With carboxamides

A process for the preparation of pyrimidine A-oxides from carboxamide oximes has been developed (98T4387). Direct oxidation of pyrimidines is inconvenient for the preparation of nonsymmetric substituted pyrimidines because it gives a mixture of oxidation products ( -N- and 3-A-oxides). Methoxybutenone with carboxamide oximes regioselectively forms A-oxides of pyrimidines 281, which indicates... 

Amides with an unsubstituted —NH2 group are named by replacing the -oic acid or -ic acid ending with -amide, or by replacing the -carboxylic acid ending with -carboxamide. 

Another domino Michael addition/SN sequence has been elaborated by the group of de Meijere. It was discovered that upon basic treatment of 2-chloro-2-cyclopropyl-idenacetates 2-168 with carboxamides 2-169 in MeCN, 4-spirocyclopropane-anne-lated oxazoline-5-carboxylates 2-172 are formed (Scheme 2.40) [91]. As intermediates, the carbanion 2-170 and 2-171 can be proposed. 

The application of arene-catalyzed hthiation to cleave an oxygen-nitrogen bond has only been used with carboxamides and nitrones. 

The majority of reactions required to form these types of heterocycles involve the condensation of a 1,2-diamine and a 1,2-dicarbonyl compound, as shown in Equation (46) <2000H(52)423>. Other examples include the reaction of enaminones with carboxamides (Equations 47 and 48) <199681012, 2000T8489> and the cyclocondensation of a-ketoesters (Equation 49) <2001FA933>. Nicolaou and Li have prepared 99 and 100 by reaction of the diol 101 with a-bromoisobutyraldehyde (Equation 50) <2001AGE4264>. 

Amides are named by replacing the -oic acid or -ic acid suffix of the parent carboxylic acids with the suffix -amide, or hy replacing the -carboxylic acid ending with -carboxamide. Alkyl groups on nitrogen atoms are named as substituents, and are prefaced by N-or N,N-, followed by the name(s) of the alkyl group(s). 

The functional groups can be attached to the macrocyclic ligands by using methods similar to Eqs. (1) and (2). The Ni(II) complexes of pentaaza macrocyclic ligands, 3b-3g, in which functional groups are appended at the bridgehead nitrogen atom, are prepared by the template reaction of [Ni(2,3,2-tet)]2+ and formaldehyde with carboxamide or sulfonamide in the presence of base. The complexes 3b and 3c are... 

Electron-rich, electron-poor, and hindered styrenes (ArCH=CH2) undergo hydroamination with carboxamides (e.g. PhCONH2) in the presence of a 1 2 mixture of [PtCl2(H2C=CH2)]2 and (4-CF3CeH4)3P (5 mol%) in mesitylene at 140 °C for 24 h, to produce (PhCONH)CH(Me)Ar in moderate to good yields with excellent Markovnikov selectivity.90... 

Bromopyridine undergoes photoassisted SrnI reaction with a variety of stabilized carbanions <1997JOC6152>. The reaction is carried out in the presence of potassium amide in liquid ammonia at —33 °C under photoirradiation at 350 nm and proceeds in moderate to good yield with anions derived from 2-benzyl-4,4-dimethyloxazoline, 2,4-dialkylthiazoles, and dimethyl methylphosphonate and also with carboxamide and ester enolates. 

More than 25 years ago Wakamatsu et al. [ 11 a] found that aldehyde 1 could be coupled with carboxamides 32 and carbon monoxide under pressure to give A -acylamino acids 33, a process catalyzed by octacarbonyldicobalt and known as... 

Treatment of the sulfinamide anhydride, prepared from anthranilic acid and thionyl chloride, with carboxamides and thiocarboxamides 1 affords quinazolin-4(3//)-ones 2. Thiocarbox-amides, being much more easily dissolved than carboxamides in nonprotic solvents such as benzene, are more suitable as starting materials. This approach has been used by Kametani et al. in the synthesis of the quinazoline alkaloids glomerine, homoglomerine, chrysoginc, and glycosminine. " ... 

Fig. 7 Strategies used in the formation of cocrystals of carbamazepine which may be applicable to APIs with carboxamide groups. Strategy I maintains the carboxamide homosynthon and uses the exterior hydrogen bond donor and acceptor sites. Strategy II forms a heterodimer by hydrogen bonds between the carboxamide and carboxylic groups. (Reproduced from Ref " l)...

Diketenes react with carboxamides in the presence of trimethylsilyl iodide to yield N-acetoacetylcar-boxamides (equation 55). ... 

The foregoing results for the most part parallel those observed with carboxamides (Section 3.11.3.8.5) and an analogous chelated transition state has been proposed (Scheme 19). Accordingly (AD) represents the lowest energy rearrangement pathway for ( )-allylic ethers. The alternative (AF) places the R -sub-... 

The starting materials for these syntheses are 2-aminonicotinic acids and derivatives such as esters. Examples of 2-aminonicotinamides and -onitriles are cited here if the amide or nitrile nitrogen is not incorporated into the pyrimidine ring, although in cyclizations with carboxamides or urea there are ambiguities. 

The range of action of carboxamides can be extended also to fungus species less sensitive to them by combination with protective fungicides, which also produce a partial synergistic effect in the combined seed-dressings. Copper oxine, chloroneb, mancozeb and other fungicides are used in combination with carboxamides (Richard and Vallier, 1969 Ranney, 1972 Baicu and Nagler, 1974). 

A great number of 2-substituted pyrimidinones 108 have been synthetized by reaction of the corresponding P-amino acid 107 (R=OH) or its derivatives (R=OEt, NHR) with ethyl benzimidates, or by reaction of orthoesters with carboxamide 107 (R=NH2). Of this set of compounds, the racemic 2-(/n-chlorophenyl)-3,4a,5,6,7,7a-hexahydrocyclopenta [d]pyrimidin-4(3/f)-one (CHINOIN 143) displayed excellent antiinflammatory activity [44, 46, 120,121]. 

The evolution of the formation constants of the binuclear triple-stranded helicates [1 2(L11)3] (NNN-S-NNN donor sets) and [R2(L13 )3] " " (ONN-S-NNO donor sets) along the lanthanide series mimics the size-discriminating effects previously established with the mononuclear precursors (Figure 31). When NNN donor sites are used in Lll, the stability constants drops for the smaller R , a trend removed when the terminal benzimidazole rings are replaced with carboxamide units in (Table 8). The connection of electron-withdrawing halo-... 

---