Aryl primary

The rates of thermal decomposition of diacyl peroxides (36) are dependent on the substituents R. The rates of decomposition increase in the series where R is aryl-primary alkyKsecondary alkyKtertiary alkyl. This order has been variously proposed to reflect the stability of the radical (R ) formed on (i-scission of the acyloxy radical, the nucleophilicity of R, or the steric bulk of R. For peroxides with non-concerted decomposition mechanisms, it seems unlikely that the stability of R should by itself be an important factor. 

Synthesis of Simple Alkyl/Aryl Primary Phosphines.123... 

Essentially, aU studies have used acetophenone-based iV-aryl ketimines as substrates or derivatives thereof. Some of the iV-aryl groups are easily deprotected to yield branched a-aryl primary amines, which can be further functionalized. 

S-Protonated Aryliminium Salts Hesse has made a much more extensive study of the reaction of aryl primary amines (58) with higher aldehydes (see 59) and a suitable alkene, usually styrene or a-methylstyrene, and found that high yields of tetra-hydroisoquinoline (60) could be obtained even when an electron-withdrawing group was present in the aryl ring. Carbonium ion (61) appeared likely as an intermediate. 

Kraft et al., 1998 Lowen and Van Dyke, 1990 Wei and Tian, 1993], Reactions other than oxidative polymerization are also being studied for producing polyaniline and polythiophene [Kraft et al., 1998 Loewe et al., 2001]. An example is the Pd-catalyzed dehydrohalogenation between aryl dihalides and aryl primary diamines to synthesize polyanilines [Kanbara et al.,... 

All these various pyrylium salts are converted by ammonia, or alkyl, arylkyl or aryl primary amines into the corresponding pyridinium salts.25 The probable reaction sequence is given in the illustrative example 1-benzyl-2,4,6-triphenyl-pyridinium tetrafluoroborate26 (Expt 8.31). 

To a stirred solution of 74.6 g (0.5 mol) of benzylisothiocyanate in 500 mL toluene was added dropwise 46.6 g (0.5 mol) of aniline. The solution was refluxed 18 hours. After cooling, the reaction mixture was concentrated under reduced pressure. The residue was recrystallized from an appropriate solvent to yield N-phenyl-N -benzylthiourea. Isothiocyanates which are not commercially available may be prepared from aliphatic or aryl primary amines by the following methods Kurita and Iwakura, Org. Synth. 59, 195 Jochims, Chem. Ber. 101, 1746 (1968) or Castro, Pena, Santos, and Vega, J. Org. Chem. 49, 863 (1984). 

This polymer-supported aldehyde was found to scavenge both alkyl as well as aryl primary amines over secondary amines and exhibit remarkable facility in the synthesis of a demonstration library of amides, ureas and secondary amines (Scheme 8.9). 

Thcnnolysis rates ( j) of dialkyidiazenes (15) show a marked dependence on the nature of R (and R ). fhe values of increase in the series where R (=R ) is arylsecondaryfree spin of the incipient radical." For example, Timberlake has found that for the case of dialkyidiazenes,... 

Olofsson, K., Sahlin, H., Larhed, M. and Hallberg, A. (2001) Regioselective palladium-catalyzed synthesis of beta-arylated primary allylamine equivalents by an efficient Pd N coordination. J. Org. Chem., 66,544—9. 

One of the best-known and most important reactions in organophosphorus chemistry is the production of P-C linkages by the Arbusov reaction. Originally formulated as a reaction between a trialkyl phosphite and an alkyl halide (3.108), this reaction was later found to be more general and can be written as (3.109), where A, B can be alkyl, aryl, primary or secondary alkoxy, aryloxy, dialkyl-amino and so on. 

These compounds are long-chain alkyl or aryl primary, secondary, and... 

Diacetoxytriphenylbismuth was found to be capable of arylating primary amines in good yield, particularly when the reactions were... 

Recent advances in developing important intermediate aromatic nitro compounds, useful in synthetic organic chemistry, have been reviewed. This article includes topics such as the nitration of aromatic hydrocarbons, aryl boronic acids, aryl halides and pseudohalides, aryl carboxylic acids, and the oxidation of aryl primary amines and azide. ... 

Formation of Allyl and Aryl Primary AUyUc and HomoallyUc Alcohols from Vinyl Epoxides and Oxetanes. Vinylic epoxides can be coupled with aryl (eq 30) or vinyl (eq 31) iodides or tri-flates to form allylic alcohols in 40-90% yield. When employing palladium acetate as the catalyst, a reducing agent such as sodium formate is required in addition to the salts normally present under phase transfer conditions. 

MeO secondary acyclic, primary aryl, primary alkyl... 

Cascade reactions triggered by the combination of chiral amines and achiral Brpnsted acid were well documented on the basis of enamine and iminium ion formation, while examples with the combination of a chiral amine catalyst and a chiral Brpnsted acid were rare, hi 2(X)7, Zhou and List reported an elegant cascade intramolecular aldol-reduction process to prepare chiral 3-substituted cyclohexyl-amines by combining achiral enamine catalysis and chiral phosphoric acid catalysis [38]. Unusually, achiral aryl primary amine was exploited as an amino catalyst to generate a transient enamine intermediate to facilitate an intramolecular aldolization-dehydration process, while chiral phosphoric acid was harnessed to accelerate the following conjugate reduction-reductive amination cascade. Starting from readily available 2,6-diketones and aryl amines, pharmaceutically relevant 3-substituted cyclohexyamine derivatives were readily produced in satisfactory yield and excellent enantioselectivity (Scheme 9.42). 

Ai-arylated primary and secondary aliphatic amines are important substituents in many biologically active compounds. The predominance of arylpiperidines and arylpiperazines in CNS drugs is particularly noteworthy [75-77]. 

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