Morpholino function

Quinoxalines with a cychc substituent other than an unsubstituted cycloalkyl, morpholino, phenyl, or piperidino group Quinoxalines bearing a substituent with more than six carbon atoms, except for an unsubstituted benzyl or benzoyl group Quinoxalines with two or more independent functional groups on a single substituent... 

A number of differently substituted A-(thiocarbamoyl)benzamidines (521) (R = Et, Bu NR2 = morpholino) have been complexed with Ni11. The ligands function in a bidentate manner, coordinating via the primary amine N and thione S atoms.1371... 

The latter sequence, as reported by Overkleeft, van Boom and coworkers, employs substrates of type 9-42 containing both azide and aldehyde functionalities. Treatment of 9-42 with PMe3 in MeOH at room temperature forms a cyclic imine 9-43 via an intermediate phosphazene. Following the addition of an acid and an isocyanide 9-43, products of type 9-44 are obtained. According to this scheme, enan-tiopure carbohydrate-derived azido aldehydes 9-45 and 9-48 led to the morpholino compounds 9-46 and 9-47, as well as to the pipecolic acid scaffolds 9-49 and 9-50, re-... 

Functionalized sugars and amino acids have been used to create unique morpholine scaffolds which were further elaborated to create a second generation of morpholino derivatives following the precepts of the build/couple/pair approach [73]. 

The addition of allenyl ether-derived anions to Weinreb [4] or to morpholino amides [5] follows a slightly different pathway (Eq. 13.2). For example, the addition of lithioallene 6 to Weinreb amide 7 at -78 °C, followed by quenching the reaction with aqueous NaH2P04 and allowing the mixture to warm to room temperature leads to cyclopentenone 9 in 80% yield [6]. The presumed intermediate of this reaction, allenyl vinyl ketone 8, was not isolated, as it underwent cyclization to 9 spontaneously [7]. These are exceptionally mild conditions for a Nazarov reaction and are probably a reflection of the strain that is present in the allene function, and also the low barrier for approach of the sp and sp2 carbon atoms. What is also noteworthy is the marked kinetic preference for the formation of the Z-isomer of the exocyclic double bond in 9. Had the Nazarov cyclization of 8 been conducted with catalysis by strong acid, it is unlikely that the kinetic product would have been observed. 

Enamines of cyclic ketones may also be used to prepare polyamides in a different type of condensation reaction (67MI11100). This polymerization involves reaction with diisocyanates (Scheme 46), with the enamine functioning as a difunctional reagent. Morpholino- and piperidino-enamines are the most effective monomers. 

The oligomers are comprised of (dimethylamino)phosphinyli-deneoxy-linked morpholino backbone moieties (Fig. I). These morpholino moieties contain a heterocyclic base recognition moiety of DNA (A, C, G, T) attached to a substituted morpholine ring system. When linked to each other via the (dimethylamino)phosphinylideneoxy function, the functional... 

Treatment of a number of substituted allylic alcohols 102 with morpholino sulfenyl chloride 103 at low temperature led to the formation of amidosulfoxy-lates 104, which rearranged readily during warm up to room temperature. In accordance with the proposed transition-state structures for [2,3]-sigmatropic rearrangements [6,40], the double bond geometry in 105 was found to be E for all cases with = H, CH3 (with a decreased selectivity for some functionalized... 

In order to functionalize the metal-coated substrates with MPA, they were immersed in an ethanolic solution of 0.02 M MPA. The MPA layer was activated using a solution of 0.002 M ethyl dimethylaminopropyl carbodiimide (EDC) and 0.005 M n-hydroxy succinimide (NHS) in 2-(Ai-morpholino) ethanesulfonic acid (MES) buffer solution (20 mM MBS, 0.1 M NaCl, pH5). The carboxylate groups of the MPA react with NHS in the presence of EDC to form NHS-esters which can then react with amine groups of proteins. After 15 min of activation, the metalized... 

Semiaminal (567) reacted with nucleophiles generally by a replacement of the hydroxy group Only few exceptions were known. For example, reaction of 567 with ketene or isocyanates caused acylation and displacement of the secondary amino moiety (equation 147) cyclopropanone (84) could be detected spectroscopically in one case. A similar removal of the amino function by tosyl isocyanate (571) was observed with 570, but here compound 574 was isolated in 47% yield (equation 148). 574 resulted from a subsequent addition of the initially formed products 572 and 573 . Steric reasons led to the sequence 570 - 574 the diastereomeric endo-morpholino semiaminal reacted with 571 by displacement of the exo-hydroxy group. 

Figure 3.84. Voxel obtained by irradiation of a mixed urethane acrylate oligomer and a urethane acrylate monomer in the presence of a mixture of benzoyl cyclohexanol and morpholino phenyl amino ketones at 780 nm using a 150-fs pulsed Ti sapphire mode-locked laser operating at 76 MHz, where light was focused by a 1.4 numerical aperture objective lens (a) scanning electronic microscopic images of the voxel and (b) longitudinal and lateral voxel size as function of the exposure time. (From Ref. [580] with permission of the American Institute of Physics.)...

Only one of the morpholino substituents in l,4-dimorpholino-7-phenylpyrido[3,4-dilute hydrochloric acid to give a mixture of 4-morpholino-7-phenylpyrido[3,4-d]pyridazin-l(2//)-one (18 37%) and 1-mor-pholino-7-phenylpyrido[3,4-[Pg.72]

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