RESUMO
Oxymercuration-demercuration of a double bond in conjugation with the 4,6-dimethyl-s-triazin-2-yl substituent as in alkenes 1a,b gave anti-Markovnikov regioselectivity, which is explained by the electron-withdrawing nature of the triazinyl substituent. However, hydroboration of the conjugated alkenes with 9-BBN-H gave the corresponding alkanes 5a-c under normal workup conditions with or without oxidation. With time and without workup the hydroboration of 1b gave spectral evidence for the formation of intermediates 9-13 resulting from the migration of the 9-BBN moiety from the alpha-carbon to a ring nitrogen with concurrent formation of an exocyclic double bond to an alpha-carbon of the ring. Hydrolysis of the intermediates gave 5a-c. A possible mechanism involving successive allylic rearrangements is presented.
RESUMO
Reactions of lithium, sodium, and potassium salts of 2,4,6-trimethyl-s-triazine (1) with 2-halomethyl-4,6-dimethyl-s-triazine (2) (X = Cl, Br) in glyme have been studied and found to give 1,2-bis(4,6-dimethyl-s-triazin-2-yl)ethane (3), 1,2-bis(4,6-dimethyl-s-triazin-2-yl)ethene (5), 1,2,3-tris(4,6-dimethyl-s-triazin-2-yl)cyclopropane (6), 1,2,3-tris(4,6-dimethyl-s-triazin-2-yl)propane (7), and 1,2,3,4-tetrakis(4,6-dimethyl-s-triazin-2-yl)butane (8). It is proposed that product 3 is formed primarily via an S(N)2 reaction, whereas the remaining products are formed primarily via carbenoid reactions that are enumerated.
Assuntos
Hidrocarbonetos Halogenados/química , Triazinas/química , Ciclização , Compostos de Lítio/química , Modelos Químicos , Estrutura Molecular , Compostos de Potássio/química , Sais/química , Compostos de Sódio/química , Estereoisomerismo , Difração de Raios XRESUMO
This study was designed to develop a method of transferring gonion from lateral to frontal cephalograms, and to use this method as gold standard when evaluating observer performance in identifying gonion in frontal cephalograms. Observer ability to identify antegonion was also evaluated. There was a range of 28 mm in the observers' identification of gonion and a statistically significant deviation from gold standard. The factors "observer" and "cephalogram," regarded as random effects in an ANOVA analysis, and their interaction, each influenced the result, P < .001. The deviation from the mean of all observations for antegonion ranged 8 mm with "cephalogram" having a statistically significant influence. The results suggest that neither gonion nor antegonion can be routinely used as valid landmarks in frontal cephalograms. Gonion can, however, be used if first identified in a lateral cephalogram and transferred to a paired frontal cephalogram aided by radiographic indicators combined with a bilateral scrutiny of projection geometry in different planes through gonion and indicator.
Assuntos
Cefalometria/métodos , Cefalometria/normas , Análise de Variância , Assimetria Facial/diagnóstico , Humanos , Mandíbula , Variações Dependentes do Observador , Padrões de Referência , Reprodutibilidade dos TestesRESUMO
Drug partition into lipid bilayers in a cubic liquid-crystalline phase was investigated. Glyceryl monooleate was used to form the lipid bilayer in a reversed bicontinuous cubic liquid-crystalline phase. The reason for using the cubic phase is that it may coexist with an external aqueous phase, and that the phase boundary (cubic phase/aqueous bulk) is well-defined due to the stiffness of the cubic phase. This makes the cubic phase a potential candidate for high throughput screening (HTS) of the lipophilicity and the dissociation constant (if any) of drug compounds. Clomethiazole (CMZ), lidocaine, prilocaine and 4-phenylbutylamine (4-PBA) were chosen as model drug compounds. It was shown that it is possible to determine a pH-dependent apparent partition coefficient, Kbl/w, of a drug compound using a lipid bilayer expressed as a cubic liquid-crystalline structure. Good agreement was found when the resulting Kbl/w vs. pH curves for CMZ, lidocaine and prilocaine were fitted to a mathematical expression. This included the bilayer/water partition coefficient for the unionised and ionised drug respectively and the pKa of the drug. The effect of different experimental conditions; such as amount of cubic phase, temperature, agitation, sample preparation and interfacial area between the cubic phase and the aqueous bulk on the partition kinetics were investigated as well. The studies reveal that the time needed to reach partition equilibrium was, as expected, substantially reduced (from days to hours) by decreasing the amount of cubic phase, increasing the interfacial area between the cubic phase and the aqueous phase, and increasing the temperature and the agitation of the sample. It was also shown that the bilayer affinity of 4-PBA was increased when a zwitterionic lipid (i.e. dioleoyl phosphatidylcholine, DOPC) was incorporated in the bilayer.
Assuntos
Química Farmacêutica/métodos , Bicamadas Lipídicas/química , Bicamadas Lipídicas/metabolismo , Anestésicos Locais/farmacocinética , Butilaminas/farmacocinética , Clormetiazol/farmacocinética , Glicerídeos/química , Concentração de Íons de Hidrogênio , Cinética , Lidocaína/farmacocinética , Octanóis/química , Fosfatidilcolinas/química , Prilocaína/farmacocinética , Solubilidade , Água/química , Difração de Raios XRESUMO
The relationship between HLA factors and allergic contact dermatitis was examined in a series of 149 patients with unequivocal positive reactions to one or several allergens on epicutaneous testing. Nine statistically significant associations involving 6 different HLA antigens and 6 different allergens were found. Four allergens (chromium, formalin, balsam of Peru and wool alcohol) were positively associated with the B7 antigen. Furthermore chromium allergy was associated with A3, formalin allergy with A2 (negative association) and A9, nickel allergy with B8 and colophony allergy with B27. The B7 antigen and the combination A3+B7 showed significant regressions on number of allergies. The results fit the hypothesis that some HLA factors (like B7) may predispose for multiple contact allergy and others for allergen specific reactions.