N- acylamines

Trimethylsilylketene reacts smoothly with u./V-diarylnitrones to give oxoin-doles in good yields. On the other hand, the reaction of trimethylsilylketene with N-arylmethylnitrones gives a mixture of N,N-diacylamines and N-acylamines (Scheme 2.315) (836). 

In contrast to the results obtained by Jacobsen et al. when utilizing Schiff base catalyst 42, the decrease of reaction temperature to -40 °C reduced the yield as well as enantioselectivity of the resulting Mannich adduct (Scheme 6.175) [201]. Catalyst 198 found to be less effective in the Mannich reaction in terms of yield and enantiomeric induction due to reduced basicity of the N-acylamine and weaker hydrogen-bonding interactions compared to the more basic Strecker substrates (Scheme 6.174). 

Support-bound C,F I-acidic compounds, such as acetoacetamides, react with isocyanates under basic conditions to yield amides through C-carbamoylation [71]. Similarly, polystyrene-bound aryllithium compounds can be converted into benzamides by treatment with isocyanates [111]. These reactions are closely related to C-thiocarbamoyla-tion, which has been used for the solid-phase synthesis of thioamides (see Section 13.9). Amides have also been prepared by C-alkylation of resin-bound N-acylaminals with allyltrimethylsilane or diethylzinc (Entry 11, Table 13.7). 

The synthesis of alkaloids described above is based on the generation of a cationic center at the position a to the nitrogen atom of an amide followed by a carbon-carbon bond formation at the a-position as the key reaction. On the other hand, developing an anionic center at the a-position of the N-acylamine generally requires a very strong base which may bring about undesirable side reactions. However, the formation of... 

Only one work has been reported using this protecting group". The thioether is obtained by an exchange reaction of the thiol with iS,j3,j3-trifluoroethyl-a-ethanesulphonyl-a-N-acylamine (10). In the case of... 

N,N-Dialkylalkanamides Cyclic N-Alkylamides Cyclic N-Acylamines Cyclic N-Acylaminoethers N,N-Dialkylimidazolidinone derivatives N-Alkylalkanamides Cyclic amides Alkanamides Nitrocompounds Nitroalkanes Nitroarenes Nitrobenzene Thlazole derivatives 1,3-Thiazole Sulfonamides... 

Through Oxidative Carbon-Carbon Bond Cleavage 184 5.2. Fragment Coupling Through N-Acylaminal Formation and ... 

The N-oxides of isoquinolines have proved to be excellent intermediates for the preparation of many compounds. Trialkylboranes give 1-alkyl derivatives (147). With cyanogen bromide in ethanol, ethyl N-(l- and 4-isoquinolyl)carbamates are formed (148). A compHcated but potentially important reaction is the formation of 1-acetonyLisoquinoline and 1-cyanoisoquinoline [1198-30-7] when isoquinoline N-oxide reacts with metbacrylonitrile in the presence of hydroquinone (149). Isoquinoline N-oxide undergoes direct acylamination with /V-benzoylanilinoisoquinoline salts to form 1-/V-benzoylanilinoisoquinoline [53112-20-4] in 55% yield (150). A similar reaction of AJ-sulfinyl- -toluenesulfonamide leads to l-(tos5larriino)isoquinoline [25770-51-8] which is readily hydrolyzed to 1-aminoisoquinoline (151). 

It has been known for a long time 82> that N-nitroso-acylamines rearrange to azo compounds ... 

Pyridazine 1-oxide is acylaminated with N-phenylbenzonitrilium hexa-chloroantimonate to give 3-N-benzoyIanilinopyridazine [Eq. (21)]. A new... 

E)-acylamine (285), which in the Diels-Alder reaction must have a transition state where the N-acyl group is endo and the ester group is exo in order to account for the formation of the trans product (286) (80JA1153). 

N -Uric acid synthesis Amines from acylamines Ureas from amines... 

Am N-Atom unsubstituierte Acylamine ergeben Nitrile (s. S. 1356)6. disubstituierte liefern Carbonsaure-imidium-chloride7. 

Cyclization of vicinal alkyl acylamines (139) induced by strong bases [the Madelung reaction and its modifications (68AHC27)] is a versatile method for preparing fused pyrroles (140) in the general representation in Scheme 31 the intermediate is depicted as a carbanion for simplicity, although N-deprotonated species are doubtless involved at some stage, as in Scheme 33. 

A. Barua, G. Bez, and N. C. Barua, A novel one pot method for reductive conversion of azides to acylamines with AC2O and trimethylchlorosilane, Synlett (1999) 553-554. 

Amides(acylamines) and urethanes as shown by Olsen [107] gave with one equivalent of NO2 BF in acetonitrile at -30 C the corresponding N-nitro derivatives (Table XXVI). 

A mixture of f erf-butanol and liq. HCN added dr op wise at 25° during 1.5 hrs to an emulsion of adamantane, n-hexane, and 96%-H2S04, stirring continued 0.5 hr. 1-formylaminoadamantane. Y 78%. — Alcohols, such as ferf-butanol, also olefins and alkyl halides, can serve as carbonium ion donors. The tert. hydrogen of isoparaffins reacts particularly easily with these donors. F. e., mostly amines after hydrolysis without isolation of the intermediate acylamines, s. W. Haaf, B. 97, 3234 (1964). 

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