Aryl secondary

Chlorooxadiazoles (82) react with amino compounds R NH2 (R = NH2, NHPh, alkyl, or aryl), secondary amines R R NH and azide ion to give products of nucleophilic displacement (76e), (76b), and (54i) respectively <84Mi 406-03, 90AP(323)595>. Reaction with anthranilic acid resulted in nucleophilic displacement with subsequent cyclization to oxadiazoloquinazolone (83) <84JIC436>. 

A further task was the construction of polymers from which a bound fungicide would not hydrolyze. Since aryl secondary alkyl ethers are only cleaved under vigorous conditions, we selected the vinyl ethers of fungicides 1-4 as target monomers. 

N-arylation. Secondary amines undergo arylation with ArCl in the presence of NaH, bipjridine, and Ni(acac)2-... 

At the same time, similar methodology to succeed the catalytic C-H activation of benzamides under oxidative coupUng conditions resulting in isoquinolones was also reported (Eqs. (5.57) and (5.58)). Both Af-alkyl and Af-aryl secondary benzamides could be employed, whereas primary benzamides reacted differently, and two alkyne units were oxidatively incorporated to give tricyclic products such as 60 [33]. 

Later Combs et al. [74] reported a general and mild method for the N-arylation of sulfonamides on solid supports. Copper acetate, triethylamine-mediated coupling of arylboronic acids at room temperature to solid-supported sulfonamides gave good to excellent yields of the desired N-arylsulfonamides. Sulfonamide bond cleavage of the 0, p-dinitrobenzene(N-aryl) sulfonamide provides a route to N-arylated secondary amine products. 

Reactions with Secondary Amides. Treatment of AT-alkyl or A -aryl secondary amides with thionyl chloride in an inert solvent such as methylene chloride results in the formation of imidoyl chlorides (eq Q)." Upon heating, the imidoyl chlorides from N-alkylamides undergo scission to generate nitriles and alkyl chlorides via the von Braun degradation (eq 10). ... 

Dilute sodium hydroxide solution. Carboxylic acids (RCOOH), sulphonic acids (RSO3H), phenols (ArOH), thiophenols (ArSH), mer-captans (RSH), imides (RCONHCOR), aryl sulphonamides (AxSOjNHj), arylsulphonyl derivatives of primary amines (AxSOjNHR), oximes (RCH=NOH), primary and secondary nitro compounds (RCH=NOOH and RjC=NOOH-oci forms), and some enols (e.g., of 1 3-diketones... 

Addition of several organomercury compounds (methyl, aryl, and benzyl) to conjugated dienes in the presence of Pd(II) salts generates the ir-allylpalladium complex 422, which is subjected to further transformations. A secondary amine reacts to give the tertiary allylic amine 423 in a modest yield along with diene 424 and reduced product 425[382,383]. Even the unconjugated diene 426 is converted into the 7r-allyllic palladium complex 427 by the reaction of PhHgCI via the elimination and reverse readdition of H—Pd—Cl[383]. 

Carbonylation of halides in the presence of primary and secondary amines at I atm affords amides[351j. The intramolecular carbonylation of an aryl bromide which has amino group affords a lactam and has been used for the synthesis of the isoquinoline alkaloid 498(352], The naturally occurring seven-membered lactam 499 (tomaymycin, neothramycin) is prepared by this method(353]. The a-methylene-d-lactam 500 is formed by the intramolecular carbonylation of 2-bromo-3-alkylamino-l-propene(354]. 

The o-keto ester 513 is formed from a bulky secondary alcohol using tricy-clohexylphosphine or triarylphosphine, but the selectivity is low[367-369]. Alkenyl bromides are less reactive than aryl halides for double carbonyla-tion[367], a-Keto amides are obtained from aryl and alkenyl bromides, but a-keto esters are not obtained by their carbonylation in alcohol[370]. A mechanism for the double carbonylation was proposed[371,372],... 

R may be methyl or primary secondary or tertiary alkyl it may also be a cycloalkyl alkenyl or aryl group)... 

The reaction is of the 8 2 type and works best with primary and secondary alkyl halides Elimination is the only reaction observed with tertiary alkyl halides Aryl and vinyl halides do not react Dimethyl sulfoxide is the preferred solvent for this reaction but alcohols and water-alcohol mixtures have also been used... 

Reduction of amides (Section 22 9) Lithi um aluminum hydride reduces the car bonyl group of an amide to a methylene group Primary secondary or tertiary amines may be prepared by proper choice of the starting amide R and R may be ei ther alkyl or aryl... 

N Nitroso amine (Section 22 15) A compound of the type R2N—N=0 R may be alkyl or aryl groups which may be the same or different N Nitroso amines are formed by ni trosation of secondary amines... 

Secondary amine (Section 22 1) An amine with any combma tion of two alkyl or aryl substituents and one hydrogen on nitrogen an amine of the type... 

Aryl—OH ca 3610 (s) 1410-1310 (s) 1260-1180 (s) 1085-1030 (s) See comments under primary aliphatic alcohols Also for unsaturated secondary aliphatic alcohols... 

Antioxidants markedly retard the rate of autoxidation throughout the useful life of the polymer. Chain-terminating antioxidants have a reactive —NH or —OH functional group and include compounds such as secondary aryl amines or hindered phenols. They function by transfer of hydrogen to free radicals, principally to peroxy radicals. Butylated hydroxytoluene is a widely used example. 

Phosgene reacts with a multitude of nitrogen, oxygen, sulfur, and carbon centers. Reaction with primary alkyl and aryl amines yield carbamoyl chlorides which are readily dehydrohalogenated to isocyanates. Secondary amines also form carbamoyl chlorides. 

Amines are derivatives of ammonia in which one or more of the hydrogens is replaced with an alkyl, aryl, cycloalkyl, or heterocycHc group. When more than one hydrogen has been replaced, the substituents can either be the same or different. Amines are classified as primary, secondary, or tertiary depending on the number of hydrogens which have been replaced. It is important to note that the designations primary, secondary, and tertiary refer only to the number of substituents and not to the nature of the substituents as in some classes of compounds. 

Sulfation by sulfamic acid has been used ia the preparation of detergents from dodecyl, oleyl, and other higher alcohols. It is also used ia sulfating phenols and phenol—ethylene oxide condensation products. Secondary alcohols react ia the presence of an amide catalyst, eg, acetamide or urea (24). Pyridine has also been used. Tertiary alcohols do not react. Reactions with phenols yield phenyl ammonium sulfates. These reactions iaclude those of naphthols, cresol, anisole, anethole, pyrocatechol, and hydroquinone. Ammonium aryl sulfates are formed as iatermediates and sulfonates are formed by subsequent rearrangement (25,26). 

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