Analogical approaches

Another design option that can be considered if a column will not fit is use of an intermediate reboiler or condenser. An intermediate condenser is illustrated in Fig. 14.5. The shape of the box is now altered because the intermediate condenser changes the heat flow through the column. The particular design shown in Fig. 14.5 would require that at least part of the heat rejected from the intermediate condenser be passed to the process. An analogous approach can be used to evaluate the possibilities for use of intermediate reboilers. Flower and Jackson," Kayihan, and Dhole and Linnhofl have presented procedures for the location of intermediate reboilers and condensers. 

GR Marshall, CD Barry, HE Bosshard, RA Dammkoehler, DA Dunn. The conformational parameter m drug design The active analog approach. ACS Symp Ser 112 205-226, 1979. YC Martin. Overview of concepts and methods in computer-assisted rational drug design. Methods Enzymol 203 587-613, 1991. 

In principle, the Maxam-Gilbert method can provide the total sequence of a dsDNA molecule just by determining the purine positions on one strand and then the purines on the complementary strand. Complementary base-pairing rules then reveal the pyrimidines along each strand, T complementary to where A is, C complementary to where G occurs. (The analogous approach of locating the pyrimidines on each strand would also provide sufficient information to write the total sequence.)... 

An analogous approach starting from monoximes 44 derived from 1,2 diketo derivatives was described in 2004 [44]. Reaction with different aldehydes in the presence of NH4OAC in acetic acid at 200 °C under microwave irradiation for 20 min gave the corresponding trisubstituted imidazoles 45... 

Marshall GR, Barry CD, Bosshard HE, Dammkoehler RA, Dunn DA. The conformational parameter in drug design The active analog approach. Computer-assisted drug design. ACS Symposium Series 112. Washington DC American Chemical Society, 1979. p. 205-26. 

In the recently published structural analog approach [44], logP of unknown chemicals is calculated from the known experimental log P of their closest struc-... 

An analogous approach has been utilized to generate the central piperazine ring of 337 via dimerization of 5-amino-4-bromo-2-phenyl-2,4-dihydro-pyrazol-3-one 336 under basic conditions in good yield (Equation 91) <2003HAC211>. 

Another refinement, that avoids the necessity of developing suitable fecal extraction and chromatographic methods, is to dose the radiolabeled compound by both the i.v. and p.o. routes in two separate studies. Knowing that, by definition, the whole of the i.v. dose must have been bioavailable, a comparison of the proportion of the dose in the urine after the two different routes allows estimation of the percent absorbed. An analogous approach can be used without the use of a radiolabel, when the urine from the two studies is analyzed either for the parent compound or, more usually, for a major common metabolite. Assuming quantitatively identical clearance after both the i.v. and p.o. doses, the ratio of the amounts of analyte in the two experiments gives the absorption. 

The variation in the antiscorbutic activity displayed by the various analogs of L-ascorbic acid makes it abundantly clear that the activity is dependent upon the stereochemical configuration of the molecule as a whole, and it would appear that the more closely the structure of a particular analog approaches that of the natural Vitamin C the greater will be the antiscorbutic power. Support for this view is illustrated by 6-desoxy-L-ascorbic acid which is obtained from L-sorbose.2 -80 Condensation of L-sorbose with acetone gives a mixture of 2,3-isopropylidene-L-sorbose (LII) and the diisopropylidene derivative. Treatment of LII with p-toluenesulfonyl chloride yields l,6-ditosyl-2,3-isopropylidene-L-sorbose (LIII). The greater reactivity of the tosyl group at C6 enables... 

An efficient procedure for the synthesis of 5-aminoisoxazoles starting from BENAs (Scheme 3.242) was described in Section 3.5.4.2.2.1. An analogous approach to the synthesis of aminooxazoles can be successfully used in the case of silyl derivatives of a-cyano-substituted oximes (476a,b) (Scheme 3.255). 

Heavy metals are removed from the atmosphere by means of surface uptake and precipitation scavenging. The ecosystem-specific dry deposition scheme is based on the resistance analogy approach and distinguishes 16 land use types. Wet removal by precipitation considers both in-cloud and sub-cloud scavenging. 

The hexahydro-l//-pyrrolo[2,l-f][l,4]oxazin-l-one 82 (obtained by radical cyclization see Section 11.11.7.3) was transformed into the proline derivative 83 by hydrogenation in the presence of the Pearlman s catalyst and a stoichiometric amount of trifluoroacetic acid (TFA) (Scheme 10). This reaction led with high yield to the disub-stituted proline 83 in an enantiomerically pure form <2003SL1058>. In an analogous approach, the chiral (4/ ,7/ ,8aA)-methyl 6,6-dimethyl-l-oxo-4-phenylhexahydro-l//-pyrrolo[2,l-r-][l,4]oxazine-7-carboxylate 84 was hydrogenated on Pd(OH)2 in the presence of TFA to give enantiomerically pure 5,5-dimethylproline derivatives 85 <2001SL1836> (Scheme 10). 

In an analogous approach, the chiral stabilized azomethine ylide 165, generated in situ via Lewis acid-catalyzed condensation of (53 )-5-phenylmorpholin-2-one 164 with 2,2-dimethoxypropane, was trapped diastereoselectively with singly and doubly activated dipolarophiles such as the acrylate (Scheme 24). The cycloadduct 84 was then employed to furnish enantiomerically pure 5,5-dimethylproline derivatives (see Section 11.11.6.3), <2001SL1836>. 

In an analogous approach explored by Dixneuf et al., a conjugated enynyl carbonate is converted into an oxolenone or a bicyclic lactone in significant yields via double carbonylation in the presence of methanol (Scheme 22) [128]. When a neighboring carbonyl group is present in the substrate, it can also participate in palladium-catalyzed cyclization-carbonylation. Indeed, 4-yn-l-ones lead to cyclic ketals that can be easily converted into 2-cyclopentenone carboxylates in an acidic medium (Scheme 22) [129]. 

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