Tertiary amines and amides

Importantly, unmodified PAMAM and PPI dendrimers have functional groups within their interior as well as on their exterior. Specifically, PAMAM dendrimer interiors contain both tertiary and secondary (amide) amines, and both of these are ligands for many metals [19,82,83,87,89]. For example, Turro et al. [87, 89] investigated the binding of Cu + ions to integer and half-integer PAMAM dendrimers. Their EPR results indicated that Cu + can bind to both exterior acid and amine groups, as well as to interior tertiary amines and amides. Similarly, PPI dendrimers have interior tertiary amines and are also able to bind metal ions, such as Cu +, Zn +, and Ni + within their interior [90,100]. 

SCHEME 38. Ruthenium-catalyzed reaction of tertiary amines and amides with TBHP... 

Shono [25] pointed out that the microsomal oxidation of tertiary amines and amides occurs via the same intermediates as the anodic oxidation in methanol solution. The dealkylation of 7V-methyl-7V,7V-dialkyl amines by both methods results in almost the same A -demethylation/A/ -dealkylation ratio. This method has been used in the pharmaceutical industry for the easy supply of metabolites of pharmaceuticals. 

Sulfation of primary amines is more common than sulfation of secondary amines. Sulfation of tertiary amines and amides is rare (Gamage et al., 2006) ... 

The RUO4 catalytic system oxidizes secondary alcohols to ketones and primary alcohols to carboxylic acids. Alkenes can be oxidized completely, to produce the corresponding carbonyl compounds, or partially, to produce epoxides this transformation will be discussed below. In addition, methylene carbons adjacent to certain functional groups can be oxidized to the corresponding carbonyl ethers are converted to esters, tertiary amines and amides to amides and imides. 

V te will not introduce the nomenclature for secondary and tertiary amines and amides in this text... 

PAMAM dendrimers are one of the most utilized dendrimers for the synthesis of nanoparticles. PAMAM dendrimers have tertiary amine and amide groups that can bind metal precursors at a tunable ratio as shown by Step (1) in Fig. 4.1 [52]. These metal precursors are reduced chemically to form metal nanoparticles inside the... 

The in-out bicyclic amines prepared by Simmons and Park bear a remarkable semblance to the cryptands but lack the binding sites in the bridges. As a result, these molecules interact with electrophiles in a fashion similar to other tertiary amines and generally do not exhibit strong interactions with alkali or alkaline earth metal ions. The in-out bicyclic amines are prepared by reaction of the appropriate acid chlorides and amines in two stages to yield the macrobicyclic amine after reduction of the amidic linkages. A typical amine is shown above as compound 18. 

In classical organic chemistry, nltrosamlnes were considered only as the reaction products of secondary amines with an acidified solution of a nitrite salt or ester. Today, it is recognized that nitrosamines can be produced from primary, secondary, and tertiary amines, and nltrosamides from secondary amides. Douglass et al. (34) have published a good review of nitrosamine formation. For the purposes of this presentation, it will suffice to say that amine and amide precursors for nitrosation reactions to form N-nitroso compounds are indeed ubiquitous in our food supply, environment, and par-... 

The hydrochloric acid is removed by the strong tertiary base, methyldibutylamine, which has a soluble hydrochloride. In B.P. s 631,549 and 652,981 it was shown that compound (II) could be prepared by the action of dimethylamine on P0C13 in chloroform containing an excess of methylbutylamine. The further reaction with water is very conveniently carried out in the same system by adding an excess of aqueous sodium hydroxide solution. The chloroform layer contains the tertiary amine and (I). The solvent and amine are stripped off leaving the product. Side reactions take place, and the commercial product also contains some triphosphoric pentadimethylamide (I A) and smaller amounts of other phosphoric amides. The compound (I A) is itself also a valuable systemic insecticide. 

In the above discussion on the mu/kappa receptor selectivity of the U-50488 (5) series, the steric properties of the tertiary amine and the distance between the amide and the aromatic ring were cited as important factors. This has been exploited by the Upjohn company to give the arylformamide-dimethyl-amine derivative (52) which is an analgesic in the mouse tail flick test (ED50 = 0.2 mg/kg s.c.) and causes mu-opioid like side-effects such as Straub tail, arched back and increased locomotor activity [81]. These behavioural effects and the association constant for the morphine receptor of compound... 

In the commercial flow sheets, these elements are left in the aqueous raffinate after platinum and palladium extraction. Indium can be extracted in the -l-IV oxidation state by amines (see Fig. 11.11), or TBP (see Figs. 11.10 and 11.12). However, although the separation from rhodium is easy, the recovery of iridium may not be quantitative because of the presence of nonextractable iridium halocomplexes in the feed solution. Dhara [37] has proposed coextraction of iridium, platinum, and palladium by a tertiary amine and the selective recovery of the iridium by reduction to Ir(III). Iridium can also be separated from rhodium by substituted amides [S(Ir/ Rh) 5 X 10 ). 

Protecting groups are needed for the few oxidations reported for primary and secondary amines, but there is a substantial chemistry of oxidation by RuO of tertiary amines and of amides... 

In 1989, a method for the peroxysilylation of alkenes nsing triethylsUane and oxygen was reported by Isayama and Mnkaiyama (eqnation 25). The reaction was catalyzed by several cobalt(II)-diketonato complexes. With the best catalyst Co(modp)2 [bis(l-morpholinocarbamoyl-4,4-dunethyl-l,3-pentanedionato)cobalt(n)] prodnct yields ranged between 75 and 99%. DiaUcyl peroxides can also be obtained starting from tertiary amines 87, amides 89 or lactams via selective oxidation in the a-position of the Af-fnnctional group with tert-butyl hydroperoxide in the presence of a ruthenium catalyst as presented by Murahashi and coworkers in 1988 ° (Scheme 38). With tertiary amines 87 as substrates the yields of the dialkyl peroxide products 88 ranged between 65 and 96%, while the amides 89 depicted in Scheme 38 are converted to the corresponding peroxides 90 in yields of 87% (R = Me) and 77% (R = Ph). 

Acylation of A-hydroxy-2-phenylbutyramidine (112-1) with 3-chloropropionyl chloride in the absence of an added base proceeds as might be expected to give the product (112-2) from acylation on the more basic nitrogen. Heating this compound leads to the formation of the oxadiazole (112-3) almost certainly via the enol tautomer of the amide. Displacement of the terminal chlorine with diethylamine leads to the tertiary amine and thus proxazole (112-4) [123], a compound that is said to exhibit antispasmodic activity. 

The primary (1), secondary (2 ), tertiary (3) and quaternary (4) nomenclature is used in a number of situations to define a carbon centre, or to define functional groups like alcohols, halides, amines and amides. Identifying functional groups in this way can be important because the properties and reactivities of these groups vary depending on whether they are primary, secondary, tertiary or quaternary. 

Fig. Primary, secondary, tertiary, and quaternary carbon centres. Amines and Amides...

Amines and amides are classified as primary, secondary, tertiary, or quaternary depending on the number of bonds from nitrogen to carbon(Following fig.). Note that a quaternary amine is positively charged and is therefore known as a quaternary ammonium ion. It is not possible to get a quaternary amide. 

Manganese dioxide conveits tertiary amines into amides. For exatiqrle, N,N-dimethylaniline gives N-methyl-N-phenylformamide in 78% yield and N-phenylpyrrolidine yields N-phenylformamide in 48% yield. 4 Dimethylaminocyclohexane on oxidation leads to cyclohexanone in 8S% yield. There is also... 

Redaction of amides to amines, Primary, secondary, and especially tertiary amides are reduced by diborane to the corresponding amines rapidly and almost quantitatively. The reaction is carried out at 25° in the case of tertiary amines, and at reflux for primary and secondary amines. The method is not suitable for unsaturated... 

Selective oxidative demethylation of tertiary methyl amines is one of the specific and important functions of cytochrome P-450. Novel cytochrome P-450-type oxidation behavior with tertiary amines has been found in the catalytic systems of low-valent ruthenium complexes with peroxides. These systems exhibit specific reactivity toward oxidations of nitrogen compounds such as amines and amides, differing from that with RUO4. It was discovered in 1988 that low-valent ruthenium complex-catalyzed oxidation of tertiary methylamines 53 with f-BuOOH gives the corresponding a-(f-butyldioxy)alkylamines 54 efficiently (Eq. 3.70) [130]. The hemiaminal type 54 product has a similar structure to a-hydroxymethylamine intermediate derived from the oxidation with cytochrome P-450. 

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