassamide induced in situ benzylation of 1-alkyl-4-cyano-3-methoxy-5,6-dihydroisoquinolines (1a-b) with benzyl iodide gave the 5-benzyl-, 5,9-dibenzyl- and 4,4-dibenzyl-5,6-dihydroisoquinolines (9a-b, 8a-b and 10a-b), isoquinoline derivatives (4a-b) and diastereomeric mixture of 4-benzyl-1,2,3,4-tetrahydroisoquinolin-3(2H)-ones (11a-b & 11'a-b). Structures were assigned on the basis of spectral data [Mass, H-1 & C-13 NMR, 2D NOESY]. A few reactions carried out to transform the diastereomeric mixture of compounds 11a and 11's to the spirobenzylisoquinoline system 7a isomeric with naturally occurring ochotensane system ga are discussed.

Reaction of spironaphthalenones with hydroxylamine hydrochloride: Part IV

Reaction of 1-methoxynaphthalene with 1-formylnaphthalene in presence of n-BuLi/TMEDA, followed by deoxygenation and demethylation gave the bisnaphthol 6. Oxidation of 6 with KOBr yielded the spironaphthalenones 4a-b and 5a-b. The spironaphthalenones 3a-c on reaction with NH2OH.HCl gave naphth[2,1-c]isoxazole derivatives 9a-c. While similar reaction of 4a-b gave the pyrrolotropones 11a-b, spironaphthalenones 5a-b afforded the naphth[1,2-c]isoxazole derivatives 12a-b.

Regioselective synthesis of bicyclo[4.2.1]nonane-2,8-diones via BF3.Et2O mediated intramolecular diazo ketone insertion reaction

Treatment of the diazo diones 11a-d with boron trifluoride diethyl etherate furnished the bicyclo[4.2.1]nonane-2,g-diones 15a-d in a highly regioselective manner. (C) 1999 Elsevier Science Ltd. All rights reserved.

Insertion Reactions of Six-Membered Cyclopalladated N,N `,N `'-Triarylguanidine, Pd{kappa(2)(C,N)-C6H3Me-3(NHC(NHAr)(=NAr))-2)(mu-Br)](2) (Ar=2-MeC6H4) with PhCC C-C(O)OR (R = Me and Et): A Gateway to Second Orthopalladation through Novel Rearrangements

The reaction of Pd{kappa(2)(C,N)-C6H3Me-3-(NHC(NHAr)(=NAr))-2}(mu-Br)](2) (Ar = 2-MeC6H4; 1) with 4 equiv of PhC C-C(O)OMe in CH2Cl2 afforded Pd{kappa(2)(C,N)-C(Ph)=C(C(O)OMe)C(Ph)=C(C(O)-OMe)C6H3Me-3(N=C(NH Ar)(2))-2}Br] (Ar = 2-MeC6H4; 2) in 70% yield, and the aforementioned reaction carried out with 10 equiv of PhC C-C(O)OR (R = Me, and Et) afforded an admixture of two regioisomers of Pd{kappa(3)(N,C,O)-O=C(OR)-C5Ph3(C(O)OR)C(C(O)OR)C6H3Me-3(N=C(NHAr)( 2))- 2}Br] (Ar = 2-MeC6H4; R = Me (3a/3b), Et (4a/4b)) in 80 and 87% yields, respectively. In one attempt, the minor regioisomer, 4b, was isolated from the mixture in 6% yield by fractional crystallization. Palladacycles 3a/3b and 4a/4b, upon stirring in CH2Cl2/MeCN (1/1, v/v) mixture at ambient condition for S days, afforded Pd{eta(3)-allyl,(KN)-N-1)-C-5(C(O)OR)(2)Ph3C-(C(O)OR)C6H3Me-3(N=C(NH Ar)(2))(-2)}Br] (Ar = 2-MeC6H4; R = Me (5a/5b), Et (6a/6b)) in 94 and 93% yields, respectively. Palladacycles 3a/3b and 4a/4b, upon reaction with AgOTf in CH2CH2/Me2C(O) (1/1, v/v) mixture at ambient temperature for 15 min, afforded Pd{kappa(3)(N,C,O)-O=C(OR)C5Ph3(C(O)OR)C(C(O)OR)C6H3Me-3(N=C(NHAr)(2 ))-2}(OTf)] (Ar = 2-MeC6H4; R = Me (7a/7b), Et (8a/8b)) in 79 and 77% yields, respectively. Palladacycles 7a/7b and 8a/ 8b, upon reflux in PhC1 separately for 6 h, or palladacycles 5a/5b and 6a/6b, upon treatment with AgOTf in CH2Cl2/Me2C(O) (7/3, v/v) mixture for 15 min, afforded Pd{(eta(2)-Ph)C5Ph2(C(O)OR)kappa(2)(C,N)-C(C(O)OR)C6H3Me-3(N=C(NHAr) (2))-2}(OTf)] (Ar = 2-MeC6H4; R = Me (9a/9h), Et (10a/10b)) in >= 87% yields. Palladacycles 9a/9b, upon stirring in MeCN in the presence of excess NaOAc followed by crystallization of the reaction mixture in the same solvent, afforded Pd{kappa(3)(N,C,C)-(C6H4)C5Ph2(C(O)OMe)(2)C(C(O)OMe)(2)C6H3Me-3(N=C( NHAr)(2))-2}(NCMe)] (Ar = 2-MeC6H4; 11a/11b) in 82% yield. The new palladacycles were characterized by analytical, IR, and NMR (H-1 and C-13) spectroscopic techniques, and the molecular structures of 2, 3a, 4a, 4b, 5a, 6a, 7a, 9a, 10a, and 11a-d(3) were determined by single crystal X-ray diffraction. The frameworks in the aforementioned palladacycles, except that present in 2, are unprecedented. Plausible pathways for the formation of new palladacycles and the influence of the guanidine unit in 1, substituents in alkynes, reaction conditions, and electrophilicity of the bromide and the triflate upon the frameworks of the insertion products have been discussed.

Design of a Low Power 64 Point FFT Architecture for WLAN Applications

This paper presents a Radix-4(3) based FFT architecture suitable for OFDM based WLAN applications. The radix-4(3) parallel unrolled architecture presented here, uses a radix-4 butterfly unit which takes all four inputs in parallel and can selectively produce one out of the four outputs. A 64 point FFT processor based on the proposed architecture has been implemented in UMC 130nm 1P8M CMOS process with a maximum clock frequency of 100 MHz and area of 0.83mm(2). The proposed processor provides a throughput of four times the clock rate and can finish one 64 point FFT computation in 16 clock cycles. For IEEE 802.11a/g WLAN, the processor needs to be operated at a clock rate of 5 MHz with a power consumption of 2.27 mW which is 27% less than the previously reported low power implementations.

Synthesis, characterization and reactivity studies of electrophilic ruthenium(II) complexes: a study of H-2 activation and labilization

Reaction of 2,2'-bipyridine (bpy) with dinuclear complexesRuCl(dfppe)(mu-Cl)(3)Ru(dmso-S)(3)](dfppe = 1,2-bis(dipentafluorophenyl phosphino)ethane (C6F5)(2)PCH2CH2P(C6F5)(2); dmso = dimethyl sulfoxide) (1) or RuCl(dfppe)(mu-Cl)(3)RuCl(dfppe)] (2) affords the mononuclear species trans-RuCl2(bpy)(dfppe)] (3). Using this precursor complex (3), a series of new cationic Ru(II) electrophilic complexes RuCl(L)(bpy)(dfppe)]Z] (L = P(OMe)(3) (5), PMe3 (6), CH3CN (7), CO (8), H2O (9); Z = OTf (5, 6, 7, 8), BAr4F (9) have been synthesized via abstraction of chloride by AgOTf or NaBAr4F in the presence of L. Complexes 5 and 6 were converted into the corresponding isomeric hydride derivatives RuH(PMe3)(bpy)(dfppe)]OTf] (10a, 10b) and RuH(P(OMe)(3))(bpy)(dfppe)]OTf] (11a, 11b) respectively, when treated with NaBH4. Protonation of the cationic monohydride complex (11a) with HOTf at low temperatures resulted in H-2 evolution accompanied by the formation of either solvent or triflate bound six coordinated species Ru(S)(P(OMe)(3))(bpy)(dfppe)]OTf](n) (S = solvent (n = 2), triflate (n = 1)] (13a/13b); these species have not been isolated and could not be established with certainty. They (13a/13b) were not isolated, instead the six-coordinated isomeric aqua complexes cis-(Ru(bpy)(dfppe)(OH2)(P(OMe)(3))]OTf](2) (14a/14b) were isolated. Reaction of the aqua complexes (14a/14b) with 1 atm of H-2 at room temperature in acetone-d(6) solvent resulted in heterolytic cleavage of the H-H bond. Results of the studies on H-2 lability and heterolytic activation using these complexes are discussed. The complexes 3, 5, 11a, and 14a have been structurally characterized.

Dynamics of pneumococcal nasopharyngeal carriage in healthy children attending a day care center in northern Spain. Influence of detection techniques on the results

8 p.

Diseño de un array de antenas en tecnología microstrip

[ES]Este trabajo de fin de grado trata sobre el diseño de un array de antenas en tecnología microstrip para ser utilizado en la banda de 5 GHz del estándar de tecnologías inalámbricas IEEE 802.11a. Se buscará aplicar la teoría de arrays para conseguir la mayor ganancia posible, pero al mismo tiempo tratando de obtener un gran ancho de banda para que la antena sea óptima dentro de la mayor parte posible de la banda especificada. El proyecto partirá de un único parche microstrip para posteriormente ir evolucionando el diseño hasta llegar a un array de 2x2 elementos. Al primer diseño se le irán añadiendo progresivamente todos los componentes necesarios (red de adaptación, desfasadores, mayor número de parches, etc.) para poder ir estudiando las simulaciones a la vez que el diseño progresa. Todos los diseños se realizarán con el software ADS (Advanced Design System) de la compañía Agilent Technologies. Finalmente se fabricará el array diseñado y se medirá para contrastarlo con las simulaciones.

Proteómica dirigida en la cirugía del cáncer gástrico

240 p. + anexos

Avaliação de carbonilas na atmosfera interior e exterior de salas de aula de escolas públicas

Compostos carbonílicos representam uma das principais classes de poluentes atmosféricos e são frequentemente reportados em estudos de poluição atmosférica de interiores. São emitidos para a atmosfera a partir de uma variedade de fontes naturais e antropogênicas. Em projeto empreendido em 2011 pela Secretaria de Estado de Educação do Estado do Rio de Janeiro,foi implementada a climatização em todas as salas de aula de todas as escolas da rede pública estadual. A escala de exposição de ocupantes à climatização, em salas de aula, não apresenta precedentes em nosso estado e representa uma tendência de todo o país. Como é um projeto recente, não há dados a respeito da qualidade do ar interior nesses ambientes e, portanto, das consequências na saúde dos ocupantes. Os procedimentos foram baseados na metodologia TO-11A da U.S.EPA. A técnica de amostragem foi por via seca com reação química, empregando-se cartuchos de sílica revestidos de octadecil (SiO2-C18) impregnados com 2,4-dinitrofenilhidrazina. As carbonilas foram analisados através de Cromatografia Líquida de Alta Eficiência com detecção por UV. Foram encontradas concentrações de formaldeído na faixa de 3,59 a 26,62 μg m-3 (interior) e 0,74 a 23,47 μg m-3 (exterior), acetaldeído na faixa de 0,19 a 259,47 μg m-3 (interior) e 1,19 a 127,51 μg m-3 (exterior), acetona+acroleína na faixa de 0,00 a 48,45 μg m-3 (interior) e 0,00 a 37,00 μg m-3 (exterior). Os valores encontrados geralmente não ultrapassaram os limites determinados por organismos internacionais

A direct-conversion mixer with a DC-offset cancellation for WLAN

This paper presents a 5GHz double-balanced mixer with DC-offset cancellation circuit for direct-conversion receiver compliant with IEEE 802.11a wireless LAN standard. The analog feedback loop is used, to eliminate the DC-offset at the output of the double-balanced mixer. The test results show that the mixer with DC-offset cancellation circuit has voltage conversion gain of 9.5dB at 5.15GHz, noise figure of 13.5dB, IIP3 of 7.6 dBm, 1.73mV DC-offset voltage and 67mW power with 3.3-V power supply. The DC-offset cancellation circuit has less than 0.1mm(2) additional area and 0.3mW added power dissipation. The direct conversion WLAN receiver has been implemented in a 0.35 mu m SiGe BiCMOS technology.

Design of Low Power Multi-Standard Active-RC Filter for WLAN and DVB-H

In this paper, a low-power, highly linear, integrated, active-RC filter exhibiting a multi-standard (IEEE 802.11a/b/g and DVB-H) application and bandwidth (3MHz, 4MHz, 9.5MHz) is present. The filter exploits digitally-controlled polysilicon resister banks and an accurate automatic tuning scheme to account for process and temperature variations. The automatic frequency calibration scheme provides better than 3% corner frequency accuracy. The Butterworth filter is design for receiver (WLAN and DVB-H mode) and transmitter (WLAN mode). The filter dissipation is 3.4 mA in RX mode and 2.3 mA (only for one path) in TX mode from 2.85-V supply. The dissipation of calibration consumes 2mA. The circuit has been fabricated in a 0.35um 47-GHz SiGe BiCMOS technology, the receiver and transmitter occupy 0.28-mm(2) and 0.16-mm(2) (calibration circuit excluded), respectively.

A 5GHz low power WLAN transceiver SiGe RFIC for personal communication terminal applications

A low-cost low-power single chip WLAN 802.11a transceiver is designed for personal communication terminal and local multimedia data transmission. It has less than 130mA current dissipation, maximal 67dB gain and can be programmed to be 20dB minimal gain. The receiver system noise figure is 6.4dB in hige-gain mode.

A multi-standard active-RC filter with accurate tuning system

A low-power, highly linear, multi-standard, active-RC filter with an accurate and novel tuning architec-ture is presented. It exhibits 1EEE 802. 11a/b/g (9.5 MHz) and DVB-H (3 MHz, 4 MHz) application. The filter exploits digitally-controlled polysilicon resistor banks and a phase lock loop type automatic tuning system. The novel and complex automatic frequency calibration scheme provides better than 4 comer frequency accuracy, and it can be powered down after calibration to save power and avoid digital signal interference. The filter achieves OIP3 of 26 dBm and the measured group delay variation of the receiver filter is 50 ns (WLAN mode). Its dissipation is 3.4 mA in RX mode and 2.3 mA (only for one path) in TX mode from a 2.85 V supply. The dissipation of calibration consumes 2 mA. The circuit has been fabricated in a 0.35μm 47 GHz SiGe BiCMOS technology; the receiver and transmitter filter occupy 0.21 mm~2 and 0.11 mm~2 (calibration circuit excluded), respectively.

一种解决无线局域网直下变频接收机直流漂移的方法

提出了一种符合IEEE802．11a无线局域网的5GHz直下变频接收机解决直流漂移的方法．该方法利用双平衡混频器输出端的模拟反馈环路消除直流漂移．该混频器经过测试，在5．15GHz频率下具有9．5dB的转换增益，13．5dB的噪声系数和7．6dBm的三阶交调，在3．3V电源电压条件下67mW的功耗，以及1．73mV的直流漂移，并能使直流漂移减少76％．该方案及整个直下变频的WLAN接收机已经采用0．35μmSiGe BiCMOS工艺流片并测试．