|
| ||
|
|
||
Butyl Substituents (butyl + substituent)
Selected AbstractsSynthesis and Reactivity of 23 - tert -Butyl- and 23 -Phenyltetraarylazuliporphyrins: an Analysis of the Effect of Bulky Substituents on Oxidative Ring Contractions to Benzocarbaporphyrins,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 24 2007Jessica A. El-Beck Abstract 6- tert -Butyl- and 6-phenylazulene reacted with pyrrole and benzaldehyde in a molar ratio of 1:3:4 in the presence of BF3·Et2O in chloroform, followed by oxidation with DDQ, to give 23 -substituted tetraphenylazuliporphyrins in 15,20,% yield. Slightly higher yields of the related meso -tetrakis(4-chlorophenyl)azuliporphyrins were obtained using 4-chlorobenzaldehyde. The presence of an electron-donating tert -butyl substituent increased the diatropic character of the azuliporphyrin system as determined by the proton NMR chemical shifts for the internal CH resonance, while intermediary results were noted for 23 -phenylazuliporphyrins. Addition of TFA afforded dications with increased aromatic ring currents, but electron-donating substituents (tBu,>,Ph) again produced a larger upfield shift for the internal CH signal due to stabilization of the tropylium character that is required so that the system can attain carbaporphyrin-type aromaticity. The substituted azuliporphyrins reacted with nickel(II) acetate or palladium(II) acetate to give the corresponding organometallic derivatives. In addition, oxidations with tBuOOH and KOH afforded benzocarbaporphyrin products in approximately 50,% yield. The presence of tert -butyl or phenyl substituents did not block these oxidative ring contraction processes, and the rate of reaction was slightly increased compared to 23 -unsubstituted azuliporphyrins. The major products were 22 - tert -butyl or phenyl-substituted benzocarbaporphyrins and minor products with an additional formyl substituent were also isolated. These products are consistent with an initial nucleophilic addition occurring at the position adjacent to the R group on the azulene ring. Detailed mechanisms are proposed to explain these observations. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] The [2+2]-Cycloaddition Reaction of Bisallenes: A Dramatic Substituent Effect,CHINESE JOURNAL OF CHEMISTRY, Issue 9 2010Ping Lu Abstract The bisallenes 1 possessing a phenylsulfonyl or n -butyl substituent at the internal position of allene moieties could be smoothly transformed to the bicyclo[5.2.0] or bicyclo[6.2.0] derivatives 2 in moderate to excellent yields with good regioselectivity upon refluxing in toluene. This [2+2]-cycloaddition reaction shows an interesting substituent effect as unveiled by comparing with the results of unsubstituted substrates. However, further attention should be paid to the control of the regioselectivity of the [2+2]-cycloaddition involving different CC bonds. [source] Synthesis and structural studies of N -(p -toluenesulfonyl)-amino acid 3,5-di- tert -butyl-2-phenolamidesHETEROATOM CHEMISTRY, Issue 2 2004Margarita Tlahuextl This paper describes the synthesis and structural studies of N -(p -toluenesulfonyl)-amino acid 3,5-di- tert -butyl-2-phenolamides by 1H, 13C, and 15N. The presence of intra - and intermolecular hydrogen bonds were studied by variable temperature NMR spectroscopy. The molecular structure of two amides in the solid state was determined by X-ray diffraction experiments. The results show that tert -butyl substituents in the phenolic ring have important effects in the nature of hydrogen bonds and conformation of these amides. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:114,120, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10223 [source] Novel aromatic polyamides and polyimides functionalized with 4- tert -butyltriphenylamine groupsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2006Sheng-Huei Hsiao Abstract A new triphenylamine-containing diamine monomer, 4,4,-diamino-4,- tert -butyltriphenylamine, was successfully synthesized by the cesium fluoride-mediated N,N -diarylation of 4- tert -butylaniline with 4-fluoronitrobenzene, followed by the reduction of the nitro group. The obtained diamine monomer was reacted with various aromatic dicarboxylic acids and tetracarboxylic dianhydrides to produce two series of novel triphenylamine-based polyamides and polyimides with pendent tert -butyl substituents. Most of the polymers were readily soluble in polar organic solvents, such as N -methyl-2-pyrrolidone and N,N -dimethylacetamide (DMAc), and could be solution cast into tough and flexible polymer films. These polymers showed high glass transition temperatures between 282 and 320 °C, and they were fairly stable up to a temperature above 450 °C (for polyamides) or 500 °C (for polyimides). These polymers exhibited UV absorption maxima around 308 to 361 nm. The photoluminescence spectra of the polyamides in DMAc exhibited a peak emission wavelength in the blue at 421,433 nm. Cyclic voltammograms of polyamides and polyimides showed an oxidation wave at 1.0,1.1 V versus Ag/AgCl in an acetonitrile solution. All the polyamides and polyimides exhibited excellent reversibility of electrochromic characteristics by continuous several cyclic scans between 0.0 and 1.1,1.3 V, with a color change from the original pale yellowish neutral form to the green or blue oxidized forms. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4579,4592, 2006 [source] Eight 7-benzyl-3- tert -butyl-1-phenylpyrazolo[3,4- d]oxazines, encompassing structures containing no intermolecular hydrogen bonds, and hydrogen-bonded structures in one, two or three dimensionsACTA CRYSTALLOGRAPHICA SECTION C, Issue 8 2009Juan C. Castillo 7-Benzyl-3- tert -butyl-1-phenyl-6,7-dihydro-1H,4H -pyrazolo[3,4- d][1,3]oxazine, C22H25N3O, (I), and 3- tert -butyl-7-(4-methylbenzyl)-1-phenyl-6,7-dihydro-1H,4H -pyrazolo[3,4- d][1,3]oxazine, C23H27N3O, (II), are isomorphous in the space group P21, and molecules are linked into chains by C,H...O hydrogen bonds. In each of 3- tert -butyl-7-(4-methoxybenzyl)-1-phenyl-6,7-dihydro-1H,4H -pyrazolo[3,4- d][1,3]oxazine, C23H27N3O2, (III), which has cell dimensions rather similar to those of (I) and (II), also in P21, and 3- tert -butyl-1-phenyl-7-[4-(trifluoromethyl)benzyl]-6,7-dihydro-1H,4H -pyrazolo[3,4- d][1,3]oxazine, C23H24F3N3O, (IV), there are no direction-specific interactions between the molecules. In 3- tert -butyl-7-(4-nitrobenzyl)-1-phenyl-6,7-dihydro-1H,4H -pyrazolo[3,4- d][1,3]oxazine, C22H24N4O3, (V), a combination of C,H...O and C,H...N hydrogen bonds links the molecules into complex sheets. There are no direction-specific interactions between the molecules of 3- tert -butyl-7-(2,3-dimethoxybenzyl)-1-phenyl-6,7-dihydro-1H,4H -pyrazolo[3,4- d][1,3]oxazine, C24H29N3O3, (VI), but a three-dimensional framework is formed in 3- tert -butyl-7-(3,4-methylenedioxybenzyl)-1-phenyl-6,7-dihydro-1H,4H -pyrazolo[3,4- d][1,3]oxazine, C23H25N3O3, (VII), by a combination of C,H...O, C,H...N and C,H...,(arene) hydrogen bonds, while a combination of C,H...O and C,H...,(arene) hydrogen bonds links the molecules of 3- tert -butyl-1-phenyl-7-(3,4,5-trimethoxybenzyl)-6,7-dihydro-1H,4H -pyrazolo[3,4- d][1,3]oxazine, C25H31N3O4, (VIII), into complex sheets. In each compound, the oxazine ring adopts a half-chair conformation, while the orientations of the pendent phenyl and tert -butyl substituents relative to the pyrazolo[3,4- d]oxazine unit are all very similar. [source] | ||||||||||