O-Alkylamines

Antiviral activity was established for bicyclo[n.l.O]alkylamines (691) Bifunctional ammonium salts of type 692 were claimed to be useful as disinfectants application of the bicyclo[n.l.O]alkyl ammonium group as counterion in penicillin salts has been tested, e.g. Ref. 341. A iV-cyclopropyl moiety is also part of the antibacterial agent ciprofloxacin (BAY 09867) (693) . 693 shows strong antibacterial activity especially against Enterobacteriaceae it was considerably more active than other agents tested . 

Other derivatives were synthesized where the 3 substituent was in turn an halide [14], a nitrogen quaternary salt-containing side chains [15], an O-alkylamine [15], a nitro group [15], an azido group [16], a functionalized C-2 unit [17]. Several fluorinated analogues of Combretastatins A-1 and A-4 were synthesized and their in vitro anticancer properties determined. The most active fluoro analogue 3 -deoxy-3 -fluoro-combretastatin A-4 retains the potent cell growth inhibitory properties of Combretastatin A-4 [14]. 

Reaction of alkyl- or arylmagnesium halides with bicyclic )V,0-acetals 2 gave the expected alkyl or arylbicyclo[n.l.O]alkylamines 3,22.4-4,45 endo-. v avlO compounds were formed in this reaction the cis or trans linkage of the bicyclic systems was not influenced by the substitution. Alkyllithiums failed to react with the A(,0-acetals. An aminoalkylation of alkyl-lithiums, however, was reported in the substitution of the tetrazole moiety in (7-mor-pholinobicyclo[4.1.0]hept-l-yl)tetrazole by alkyllithium. ... 

Triazine 3-oxide ring from o-alkylamines f rimido[5,4-d] [1,2,3] triazine-6,8(5H,7H)dione 3-oxides... 

O-Alkylation of 4-hydroxy-3-morpholino-l,2,5-thiadiazole 132 has been achieved with the chiral cyclic chloro-methyl sulfite 133 which subsequently suffers ring opening on treatment with simple alcohols <2001RCB436> or alkylamines <2002RJ0213> to afford the timolol analogues 134 with very little racemization (Scheme 20). This indicated an almost exclusive attack of the oxy anion on the exocyclic carbon atom and is a significant improvement on the previous oxirane method, which suffers from racemization. An alternative biocatalytic asymmetric synthesis of (A)- and (R)-timolol has also appeared <2004S1625>. 

Amines are another important group of analytes. Mellbin and Smith [72] compared three different fluorescent reagents, dansyl chloride, 4-chloro-7-nitrobenzo-1,2,5-oxadiazole, and o-phthaldialdehyde, for derivatization of alkylamines. The dansyl tag was found to be the most effective. Hamachi et al. [73] described the application of an HPLC-POCL method for determination of a fluorescent derivative of the synthetic peptide ebiratide. Another comparative study was done by Kwakman et al. [74], where naphthalene-2,3-dialdehyde and anthracene-2,3-dial-dehyde were evaluated as precolumn labeling agents for primary amines. The anthracene-2,3-dialdehyde derivatives were not stable, especially in the presence of hydrogen peroxide, and the POCL detection of these derivatives was therefore... 

CARBAMIC acid, krt-BUTYL ESTER, 48, 32 Carbazole, 2-nitro-, 46, 85 Carbazoles, from o-azidobiphenyls,46,SS from o-nitrobiphenyls and triethyl phosphite, 48, 115 2-Carbethoxycyclodecanone, 47, 22 2-Carbethoxycyclododecanone, 47, 22 2-Carbethoxycyclohexanone, 45, 82 2-Carbethoxycyclononanone, 47, 22 2-Carbethoxycyclooctanone, 47, 20 t-Carbinamines, see /-Alkylamines Carbodiimide, [3-(dimethylamino)-propyl]ethyl-, hydrochloride, 48, 83... 

Deprotonation is the most convenient manner for the generation of alkyllithium derivatives. However, most of the potential precursors have insufficient acidity. Notable exceptions are those substrates which lead to dipole-stabilized carbanions , among them O-alkyl iV,A-dialkylcarbamates 15 ° and A-Boc-(cyclo)alkylamines 18 ° (equation 5). A... 

The lipids used in the syntheses of neoglycolipids are often commercially available most of the long-chain carboxylic acids, n-alcanols, n-alcanethiols or -alkylamines are readily available as well as a,o)-dicarboxylic acids, diols or diamines useful for the syntheses of bola-amphiphiles. 

The dichalcogenides of group VI do not readily form intercalates with organic molecules. But n-alkylammonium compounds can be prepared by ion-exchange reactions of the hydrated sodium intercalation compounds such as Na j(H20)o g M0S2. Alkylammonium compounds prepared by this route show lattice expansions that depend on the alkyl chain length, very similar to the MX2-n-alkylamine systems described above. This raises the fundamental question whether protonated amines are the actual intercalated species in both the cases, involving reduction of the host. In fact, this constitutes the basis of the new model for the intercalation reaction in MX2 proposed by Schollhorn (1980). 

Acceptor-substituted haloarenes have been successfully used to O-arylate phenols by aromatic nucleophilic substitution (Table 7.14). The most common arylating agents are 2-fluoro-l-nitroarenes, 2-halopyridines, 2-halopyrimidines, and 2-halotriazines. When sufficiently reactive haloarenes are used, the reaction proceeds smoothly with either the arylating agent or the phenol linked to the support. The thallium(III) nitrate catalyzed arylation of phenols with aryl iodides has been used for macrocycli-zations on solid phase [184], Burgess and co-workers have developed a solid-phase synthesis of 3-turri mimetics based on ring-closure by aromatic nucleophilic substitution (Entry 4, Table 7.14 see also Table 10.5). Phenols, alkylamines, and thiols have been successfully used as nucleophiles for this type of macrocyclization [185],... 

---