Quinolines vinylation

Quinoline, 2,2,4-trimethyl-1,2-dihydro-antioxidant in polymers, 1, 395 Doebner-von Miller synthesis, 2, 468 Quinoline, trimethylstannyl-reactions, 2, 364 Quinoline, 4-vinyl-polymers, 1, 286... 

Abbreviations aapy, 2-acetamidopyridine Aik, alkyl AN, acetoniuile Ar, aryl Bu, butyl cod, 1,5-cyclooctadiene COE, cyclooctene COT, cyclooctatetraene Cp, cyclopentadienyl Cp , penta-methylcyclopentadienyl Cy, cyclohexyl DME, 1,2-dimethoxyethane DME, dimethylformamide DMSO, dimethyl sulfoxide dmpe, dimethylphosphinoethane dppe, diphenylphosphinoethane dppm, diphenylphosphinomethane dppp, diphenylphosphinopropane Et, ethyl Ec, feirocenyl ind, inda-zolyl Me, methyl Mes, mesitylene nb, norbomene orbicyclo[2.2.1]heptene nbd, 2,5-norbomadiene OTf, uiflate Ph, phenyl PPN, bis(triphenylphosphoranylidene)ammonium Pi , propyl py, pyridine pz, pyrazolate pz, substituted pyi azolate pz , 3,5-dimethylpyrazolate quin, quinolin-8-olate solv, solvent tfb, teti afluorobenzobaiTelene THE, tetrahydrofuran THT, tetrahydrothiophene tmeda, teti amethylethylenediamine Tol, tolyl Tp, HB(C3H3N2)3 Tp , HB(3,5-Me2C3HN2)3 Tp, substituted hydrotiis(pyrazol-l-yl)borate Ts, tosyl tz, 1,2,4-triazolate Vin, vinyl. 

TL2403). Thus, or /io-cyclopalladation of acetanilide 138 gave organo-palladium reagent 139. The or /io-vinylation of 139 afforded enone 140, which was then cyclized to quinoline 141 under acidic conditions. Notice this reaction requires stoichiometric amounts of Pd(OAc)2. 

Quinoline 2-thiols are excellent precursors for construction of this ring system. Thus, allylation or vinylation of quinoline thiol 640 gave 2-vinylthioquinolines 641 or 2-allylthioquinolines 642 which were... 

Treatment of 8-fluoro-l,2-dihydro-4 7,67/-[l,4]oxazino[4,3-a]quinoline-4,6-dione with 6N aqueous NaOH and PhCH2Br under reflux overnight and with NaOMe in DMF at ambient temperature yielded l-(2-benzyloxyethyl)- and l-vinyl-6-fluoro-l, 4-dihydroquinoline-2-carboxylic acids, respectively (01SL833). 

For the synthesis of quinolines and isoquinolines the classical approaches are the Skraup and the Bischler-Napieralski reactions. The reaction of substituted anilines with different carbonyl compounds in acid medium has been reported to be accelerated under microwave irradiation to give differently substituted quinolines and dihydro quinolines [137]. Although the yields are much better and the conditions are milder than under conventional heating, the acidity of the medium may prevent the preparation of acid-sensitive compounds. Thus, alternative approaches have been investigated. Substituted anilines and alkyl vinyl ketones reacted under microwave irradiation on the surface of sihca gel doped with InCU without solvent [137] to furnish good yields of quinohnes 213 (Scheme 77). 

Palladium-catalyzed reaction of alkyne 47 with a variety of aryl and vinyl halides afforded alkenes 48 in good yield. Cyclization to quinolines 49 was performed by treating 4 8 with TsOH in EtOH <96T(52)10225>. 

The [4+2] cycloaddition reaction of N-atylaldimines with vinyl ethers is effectively catalyzed by ytterbium(III) triflate to give quinoline derivatives (e.g., 50) in good yield <95S801>. 

The reduction of aromatic nitro compounds to amino derivatives and cyclizations to various heterocyclic compounds are presented in Chapter 9. Recent advances are presented here. Reaction of 2-nitrobenzaldehyde with vinyl carbonyl compounds in the presence of 1,4-diazbi-cyclo[2.2.2]octane affords Baylis-Hillman products, the catalytic reduction of which results in direct cyclization to quinoline derivatives (Eq. 10.78).134... 

The preparation of quinoline and tetrahydroquinoline derivatives from metal carbonyl-catalyzed reactions of Schiff bases with alkyl vinyl ethers in... 

JOC6503>, and new pyridazino-psoralens 15 were prepared via a furan ring expansion reaction <05T4805>. The reaction of 3-acetylcoumarins with alloxan followed by NH2NH2 easily produced 3-(2-oxo-2//-chromen-3-yl)-6//,8//-pyrimido[4,5-c]pyridazine-5,7-diones <05JHC1223>. Furano- and pyrano[2,3-c]pyridazines 17 and 18a,b as well as substituted quinolines were conveniently prepared from pyridazinone 16 and vinyl- and allyltriphenyl-phosphonium salts <05HAC56>. 

Formate esters behave as typical carbonyl compounds in reactions with a number of ylides, eliminating phosphine oxide and forming vinyl ethers, e.g. (33).35 Stabilized phosphoranes are able to condense with the carbonyl group of cyclic thioanhydrides (34).38 Quinoline derivatives, e.g. (35), are obtained from the condensation of dicar-boalkoxy-ylides with isocyanates.37 Benzoyl isothiocyanates and keto-phosphoranes give quantitative yields of (36), which are unreactive in Wittig reactions but can be readily oxidized by selenous acid.38 The products obtained from reactions (Scheme 9) with the triazolinedione (37) depend upon the stability of the ylide used.39... 

The mechanisms of aminolysis of substituted phenyl quinoline-8- and -6-carboxylates, (36) and (37), have been evaluated using AMI semiempirical and HF/6-31- -G(d) ab initio quanmm mechanical methods to study the ammonolyses of the model systems vinyl c/x-3-(methyleneamino)acrylate (38), c/x-2-hydroxyvinyl di-3-(methyleneamino)acrylate (39) and vinyl rranx-3-(methyleneamino)acrylate (40). Both experimental and computational results support the formation of a tetrahedral intermediate in the reaction. The results of this study are fully consistent with the experimental observations for the aminolyses of variously substituted phenyl quinoline-8- (36) and -6-carboxylates (37). ... 

V-(Methoxyprop-2-yl) -8-methyl-2 oxo-1,2,3,4-tetrahyd ro-quinoline, see Metolachlor 7V-(Methoxyprop-2-yl)-yV-(2-methyl-6-vinyl) aniline, see Metolachlor... 

Oxime derivatives having allyl and vinyl groups can be intramoleculary cyclized to pyridine or quinoline derivatives ... 

Makioka Y, Shindo T, Taniguchi Y, Takaki K, Fujiwara Y (1995) Ytterbium(III) triflate catalyzed synthesis of quinolinic derivatives from V-arylaldimincs and vinyl ethers. Synthesis 801-804... 

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