Chemical Modification of Poly(Vinyl Chloroformate)

Meunier, G.; Boivin, Sylviane; Hémery, Patrick; Senet, J.‐P. G.; Boileau, Sylvie

doi:10.1007/978-1-4613-3748-5_21

Cited by 2 publications

(7 citation statements)

References 15 publications

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“…(13) We originally attempted alkylation of 2-methyl-5,6,7,8-tetrahydroquinoline using alkyllithium reagents or LDA in THF at low temperatures, but poor selectivity was obtained, and the product mixtures were difficult to separate. Light brown needles (14.7 g, 51.5 mmol, 82%) were thus obtained, which were only slightly hygroscopic and could be stored in a desiccator for weeks: mp 128-129 °C (lit.15 mp 125-128 °C); IR (neat film) 3020,1609,1582,1491,1413 cm"1; NMR (200 MHz, CDC13) 7.95 (d, J = 8 Hz, 1 H, Ar-H), 7.62 (d, J = 8 Hz, 1 H, Ar-H), 4.20 (s, 3 H, NCH3), 3.18 (t, J = 6.6 Hz, 2 H, ArCH2), 2.93-2.89 (m, 5 H, overlapping frequencies), 2.18-1.97 (m, 2 H, CH2), 1.90-1.78 (m, 2 H, CH2); 13C NMR (22.5 MHz, CDC13) b 154.0, 152.6, 144.0, 136.0, 125.9, 40.9, 28.6, 28.0, 22.4, 20.9, 19.4. 4,4a,5,6,7,8-Hexahydro-2(3H)-naphthalenone (3).…”

Section: Methodsmentioning

confidence: 99%

“…2-Ethy 1-iV-methy 1-5,6,7,8-tetrahydroquinolinium Iodide. Freshly distilled 2-ethyl-5,6,7,8-tetrahydroquinoline was treated as described for the preparation of 2 with the exception that the iodomethane solution was stirred for 24 h. Light brown crystals were obtained (16.0 g, 52.8 mmol, 80%) after recrystallization: mp 109-110 °C; IR (KBr) 3020, 2932, 1605,1578,1050 cm"1; NMR (200 MHz, CDC13) 7.94 (d, J = 8.3 Hz, Ar-H), 7.57 (d, J = 8.3 Hz, 1 H, Ar-H), 4.15 (s, 3 H, NCH3), 3.14-3.08 (m, 4 H, Ar-CH2), 2.89-2.83 (m, 2 H, Ar-CH2), 2.0-1.8 (m, 2 H, CH2), 1.80-1.75 (m, 2 H, CH2), 1.33 (t, J = 7.3 Hz, 3 H, CH2CH3); 13C NMR (22.5 MHz, CDC13) b 158.8,155.9,145.5,136.9,125.0, 40.1, 29.5, 28.9, 22.4, 20.9, 12.3, 7.0. 4,4a,5,6,7,8-Hexahydro-l-methyl-2(3H)-naphthalenone (6).…”

Section: Methodsmentioning

confidence: 99%

“…1979, 101, 5070-5072. 7 was prepared by deprotonation of quinaldine13 and alkylation with the iodo ketal 4.14 Although the hydrogenation in concentrated acid did not proceed cleanly, we found that if the reaction was stopped at 40% conversion to the tetrahydro product, the yield of the ketone was 92%, with very little alcohol being formed. The partially hydrogenated and unhydrogenated materials were readily separable by flash chromatography so that the 2-(4-oxopentyl)quinoline could be recycled.…”

Section: Synthesis Of 2-octalones From Quinaldinementioning

confidence: 96%

“…As shown in Scheme I, quinaldine was hydrogenated in neat trifluoroacetic acid (TEA) as described by Vierhapper and Eliel. 7 The methiodide 2 was formed by allowing the above compound to stir in iodomethane followed by recrystallization from 2-propanol/ ether. This material was not very hygroscopic and was easy to handle when prepared in this way.…”

Section: Synthesis Of 2-octalones From Quinaldinementioning

confidence: 99%

“…Caled for C16H20O2S: C, 69.53; H, 7.29. Found: C, 69.41; H, 7.24. 2-Phenylethyl phenyl sulfone (4e): NMR (CC14) 2.7-3.3 (m, 4), 7.0 (s, 5), 7.2-7.9 (m, 5). Anal.…”

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Synthesis of 2-octalones from quinaldine

Stevens¹,

Canary²

1990

J. Org. Chem.

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General. Reactions were carried out in an inert atmosphere using predried (sodium benzophenone ketyl) and distilled THF. Haloalkanes were obtained commercially. Product mixtures were separated to obtain analytical data by medium-pressure chromatography using an EM Lobar Si 60 column with 10% diethyl ether-gO% ligroin (60-80 "C) as eluent. Quantitative analysis of the reaction mixtures was accomplished on a Waters 6000 HPLC using an IBM silica column with 15% diethyl ether-85% ligroin (60-80 "C). The UV detector was calibrated on known product mixtures. NMR spectra were obtained using a Varian EM-390 spectrometer.General Alkylation Procedure. One millimole each of the sulfone and base were added to 7-15 mL of T H F and allowed to stir for 1 h at 0 "C. One millimole of the alkylating agent was added a t that same temperature, and the mixture was allowed to stir a t room temperature for 5 h. Addition of 5 mL of water, ether extraction, drying with MgS04, and removal of the solvent via a rotary evaporator provided the product mixture.Kinetic Reactions. Six millimoles of the appropriate sulfone in T H F and of butyllithium were mixed a t 0 "C. After 1 h the slurry was brought to room temperature, and then 6 mmol of bromoalkane was added. Alliquots (1 mL) were removed and quenched with water a t specific times. The samples were recovered as above and analyzed by HPLC.Equilibration-Deuterium Quench. An equimolar mixture of butyllithium, sulfone 1, and sulfone 4a were stirred for 1 h at 0 "C in 7 mL of THF. Deuterium oxide was added to the mixture, and the products were recovered as above, separated by medium-pressure chromatography, and analyzed for deuterium content by NMR spectroscopy.Deuterium Quench. An equimolar mixture of 1 and butyllithium were stirred in 7 mL of T H F a t 0 "C for 1 h. Deuteriosulfuric acid (1 M) was added, and the product was recovered as above and analyzed for deuterium content by NMR spectroscopy.Methyl phenyl sulfone (1): via oxidation of methyl phenyl sulfide with 30% hydrogen peroxide in acetic acid;18 91%; mp 87.4-89.6 "C (lit.IEb mp 86-88 "C); 'H NMR (CDCl,) 6 3.0 (9, 3), 7.5-7.8 (m, 5).Butyl phenyl sulfone (4a): 'H NMR (CC14) 6 0.9 (t, 3, J = 6 Hz), 1.1-1.9 (m, 41, 3.0 (t, 2, J = 6 Hz), 7.3-7.9 (m, 5 ) . Anal. Calcd for CI0Hl4O2S: C, 60.58; H, 7.12. Found C, 60.71; H, 7.20. 4-Heptyl phenyl sulfone (5a): 'H NMR (CC14) 6 0.9 (t, 6, J = 6 Hz), 1.1-1.9 (m, a), 2.6-2.9 (m, l), 7.2-7.9 (m, 5). Anal. Calcd for C13H,o0,S: C, 64.96; H, 8.39. Found: C, 64.79; H, 8.07. 4-(4-Propylheptyl) phenyl sulfone (6a): 'H NMR (CDCl,) 6 0.8 (t, 9, J = 6 Hz), 1.2-1.8 (m, 12), 7.3-7.8 (m, 5 ) .

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Synthesis Of 2-octalones From Quinaldinementioning

confidence: 96%

Section: Synthesis Of 2-octalones From Quinaldinementioning

confidence: 99%

“…Caled for C16H20O2S: C, 69.53; H, 7.29. Found: C, 69.41; H, 7.24. 2-Phenylethyl phenyl sulfone (4e): NMR (CC14) 2.7-3.3 (m, 4), 7.0 (s, 5), 7.2-7.9 (m, 5). Anal.…”

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