Search results for " Rearrangement"

Eine oligomeranaloge friessche umlagerung oligomerer 2-acetoxy-1,3-phenylenmethylene

1979

α-Hydro-ω-hydroxypoly(5-chloro-2-hydroxy-1,3-phenylenemethylene)s (1a, b), the oligomeric condensation products from 4-chloro-2,6-bis(hydroxymethyl)phenol and 4-chlorophenol with hydrochloric acid in 1,4-dioxane, could be completely dehalogenated at room temperature and atmospheric pressure with hydrogene/Raney-Ni. The resulting oligomers 2a, b were esterified with acetic anhydride, and the esters 3a, b were subjected to a oligomer analogous Fries rearrangement to form the linear α-hydro-ω-hydroxypoly(5-acetyl-2-hydroxy-1,3-phenylenemethylene)s 4a and 4b. The characterization of the products was mainly done by spectroscopic methods.

Influence of enol acetylation on the photo-fries rearrangement of anortho-acylaryl benzoate

1982

The enol acetate 1b undergoes benzoyl-oxygen bond rupture upon irradiation, giving a mixture of benzophenones 4 and 5. The primary photo-Fries products 2 and 3 could not be isolated, due to a rapid intramolecular transacetylation. The acetophenone 6 rearranges to give the benzophenones 7 and 8 under the same conditions, but the yields are significantly lower than in the former case. Compounds 7 and 8 are separately correlated with 4 and 5 by treatment with acetic anhydride in the presence of pyridine. Einflus der Enol-Acetylierung auf die Photo-Fries-Umlagerung eines Benzoesaure-ortho-acylarylesters Das Enolacetat 1b erleidet bei Bestrahlung Spaltung der Benzoyl-Sauerstoff-Bindung, wobei ei…

Synthesis of (+)-pechueloic acid and (+)-aciphyllene. Revision of the structure of (+)-aciphyllene

2007

Abstract 1α H ,7α H ,10α H -Guaia-4,11-dien-3-one and its 1β H ,10β H diastereomer, easily obtained from (+)-dihydrocarvone, are good starting materials for the synthesis of natural guaiane derivatives. Allylic oxidation of the 1α H ,10α H isomer gave as main product its 13-hydroxy derivative and a small amount of (+)-7β-hydroxy-1α H ,10α H -guaia-4,11-dien-3-one, whereas the 1β H ,10β H diastereomer afforded selectively the (−)-7α-hydroxy-1β H ,10β H enantiomer in excellent yield. From the 13-hydroxy derivative (+)-pechueloic acid and (+)-methyl pechueloate were synthesized. Deoxygenation at C 3 of the 1β H ,10β H guaiadienone afforded a guaiadiene with the reported structure for aciphylle…

ChemInform Abstract: Synthesis of Fluorinated Allylic Amines: Reaction of 2-(Trimethylsilyl)ethyl Sulfones and Sulfoxides with Fluorinated Imines.

2008

A new synthesis of fluorinated allylamines through the reaction of 2-(trimethylsilyl)ethyl sulfones and sulfoxides (as vinyl anion equivalents) with imines and imino esters has been described. The process includes a TBAF-mediated fragmentation of 2-(trimethylsilyl)ethyl sulfones to afford the desired allylic amines. When the reaction is performed with the corresponding sulfoxides, the fragmentation takes place under the addition conditions, affording the final products in a single step.

ChemInform Abstract: A Simple Procedure for the Oxidation of Alcohols Using [Bis(acetoxy)iodo]benzene and a Catalytic Amount of Bromide Ions in Ethyl…

2015

Primary and secondary benzylic alcohols and secondary aliphatic alcohols were oxidized to the corresponding aldehydes and ketones by using [bis(acetoxy)iodo]benzene (BAIB) and a catalytic amount of bromide ions, from tetrabutylammonium bromide or KBr, in ethyl acetate. The catalytic role of the bromide ions was also highlighted in the oxidation of primary aliphatic alcohols and secondary allylic alcohols carried out in the presence of 1 mol% TEMPO.

Diphosphines of dppf-Type Incorporating Electron-Withdrawing Furyl Moieties Substantially Improve the Palladium-Catalysed Amination of Allyl Acetates

2005

Highly active Pd/diphosphine catalytic systems incorporating new, air-stable ferrocenyl-furylphosphines allow nucleophilic allylic amination at room temperature with unprecedented turnover frequencies. For instance, in the presence of 0.01 mol % catalyst the coupling of aniline to allyl acetate occurs at a TOF of more than 10,000 h - 1 ; even the addition of the less nucleophile morpholine to allyl acetate is observed with a TOF of 4250 h - 1 . The amination of the sterically demanding geranyl acetate, a monoterpene derivative of interest in the flavour industry, at low catalyst loadings demonstrates the scope of this methodology, which provides in addition noticeable advantages in terms of…

ChemInform Abstract: Enantioselective Allylic Substitution Using a Novel (Phosphino-α-D-glucopyrano-oxazoline)palladium Catalyst.

2010

Zur herstellung molekulareinheitlicher, über schwefelhaltige brücken verbundener, phenolischer zweikernverbindungen

1963

Phenole lassen sich mit Thionylchlorid mittels Aluminiumchlorid in hohen Ausbeuten zu molekulareinheitlichen Sulfoxyden kondensieren, die sich im praparativen Masstab einerseits zu Sulfiden reduzieren und andererseits zu Sulfonen oxydieren lassen. Die Sulfone konnen auch in guten Ausbeuten mittels Aluminiumchlorid durch Kondensation von Phenolathersulfochloriden mit Phenolathern und durch FRIESsche Verschiebung entsprechender Sulfonsaureester erhalten werden. Phenols can be condensed with thionylchloride using aluminium chloride as catalyst in good yields to molecularly defined sulfoxides, which can be preparatively reduced to sulphides or oxidised to sulphones. The sulphones were also obta…

NMR-Spektroskopie an Heterocyclen, 6. Mitt. Favorskii-Umlagerung von α-Brom-β-methoxy-ketonen bei der Imidazol-Cyclisierung in flüssigem Ammoniak

1979

Bei der Imidazolsynthese aus α-Bromketonen und Formiminoethylester in flussigem Ammoniak werden α-alkylsubstituierte Buttersaure-Amide als Nebenprodukte erhalten, deren Entstehen einer Favorskii-Umlagerung zugeschrieben wird. Die isolierten Verbindungen wurden NMR-spektroskopisch untersucht. NMR Spectroscopy of Heterocycles. VI: Favorskii Rearrangement of α-Bromo-β-methoxy Ketones During Imidazole Cyclisation in Liquid Ammonia. During imidazole synthesis with α-bromo ketones and formiminic ethyl ester in liquid ammonia α-alkylbutyric amides were obtained as by-products. Their formation is attributed to a Favorskii rearrangement. The compounds were investigated by NMR spectroscopy.

Synthesis of Isoxazoline Derivatives through Boulton-Katritzky Rearrangement of 1,2,4-Oxadiazoles

2013

The base-induced rearrangement of 1,2,4-oxadiazoles into isoxazoline derivatives is reported. This represents the first example of a three-atom side-chain rearrangement that involves a saturated CCO side chain at C-3 of the oxadiazole. Nonaromatic 3-amino-isoxazoline derivatives are obtained in good yields. Interestingly, this reaction occurs through the rearrangement of aromatic oxadiazoles to form less stable bonds than those that are broken.