Amines, cyclic nitriles

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

A considerable amount of work has been published dealing with the electro-oxidation of organics at Ni anodes in aqueous base [548-552], These reactions have generally been dehydrogenations, e.g. primary alcohols to aldehydes, secondary alcohols to ketones and primary amines to nitriles. The reactions occur on a relatively thick layer of oxide on the Ni anodes. Pletcher and co-workers [529, 548, 549] observed that most of the oxidizable compounds were found to oxidize at the same potential and this potential coincided with that at which the surface of the Ni became oxidized. A typical cyclic voltammogram recorded at Ni in dilute KOH in the presence and absence of n-propylamine is shown in Fig. 23. It can be seen that addition of n-propylamine results in an oxidation wave being observed which is... 

The above nucleophilic addition reactions involve N—C bond formation, a bond that can also be created by insertion (at least formally) of a nitrile into a metal-N bond.148-150 Stereochemical and kinetic4,8 studies have been reported, although with few examples, for the addition of amines to nitriles at Pt11 centers, and the latter are indicative of the involvement, similar to the addition of alcohols (see above), of cyclic 4- and 6-center transition states, with one or two amine molecules, respectively, interacting with N=C. 

In general, aldehydes, ketones, acids, esters, and acid chlorides are all reduced to the corresponding alcohols hy this reagent. Alkyl halides are unreactive towards DIBAL. Amides are reduced to amines, while nitriles afford aldehydes upon hydrolysis of an intermediate imine. Isocyanates are also reduced to the corresponding imines. Nitro compounds are reduced to hydroxy-lamines. Disulfides are reduced to thiols, while sulfides, suhbnes, and sulfonic acids are unreactive in toluene at 0°C. Tosylates are converted quantitatively to the corresponding alkanes. Cyclic imides can be reduced to carbinol lactams. 

Allylic amine is a less reactive leaving group[7], but the allylic ammonium salts 214 (quaternary ammonium salts) can be used for allylalion(l30,131]. Allylic sulfonium salts are also used for the allylation[130]. The allylic nitrile in the cyclic aminonitrile 215 can be displaced probably via x-allylic complex formation. The possibility of the formation of the dihydropyridinium salts 216 and subsequent conjugate addition are less likelyfl 32],... 

Ene-nitrile oxidoisoquinolinium betaine 131 was readily prepared from vinyl triflate aldehyde 79 (Scheme 1.14). Palladium-catalyzed cyanation of vinyl triflate 79 with Zn(CN)2 in DMF at 60 °C produced ene-nitrile aldehyde 129 in 85 % yield [54]. Using the previously developed Staudinger-aza-Wittig reduction sequence, aldehyde 129 was coupled with cyclic ketal azide 121 to afford a 79 % yield of amine 130. The cyclic ketal amine 130 was then treated with 9 1 mixture of CH2CI2/TFA to provide ene-nitrile oxidoisoquinolinium betaine 131 in 93 % yield. 

The only cationic surfactant (Fig. 23) found in any quantity in the environment is ditallow dimethylammonium chloride (DTDMAC), which is mainly the quaternary ammonium salt distearyldimethylammonium chloride (DSDMAC). The organic chemistry and characterization of cationic surfactants has been reported and reviewed [330 - 332 ]. The different types of cationic surfactants are fatty acid amides [333], amidoamine [334], imidazoline [335], petroleum feed stock derived surfactants [336], nitrile-derived surfactants [337], aromatic and cyclic surfactants [338], non-nitrogen containing compounds [339], polymeric cationic surfactants [340], and amine oxides [341]. 

During the coverage period of this chapter, reviews have appeared on the following topics reactions of electrophiles with polyfluorinated alkenes, the mechanisms of intramolecular hydroacylation and hydrosilylation, Prins reaction (reviewed and redefined), synthesis of esters of /3-amino acids by Michael addition of amines and metal amides to esters of a,/3-unsaturated carboxylic acids," the 1,4-addition of benzotriazole-stabilized carbanions to Michael acceptors, control of asymmetry in Michael additions via the use of nucleophiles bearing chiral centres, a-unsaturated systems with the chirality at the y-position, and the presence of chiral ligands or other chiral mediators, syntheses of carbo- and hetero-cyclic compounds via Michael addition of enolates and activated phenols, respectively, to o ,jS-unsaturated nitriles, and transition metal catalysis of the Michael addition of 1,3-dicarbonyl compounds. ... 

As a class of compounds, nitriles have broad commercial utility that includes their use as solvents, feedstocks, pharmaceuticals, catalysts, and pesticides. The versatile reactivity of organ onitriles arises both from die reactivity of the C=N bond, and from die ability of the cyano substituent to activate adjacent bonds, especially C-H bonds. Nitriles can be used to prepare amines, amides, amidines, carboxylic acids and esters, aldehydes, ketones, large-ring cyclic ketones, imines,... 

In the course of the catalytic hydrogenation of a,us dinitriles over Raney nickel, by-products are obtained from C-N and C-C bond formation. The mechanism of the formation of these compounds was investigated. Cyclic and linear secondary amines can result from the same secondary imine through a transimination process involving a ring-chain tautomerism. Stereochemical results for 2-aminomethyl-cyclopentylamine (AMCPA) are in accordance with a specific cyclisation pathway favored by an intramolecular hydrogen bond giving rise to the cis isomer from aminocapro-nitrile, unfavored in the case of adiponitrile which leads to the trans AMCPA as the major isomer. 

Aromatic fluorides, chlorides, nitriles and amines Saturated cyclic compounds... 

Hydrazone A in Figure 17.37 undergoes oxidationjust like an amine, and amine N-oxide B is formed. Immediately, B undergoes a /1-elimination via a cyclic transition state, and nitrile C... 

Vinylic substitution of bromine by noncyclic primary and secondary amines in 3-bromo-4,4-dimethoxy-2-butenoates and corresponding nitriles occurs in a stereocontrolled fashion. Regardless of the starting stereochemistry, the product possesses trans amino and ester (or nitrile) groups (equation 20)174. Also, displacement of bromine from 5-bro-mouracils, by cyclic amines, has been used as a preparation of novel pyrimidine inhibitor intermediates1. This reaction has been shown to be assisted by the presence of fluoride ion... 

Hydrazone A in Figure 14.31 (the procedure in Figure 10.31 shows one possibility for the preparation) undergoes oxidation just like an amine, and amine A-oxidc B is formed. Immediately, B undergoes a /1-elimination via a cyclic transition state, and nitrile C and a hydroxylamine are formed. Since the hydrazone precursor is accessible as a pure enantiomer, the nitrile also can be generated as a pure enantiomer. 

Monoamines, primary diamines and secondary amines react with nitriles to give amidines, cyclic amidines and pyrimidines, respectively, in the presence of Yb(OTF)3 as a catalyst. Reaction of ammonia with acetonitrile is shown below. 

---