Perhaloketones XIX . Derivatives of benzo-N-heterocycles

A study was made of the behavior of imidazole and six benzo-N-heterocyclic compounds upon direct treatment with anhydrous and hydrated hexafluoro- and sym-tetrafluorodichloroacetones. Two of the compounds did not react, and four gave addition compounds. Indole reacted with both ketones in the 3-position. Heterocyclic precursors were made by reacting o-phenylenediamine, o-aminophenol, and o-aminobenzenethiol with hexafluoroacetone hydrate, thus introducing the 2-hydroxyhexafluoro-2-propyl moiety into the ring para to the amino group. A similar product was made from o-phenylenediamine and tetrafluorodichloroacetone. These compounds were then converted to twenty-eight heterocyclic derivatives. Four of the latter underwent haloform cleavage of the hydroxyhexahalopropyl group, a novel, but not widely applicable, preparative approach to the corresponding heterocyclic carboxylic acids.     

Synthesis of Adamantane Derivatives. XVIII. On the Bromination of 1- and 3-Homoadamantanecarboxylic Acids. an Improved Synthesis of L-Bromomethyladamantane-3-Carboxylic Acid and Some Derivatives Thereof

Although the ionic bromination of adamantane and its derivatives has been well established,² direct bromination of homoadamantane derivatives seems not to be strdied extensively.³ We wish to report the bromination of 1- (IIb) and 3-homoadaman-tanecarboxy acid (IIa), which provided an improved preparative method for 1-bromomethy ladamantane-3-carboxylic acid (III).     

Synthesis and Reactions of Some 1-Thiapyran-4-One Derivatives

The preparation of some 3,5-diarylidene-1-thipyran-4-one derivatives (Ia-e) was described. Oxidation of Ia, b and Ie with hydrogen peroxide gave the corresponding dioxides (IIa-c). Reaction of the 1-thiapyran-4-one derivatives with bromine, Grignard reagents, and amines were studied. Structural assignments are supported by spectral (UV, IR, and ¹HNMR) data.     

Reactions of Phenols with Lewis Acids: XIX. Complexes of ortho-Quinones and Benzenediols with Aluminum Bromide

Enthalpies of the reactions of Al₂Br₆ with 3,5-di-tert-butyl-1,2-benzoquinone, 1,2-naphthoquinone, 9,10-phenanthrenequinone, dimedone, isomeric benzenediols, and 4-methoxyphenol have been determined.     

N-Substituted S-Alkyl Carbamothioates in the Synthesis of Nitrogen-containing Functional Derivatives of the Adamantane Series

Russian Journal of Organic Chemistry - A series of new asymmetric ureas, urethanes, and other derivatives of the framework structure have been synthesized by the reactions of adamantan-1-yl...     

Synthesis of Novel Benzothiophene Derivatives via Cyclization Reactions

Russian Journal of Organic Chemistry - The Sonogashira cross coupling reaction of 2-bromo-5-(4-methoxyphenyl)thiophene and 1-ethynyl-2-(methylsulfanyl)benzene gave...     

Synthesis of Adamantane Derivatives. Xxiii. Facile Photo-Ring-Cleavage of 4-Homoadamantanone to Bicyclo[3.3.1] -Nonan-3 -Endo-Acetate

Type I (α-) and II cleavages are two of the best known photochemical processes of alkanone.² Extensive and intensive investigations have been done on both types of reactions in order to clarify the influence of structural changes on the reactivity, specificity, and efficiency of photoreactions of alkanones.³ The type I cleavage of medium-ring alkanones is believed to produce a radical pair, the fate of which will be determined by the ready formation of transition states for transfer of Ha, Hb, and recyclization. We now wish to report     

Intramolecular Carbenoid Reactions of Pyrrole Derivatives. A Total Synthesis of (±)-Ipalbidine

A new method for alkaloid synthesis is described. The rhodium(II)-acetate-catalyzed decomposition of 3-(4-acetoxyphenyl)-1-diazo-4-(pyrrol-1-yl)-2-butanone ( 5d ) gave 6-(4-acetoxyphenyl)-5,6-dihydro-7(8H)-indolizinone ( 6d ) in 82% yield via an intramolecular carbenoid reaction. The latter compound was converted in four steps in 13% overall yield to (±)-ipalbidine ( 1b ).     

Nitronium Ion Mediated Functionalization of Adamantane and Its Derivatives

Functionalization of adamantane and its derivatives using claycop and nitronium trifluoromethanesulfonate is described.     

Iodine-Catalyzed Synthesis of 3-Arylbenzoquinoline Derivatives by Three-Component Reactions

A mild, efficient, and general method for the synthesis of benzo[f]quinoline derivatives via three-component reaction of arylaldehyde, naphthalen-2-amine, and acetone or acetophenone is described using iodine as catalyst. The features of this procedure are mild reaction conditions, high yields, and operational simplicity.     

Convenient Synthesis of 1,2,3,4-Tetrahydroisoquinoline-1-carboxylic Acid Derivatives via Isocyanide-Based,Three-Component Reactions

The three-component reactions of 3,4-dihydroisoquinolines, isocyanides, and benzyl chloroformate furnished 2-benzyloxycarbonyl-1,2,3,4-tetrahydroisoquinoline-1-carboxamides in moderate to good yields. Hydrogenolysis or selective hydrolysis of the benzyloxycarbonyl group provided 1,2,3,4-tetrahydroisoquinoline-1-carboxamides, further hydrolysis of which resulted in the corresponding 1,2,3,4-tetrahydroisoquinoline-1-carboxylic acids.     

Synthesis of Surfactants Derived from Adamantane

Quaternary [1-(1-adamantyl)ethyl]- and (1-adamantyl)trimethylammonium, and also 3-(1-adamantyl)-3-chloro-2-propenylammonium salts were prepared, and their surface activity was studied.     

Studies on Pyrazine Derivatives. 38. Synthesis, Reactions, and Tuberculostatic Activity of Pyrazinyl-substituted Derivatives of Hydrazinocarbodithioic Acid

The synthesis of N'-[amino(6-chloro- and 6-cycloaminopyrazin-2-yl)methylene]carbodithioic acid mono- and diesters and their reactions are described. Cyclization of monoesters with secondary amines in acidic media gave the 1,3,4-thiadiazole derivatives, while the cyclization of diesters with amines yielded 1,2,4-triazoles with the amine substituent in position 3. The in vitro tuberculostatic activity of the prepared compounds was tested.     

Asymmetric Pictet-Spengler Reactions：Synthesis of Tetrahydroisoquinoline Derivatives from L-DOPA

The cis-l-substituted-6,7-dihydroxy-l,2,3,4-tetrahydroisoquinoline-3-carboxylic acid esters 3 can be obtained in a highly diastereoselective fashion through 1,3-induction Pictet- Spengler(P-S) cyclization of the L-DOPA (3,4-dihydroxyphenylalanine) methyl ester with aromatic or aliphatic aldehydes under acidic conditions. Their epimers 4 are also obtained as minor products.     

Reactions of Trisdialkylaminophosphines with Acrylohydrazide and Imidazolinone Derivatives for the Synthesis of New Organophosphorus Derivatives

Trisdimethylaminophosphine reacts with 2-benzamido-N-arylidene-3-aryl-acrylohydrazide to give phosphoryl benzamide and phosphoryl-cyano-benzamide adducts depending on the reaction conditions. Moreover, 1-aryliden-amino-2-phenyl-4-aryliden-2-imidazolin-5-ones react with trisdialkylaminophosphines to yield tetraalkylphosphonic diamide adducts. Possible reaction mechanisms are considered, and the structural assignments are based on analytical and spectroscopic evidence and X-ray analysis.     

Synthesis of Aminoalcohols of the Adamantane Series

The reduction of - and -aminoketones and enaminoketones of the adamantane series with sodium borohydride in methanol at room temperature gives the corresponding adamantylaminoalkanols.