3034-28-4Relevant articles and documents
Rapid synthesis of isoquinolinones by intramolecular coupling of amides and ketones
Wei, Wen-Tao,Liu, Yu,Ye, Lin-Miao,Lei, Rong-Hui,Zhang, Xue-Jing,Yan, Ming
supporting information, p. 817 - 824 (2015/02/19)
Amides and ketones were intramolecularly coupled in the presence of KOt-Bu/DMF. The reaction provided good yields of a variety of isoquinolinones. A reaction mechanism of radical addition and subsequent E2-elimination is proposed.
Rhodium-catalyzed oxidative ortho -acylation of benzamides with aldehydes: Direct functionalization of the sp2 C-H bond
Park, Jihye,Park, Eonjeong,Kim, Aejin,Lee, Youngil,Chi, Ki-Whan,Kwak, Jong Hwan,Jung, Young Hoon,Kim, In Su
supporting information; experimental part, p. 4390 - 4393 (2011/10/08)
A rhodium-catalyzed oxidative acylation of benzamides with aryl aldehydes via direct sp2 C-H bond cleavage is described. In the presence of [Cp*RhCl2]2, AgSbF6, and silver carbonate as an oxidant, N,N-diethyl be
Application of directed orthometalation toward the synthesis of aryl siloxanes
Seganish, W. Michael,DeShong, Philip
, p. 6790 - 6795 (2007/10/03)
A selection of ortho-substituted aryl siloxanes have been prepared by directed orthometalation protocols. These siloxanes can be prepared in high yields and purity by use of a diverse selection of ortho-directing groups and electrophilic siloxane derivatives. The siloxanes are employed in palladium-catalyzed cross-coupling reactions with aryl bromides to generate unsymmetrical orthosubstituted biaryls in good to excellent yields.
Probes for narcotic receptor-mediated phenomena. 25.1 Synthesis and evaluation of N-alkyl-substituted (α-piperazinylbenzyl)benzamides as novel, highly selective δ opioid receptor agonists
Katsura, Yousuke,Zhang, Xiaoyan,Homma, Koichi,Rice, Kenner C.,Calderon, Silvia N.,Rothman, Richard B.,Yamamura, Henry I.,Davis, Peg,Flippen-Anderson, Judith L.,Xu, Heng,Becketts, Karen,Foltz, Eric J.,Porreca, Frank
, p. 2936 - 2947 (2007/10/03)
A series of N-alkyl- and N,N-dialkyl-4-[α-{(2S,5R)-4-allyl-2,5- dimethyl-1-piperazinyl}benzyl]-benzamides were synthesized and evaluated for binding affinities at μ, δ, and κ opioid receptor subtypes. Several compounds (2e,f,h,i,m) strongly bound to the δ receptor with IC50 values in the nanomolar range. On the other hand, the binding affinities of these compounds for the μ and κ receptors were in the micromolar or greater range indicating excellent δ opioid receptor subtype selectivities. In this series, two important structure-activity relationships were found for the δ receptor binding affinity. First, the spatial orientation of the α-benzylic position influenced the affinities with the αR derivatives 2a-n generally showing more than 10-fold greater affinity than the αS derivatives 3a-n. Second, the binding affinities were strongly influenced by the number of alkyl substituents on the amide nitrogen. N-Monoalkylbenzamide derivatives 2b-d showed lower affinity than N,N-dialkylbenzamide derivatives 2e-n, and the N-unsubstituted benzamide derivative 2a had the lowest affinity for the δ receptor in the series. The dramatic effect of the amide group substitution pattern on the binding affinity for the δ receptor strongly suggests that the amide function is an important structural element in the interaction of this series of compounds at the δ receptor. Selective compounds in this series were examined for binding affinity in cloned human μ and δ receptors. The results obtained generally paralleled those from the rat brain binding assay. Compounds 2e,f with potent δ binding affinities and high δ selectivities were shown to be δ agonists with high selectivity by studies in the guinea pig ileum (GPI) and mouse vas deferens (MVD) preparations. Compound 2f was the most selective compound in the rat brain and GPI/MVD assays with 1755- and 958-fold δ vs μ selectivity, respectively.
Preparation of 3-Hydroxyindolin-1-ones and o-Acylbenzamides. A Study of Ring-Chain Tautomerism
Nishio, Takehiko,Yamamoto, Hiroshi
, p. 883 - 892 (2007/10/02)
3-Hydroxyisoindolinones (ring form) as well as their chain tautomers, o-acylbenzamides, were prepared from the reactions of 3-benzalphthalide 1, 3-halophthalides 3, and o-acylbenzoic acids 6 or their esters 7 with amines 2, and those of phthalimides 4 wit
A Novel Aromatic Electrophilic Substitution: Acylation of Aromatics with Cyclic Isoimidium Salts to Yield N,N-Disubstituted β-Aroylcarboxamides
Balaban, Alexandru R.,Balaban, Theodor-Silviu,Boyd, Gerhard V.
, p. 577 - 578 (2007/10/02)
Cyclic isoimidium perchlorates derived from N,N-diethylphthalamic acid and the monomorpholides of succinic and maleic acid react with benzene, toluene or anisole in the presence of aluminium chloride to give the corresponding β-aroylcarboxamides in modera
A COMPARISON OF SECONDARY AND TERTIARY AMIDES AS DIRECTORS OF ORTHO AND ADJACENT BENZYLIC LITHIATION AND OF ASYMMETRIC INDUCTION IN ORTHO LITHIATED BENZAMIDES
Beak, Peter,Tse, Anthony,Hawkins, Joel,Chen, Chin-Wen,Mills, Sander
, p. 1983 - 1989 (2007/10/02)
Comparisons are made between the influence of secondary and tertiary amides on ortho and adjacent benzylic metallations of benzamides.In the intramolecular competition offered by N,N-diethyl-N-ethylterephthalamide (1) the tertiary amide is the more effective director of ortho lithiation, while the secondary amide is better in the intermolecular competitions offered by the pairs N-ethyl-(9):N,N-diethylbenzamide(10) and N-isopropyl-(11):N,N-diisopropylbenzamide(12).Both secondary and tertiary amides are found to direct metallation ortho to the amide in the 2-isopropylbenzamides 25 and 26; however, benzylic metallation is observed with secondary 2-ethyl- and 2-methylbenzamides 21 and 22 and with the tertiary 2-ethylbenzamide 19.Magnetic non-equivalence is noted for the anti-N-methylene group of 19.The reaction of an ortho lithio (S)-O-methyl-N-benzoylleucinol (34) with 1-naphthaldehyde-1-d gives, after lactonization, 3-(1-naphthyl-1-d)-phthalide with 10percent enantiomeric excess.The phthalide can be obtained in high enantiomeric purity by separation of the diastereoisomers prior to cyclization.Control experiments establish that the observed asymmetric induction is attributable to diastereomeric transition states.The corresponding tertiary benzamide is ineffective in inducing asymmetry.Structural and mechanistic rationales are offered for these observations.
Photochimie organique: photolyse de O-benzoylbenzamides secondaires et tertiaires
Gramain, Jean-Claude,Lhomme, Marie-France
, p. 141 - 146 (2007/10/02)
Intramolecular photoreduction of ketones leads to a diradical likely to undergo cleavage or cyclization to yield cyclobutanols (Norrish type II reaction).Examples of intramolecular δ- or ε-H-abstraction are known to lead to 1,5- or 1,6-diradicals, the cyclization of which gives rise to five or six-membered rings.We have prepared a series of O-benzoyl-benzamides and studied their photolysis in order to establish a pathway to phenyltetrahydroisoqoinolines.We have thus prepared N-ethyl, N-isopropyl and N-benzyl-O-benzoylbenzamides and shown that in solution these compounds have a cyclic structure (3-hydroxy-3-phenylphtalimidine) in which the ketone carbonyl is hidden.These compounds are photochemically inert.Four tertiary O-benzoylbenzamides have been prepared (N,N-diethyl, N,N-di-n-butyl, N-butyl-N-methyl, and N-benzyl-N-methyl).These compounds exhibit an n?* absorption above 300 nm.Their photolysis (λ > 300 nm) gives rise in all four cases to the 3-phenylphtalide 9 and to their dimer 10 of the 3-phenylphtalid-3-yl radical (meso and d,l) mixture.Upon irradiation below 300 nm (253.7 nm in quartz), formation of the diphtalide (dimer 10), not of the phenylphtalide 9, is observed.Finally no cyclic photoproducts derived from a 1,6-diradical are observed.In thus appears that deactivation of the excited state of tertiary O-benzolylbenzamides does not occur by intramolecular abstraction of the hydrogen α to the amide nitrogen atom, but rather by homolytic cleavage of the amide C-N bond.The radical thus formed cyclizes, giving a 3-phenylphtalid-3-yl radical which further yields, either the 3-phenylphtalide 9 by hydrogen capture, or the dimer 10 by coupling.During irradiation at 253.7 nm the optical density of the solution is very high (of the order of 1000) because of the high ε values of the starting compounds.The local concentration of 3-phenylphtalid-3-yl radicals is thus high, promoting their coupling to dimer at the expense of hydrogen capture, which would lead to the 3-phenylphtalide 9.
