Free tertiary

Cool the solution thoroughly in ice-water, and then make it alkaline by the cautious addition (with stirring or shaking) of a solution of 80 g. of sodium hydroxide in ca, 150 ml. of water. Now isolate the free tertiary amine by steam-distillation into hydrochloric acid, etc., precisely as for the primary amine in Stage (D), but preferably using a smaller flask for the final distillation. Collect the 2-dimethylamino- -octane, b.p. 76-78715 mm. Yield, 13-14 g. At atmospheric pressure the amine has b.p. 187-188°. 

The vast majority of compounds having the bisindole nucleus characteristic of the vinca structure with antitumor activity in experimental tumor systems bear a carboxyl function and a free tertiary hydroxyl group at C-3 of the vindoline moiety. The group of semisynthetic derivatives distinguished by the presence of a C-3 spiro-fused oxazolidine-l,3-dione are important exceptions to this generalization. 

An efficient resolntion of the racemic lithinm tert-bntylphosphine-borane complex 203 dnring deprotonation by n-BnLi/(—)-sparteine (11) and alkylation was reported by Liv-inghonse and Wolfe (eqnation 47) . One of the epimers 204/cp/-204 on warming to 0 °C crystallizes during a dynamic thermodynamic resolntion, and reaction with alkyl halides fnmishes the alkylation prodncts 205 with high ee values. Applying dihalides, essentially enantiomerically pure diphosphines snch as 206, besides few of the mcio-diastereomer, were obtained. Borane is removed by treatment with diethylamine to yield the free tertiary phosphines 207. 

N-Bromosuccinimide (NBS) reacted with the free tertiary alcohol group of veracevine D-orthoacetate triacetate 34 to cause a (presumably) free radical insertion into ring F, giving the carbinolamine 35. Cevine D-orthoacetate triacetate similarly gave 36, which on alkaline hydrolysis gave 37 (see Table XVIII) (47,53). Treatment of triacetylcevine with NBS gave 38 (47). 

Combining UF or MF membrane technologies with biological reactors for the treatment of wastewater in a one-stage process has led to the generation of the MBR concept in which MF or UF membranes have replaced the traditional sedimentation tank. An efficient clarification of the treated wastewater is achieved, membranes can reduce the disinfection practices such as chlorination, and a pathogen-free, tertiary quality effluent is thus obtained [11]. 

The quaternary salts of aromatic heterocyclic bases react with nucleophilic reagents much more readily than do the free tertiary bases. The increased reactivity reflects the immonium, as distinct... 

One problem is that coordinated oxygen oxidizes the tertiary phosphine ligands to form free tertiary phosphine oxide. Often the course of this reaction is solvent dependent in ethanol the phosphine oxide is more likely to be formed than in hydrocarbon solvents.945 The oxidation of ligands also occurs in the solid state reaction.942... 

Neurine. Neurine is trimethylvinylammonium hydroxide, C5H13NO [463-88-7]. Tertiary amines and their salts vinylate readily at low temperatures with catalysis by free tertiary amines. 

Cathedulin K17 (C59H62N2O23) (62), isolated as crystalline but only as a 2.5-mg sample, revealed in its H-NMR spectrum an euonyminol core carrying eight ester groups, with the usual free tertiary 4-hydroxyl. The same 3,13-bridging edulinic residue was present as was found in K19. Two acetate units, a benzoate. 

Migration of the double bond of the cyclic olefin formed by the RCM has also been observed [35]. RCM of the diene 77 by 69 in refluxing dichloromethane resulted in the formation of considerable amounts of the unexpected cyclic olefin 79 in addition to 78 (Eq. 12.31) [35a[. It was also noted that the formation of 79 was effectively suppressed by the addition of amine to the dichloromethane solution or employment of diethylether as solvent, which implies participation of proton in the isomerization reaction. It was also noted that a terminal vinyl group with a free tertiary allylic hydroxyl group accelerates RCM, rather than its methyl ether derivative. These results suggested some interaction between the alkylidene complex 69 with hydroxyl proton in situ. 

Kreulen H, Smolders CA, Versteeg GF, and Swaaij WPM. Selective removal of H2S from sour gases with microporous membranes. Part n. A liquid membrane of water-free tertiary amines. J Mem Sci, 1993 82(1-2) 185-197. 

By controlling the reaction conditions it was possible to afford selectively the acetylation of secondary hydroxyls obtaining the triacetylderivative 13c in which there is the only free tertiary hydroxyl. Triacetylderivative 13c undergoes to dehydration by treatment with thionyl chloride in pyridine. Such reaction allows the regiospecific achievement of the only isomer 13d which has the double bond in 1,2 position. 

Neckers and his co-workers have investigated the photochemical reactivity of ammonium borate salts both in solution and tethered to a polymer substrate as a means of producing free tertiary amines. The reactions are carried out in acetonitrile solution on the benzoylbenzyl molecules (201) using wavelengths > 300 nm. Irradiation of (202) results in the formation of the products shown in Scheme 6. More detailed studies examined the influence of different borate salts as the counterions to the ammonium salts. Some of these results are shown for the decomposition of the salt (201). From these data, it can be seen that the most efficient quantum yield for the release of tri- -butyIamine is obtained with the triphenylbutylborate counterion. 

The metabolite, however, was not enantiopure and its absolute configuration had only been estimated empirically, based on the reaction mechanism. To obtain the enantiopure diol 42 and to determine its absolute configuration unambiguously, the method of CSDP acid was apphed to (+)-42 (Fig. 9.7) [40]. In this case, only the primary alcohol part was esterified, and the diastereomeric mixture obtained was clearly separated by HPLC on silica gel hexane/EtOAc = 4 1,7= 1.27, Rs = 1.14 (entry 29 and Fig. 9.8). In this HPLC, the presence of a free tertiary hydroxy group is important, because the protection of the tertiary alcohol group led to poor separation. 

This reaction is carried out as follows First the formic ester is prepared of the tertiary alcohol that is to be esterified with a desired carboxylic acid. This is done by heating the tertiary alcohol for several days with the mixed anhydride of formic and acetic acid. This formic ester, isolated as usual, is mixed with an equivalent amount of the methyl ester of the other carboxylic acid, treated with 0.05 equivalent each of the free tertiary alcohol and sodium, and heated at 100-120°. The lowest-boiling component of the equilibrium mixture slowly distils off, namely, methyl formate. The reaction is sometimes quite vigorous and is usually complete in 3-4 h. After the free alkali has been neutralized with acetic acid, the distillation residue is worked up in the usual way. 

The determination of amine oxides is straightforward they can be titrated in acid solution with sodium dodecyl sulphate or NaTPB, either poten-tiometrically or in a two-phase system, for which purposes the solution must be at least 0.1 M in hydrogen ion, and they can be titrated with acid. However, for quality-control purposes it is necessary to determine the free tertiary amine content. This can be done by potentiometric titration, either in a solvent which permits discrimination on the basis of base strength, or before and after removal of the amine oxide. Methods are described for both of these. 

Akzo Chemie Method VE/2.008 Fatty amine oxides Determination of amine oxide and of free tertiary base. 

Free tertiary amine associates with the secondary hydrojQrl groups and leads to an amino alcohol, M (Rxn. 29). The amino alcohol forms an activated complex, C2, with the epoxy dipole (Rxn. 30). C2 dissociates to form the branched product (Rxn. 31). This mechanism accounts for the observation that branching takes place only after a certain extent of epoxy conversion, i.e., when the fi ee amine concentration increases as it is released fi om the phenol ion pair BPi in Rxn. 24. Free amine is a true catalyst in this branching reaction since it is r enerated. 

More recently, cationic polymerization of oxetane has been studied in the presence of an ether additive that converts strained tertiary oxonium ion active species into strain-free tertiary oxonium ion (dormant species) that may be reactivated by monomer addition as shown in Scheme... 

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