Relativity, xiii

The halo-2-nitronaphthalenes (Table XIII) enable one to draw tentative conclusions about intranitclear and internitclear activation in the isoquinolines for which data are not available. These compounds are numbered so as to show their relation to their isoquinoline analogs. The relative rates are summarized in the following tabulation along with the ratio of the rates of piperidino-debromination to that of the appropriate bromonaphthalene (res. = resonance activation, ind. = inductive activation). 

The effect of solvent on the rate, E, and dS can be derived from the data on haloquinolines and their A-oxides (Tables X and XI), on halonitronaphthalenes (Tables XII and XIII), and on halodinitro-naphthalenes (Table XVI). Depending on the nature of the reaction, the relative reactivity of two compounds can be substantially different in different solvents. For example, piperidination of 2-chloroquinoline (Table X, lines 3 and 4) compared to 2-chloroquinoxaline (Table XV,... 

Recessively inherited coagulation disorders (RICDs) refer to relatively rare deficiencies in factor II, V, VII, and X-XIII resulting in either decreased clotting factor production or production of a dysfunctional molecule with reduced activity.19 The clinical severity of bleeding varies and generally is poorly correlated with the factor blood levels. Table 64-6 illustrates these clotting factor deficiencies and some of their characteristics. 

The five routes presented (A-E) can be detected in the mass spectra of all 3-hydroxytropane esters. However, their contribution to the general fragmentation may vary widely. Table XIII shows the relative intensities of the characteristic peaks, corresponding to the ions a-g given below for atropine 26 (Fig. 8). Route A strongly dominates the fragmentation of pyranotropane alkaloids, leading in the case of strobiline (112), for example, to the ion m/z 162 (ion e) (base peak) (Scheme 30). 

The energies reported in Table XIII for the externally bound forms are measured relative to that for the intercalative covalently bound form. Thus, the trans BPDE l(+)-N2(G) adduct is 10.1 kcal/ mole more stable and the trans BPDE II(-)-N6(a) adduct is 12.7 kcal/mole less stable in the externally bound form. Similarily, the trans BPDE Il(+)-N2(G) adduct is -13.8 kcal/mole more stable and the trans BPDE I(-)-N6(a) adduct is 7 5 kcal/mole less stable. Therefore, site IQ (intercalative covalent) which is favored by the i(-) isomer (5l) may be due to n6(a) and NH(c) adduct formation, specifically trans addition. 

The l(+) and Il(+) isomers are stereoselected by N2(G), whereas the i(-) and II(—) isomers are stereoselected by the n6(a) and 06(G) during intercalative covalent steps with trans addition. The l( + )-and Il(+)-N2(G) adducts are rearranged to an externally bound form with the pyrene in the minor groove, but the I(-)-N6(a) and II(-)-06(g) adducts remain quasi intercalated. This is determined by the relative energy change between the two forms as we see from Table XIII. However, there is a superposition of the two types of sites, IQ and IIX (51 57,58), and BPDE i(-) DNA adducts exhibit both types of binding. By symmetry, the cis BPDE l(-)-N2(G) adduct is predicted to behave similarily to the trans l(+)-N2(G) adduct. It should be externally bound. 

The 200GW line proved to be quite different, and of particular interest was the discovery that this line produced catharanthine (4) at levels about three times that of the intact plant (0.005%) (155,159,160). Curiously, the predominant alkaloid (60.48%) was strictosidine lactam (41), which is not normally seen in extracts of intact plants. Variation of the pH and added phytohormones did not significantly alter the pattern of alkaloids produced by this cell line (160). Further cell line studies (161) afforded one line (176G) which produced mainly ajmalicine (39) and lochnericine (73) and one (299Y) which apparently contained relatively inactive p-glucosi-dases, since the major alkaloids produced were strictosidine (33) (83%) and strictosidine lactam (41) (Table XIII). 

The data of Tables XII and XIII appear to demand an oxidation mechanism similar to that observed for fluorene itself and involving a carbanion intermediate. The greater acidity of fluorene and xanthene relative to diphenylmethane (approximately 10 pKa units) (28) apparently promotes ionization to yield a dianion which can react directly with oxygen or undergo a catalyzed reaction—e.g., by nitroaromatics or Fe111. 

XIII 3.1. Exemple d un schema ab lien A projectif (de dimension relative 1 si l on veut), sur une base S locale integre, noetherienne, de dimension 1, qui possede un S-torseur representable X, qui n est pas projectif, ou ce qui revient au mgme (XIII 2.4) qui est d ordre infini. 

The mean ionic activity coefficients of hydrobromic acid at round molalities (calculated by means of Equation 2) are summarized in Tables XI, XII, and XIII for x = 10, 30, and 50 mass percent monoglyme. Values of —logio 7 at round molalities from 0.005 to 0.1 mol-kg-1 were obtained by interpolating a least squares fit to a power series in m which was derived by means of a computer. These values at 298.15° K are compared in Figure 2 with those for hydrochloric acid in the same mixed solvent (I) and that for hydrobromic acid in water (21). The relative partial molal enthalpy (H2 — Hj>) can be calculated from the change in the activity coefficient with temperature, but we have used instead the following equations ... 

From the values given in Table XIII it is noted that Kd is apparently much more sensitive to variation of the nonbridging ligands than to variation of the metal ion. It is seen that Kd for all the aqua metal ions lies within a relatively narrow range of about 103 5 M-1. In contrast, chromium(III) and cobalt(III) amine complexes have Kd values which vary by at least five orders of magnitude. 

Under these relatively harsh conditions, the structure of the initial alkyl phenyl ketoximes does not much affect the yield of JV-vinylpyrroles (6), although a tendency towards some gains in yield with increasing number of carbon atoms in the alkyl radical is noted (Table XIII). 

Similar extensive calculation have also been performed with the data from PBMA and PHMA(8). Selected data for C-l of the poly (ri-alkyl acrylates) are shown in Table XIII. Rather than trying to closely fit each of the data sets with variable parameterization of T, p, and, values were chosen to encompass the relaxation characteristics of the entire temperature range used in the study. The same insensitivity of T to temperature variation observed in the experimental data is also seen in the calculated data when T is changed by two orders of magnitude (Table XIII). Even with a relatively narrow distribution (p=50) a large T field dependence and low NOEF is observed. 

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