Octahydro quinoline

The lithium- -propylamine reducing system has been found capable of reducing julolidine (113) to /d -tetrahydrojulolidine (114, 66% yield) and 1-methyl-1,2,3,4-tctrahydroquinoline to a mixture of enamines (87% yield), l-methyl-J -octahydroquinoline (115) and 1-methyl-al -octahydro-quinoline (116) 102). This route to enamines of bicyclic and tricyclic systems avoids hydroxylation, which occurs during mercuric acetate oxidation of certain bicyclic and tricyclic tertiary amines 62,85 see Section III.A). 

The reductive route used to prepare heterocyclic enamines has the advantage of avoiding the hydroxylation reaction sometimes found in the mercuric acetate oxidation of saturated heterocyclic amines [126]. The lithium-n-propyl-amine reducing system has been used by Leonard to reduce julodine to A5-tetrahydrojulolidine (66% yield) and l-methyl-l,2,3,4-tetrahydroquinoline to a mixture of enamines (87% yield), consisting of l-methyl-A8-octahydro-quinoline and 1-methyl-A9-octahydroquinoline [135] (Eqs. 51, 52). 

Chiral 1,2,3,4-tetrahydropyridine 192 derived from (h )-l -phenylcthylarninc undergoes base-induced addition of methyl vinyl ketone to give a 2 1 separable diastereomeric mixture of m-fused octahydro-quinolin-7-ones 193 and 194 (Equation 16) <2001TA2099>. 

A situation analogous to that of the pyrroline derivatives also exists, according to spectroscopic data, with N-unsubstituted piperideine compounds. There is little experimental data because A 2-piperideines have not been studied as extensively as the analogous pyrrolines. The A structure has been established for some aliphatically substituted piperideines, e.g., J1(8)-hexahydropyrindene,12,13 J1(10)-octahydro-quinoline,13 and the alkaloid y-coniceine.14,15 According to conformational considerations, structures other than A piperideine could be expected more frequently in the piperideine series. The thia analog16 3 occurs in the amino form as shown by infrared spectral data and the estimation of active hydrogen. 

D. CijHzjN, —,—, ion trap, miz 193(5), 150(100), 122(12), 96(12). ID. Infrared data (75). Tentative structure a2-propyl-5-methyl octahydro-quinoline. 

Another intramolecular version of the aza-Diels-Alder reaction was realized with the condensation of a dienyl aldehyde and benzylamine hydrochloride at 70 °C in 50% aqueous ethanol (Scheme 10) [59]. This methodology was used in the synthesis of racemic dihydrocannivonine [60] and substituted octahydro-quinolines related to pumiliotoxin C [61]. 

The stereochemical rationale put forth for the observed stereoisomers involves examination of four transition states (I-IV). Adducts 52 and 53 would arise from the chair-like conformations I and II respectively (Scheme 2.7). The formation of 52 as the major product was anticipated since the related transition-state conformation II leading to 53 is destabilized by an eclipsing interaction between Ha and Hb. Not surprisingly, the octahydro-quinoline products, 54 and 55, derived from the two boatlike conformations, III and IV, are not detected. 

Pyrazino[l, 2-c]pyrimidin-6-one, octahydro-reactions, 3, 351 Pyrazino[2,3 -6]quinoline synthesis, 3, 256... 

The infrared, ultraviolet and NMR spectra of /) -octahydro-7-quinoline were compared with the corresponding spectra of the N-ethyl and O-ethyl derivatives in order to determine whether it is in the enamine (64), enolimine (65), or ketimine (66) form. 

Deca/octahydro 6-alkyloxazolo /-fused quinolines 17 were prepared and evaluated as dopaminergics (87EUP1). A series of linearly annelated 8-alkyl-deca/ octahydrooxazoloquinolines 18 and their salts were prepared for use as dopamine D2-agonists and hypertensive agents. The rran.s-( )-l-propyl-6-oxodecahydro-quinoline was brominated, then treated with urea in methanol to give the 2-amino... 

The intramolecular formal [3+3] cycloaddition reaction of l- [l-phenyl-2-(4-oxobut-2-enyloxy)ethyl]amino cyclo-hexen-3-one at 150°C in the presence of piperidinium acetate afforded /ra 3--l,4a-77-l-phenyl-l,2,4,4a,7,8,9,10-octahydro[l,4]oxazino[4,3- ]quinolin-7-one <2002JA10435>. At 85°C, the 6-(l-piperidnyl)-l,2,4,4a,5,6,7,8,9,10-dec-ahydro derivative formed, which could be converted into the l,2,4,4a,7,8,9,10-octahydro derivative by heating at 150 °C. Cyclization of iV-[(2-butyl-2-oxoethoxy)acetyl]-3,4-dimethoxyphenylethylamine on the action of TFA gave llb-butyl-1,3,4,6,7,1 lb-hexahydro[l,4]oxazino[3,4- ]isoquinolin-4-one <1997JOC2080>. 

Hydrogenation of benzo[/]quinoline over Raney nickel at 150 °C and 70 atm gives l,2,3,4,7,8,9,10-octahydrobenzo[/]quinoline (52) as the main product, together with some m-l,2,3,4,4a,5,6,10b-octahydro isomer (53 Scheme 38). Use of sodium in pentyl alcohol gives the trans isomer of (53) together with (52) (64JOC1419). 

Benzo[f]quinoline. Bcnzo[/lquinolinc was hydrogenated to the 1,2,3,4-tetrahydro derivative almost quantitatively over Raney Ni at 100°C, while at 150°C a mixture of two octahydro derivatives was produced a greater part of this mixture was 1,2,3,4,7,8,9,10-octahydro compound (eq. 12.54).108 No trans isomer of l,2,3,4,4a,5,6,10b-octahydro derivative was isolated. 

Hydrogenation of l,2,3,4-tetrahydrobenzo[/]quinoline over platinum oxide gave also the 1,2,3,4,7,8,9,10-octahydro compound as the major product together with small amounts of cis- and trans-1,2,3, 4,4a,5,6, lOb-octahydro derivative (eq. 12.55). The hydrochloride of the tetrahydro compound was hydrogenated over platinum oxide in ethanol to give the 1,2,3,4,7,8,9,10-octahydro derivative in a better yield of 84% together with 4.5% of m-1,2,3,4,4a,5,6,lOb-octahydro compound.108... 

Benzo[h]quinoline. In contrast to the case of acridine, the hydrogenation of benzo /t quinolinc over platinum oxide in trifluoracetic acid afforded a mixture of two octahydro derivatives together with a small amount of the 7,8,9,10-tetrahydro derivative, although the octahydro compound hydrogenated in the benzene rings was the major product (eq. 12.56).37... 

Benzo[(i]quinolines, 1,2,3,4,4a,5,6,1 Ob-octahydro-, stereoisomers, 57, 57 Benzoquinolizinium (ions/salts) reactivity indexes, 55, 344 reactivity with nucleophiles, 55, 346 Benzo[a]quinolizinium (ions/salts) calculated electron densities, 55, 275 calculated electronic spectrum, 55, 324 nitration, 55, 342 synthesis, 55, 282 Benzo[a]quinolizinium (ions),... 

QDX or SEX. See l-Acetyl-3,5,7-trinitro-octahydro-s-triazine A49 R Quinolylamine. See Amino quinoline A255-R... 

Cyclocondensation of 3-amino-5-methylpyrazole with 2-arylmethyli-dene-5,5-dimethylcyclohexane-l,3-diones or 9-aryl-3,3,6,6-tetramethyl-2,3,4,5,6,7,8,9-octahydro-lH-xanthene-l,8-diones, in DMF or methanol gave 4-aryl-3,7,7-trimethyl-l,4,6,7,8,9-hexahydropyrazolo[3,4- 7]quinolin-5-ones 323 whose structure was proved by the X-ray diffraction data (06RJOC1015). 

Oa-Methoxy-1 -methyl-dihydrolysergol 5-bromonicotinate 5-Bromopyridine-3-carboxylate of [(6aR, 9R, 10aS)-10a-methoxy-4,7-dimethyl-4,6,6a, 7,8,9,10, lOa-octahydro-indolo- [4, 3-fg] quinoline-9-yl]methyl... 

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