Alkanes optical

The alkane formed by hydrogenation of (S) 4 methyl 1 hexyne is optically active but the one formed by hydrogenation of (S) 3 methyl 1 pentyne is not Explain Would you expect the products of hydrogenation of these two compounds in the presence of Lindlar palladium to be optically active" ... 

Vanadium atom depositions were further studied in alkane matrices 109) in an effort to observe the influence of other low-temperature, matrix environments on the optical spectra and clustering properties of metal atoms. Thus, vanadium atoms were deposited with a series of normal, branched, and cyclic alkanes over a wide range of temperature. The atomic spectra were somewhat broadened compared to those in argon, but the matrix-induced, frequency shifts from gas-phase values were smaller. As shown in Fig. 3, these shifts decrease with in-... 

Mueller et al. [6] discovered in 1962 that when a small quantity of a phospholipid (2% wt/vol alkane solution) was carefully placed over a small hole (0.5 mm) in a thin sheet of Teflon or polyethylene (10-25 pm thick), a thin film gradually forms at the center of the hole, with excess lipid flowing towards the perimeter (forming a Plateau-Gibbs border ). Eventually, the central film turns optically black as a single (5 nm-thick) bilayer lipid membrane (BLM) forms over the hole. Suitable lipids for the formation of a BLM are mostly isolated from natural sources, e.g.,... 

Typically, solvents are screened to identify one that gives optimal results. Assuming that the substrate and catalyst are soluble, solvent polarities varying from alkanes, aromatics, halogenated, ethers, acetonitrile, esters, alcohols, dipolar aprotic to water have been used. An example of this, using a ketone and the rhodium cp TsDPEN catalyst, is shown in Table 35.3. Further optimization of this reaction improved the enantiomeric excess to 98%. A second example involved the reduction of 4-fluoroacetophenone in this case the enantioselectivity was largely unaffected but the rate of reduction changed markedly with solvent. Development of this process improved the optical purity to 98.5% e.e. 

Treatment of the optically active gem-borazirconocene alkanes with deuterium oxide followed by alkaline oxidation affords the corresponding optically active 1-deuterio primary alcohols. The enantiomeric excess of the resulting primary alcohols represents the diaster-eoselectivity of the asymmetric hydrozirconation (Scheme 7.13). Based on the cost and availability of optically active ligands, three types were explored monoterpenes, 1,2-diols, and 1,2-amino alcohols. Hydrozirconation of optically pure 1-alkenyl boranes 39 provided optically active 1,1-bimetallics 40. 

Ozin GA, Flugues F, Mattar SM, McIntosh DF (1983) Low nuclearity silver clusters in faujasite-type zeolites optical spectroscopy, photochemistry and relationship to the photodimerization of alkanes. J Phys Chem 87 3445-3450... 

In regard to the stereoselectivity of the insertion process, Murray and coworkers have shown that the CH oxidation of substituted cyclohexanes by dioxiranes is, like the already discussed epoxidation, highly stereo-controUed . A specific case is c -decalin, which gives only the cis alcohol, as exemplarily displayed in equation 27. A similar stereoselective retention of configuration was also obtained for frawi-decalin and cis- and frawi-dimethylcyclohexanes"°. In fact, complete retention of configuration was demonstrated in the CH oxidation of chiral alkanes ". For example, the optically active (f )-2-phenylbutane was converted by either DMD or TFD" to (5 )-2-phenylbutan-2-ol (equation 28) without any loss of the enantiomeric purity (ep) in the product. 

To exhibit optical activity an alkane must contain at least one asymmetric carbon atom. Simplest optically active alkane is 3-methyl hexane. 

Electrons have not been detected by optical absorption in alkanes in which the mobility is greater than 10 cm /Vs. For example, Gillis et al. [82] report seeing no infrared absorption in pulse-irradiated liquid methane at 93 K. This is not surprising since the electron mobility in methane is 500 cm /Vs [81] and trapping does not occur. Geminately recombining electrons have, however, been detected by IR absorption in 2,2,4-trimethyl-pentane in a subpicosecond laser pulse experiment [83]. The drift mobility in this alkane is 6.5 cm /Vs, and the quasi-free mobility, as measured by the Hall mobility, is 22 cm /Vs (see Sec. 6). Thus the electron is trapped two-thirds of the time. 

Probidin 5.38 Deduce the structural formula for an optically active alkene, C H,2, which reacts with H. to form an optically inactive alkane, C(,H,4. M... 

The compound has four degrees of unsaturation (if it were a substituted alkane, its formula would be C,Hn,N), which indicates the presence of a phenyl ring, (A) dissolves in HCI and therefore is an amine. Since (A) releases with HONO, it is a 1° amine. Since (A) is optically active, it has a chiral C. The —NH cannot be on the ring since the two remaining C s cannot be positioned to give a chiral C. The —NH must be on the side chain. The compound is C H5CH(NH2)CH,. 

It may be desirable to define certain basic physical processes afresh, when we are dealing with systems essentially subject to two-dimensional conformations and hence two-dimensional constraints. This is the case for membranes, and also for a number of alkali salts of alkali -alkane carboxylates. These melt to give mesophases, in which the anions and cations are arranged in layerlike structures. At considerably higher temperatures the mesophases pass into isotropic ionic melts, but in the intervening temperature range they exhibit marked anisotropy of optical and physical properties. In these mesophases, which are ordered fluid... 

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