Addition of morpholine

Electrophilic reaction can account for the additions of morpholine or phosphonyl (Scheme 14), or... 

Environmentally the most important variables are pH, oxygen content and temperature of the water (Figure 1.96). In single phase conditions both high pH and additions of low levels of oxygen have been used to prevent erosion corrosion . However, because of partitioning effects between water and steam this is more difficult to achieve in two-phase flow. Although additions of morpholine or AMP (2-amino-2-methyl-propan-l-ol) have been successfully used to control pH. 

A solvent-free synthesis of substituted spiroindolinonaphth[2,l-fo][l,4]oxazines through condensation of 2-methylene-l,3,3-trimethylindoline derivatives with 1-nitroso-2-naphthol under microwave irradiation has been described by Fedorova and colleagues (Scheme 6.263) [453], In a typical reaction, an equimolar mixture of the two starting materials was irradiated at 65-110 °C for 15 min to produce the desired spiroindolinonaphth[2,l-fo][l,4]oxazines, which are useful as photochromic compounds. In a related procedure, addition of morpholine to the reaction mixture led to the formation of the corresponding 6 -amino-functionalized spiroindolino-naphth[2,l-fo][l,4]oxazines, which exhibit a strong hypsochromic color shift (not shown) [453]. 

The addition of morpholine to 2,3-dihydrofuran in the presence of palladium(II) thiocyanate-bis(triphenylphosphine) yields 2-(morpholin-4-yl)tetrahydrofuran (276)303. Irradiation of mixtures of 2-(2-methylpropenyl)phenol (277) and alkylamines yields adducts, e.g. 278 with isopropylamine304. 

The influence of the substrates 1-octene and morpholine was measured by repeating the cloud titrations with addition of these substances to determine the appropriate composition of the solvent mixture for the reaction. While the addition of 1-octene has almost no effect on the TMS systems the addition of morpholine leads to a decrease of the miscibihty gap (Fig. 14). As morphoHne itself is semi-polar and can be used as a mediator a smaller amount of s3 is needed to obtain a homogeneous system. 

The Michael-type addition of morpholine to propiolic, tetrolic, phenylpropiolic, and acetylenedicarboxylic esters has been described by Postovskii et al.500... 

Addition of morpholine, H2N-GlyGlyOH or N2H4 to HC=CCOMc gives the expected oxo enamines via a second-order process (first order in each reactant). The product of the hydrazine addition, H2NNHCH=CHCOMe, reacted with additional... 

Shenhav, Rappoport and Patai examined the kinetics of addition of morpholine and pyrrolidine to various activated olefins in methanol and obtained an order similar to Figure 1, as shown in Table l10. They pointed out that data in the literature suggested that CC>2Me and CN are sometimes reversed11. 

Relative rate constants for the addition of morpholine to CH2=CHZ in methanol10. 

Nitromethane. Addition of morpholine makes nitromethane susceptible to initiation by a detonator.4... 

Butadienes of this type are readily available by addition of morpholine to 3-alkene-l-ynes in the presence of Hg(OAc)2 (45-65% yield).1... 

Complex 49 catalyzes, among other reactions, the addition of morpholine to methylacrylonitrile giving the amination product with modest selectivity (37% ee) (Scheme 35). In order to obtain catalytically active species with palladium, complex 48 was converted into dicationic derivatives of the general type [Pd(NCCH3)(PCP)](PF6)2. Using this catalyst, the addition of morpholine to methylacrylonitrile could be achieved with 47% ee. Further improvement in selectivity was obtained by the introduction of methyl substituents at the 3- and 5-positions of the phenyl groups in diphenylphosphanyl derivative leading to ee s of over 70% [94]. 

Alcohol protection. Primary and secondary hydroxyl groups are esterified by 1 in the presence of pyridine (71-92% yield). The usual selectivity for acylation of primary versus secondary hydroxyl functions obtains. The resulting 2-di-bromomethylbenzoates 2 are deprotected under neutral conditions by silver perchlorate mediated hydrolysis to 2-formylbenzoate esters 3 (2,6-lutidine or 2,4,6-collidine is added to maintain a virtually neutral reaction medium). Addition of morpholine then leads to rapid dcacylation with release of the alcohol in high yield... 

The addition of morpholine to cycloprop-l-ene-l-carboxylates 5 was also successful. ... 

In the majority of reactions studied, a constant selectivity relationship does not apply. In the addition of morpholine, glycine, and MeO- to CH2=CHX systems, X=PO(OEt)3, CONH2, CN, C02Me, S02Me, COMe, COPh, and CHO plots of log k versus pKa (MeX) are linear but not parallel (28) thus, the reactivity ratios for each pair of nucleophiles are not constant. 

Aliphatic primary and secondary amines react with C q and C70 rather efficiently, typically forming multiple addition products [76,115,116], One of a few examples in which the reaction products are well characterized is the nucleophilic additions of morpholine and piperidine to Cjo in the presence of oxygen, resulting in the formation of products 11-13 [76],... 

The ketone is protonated, and nucleophilic addition of morpholine to the ketone then proceeds, but in this case only elimination of the intermediate to an enamine is possible. 

Pd(OAc)2 was reacted with an imidazolium salt with two ferrocenyl phosphine substituents to give a complex 122 with a chiral tridentate PGP ligand. Treatment with [Et30]PF6 gave a dicationic complex, [Pd(PGP)(NGMe)](PF6)2, which was an effective catalyst for the enantioselective addition of morpholine to... 

A method for the asymmetric hydrogenation of seven-membered cyclic imines of benzodiazepinones and benzodiazepines has recently been published. The chiral cyclic amines generated from these reactions make up the cores of many natural products and clinical drugs. Iridium-bisphosphine catalyst systems were investigated and found to give promising enantios-electivities which could be improved upon addition of morpholine tri-fluoroacetate. The optimum conditions, applied to model compound 50, are shown in Scheme 14.19, giving 51 in excellent enantioselectivity and complete conversion. 

---