Amines reaction with amides

Reactions with Amines and Amides. Hydroxybenzaldehydes undergo the normal reactions with aUphatic and aromatic primary amines to form imines and Schiff bases reaction with hydroxylamine gives an oxime, reaction with hydrazines gives hydrazones, and reactions with semicarbazide give semicarbazones. The reaction of 4-hydroxybenzaldehyde with hydroxylamine hydrochloride is a convenient method for the preparation of 4-cyanophenol (52,53). 

Reaction with water to yield a carboxylic acid Reaction with an alcohol to yield an ester Reaction with ammonia or an amine to yield an amide Reaction with a hydride reducing agent to yield an aldehyde or an alcohol... 

Lactams can be opened to -amino amides by reaction with amines at 10kbar. ° ... 

Palladium complexes also catalyze the carbonylation of halides. Aryl (see 13-13), vinylic, benzylic, and allylic halides (especially iodides) can be converted to carboxylic esters with CO, an alcohol or alkoxide, and a palladium complex. Similar reactivity was reported with vinyl triflates. Use of an amine instead of the alcohol or alkoxide leads to an amide. Reaction with an amine, AJBN, CO, and a tetraalkyltin catalyst also leads to an amide. Similar reaction with an alcohol, under Xe irradiation, leads to the ester. Benzylic and allylic halides were converted to carboxylic acids electrocatalytically, with CO and a cobalt imine complex. Vinylic halides were similarly converted with CO and nickel cyanide, under phase-transfer conditions. ... 

Finally, a new water-soluble polyphosphazene was recently synthesized that has the structure shown in 36 (46). This polymer has two attributes as a biomedical macromolecule. First, the pendent carboxylic acid groups are potential sites for condensation reactions with amines, alcohols, phenols, or other carboxylic acid units to generate amide, ester, or anhydride links to polypeptides or bioactive small molecules. Second, polymer forms ionic crosslinks when brought into contact with di- or trivalent cations such as Ca or Ai3+. The crosslinking process converts the water-soluble polymer to a hydrogel, a process that can be reversed when the system... 

Zinc carbamate complexes are well known, and the structural types and stabilities can be compared with thiocarbamates and dithiocarbamates which are discussed in Sections 6.8.11.1.3 and 6.8.7.1.4482 Carbamates of zinc can be formed from the reaction of carbon dioxide with alkylzinc alkyl amides and further reaction with alkylzinc can give a distorted cubane structure.483 The tetrameric diethylcarbamate species initially formed can also be used to produce monomeric or dimeric carbamate structures in reaction with amines tetramethylethylenediamine forms a monomer [(Me2NCH2)2Zn(02CN(C2H5)2)2] with an octahedral zinc center and pyridine forms a dimer[CsH5NZn2Me(02CN(C2H5)2)3] with tetrahedral zinc centers.484... 

Figure 11.4 NHS-LC-biotin provides an extended spacer arm to allow greater distance between the biotin rings and a modified molecule. Reaction with amines forms amide linkages.

Benzotriazol-l-yl)methyl]triphenylphosphonium chloride 848 reacts with BunLi and aldehydes to give l-(alken-l-yl)benzotriazoles 849. Addition of bromine to the double bond of derivatives 849 followed by a reaction with amines furnishes amides 850. A variety of primary or secondary amines can be used. This way aldehydes are conveniently homologated and converted to amides with a one-atom longer chain (Scheme 136) <2004ARK(ix)44. 

An electrochemical method for the synthesis of a series of 4-(alkylamino)-2-phenyloxazolines 139a-f from A -(2,2-dichlorovinyl)amides 135 has been reported. The starting A -(2,2-dichlorovinyl)amide 135, readily available from chloral and amides, undergoes facile reaction with amines to give 136. Cathodic reduction of 136 generates chlorocarbanionic intermediates 137 and 138 that... 

Both aliphatic and aromatic amines have been investigated in this reaction with similar results. This confirms that the reaction is a general reaction with amines in aqueous medium. The conversions of aromatic amines to secondary amides are lower than that of the aliphatic amines. This is because aromatic amines are generally weaker bases and poorer nucleophiles. 

There are several examples in the literature of activation of hydroxy compounds by various organophosphorus compounds. For example, in the presence of pyridine, ji-butyltriphenoxyphosphonium bromide (1) activates carboxylic acids towards reaction with amines or phenols to give, respectively, amides or esters (1). 

There are also several reactive diluents that do not contain epoxy groups. These are represented by triphenyl phosphite and y-butyrolactone (Fig. 6.7). The phosphite is a low-viscosity colorless liquid, which is sensitive to moisture. It reacts with hydroxyl groups in the resin. The y-butyrolactone is a very effective viscosity reducer. It can reduce the viscosity of a liquid DGEBA from about 15,000 to 2000 cP with only 10 pph. In the curing reaction with amines (Fig. 6.8), the lactone forms an amide, which can then crosslink with the polymer via the hydroxyl groups. 

Anhydrides are also highly reactive toward nucleophiles however, only the reaction with amines towards amide linkages results in products that are stable against hydrolysis [44] (Scheme 10). In contrast, the reaction with both thiol and hydroxyl functionalities leads to the formation of unstable thioesters and esters, respectively. 

A transformation of formamides to ureas was reported by Watanabe [67]. In place of CO, formamide derivatives are used as the carbonyl source. The reaction of for-manilide with aniline was conducted in the presence of a catalytic amount of RuCl2(PPh3)3 in refluxing mesitylene, leading to N,N -diphenylurea in 92% yield (Eq. 9.52) [68]. These authors proposed that the catalysis starts with the oxidative addition of the formyl C-H bond to the active ruthenium center, although they did not provide any experimental evidence for this. In the case of the reaction of form-amide (HCONH2) with amines, two molecules of the amine react with the amide to afford symmetrically substituted ureas in good yields. In this reaction, one molecule of NH3 and one molecule of H2 is evolved. 

Analogous reactions with amines or alcohols afford amides (Scheme 10.11) [15], and esters in high yield (Scheme 10.12) [16[. 

With primary or secondary amides, reaction with LiAlH4 is wasteful in that hydrogen gas is evolved and reduction usually proceeds through to the amine. Nevertheless, it has been shown that r-butylamides, refluxed with an excess of LiAlD4 for 15 h in diethyl ether, give very good yields of deuteriated aldehydes, RCDO. O ... 

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