Part III
Chapter 6
Experimental section
6.1 Chemicals and instruments
6.1.1 Purification of solvents and reagents
All the solvents employed were purified and dried immediately before use. Tetrahydrofuran (THF) was stirred in the presence of KOH for 12 h, then refluxed on, and distilled from, sodium and LiAlH4 subsequently.217 Diethyl ether and hexane were refluxed on, and distilled from, sodium and LiAlH4.217 Dichloromethane (CH2Cl2) was refluxed on, and distilled from, P2O5.217 Pyridine was refluxed on, and distilled from, potassium hydroxide (KOH), then stored in the dark under N2 atmosphere.217 Tosyl chloride was purified by estraction in a Soxhlet apparatus, using benzene as solvent. Alkynes were distilled immediately before use. Quinoline and isoquinoline were purified by distillation. Trimethylsilyl chloride was distilled immediately before use. Triethyl aluminum was purified by distillation (b.p. 51 oC/0.1 mmHg). The Grignard reagents employed were available in the laboratory and were used after titration.
6.1.2 Instruments
Gas chromatographic analyses were performed on a Perkin-Elmer 8500 or on a Perkin-Elmer Clarus 500 gas chromatograph, equipped with a split-splitless injector and a FID detector, using a capillary column ZB-1 (15 m*0.25 mm, film thickness 0.25 μm), and He as carrier gas. NMR spectra were recorded on a Varian Gemini NMR spectrometer, at the frequencies of 200 MHz (1H) and 50
MHz (13C) respectively, using TMS and CDCl3 as internal standard, unless otherwise stated. Mass spectra were recorded on an Agilent 5995A spectrometer, interfaced with an Agilent 5980 gas chromatograph, equipped with a split-splitless injector and a ZB-1 column (30 m*0.25 mm, film thickness 0.25 μm), using He as carrier gas.
6.2 Synthesis of the starting reagents
6.2.1 Synthesis
of
di-i-butyl aluminum hydride (DIBAL-H)
As previously reported, triisobutyl aluminum (50 ml), was transferred via cannula into a three-necked flask equipped with a condenser and a magnetic stirrer, dried and maintained under N2 atmosphere. The reaction mixture was slowly heated to 130 oC, and the apparatus was placed under vacuum (18 mmHg). After 6h the product was transferred under inert atmosphere into a distillation apparatus and distilled under vacuum (b.p. 86 oC/0.1 mmHg). The purified product was maintained under N2.
6.2.2 Synthesis of benzenesulfinyl chloride
A 250 ml, two-necked flask equipped with a reflux condenser and a magnetic stirrer was dried and placed under a N2 atmosphere. Freshly distilled thionyl chloride (50 ml) was added; 21.473 g (139.9 mmol) of sodium benzenesulfinate were cautiously added in small portions to the stirred reaction mixture. The reaction mixture was stirred for 2h, and filtered under inert atmosphere. When the exothermic reaction ceased, the excess of thionyl chloride was removed under vacuum and the residue was washed several times with anhydrous diethyl ether. The crude reaction product was transferred into a distillation apparatus. Distillation at reduced pressure (85-90 oC/0.05 mmHg) afforded 13.45 g (64%) of product.
6.2.3 Synthesis of 1-N-benzoyl imidazole
According to a reported procedure,218 a 50 ml three-necked flask, equipped with a reflux condenser and a magnetic stirrer, dried and placed under N2 atmosphere, was filled with 1.74 ml (15 mmol) of benzoyl chloride and 25 ml of dry THF. The reaction mixture was cooled to 0 oC, and imidazole (2.04 g, 30 mmol), dissolved in 25 ml of dry THF, was added dropwise during 10 minutes. After the appearance of an
N N
abundant white precipitate, the mixture was stirred for additional 3h, then filtered. The clear ethereal solution was quickly washed with 100 ml of cold water and dried over Na2SO4. After removal of the solvent at reduced pressure, 2.008 g (11.7 mmol, 78%) of chemically pure product were recovered, as a colorless liquid; GC-MS (m/z, I%): 172 (M.+, 21), 105 (100), 95 (14), 77(32), 65(8); 1H NMR: 7.15 (d, J=0.6 Hz, 1H), 7.5-7.85 (m, 6H), 8.08 (s, 1H); 13C NMR: 118.1, 129.0, 129.8, 130.9, 132.0, 133.6, 138.2, 166.1.
6.2.4 Synthesis
of
8-trimethylsilyloxyquinoline
Analogously to what previously reported,219 a two-necked flask equipped with a magnetic stirrer and a reflux condenser, maintained under inert atmosphere, was successively charged with 50 ml of dry CH2Cl2, 4.785 g (33 mmol) of 8-hydroxyquinoline, 2.357 g of imidazole (34.65 mmol), and 4.62 ml (36.3 mmol) of trimethylsilyl chloride. The mixture was stirred overnight, then diethyl ether (100 ml) was added; the resulting suspension was filtered through synthered glass. The organic layer was dried over Na2SO4 and the solvent evaporated under reduced pressure (18 mmHg), affording the chemically pure product as a yellowish oil (6.323 g, 88%); GC-MS (m/z, I%): 216 (M.+, 3), 204 (5), 203 (20), 202 (100), 186(2), 172 (34), 142 (4), 128 (5), 101 (5), 94 (4); 1H NMR: 0.2 (s, 9H), 7.21 (dd, J=7.2 Hz, J’= 1.4 Hz, 1H), 7.36 (dd, J=8.2 Hz, J’=1.4 Hz, 1H), 7.45 (dd, J=4.2 Hz, J’=4.4 Hz, 1H), 7.48 (dd, J=4.2 Hz, J’=0.9 Hz, 1H), 8.18 (dd, J=8Hz, J’=0.9 Hz, 1H), 8.81 (dd, J=4.4 Hz, J’=1.4 Hz, 1H); 13C NMR: 5.4, 110.4, 118.0, 121.9, 127.9, 128.7, 136.3, 138.4, 148.1, 152.4..
6.3 General
procedures
General procedures for the previously described reactions are here reported. Characterization of the synthesized products are reported in Section 6.4.
6.3.1 Hydroalumination of alkynes
In a typical run, a 100 ml three-necked flask equipped with reflux condenser, magnetic stirrer and dropping funnel, dried and maintained under N2, was successively charged with 20 ml of dry hexane and 4.4 mmol of the appropriate alkyne. The solution was cooled to 0 oC and 4.0 mmol of DIBAL-H in 5 ml of dry hexane were added dropwise through the dropping funnel. The mixture was
N O Me3Si
refluxed until a complete conversion (GLC) of the reagent was achieved (usually after 6h), then allowed to cool to room temperature. The resulting alane was employed in the subsequent reactions without further purification.
6.3.2 Synthesis of unsolvated dialkyl alk-1-ynyl alanes
In a typical run, a three-necked flask equipped with a reflux condenser, a magnetic stirrer and a dropping funnel, mantained under N2, was charged with 4.0 mmol of the appropriate alkyne dissolved in 20 ml of dry hexane. The reaction mixture was cooled to -20 oC and then added dropwise of butyllithium (4.0 mmol) in 5 ml of hexane. After stirring for 30min, the resulting white suspension was warmed to 0 oC and 4.0 mmol of Et2AlCl were added to the reaction mixture. After 30 min the homogeneous solution was allowed to warm at room temperature and the resulting organoalane was employed in the subsequent reactions without further purification.
6.3.3 Synthesis of alk-1-enyl sulfoxides via aluminum sulfinates
In a typical run, a three-necked flask dried and maintained under N2, equipped with a magnetic stirrer, a reflux condenser and a dropping funnel, was charged with 2.0 mmol of the appropriate sulfonyl chloride dissolved in 3 ml of dry CH2Cl2. The solution was cautiously added of 0.27 ml (2.0 mmol) of triethyl aluminum in 5 ml of dry CH2Cl2. After the exothermic reaction ceased, the solution was allowed to cool to room temperature, then diluted with 20 ml of dry hexane and 3 mmol of the appropriate di-i-butyl alk-1-enyl alane, prepared according to the procedure described in Section 6.3.1. The reaction mixture was refluxed for 5 hours, then cooled and siphoned onto a short column of silica gel. After elution with 200 ml of CH2Cl2 and drying on anhydrous Na2SO4, removal of the solvent at reduced pressure afforded the chemically pure sulfoxide.
6.3.4 Synthesis of aryl alk-1-enyl sulfoxides using pyridinated
organo alanes
In a typical run, a three-necked flask, equipped with a reflux condenser, a dropping funnel and a magnetic stirrer, was thoroughly dried and placed under N2. The appropriate alane (2.0 mmol), prepared according to Section 6.3.1, was introduced. The hexane was removed at reduced pressure, and CH2Cl2 (20 ml) was added. Pyridine (0.16 ml, 2.0 mmol) was added to the organometallic reagent, and the resulting bright yellow solution was cooled to 0 oC; tosyl chloride (0.350 g, 1.84 mmol) and triphenylphospine (707 mg, 2.7 mmol) were quickly
introduced in the reaction flask. After stirring for 15 min the solution was allowed to warm to room temperature, siphoned onto a short column of silica gel and eluted with 200 ml of CH2Cl2. After removal of the solvent at reduced pressure, the product was further purified by flash chromatography.
6.3.5 Synthesis of unsaturated sulfoxides from unsolvated alanes
and benzenesulfinyl chloride in the presence of Ph
3PO
In a typical run, a three necked flask, equipped with a reflux condenser, a dropping funnel and a magnetic stirrer, dried and maintained under a N2, was charged with benzenesulfinyl chloride (3 mmol) dissolved in 10 ml of dry CH2Cl2; Ph3PO (1.5 mmol) was then added to the stirred solution. The reaction mixture was cooled to 0 oC, and 3.3 mmol of the appropriate organoalane was quickly introduced through the dropping funnel. After stirring for 1 h at 0 oC, the solution was syphoned onto a short column of silica gel, and eluted with 200 ml of CH2Cl2. The solution was dried with anhydrous Na2SO4 and the solvent was removed at reduced pressure. The product was further purified by flash chromatography.
6.3.6 Synthesis of alk-1-enyl sulfones from sulfonyl chlorides and
pyridine-coordinated alanes in the presence of Ph
3PO
In a typical reaction, a three-necked flask, equipped with a reflux condenser, a dropping funnel and a magnetic stirrer was dried and charged with 2.0 mmol of the appropriate alane, prepared according to Section 6.3.1. The solvent was removed at reduced pressure and CH2Cl2 (20 ml) and pyridine (2.0 mmol) were added to the organometallic reagent. A catalytic amount (0.3 mmol) of Ph3PO and tosyl chloride (1.8 mmol) were added to the resulting bright yellow solution. The reaction mixture was refluxed for 1 h, cooled and hydrolyzed with the addition of an aqueous solution (1% v/v) of H2SO4. After extraction with CH2Cl2, the organic layer was dried on Na2SO4 and the solvent was removed at reduced pressure (18 mmHg). The product was further purified by flash chromatography.
6.3.7 Synthesis of alk-1-enyl sulfones using sulfonyl
chloride-pyridine complexes and uncomplexed alanes
In a typical reaction, a three-necked flask equipped with reflux condenser, dropping funnel and magnetic stirrer was thoroughly dried and maintained under N2; the flask was charged with tosyl chloride (0.381 g, 2.0 mmol) CH2Cl2 (20 ml) and pyridine (0.16 ml, 2 mmol). The solution was stirred for 30 min, and very
quickly (10 seconds) added of a CH2Cl2 solution (10 ml) of the appropriate dialkyl alk-1-enyl alane (2.0 mmol). After stirring for 4 h the reaction mixture was hydrolyzed with an aqueous solution of H2SO4 (1%), extracted with CH2Cl2 and dried on anhydrous Na2SO4. After removal of the solvent at reduced pressure (18 mmHg) the product was further purified by flash chromatography.
6.3.8 Synthesis of alk-1-enyl sulfones using sulfonyl
chloride-pyridine complexes and uncomplexed alanes in the
presence of CuCl
In a typical run, tosyl chloride (2.0 mmol) and CH2Cl2 (20 ml) were introduced under N2 into a dry three-necked flask equipped with reflux condenser, dropping funnel and magnetic stirrer.After addition of pyridine (0.16 ml, 2.0 mmol) to the reaction mixture, the solution was stirred for 30 min. The appropriate dialkyl alk-1-enyl alane, dissolved in CH2Cl2, was quickly added to the reaction mixture. The solution was stirred at room temperature until the conversion was stationary (usually overnight), and the appropriate amount of CuCl (1.0-2.0 mmol) was added to the reaction mixture. The resulting blue solution was stirred at room temperature until the maximum conversion was achieved, then hydrolyzed with an aqueous solution (1%) of H2SO4. After extraction with CH2Cl2, the organic layer was dried over Na2SO4. The solvent was removed at reduced pressure (18 mmHg) and the crude product was further purified by flash chromatography.
6.3.9 Synthesis of unsaturated sulfones using sulfonyl
chloride-pyridine complexes and Grignard reagents
In a typical run, tosyl chloride (4.5 mmol) and dry THF (20 ml) were introduced under N2 in a dry three-necked flask equipped with reflux condenser, dropping funnel and magnetic stirrer. Pyridine (0.36 ml, 4.5 mmol) was added, and the solution was stirred for 30 min; the Grignard reagent was quickly added through the dropping funnel, and the solution was stirred overnight. After hydrolysis (1% aq. H2SO4) the mixture was extracted with Et2O and dried over anhydrous Na2SO4. After removal of the solvent at reduced pressure the crude product was further purified by flash chromatography.
6.3.10 Synthesis of alkenylated dihydropyridine and
2H-dihydroisoquinoline derivatives
In a typical reaction, a two-necked flask equipped with reflux condenser, magnetic stirrer and dropping funnel was thoroughly dried; the appropriate alane
(3.0 mmol), prepared according to Section 6.3.1 or 6.3.2, was introduced under N2; hexane was removed at reduced pressure (18 mmHg) and CH2Cl2 (20 ml) and the appropriate heteroaromatic substrate was added. The solution was cooled to 0 or -20 oC (depending on the nature of the nitrogen ligand) and the acid halide (2.7 mmol) was quickly added. After stirring for 30 min the reaction mixture was siphoned onto a short column of silica gel and eluted with 200 ml of CH2Cl2. The solution was dried over anhydrous Na2SO4 and the solvent was removed at reduced pressure (18 mmHg). The crude product was purified by flash chromatography.
6.3.11 Cyclization of
1-(2-bromoacetyl)-2-(hex-1-enyl)-8-trimethylsilyloxy-2H-dihydroquinoline
A flask was charged with 30 ml of an aqueous solution of KF (5% w/v); a solution of the crude intermediate 42 in Et2O (30 ml) was added, and the mixture was vigorously stirred at r.t. until complete conversion of the product (GLC) was achieved (45 min). The organic layer was then separated, washed with water and dried. After evaporation of the solvent at reduced pressure the analytically pure 43 was recovered.
6.4 Characterization of the products synthesized
Physical and spectroscopic characterizations are reported for each isolated product. The following data are reported: eluting mixture employed in the flash chromatography when used, physical state, mass spectrum, 1H NMR and 13C NMR spectrum, infrared spectrum (neat).
6.4.1 Alk-1-enyl and alk-1-ynyl sulfoxides
(E) Phenyl hex-1-enyl sulfoxide
Hexane/Ethyl acetate 75/25; yellowish oil; GC-MS (m/z, I%): 208 (M.+, 14), 192 (36), 160 (60), 149 (52) 117 (100), 111 (66) 104 (57) 91 (21), 78 (36); 1H NMR: 0.89 (t, J=7.2 Hz, 3H), 1.25-1.50 (m, 4H), 2.23 (dtd, J=7.0 Hz, J =6.5 Hz, J =1.4 Hz, 2H), 6.23 (dt, J=15.0 Hz, J =1.4 Hz, 1H), 6.62 (dt, J=15.0 Hz, J =7.2 Hz, 1H), 7.45-7.65 (m, 5H);13C NMR: 13.4, 21.7, 29.7, 31.3, 124.0, 128.9, 130.4, 134.5, 141.2, 143.8; IR (cm-1): 2954, 2921, 2855, 1627, 1466, 1444, 1377, 1077, 1038, 960, 916, 745, 683.
(E) Phenyl cyclohexylethenyl sulfoxide
Hexane/Ethyl acetate 75/25; yellowish oil; GC-MS (m/z, I%): 234 (M.+, 5), 219 (18), 218 (100), 186 (18), 136 (36), 109 (71), 67 (63); 1H NMR: 1.0-1.2 (m, 5H), 1.5-1.8 (m, 5H), 2.10 (m, 1H), 6.10 (dd, J=15.4 Hz, J =1.1 Hz, 1H), 6.51 (dd, J=15.4 Hz, J =6.2 Hz, 1H), 7.4-7.6 (m, 5H); 13C NMR: 25.5, 25.7, 31.5, 40.25, 124.4, 129.2, 130.7, 132.8, 144.15, 146.4; IR (cm-1): 3023, 2921, 2855, 2657, 1622, 1594, 1446, 1397, 1083, 1048, 1021, 967, 811, 770, 624.
(E) Phenyl oct-1-enyl sulfoxide
Hexane/Ethyl acetate 75/25; yellowish oil; GC-MS (m/z, I%): 236 (M.+, 10), 219 (28), 188 (47), 149 (18), 117 (96), 110 (50), 91 (27), 78 (31), 77 (23); 1H NMR: 0.87 (t, J=6.6 Hz, 3H), 1.20-1-60 (m, 8H), 2.22 (dtd, J=6.6 Hz, J’=7.0 Hz, J”=1.1 Hz, 2H), 6.23 (dt, J=15.3 Hz, J’=1.5 Hz, 1H), 6.62 S O Bu-n S Hex-c O S O Hex-n
(dt, J= 15.3 Hz, J’=6.6 Hz), 7.45-7.65 (m, 5H); 13C NMR: 13.8, 22.3, 27.8, 28.5, 31.3, 31.8, 124.2, 129.0, 130.6, 134.7, 141.3, 144.0; IR (cm-1): 2956, 2911, 2844, 1622, 1461, 1439, 1078, 1039, 956, 744, 683.
(E) Phenyl 3,3-dimethylbut-1-enyl sulfoxide
Hexane/Ethyl acetate 75/25; yellowish oil; GC-MS (m/z, I%): 208 (M.+, 19), 177 (17), 160 (41), 145 (100), 110 (31), 77 (24); 1H NMR: 1.09 (s, 9H), 6.14 (d, J=15.3 Hz, 1H), 6.62 (d, J=15.3 Hz, 1H), 7.45-7.65 (m, 5H); 13C NMR: 21.8, 26.0, 31.5, 127.8, 128.9, 130.1, 138.2, 144.3, 151.4; IR (cm-1): 2954, 2921, 2855, 1627, 1466, 1444, 1377, 1077, 1038, 960, 916, 745, 683.
(E) 4’-Methylphenyl hex-1-enyl sulfoxide
Hexane/Ethyl acetate 75/25; yellowish oil; GC-MS (m/z, I%): 222 (M.+, 5), 206 (11), 174 (67), 131 (100), 123 (29), 91 (29); 1H NMR: 0.88 (t, J=7.0 Hz, 3H), 1.2-1.5 (m, 4H), 2.22 (dtd, J=7.0 Hz, J =6.6 Hz, J =1.5 Hz, 2H), 2.4 (s, 3H), 6.2 (dt, J= 15.0 Hz, J =1.5 Hz, 1H), 6.59 (dt, J=15.0 Hz, J =7.0 Hz, 1H), 7.3-7.5 (m, 4H); 13C NMR: 14.0, 21.6, 22.3, 30.4, 31.9, 124.8, 130.2, 135.3, 141.2, 141.4, 141.5; IR (cm-1): 2944, 2922, 2856, 1628, 1589, 1494, 1450, 1078, 1044, 961, 806.
(E) 4’-Methylphenyl oct-1-enyl sulfoxide
Hexane/Ethyl acetate 75/25; yellowish oil; GC-MS (m/z, I%): 250 (M.+, 4), 234 (30), 202 (56), 163 (29), 131 (100), 124 (49), 118 (51), 105 (18), 91 (36), 77 (9); 1H NMR: 0.86 (t, J=6.6, 3H), 1.2-1.5 (m, 8H), 2.21 (dtd, J=6.2, J’=7.0, J”=1.4, 2H), 2.40 (s, 3H), 6.20 (dt, J=15.4, J’=1.4, 1H), 6.59 (dt, J=15.4, J’=7.0, 1H), 7.26-7.35 (m, 2H), 7.46-7.54 (m, 2H); 13C NMR: 13.9, 21.2, 22.4, 27.9, 28.5, 31.3, 31.8, 124.4, 129.8, 134.8, 140.9, 141.5; IR (cm-1): 2956, 2911, 2844, 1628, 1489, 1456, 1300, 1089, 1044, 1011, 956, 806, 617. S O Bu-t S O Bu-n Me S O Hex-n Me
(E) 4’- Methylphenyl 3,3-dimethylbut-1-yl sulfoxide
Hexane/Ethyl acetate 75/25; yellowish oil; GC-MS (m/z, I%): 222, (M.+, 2), 206 (6), 191 (11), 174 (53), 159 (100), 137 (17), 123 (26), 91 (25), 77 (8), 65 (14), 57 (16); 1H NMR: 1.16 (s, 9H), 2.49 (s, 3H), 6.11 (d, J=15.4, 1H), 6.60 (d, J=15.4, 1H), 7.23-7.32 (m, 2H), 7.42-7.52 (m, 2H); 13C NMR: 21.6, 29.0, 34.4, 124.9, 130.2, 131.3, 141.4, 141.5, 151.0; IR (cm-1): 2956, 2856, 1617, 1589, 1494, 1461, 1361, 1261, 1078, 1044, 967, 811.
(E) 4’- Methylphenyl 2-cyclohexyl ethenyl sulfoxide
Hexane/Ethyl acetate 75/25; yellowish oil; GC-MS (m/z, I%): 1H NMR: 1.1-1.4 (m, 5H), 1.6-1.9 (m, 5H), 2.1-2.2 (m, 1H), 2.40 (s, 3H), 6.15 (dd, J=15.0, J’=1.1, 1H), 6.56 (dd, J=15.0, J’=6.6, 1H), 7.27-7.33 (m, 2H), 7.46-7.53 (m, 2H); 13C NMR: 21.6, 25.9, 26.0, 32.0, 40.5, 124.8, 130.2, 133.3, 141.4, 141.5, 146.0; IR (cm-1): 3021, 2925, 2851, 2667, 1622, 1595, 1448, 1398, 1083, 1048, 1015, 964, 810, 773, 622.
(E) Methyl hex-1-enyl sulfoxide
Hexane/Ethyl acetate 40/60; yellowish oil; GC-MS (m/z, I%): 146 (M.+, 49), 129 (11), 117 (12), 103 (10), 81 (51), 55 (100), 41 (72); 1H NMR: 0.91 (t, J=7 Hz, 3H), 1.25-1.55 (m, 4H), 2.24 (dtd, J=7.0 Hz, J = 6.4 Hz, J =1.5 Hz, 2H), 2.60 (s, 3H), 6.27 (dt, J=15.0 Hz, J =1.5 Hz, 1H), 6.49 (dt, J=15.0 Hz, J =6.6 Hz, 1H); 13C NMR: 14.0, 22.4, 30.4, 31.9, 41.0, 134.2, 141.2; IR (cm-1): 2944, 2911, 2856, 1628, 1467, 1417, 1038, 961, 717, 683.
(E) 4’-Methylphenyl 4-phenylbut-1-enyl sulfoxide
Hexane/Ethyl acetate 75/25; white solid m.p. 49-50 oC; GC-MS (m/z, I%): 284 (M.+, 3), 268 (46), 236 (100), 225 (15), 193 (99), 185 (62), 178 (40), 165 (23), 152 (71), 141 (14), 115 (16), 77 (7), 55 (12), 41 (16); 1H NMR: 2.49 (s, 3H), 2.63 (dtd, J=7, J =7.4, J =1, 2H), 2.87 (t, J=7.2, 2H), 6.28 (dt, J=15.4, J =1, 1H), 6.69 (dt, J=15.4, J =7.4, 1H), 7.2-7.55 (m, 9H); 13C NMR: 21.7, 33.8, 34.6, 125.0, 126.5, 128.7, 128.8, 130.3, 136.0, 139.5, 140.7, 141.1, S O Bu-t Me S O Hex-c Me Me S O Bu-n S O Me Ph
141.6; IR (cm-1): 3011, 2911, 2844, 1622, 1594, 1489, 1450, 1433, 1189, 1146, 1083, 1039, 950, 806, 722, 694.
(E) 4’-Biphenyl hex-1-enyl sulfoxide
Hexane/Ethyl acetate 75/25; yellowish oil; GC-MS (m/z, I%): 270 (M.+, 1), 254 (5), 222 (17), 163 (21), 131 (110), 123 (14), 91 (73), 77 (10), 65 (16); 1H NMR: 0.99 (t, J=6.6, 3H), 1.3-1.6 (m, 4H), 2.34 (dtd, J=6.6, J =6, J =1.4, 2H), 6.36 (dt, J=15.4, J =1.4, 1H), 6.74 (dt, J=15.4, J =6.6, 1H), 7.45-7.60 (m, 4H), 7.65-7.90 (m, 5H); 13C NMR: 14.1, 22.4, 24.0, 26.1, 30.4, 30.6, 32.0, 125.3, 127.5, 128.3, 128.4, 129.2, 134.9, 140.0, 142.1, 143.0, 144.2; C, 76.01; IR (cm-1): 3033, 2955, 2922, 2856, 1622, 1589, 1478, 1444, 1389, 1317, 1139, 1089, 1044, 1000, 833, 761, 691.
Phenyl hex-1-ynyl sulfoxide
Hexane/Ethyl acetate 70/30; yellowish oil; GC-MS (m/z, I%): 206 (M.+, 6), 190 (17), 163 (22), 157 (20), 143 (56), 129 (71), 121 (16), 115 (100), 103 (35), 91 (20), 81 (28), 77 (46), 71 (16), 51 (32); 1H NMR: 0.97(t, J= 7 Hz, 3H), 1.4-1.7 (m, 4H), 2.50 (t, J= 7 Hz, 2H), 7.58-7.66 (m, 3H), 7.84-7.92 (m, 2H); 13C NMR: 13.6, 19.6, 22.1, 29.7, 76.9, 106.3, 125.1, 129.7, 131.7, 144.6; IR (cm-1): 3056, 2956, 2922, 2856, 2167, 1461, 1439, 1378, 1317, 1133, 1083, 1050, 878, 744, 683.
Phenyl 3,3- dimethylbut-1-ynyl sulfoxide
Hexane/Ethyl acetate 80/20; yellowish oil; GC-MS (m/z, I%): 206 (M.+, 4), 191 (100), 175 (13), 150 (24), 143 (96), 128 (45), 121 (17), 115 (24), 105 (24), 97(10), 77 (35), 65 (10), 57 (16), 51 (22); 1H NMR: 1.33 (s, 9H), 7.58-7.61 (m, 3H), 7.83-7.89 (m, 2H); 13C NMR: 15.8, 30.1, 78.0, 113.3, 125.3, 129.7, 131.8, 132.3; IR (cm-1): 3062, 2950, 2929, 2843, 2157, 1469, 1448, 1307, 1122, 1091, 1034, 746, 678. S Bu-n Ph O S O Bu-n S O Bu-t
Phenyl hex-5-en-1-ynyl sulfoxide
Hexane/Ethyl acetate 80/20; yellowish oil; GC-MS (m/z, I%): 204 (M.+,3), 187 (7), 161 (6), 155 (27), 147 (12), 141 (17), 128 (17), 115 (100), 103 (17), 91 (15), 77 (30), 65 (8), 51 (18); 1H NMR: 2.10 (td, J=7 Hz, J’=1.1 Hz, 2H), 2.32(td, J=7 Hz, J’=1.5 Hz, 2H), 4.94(dd, J=9.8 Hz, J’=2.2 Hz, 1H), 5.05 (dd, J=13.5 Hz, J’=2.2 Hz, 1H), 5.86 (ddt, J=13.5 Hz, J’=9.8 Hz, J”=1.5 Hz, 1H), 7.6-7.8 (m, 5H); 13C NMR: 19.6, 31.6, 78.9, 105.1, 116.6, 125.0, 129.5, 131.6, 135.6, 144.5; IR (cm-1): 3067, 2967, 2922, 2356, 2178, 1722, 1639, 1481, 1439, 1378, 1228, 1089, 1050, 916, 750, 683. S O
6.4.2 Unsaturated
sulfones
(E) 4’-Methylphenyl hex-1-enyl sulfone
Hexane/Ethyl acetate 80/20; yellowish oil; GC-MS (m/z, I%): 238 (M.+,42), 223 (2), 209 (100), 157 (50), 139 (59), 91 (54), 82 (33), 67 (30); 1H NMR: 0.89 (t, J=7.3 Hz, 3H), 1.2-1.4 (m, 4H), 2.22 (dtd, J=6.7 Hz, J’=6.7 Hz, J”=1.5 Hz, 2.43 (s, 3 Hz), 6.29 (dt, J=15 Hz, J’=1.5 Hz, 1H), 6.96 (dt, J=15 Hz, 6.7 Hz, 1H), 7.32 (d, J=7.7 Hz, 2H), 7.75 (d, J=7.7 Hz, 2H); 13C NMR: 13.9, 21.8, 22.3, 29.9, 31.4, 127.8, 130.9, 136.5, 138.1, 144.3, 146.8; IR (cm-1): 3044, 2956, 2922, 2867, 2344, 1628, 1594, 1456, 1317, 1283, 1144, 1083, 972, 833, 811, 655.
(E) Phenyl oct-1-enyl sulfone
Hexane/Ethyl acetate 80/20; yellowish oil; GC-MS (m/z, I%): 236 (M.+, 10), 219 (28), 207 (17), 188 (47), 149 (17), 126 (22), 124 (53), 117 (96), 110 (50), 104 (100), 91 (26), 78 (30), 69 (16), 55 (30), 41 (27); 1H NMR: 0.86 (t, J=6.6 Hz, 3H), 1.2-1.5 (m, 8H), 2.22 (dtd, J=7.3 Hz, J’=7.4 Hz, J”=1.6 Hz, 2H), 6.23 (dt, J=15.4 Hz, J’=1.5 Hz, 1H), 6.62 (dt, J=15.4 Hz, J’=6.6 Hz, 1H), 7.4-7.7 (m, 5H); 13C NMR: 13.8, 22.3, 27.8, 28.5, 31.3, 31.8, 124.2, 129.1, 130.6, 134.7, 141.3, 144.0; IR (cm-1): 3084, 2950, 2912, 2873, 2337, 1623, 1593, 1458, 1312, 1287, 1146, 978, 807.
(E) 4’-Methylphenyl 3,3-dimethylbut-1-enyl sulfone
Hexane/Ethyl acetate 80/20; yellowish oil; GC-MS (m/z, I%): 238 (M.+, 3), 223 (1), 157 (8), 139 (31), 91 (20), 83 (100), 67 (16), 55 (26); 1H NMR: 1.08 (s, 9H), 2.44 (s, 3H), 6.18 (d, J=15 Hz, 1H), 6.92 (d, J=15 Hz, 1H), 7.33 (d, J=8.1 Hz, 2H), 7.75 (d, J=8.1 Hz, 2H); 13C NMR: 21.8, 28.6, 34.3, 127.8, 130.1, 136.3, 144.3, 150.1, 156.1; IR (cm-1): 2967, 2856, 2356, 1617, 1594, 1461, 1361, 1311, 1289, 1178, 1139, 1093, 978, 917, 833, 806, 756. S Bu-n Me O O S Hex-n O O S Bu-t Me O O
(E) 4’-Methylphenyl 2-cyclohexylethenyl sulfone
Hexane/Ethyl acetate 80/20; yellowish oil; GC-MS (m/z, I%): 264 (M.+, 11), 207 (5), 183 (24), 157 (16), 139 (26), 109 (100), 91 (33), 79 (29), 67 (53); 1H NMR: 1.1-1.3 (m, 5H), 1.65-1.85 (m, 5H), 2.1-2.2 (m, 1H), 2.43 (s, 3H), 6.22 (dd, J=15.5 Hz, J’=1.5 Hz, 1H), 6.92 (dd, J=15.5 Hz, J’=6.2 Hz, 1H), 7.32 (d, J=8.1 Hz, 2H), 7.74 (d, J=8.1 Hz, 2H); 13C NMR: 21.8, 28.6, 34.3, 38.4, 127.0, 127.8, 130.1, 138.1, 144.4, 156.1; IR (cm-1): 2922, 2844, 1627, 1594, 1444, 1322, 1294, 1277, 1138, 1083, 972, 833, 811, 667, 544.
(E) 4’-Methylphenyl 4-phenylbut-1-enyl sulfone
Hexane/Ethyl acetate 80/20; white solid m.p. 42-45 oC; GC-MS (m/z, I%): 285 (1), 157 (2), 130 (40), 115 (3), 91 (100), 77 (3), 65 (10); 1H NMR: 2.46 (s, 3H), 2.63 (dtt, J=7.0 Hz, J’=6.9 Hz, J”=1.5 Hz, 2H), 2.86 (t, J=7.0 Hz, 2H), 6.37 (dt, J=15.0 Hz, J’=1.5 Hz, 1H), 7.06 (dt, J=15.0 Hz, J’= 6.9 Hz, 1H), 7.15-7.45 (m, 7H), 7.95 (dt, J=8.4 Hz, J’=1.8 Hz, 2H); 13C NMR: 21.6, 33.1, 33.9, 126.4, 127.6, 128.4, 128.6, 129.9, 131.4, 137.7, 140.1, 144.2, 145.4; IR (cm-1): 2934, 2827, 1632, 1600, 1450, 1318, 1290, 1270, 1130, 1067, 982, 843, 801, 672, 538.
(E) Methyl hex-1-enyl sulfone
Hexane/Ethyl acetate 50/50; yellowish oil; GC-MS (m/z, I%): 162 (M.+, 100), 143 (21), 125 (8), 111 (43), 97 (76), 83 (51), 69 (93), 55 (97), 41 (40); 1H NMR: 0.99 (t, J=6.9, 3H), 1.3-1-6 (m, 4H), 2.34 (dtd, J=6.6 Hz, J’=6.6 Hz, J”=1.5 Hz, 2H), 2.99 (s, 3H), 6.44 (dt, J=14.8 Hz, J’=1.5 Hz, 1H), 7.02 (dt, J=14.8 Hz, J’=6.6 Hz, 1H); 13C NMR: 14.0, 22.4, 29.9, 31.3, 43.1, 129.6, 149.0; IR (cm-1): 2956, 2922, 2856, 2344, 1633, 1461, 1305, 1283, 1128, 967, 817.
(E) 4’-Biphenyl hex-1-enyl sulfone
Hexane/Ethyl acetate 80/20; yellowish oil; GC-MS (m/z, I%): 300 (M.+, 100), 271 (5), 245 (5), 217 10), 201 (80), 169 (67), 152 (79), 141 (16); 1H NMR: 0.98 (t, J=7 Hz, 3H), 1.3-1.6 (m, 4H), 2.34 (dtd, J=6.6 Hz, J’=7 Hz, J”= 1.5 Hz, 2Hz), 6.44 (dt, S Hex-c Me O O S Me O O Ph Me S Bu-n O O S Bu-n Ph O O
J=15 Hz, J’=1.5 Hz, 1H), 7.11 (dt, J=15 Hz, J’=6.6 Hz, 1H), 7.5-7.6 (m, 3 H), 7.65-7.75 (m, 2H), 7.8-7.85 (m, 2H), 7.95-8.05 (m, 2H); 13C NMR: 14.0, 22.4, 29.9, 31.5, 127.6, 128.1, 128.3, 128.8, 129.3, 130.7, 139.5, 139.6, 146.4, 147.5; IR (cm-1): 3033, 2922, 2355, 1622, 1594, 1500, 1450, 1405, 1322, 1283, 1144, 1073, 956, 811, 750, 700, 657, 570, 528.
(R,S)-(E) 4’-Methylphenyl 2-methylbutyl sulfone
Hexane/Ethyl acetate 80/20; yellowish oil; GC-MS (m/z, I%): 207 (2), 173 (22), 155 (72), 91 (79), 70 (100); 1H NMR: 0.90 (t, J=7.3 Hz, 3H), 0.96 (d, J=6.5 Hz, 3H), 1.2-1.3 (m, 2H), 1.3-1.4 (m, 1H), 3.88 (dd, J=9.2 Hz, J’=6.2 Hz, 1H), 3.97 (dd, J=9.2 Hz, J’=6.2 Hz, 1H), 7.42 (d, J=8 Hz, 2H), 7.87 (d, J=8Hz, 2H); 13C NMR: 11.2, 16.2, 21.9, 25.7, 34.6, 75.1, 127.3, 128.1, 130.0, 130.5; IR (cm-1): 2956, 2922, 2867, 2356, 1594, 1461, 2478, 1189, 1172, 1094, 961, 844, 811, 783, 661.
(E) 4’-Methylphenyl hex-1-ynyl sulfone
Hexane/Ethyl acetate 80/20; yellowish oil; GC-MS (m/z, I%): 236 (40), 194 (43), 155 (49), 139 (88), 129 (43), 107 (28), 91 (100), 79 (49), 65 (50), 53 (18), 41 (25); 1H NMR: 0.86 (t, J=7.0 Hz, 3H), 1.2-1.6 (m, 4H), 2.34 (t, J=7.3 Hz, 2H), 2.44 (s, 3H), 7.35 (d, J=7.5 Hz, 2H), 7.86 (d, J=7.5 Hz, 2H); 13C NMR: 13.4, 18.6, 21.6, 21.9, 29.0, 78.4, 97.4, 127.1, 130.0, 139.3, 145.2; IR (cm-1): 2955, 2867, 2356, 2200, 1594, 1461, 1327, 1156, 1089, 811, 700, 672.
(E) 4’-Methylphenyl 3,3-dimethylbut-1-ynyl sulfone
Hexane/Ethyl acetate 80/20; white solid m.p. 43-45 oC; GC-MS (m/z, I%): 236 (M.+, 49), 157 (36), 139 (53), 115 (10), 91 (28), 81 (100), 65 (28), 53 (17), 41 (17); 1H NMR: 1.25 (s, 9H), 2.48 (s, 3H), 7.37 (d, J=7.5 Hz, 2H), 7.89 (d, J=7.5 Hz, 2H); 13C NMR: 21.6, 27.9, 29.3, 78.1, 103.5, 127.0, 130.0, 139.3, 145.1; IR (cm-1): 2974, 2931, 2870, 2211, 2174, 1595, 1492, 1475, 1456, 1356, 1318, 1253, 1188, 1176, 1147, 1086, 1006, 917, 815, 777, 670. S Me O O Bu-n S Ph O O Bu-t S Me O O Et Me
(E) 4’-Methylphenyl 4-phenyl-but-1-ynyl sulfone
Hexane/Ethyl acetate 80/20; yellowish oil; GC-MS (m/z, I%): 284 (M.+, 1), 283 (3), 249 (3), 219 (5), 204 (9), 128 (36), 117 (5), 91 (100), 77 (5), 65 (15); 1H NMR: 2.49 (s, 3H), 2.66 (t, J=6.3 Hz, 2H), 2.86 (t, J=6.3 Hz, 2H), 7.1-7.2 (m, 2H), 7.2-7.3 (m, 3H), 7.2-7.37 (d, J=8 Hz, 2H), 7.85 (d, J=8 Hz, 2H); 13C NMR: 21.2, 21.8, 33.2, 79.3, 96.3, 126.9, 127.4, 128.5, 128.7, 130.0, 139.1, 139.2, 145.3; IR (cm-1): 3086, 3062, 3029, 2927, 2865, 2200, 1596, 1494, 1454, 1328, 1304, 1185, 1159, 1089, 1050, 1017, 814, 750, 705, 678, 618.
(E) 4-Methylphenyl 4’-methoxyphenyl sulfone
Hexane/Ethyl acetate 80/20; yellowish oil; GC-MS (m/z, I%): 262 (M.+, 71), 230 (3), 207 (4), 183 (7), 171 (4), 155 (77), 139 (14), 123 (100), 107 (8), 91 (17), 77 (17), 65 (17); 1H NMR: 2.39 (s, 3H), 3.84 (s, 3H), 6.96 (d, 8.2 Hz, 2H), 7.28 (d, 8.2 Hz, 2H), 7.81 (d, 8.2 Hz, 2H), 7.87 (d, 8.2 Hz, 2H); 13C NMR: 21.6, 55.7, 114.6, 127.4, 128.4, 129.8, 129.9, 133.6, 139.5, 143.7; IR (cm-1): 3096, 3068, 2972, 2938, 2925, 2837, 2537, 1916, 1596, 1578, 1495, 1456, 1413, 1319, 1299, 1264, 1183, 1151, 1106, 1072, 1019, 831, 802, 708, 680, 634, 562, 548.
(E) 4-Methylphenyl 3’-fluorophenyl sulfone
Hexane/Ethyl acetate 80/20; white solid m.p. 88-90 oC; GC-MS (m/z, I%): 250 (88), 183 (6), 170 (6), 139 (79), 107 (100), 95 (18), 91 (65), 77 (23), 65 (28), 51 (7); 1H NMR: 2.43 (s, 3H), 7.2-7.4 (m, 3H), 7.49 (td, J=8.1 Hz, J’=5.1 Hz, 1H), 7.63 (td, J=2.2 Hz, J’=8.1 Hz, 1H), 7.74 (td, J=1.1 Hz, J’=8.1 Hz, 1H), 7.84 (d, J=8.0 Hz, 2H); 13C NMR: 21.7, 114.7, 115.2, 120.1, 120.6, 123.3, 123.4, 127.9, 130.2, 131.1, 131.3; IR (cm-1): 3064, 2962, 2943, 2820, 2530, 1922, 1604, 1582, 1440, 1319, 1254, 1200, 1100, 1078, 1023, 700, 630. S Me O O OMe S Me O O F S Me O O Ph
6.4.3 Dihydropyridine and dihydroquinoline derivatives
1-Benzoyl-2-[(1E)-hex-1-en-1-yl]-1,2-dihydropyridine
Hexane/Ethyl acetate 85/15; yellowish oil; GC-MS (m/z, I%): 267 (M.+, 7), 224 (1), 210 (2), 184 (18), 162 (22), 132 (1), 118 (3), 105 (100), 77 (32); 1H NMR: 0.88 (t, J= 7.0 Hz, 3H), 1.2-1.4 (m, 4H), 2.03 (dtd, J=7.0 Hz, J’=6.6 Hz, J”=1.0 Hz, 2H), 5.25 (bt, J=7.0 Hz, 1H), 5.5-5.8 (m, 3H), 6.03 (dd, J=9.2 Hz, J’=5.4 Hz, 1H), 6.30 (bs, 1H), 7.4-7.7 (m, 5H); 13C NMR: 14.1, 22.4, 31.4, 32.1, 51.4, 109.1, 121.7, 123.1, 125.6, 128.6, 129.2, 130.7, 133.5, 135.1; IR (cm-1): 3061, 3030, 2956, 2928, 2871, 2859, 1719, 1637, 1578, 1530, 1489, 1448, 1413, 1358, 1263, 1109, 1071, 1027, 970, 790, 755, 712. 1-Pentanoyl-2-[(1E)-hex-1-en-1-yl]-1,2-dihydropyridine
Hexane/Ethyl acetate 85/15; yellowish oil; GC-MS (m/z, I%): 247 (M.+, 14), 218 (1), 204 (1), 190 (3), 162 (40), 132 (2), 120 (16), 106 (11), 93 (4), 80 (100), 67 (2), 57 (10); 1H NMR: 0.90 (t, J=7 Hz, 3H), 0.93 (t, J=7 Hz, 3H), 1.2-1.4 (m, 4H), 1.55-1-75 (m, 4H), 1.97 (dt, J=7.0 Hz, J’=6.6 Hz, 2H), 2.41 (td, J=7.7 Hz, J’= 0.9 Hz, 2H), 4.92 (m, 1H), 5.2-5.7 (m, 4H), 5.95 (dd, J=8.4 Hz, J’= 5.5 Hz, 1H), 6.49 (d, J=7.7 Hz, 1H); 13C NMR: 14.1, 22.4, 22.7, 27.1, 31.4, 32.0, 33.3, 51.5, 107.2, 121.2, 123.7, 124.7, 126.0, 133.2, 171.9; IR (cm-1): 3023, 2957, 2930, 2871, 1672, 1625, 1569, 1491, 1456, 1412, 1379, 1290, 1218, 1105, 966, 920, 775, 752. 1-Benzoyl-2-[3,3-dimethyl-(1E)-but-1-en-1-yl]-1,2-dihydropyridine
Hexane/Ethyl acetate 85/15; yellowish oil; GC-MS (m/z, I%): 267 (M.+, 7), 224 (2), 184 (22), 162 (5), 131 (15), 118 (14), 105 (100), 77 (38), 55 (6); 1H NMR: 0.91 (s, 9H), 5.28 (bd, J=7.0 Hz, 1H), 5.5-5.8 (m, 3H), 5.98 (dd, J=9.0 Hz, J’=5.6 Hz, 1H), 6.35 (bs, 1H), 7.4-7.7 (m, 5H); 13C NMR: 23.0, 31.4, 51.8, 109.0, 121.6, 123.3, 125.5, 128.7, 129.2, 130.2, 133.4, 135.0; IR (cm-1): 3058, 3027, 2960, 2930, 2864, 2845, 1725, 1638, 1585, 1532, 1484, 1450, 1412, 1314, 1262, 1111, 1073, 1024, 967, 787, 754, 711. N O Bu-n N n-Bu O n-Bu N Ph O Bu-t
1-Napht-1-oyl-2-[(1E)-hex-1-en-1-yl]-1,2-dihydropyridine
Hexane/Ethyl acetate 85/15; yellowish oil; GC-MS (m/z, I%): 317 (M.+, 3), 289 (1), 260 (1), 234 (2), 232 (2), 219 (1), 162 (15), 156 (17), 155 (100), 127 (47), 118 (2), 101 (2), 91 (1), 77 (3); 1H NMR: 0.91 (t, J= 7.0 Hz, 3H), 1.2-1.4 (m, 4H), 2.10 (dtd, J=7.1 Hz, J’=6.7 Hz, J”=1.1 Hz, 2H), 5.27 (bt, J=7.1 Hz, 1H), 5.5-5.8 (m, 3H), 6.07 (dd, J=9.2 Hz,J’=5.4 Hz, 1H), 6.30 (bs, 1H), 7.4-7.8 (m, 6H), 9.05 (dd, J=8.4 Hz, J’=1.1 Hz, 1H); 13C NMR 14.1, 22.4, 31.4, 32.1, 51.4, 109.1, 120.3, 121.7, 123.1, 125.6, 128.6, 129.2, 130.7, 131.1, 132.4, 133.1, 133.5, 134.7, 135.1; IR (cm-1): 3048, 2956, 2928, 2870, 2858, 1713, 1635, 1592, 1579, 1509, 1463, 1414, 1351, 1255, 1214, 1196, 1132, 1027, 970, 780, 737, 634. 2-Pentanoyl-1-[(1E)-hex-1-yn-1-yl]-1,2-dihydro isoquinoline
Hexane/Ethyl acetate 85/15; yellowish oil; GC-MS (m/z, I%): 297 (M.+,18), 282 (7), 275 (9), 268 (45), 254(25), 240 (7), 230 (8), 214 (32), 212(14), 195(18), 168 (39), 154 (3), 129 (12), 85 (4); 1H NMR: 0.90 (t, J= 7 Hz, 3H), 0.99 (t, J=6.9 Hz, 3H), 1.3-1.6 (m, 8H), 2.01 (t, J= 6.8 Hz, 2H), 2.35 (td, J=7.1 Hz, J’=6.9 Hz, 2H), 5.52 (dt, J=14.1, J’=7 Hz, 1H), 5.98 (bd, 1H), 6.1-6.8 (m, 4H), 7.5-7.8 (m, 3H); 13C NMR: 12.9, 13.5, 18.4, 19.0, 21.5, 22.4, 31.2, 32.3, 47.0, 110.2, 125.9, 127.6, 128.9, 129.4, 130.0, 131.2, 131.7, 134.3, 135.5, 169.2; IR (cm-1): 3067, 2958, 2917, 2215, 1772, 1661, 1618 1583, 1451, 1337, 1260, 1241, 1163, 1102, 921, 752, 722, 685. 2-Benzoyl-1-[(1E)-hex-1-yn-1-yl]-1,2-dihydro isoquinoline
Hexane/Ethyl acetate 85/15; yellowish oil; GC-MS (m/z, I%): 317 (M.+,15), 288 (5), 275 (18), 274 (22), 260 (37), 242 (4), 230 (13), 212 (25), 168 (21), 154 (1), 129 (17), 105 (100), 83 (19) 77 (56); 1H NMR: 0.96 (t, J= 7 Hz, 3H), 1.3-1.6 (m, 4H), 2.27 (td, J=7 Hz, J’=6.9 Hz, 2H), 5.48 (dt, J=13.8, J’=6.9 Hz, 1H), 6.10 (bd, 1H), 6.2-6.8 (m, 4H), 7.2-7.4 (m, 5H), 7.5-7.8 (m, 3H); 13C NMR: 13.5, 19.0, 22.4, 31.2, 47.0, 110.2, 125.9, 126.2, 127.6, 128.2, 128.9, 129.4, 129.7, 130.0, 131.1, 131.7, 134.3, 135.5, 169.2; IR (cm-1): 3056, 2946, 2929, 2223, 1784, 1673, 1629 1573, 1444, 1343, 1265, 1238, 1159, 1098, 910, 760, 729, 699. N O Bu-n N Ph O Bu-n N Bu-n O Bu-n
2-Benzoyl-1-[(1E)-hex-1-yn-1-yl]-1,2-dihydro isoquinoline
Hexane/Ethyl acetate 85/15; yellowish oil; GC-MS (m/z, I%): 315 (M.+,14), 286 (7), 273 (13), 272 (24), 258 (21), 244 (9), 230 (4), 210 (33), 180 (5), 168 (12), 154 (4), 129 (10), 105 (100), 77 (45); 1H NMR: 0.92 (t, J= 7 Hz, 3H), 1.3-1.6 (m, 4H), 2.20 (td, J=7 Hz, J’=0.2 Hz, 2H), 6.07 (bd, 1H), 6.4-6.8 (m, 3H), 7.2-7.4 (m, 5H), 7.5-7.8 (m, 3H); 13C NMR: 13.8, 18.7, 22.1, 30.7, 47.2, 78.4, 84.7, 110.3, 125.4, 126.4, 127.9, 128.5, 128.7, 129.0, 129.3, 131.3, 131.6, 134.3, 135.6, 169.0; IR (cm-1): 3061, 2957, 2931, 2216, 1773, 1664, 1625 1569, 1455, 1349, 1272, 1231, 1154, 1102, 919, 773, 726, 701. Methyl 1-[(E)-hex-1-enyl]isoquinolin-2(1H)-carboxilate
Hexane/Ethyl acetate 80/20; yellowish oil GC-MS (m/z, I%): 271 (M.+, 20), 214 (2), 188 (100), 168 (5), 156 (1), 144 (25), 129 (8), 115 (5), 103 (6), 77 (2), 59 (3); 1H NMR: 0.83 (t, J=7.3, 3H), 1.2-1.4 (m, 4H), 1.93 (bdt, J= 6.2 Hz, J’=6.6 Hz, 2H), 3.82 (s, 3H), 5.4-5.55 (m, 2H), 5.75-5.9 (m, 2H), 6.75-6.95 (m, 1H), 7.0-7.25 (m, 4H); 13C NMR: 13.9, 22.2, 31.2 31.7, 53.2, 57.3(broad), 108.3, 124.8, 126.1, 126.7, 127.0, 127.7, 128.0, 130.4, 131.7, 132.1; IR (cm-1): 2955, 2927, 2871, 2856, 1718, 1633, 1571, 1456, 1441, 1413, 1352, 1235, 1193, 1121, 1101, 968, 923, 771. 1,10-Bis-1-[(E)-hex-1-enyl]isoquinolin-2(1H)-yldecan-1,10-dione
Hexane/Ethyl acetate 85/15; yellowish oil; GC-MS (m/z, I%): could not be recorded due to the low volatility of the product; 1H NMR: 0.8-0.9 (m, 6H), 1.1-1.5 (m, 8H), 1.6-1.8 (m, 8H), 1.92 (dt, J=5.8 Hz, J’=5.6 Hz, 4H), 2.2-2.6 (m, 4H), 5.3-5.5 (m, 2H), 5.8-6.0 (m, 2H), 5.84 (d, J=12.1 Hz, 2H), 5.88 (d, J=12.1 Hz, 2H), 6.15-6.2 (bd, 2H), 6.65 (d, J= 12.4 Hz, 2H), 6.69 (d, J= 12.4 Hz, 2H), 7.0-7.3 (m, 8H), 7.6-8.1 (m, 2H); 13C NMR: 13.9, 22.2, 24.9, 29.2, 31.7, 34.1, 44.5, 54.9, 109.9, 124.7, 126.0, 126.7, 127.3, 127.7, 129.8, 130.2, 131.1, 132.4, 132.6, 171.2; IR (cm-1): 3062, 3018, 2946, 2921, 2864, 2852, 1724, 1664, 1613, 1578, 1562, 1449, 1405, 1352, 1286, 1227, 1157, 1113, 925, 754, 712, 685. N O O Me n-Bu N O (CH2)4 n-Bu 2 N Ph O Bu-n
1,2-Bis2-1-[(E)-hex-1-enyl]isoquinolin-2(1H)-ylbenzene dione
Hexane/Ethyl acetate 85/15; yellowish oil GC-MS (m/z, I%): could not be obtained due to the low volatility of the product; 1H NMR: 0.84 (m, 6H), 1.1-1.3 (m, 8H), 1.8-2.0 (m, 4H), 5.3-5.6 (m, 4H), 5.6-5.8 (m, 2H), 6.1-6.2 (m, 2H), 6.4-6.6 (m, 2H), 6.9-7.3 (m, 8H), 7.3-7.8 (m, 8H); 13C NMR: 14.0, 22.2, 31.2, 31.7, 55.5, 109.4, 124.9, 125.8, 127.2, 127.7, 128.1, 128.5, 128.7, 129.8, 130.1, 132.0, 132.3, 134.8, 167.5; IR (cm-1): 3058, 3023, 2956, 2927, 2870, 2857, 1720, 1660, 1625, 1595, 1569, 1489, 1455, 1413, 1359, 1290, 1234, 1198, 1157, 1118, 1090, 967, 919, 774, 749, 722, 709, 695. 2-(2-Bromoetanoyl)-1-[(1E)-hex-1-en-1-yl]-1,2-dihydro isoquinoline
Hexane/Ethyl acetate 80/20; yellowish oil GC-MS (m/z, I%): 334 (12), 333 (12), 254 (33), 252 (38), 250 (39), 212 (9), 196 (3), 182 (3), 168 (14), 156(4), 154 (4), 143 (6), 130 (100), 115 (7), 102 (5), 89 (1), 77 (3); 1H NMR: 0.86 (t, J= 7.0, 3H), 1.2-1.4 (m, 4H), 1.9-2.05 (m, 2H), 3.98 (d, J= 0.3 Hz, 2H), 5.46 (dd, J=3.3 Hz, J’=1.5 Hz, 1H), 5.58 (m, 1H), 6.03 (d, J=7.7 Hz, 1H), 6.13 (m, 1H), 6.69 (dd, J=7.7 Hz, J’=1 Hz, 1H), 7.1-7.35 (m, 4H); 13C NMR: 13.9, 22.2, 25.6, 31.1, 31.7, 55.5, 111.7, 123.9, 125.2, 126.4, 127.0, 127.8, 127.9, 129.6, 132.5, 133.0, 164.3; IR (cm-1): 2960, 2930, 2865, 2850, 1707, 1621, 1561, 1432, 1423, 1408, 1360, 1231, 1187, 1112, 1098, 972, 920, 765. 1,3-Dibenzoyl-2-[(1E)-hex-1-en-1-yl]-2,3-dihydro-1H imidazole
Hexane/Ethyl acetate 80/20; white waxy solid m.p. 29-31 oC; GC-MS (m/z, I%): 360 (M.+, 6), 277 (3), 255 (4), 195(1), 145 (6), 105 (100), 77 (24); 1H NMR: 0.89 (m, 3H), 1.2-1.6 (m, 4H), 1.9-2.1 (m, 2H), 5.5 (m, 1H), 6.0-6.4 (m, 2H), 6.5-6.9 (m, 2H), 7.2-7.6 (m, 10H); 13C NMR: 13.9, 22.2, 27.0, 30.8, 31.6, 114.8 (broad), 122.5, 127.8, 128.7, 131.1, 168.2. IR (cm-1): 3143, 3060, 2956, 2928, 2870, 2857, 1651, 1645, 1578, 1447, 1387, 1347, 1276, 1151, 1076, 968, 862, 787, 718, 701. N O O N n-Bu n-Bu N O n-Bu Br N N Ph O O Ph Bu-n
5-((E)-Hex-1-enyl)-2H-[1,4]-oxazino-[2,3,4-ij]-quinolin-3(5H)-one
Yellowish oil GC-MS (m/z, I%): 269 (M.+,38), 252 (2), 240 (9), 227 (19), 212 (14), 198 (12), 186 (99), 167 (6), 158 (100), 128 (28), 115 (6), 101 (5), 89 (5), 77 (7); 1H NMR: 0.86 (t, J=7.3 Hz, 3H), 1.1-1.4 (m, 4H), 1.98 (dt, J=6.6 Hz, J’=7.3 Hz, 2H), 4.48 (d, J=15 Hz, 1H), 4.72 (d, J=15 Hz, 1H), 5.45 (dd, J=15 Hz, J’= 6.6 Hz, 1H), 5.6-5.8 (m, 2H), 5.86 (dd, J=10 Hz, J’=5.5 Hz, 1H), 6.47 (d, J=10 Hz, 1H), 6.75-7.0 (m, 3H); 13C NMR: 14.0, 22.3, 31.1, 31.8, 51.7, 68.0, 116.6, 120.8, 122.8, 123.3, 123.7, 125.9, 126.1, 134.2, 144.5, 163.9; IR (cm-1): 3045, 2957, 2927, 2871, 2857, 1688, 1580, 1477, 1386, 1358, 1311, 1277, 1252, 1181, 1085, 1055, 1035, 967, 802, 726, 705. N O O Bu-n
6.4.4 NMR studies of di-i-butyl hex-1-enyl alane derivatives
All the above reported spectra were recorded on a Varian Infinity spectrometer, at the frequency of 300 MHz for 1H NMR and 75 MHz for 13C NMR, using C6D6 solutions. All signals are referred to the frequency of residual signal of the solvent set exactly at 2134.36 Hz. Chemical shift are expressed in Hertz.
Tosyl chloride 1H NMR: 503 (s, 3H), 1936 (d, J=8 Hz, 2H), 2258 (d, J=8 Hz, 2H); 13C NMR: 21.0, 126.9, 129.9, 142.0, 146.1. Pyridine 1H NMR: 2002 (m, 2H), 2101 (tt, J=7 Hz, J’=2 Hz, 1H), 2543 (m, 2H); 13C NMR: 123.4, 135.2, 150.1.
4-(N,N-Dimethyl)-amino pyridine (DMAP)
1H NMR: 664 (s, 6H), 1824 (d, J=7 Hz, 2H), 2523 (d, J=7 Hz, 2H).
Di-i-butyl hex-1-enyl aluminum-DMAP complex and pyridine
1H NMR: 165 (d, J=7 Hz, 4H), 276 (t, J=7 Hz, 3H), 392 (s, 12H), 390-482 (m, 4H), 622 (s, 6H), 678 (m, 2H), 723 (m, 2H), 1746 (d, J=7 Hz, 2H), 1941 (dt, J=20 Hz, J’=1.5 Hz, 1H), 2001 (dt, J=20 Hz, J’=6 Hz, 1H), 2099 (tt, J=7 Hz, J’=2 Hz, 1H), 2469 (d, J=8 Hz, 2H), 2541 (d, J=7 Hz, 2H). S Cl O O Me N N N Me Me Al Bu-n N (i-Bu)2 N Me Me
Di-i-butyl hex-1-enyl aluminum
1H NMR: 111 (d, J=7 Hz, 4H), 227 (t, J=7 Hz), 330.3 (s, 12H, ), 345-390 (m, 4H), 601 (m, 2H), 629 (m, 2H), 1770 (dt, J=20Hz, J’=1.5Hz, 1H), 2242 (dt, J=20Hz, J’=6Hz, 1H); 13C NMR: 13.7, 22.4, 26.8, 28.3, 29.4, 40.3, 126.3, 186.2.
Di-i-butyl hex-1-enyl aluminum-pyridine complex
1H NMR: 126 (d, J=7 Hz, 4H), 269 (t, J=7 Hz, 3H), 364 (s, 12H), 405-480 (m, 4H), 646 (m, 2H), 708 (m, 2H), 1895 (dt, J=20 Hz, J’=1.5 Hz, 1H), 1935 (dt, J=20 Hz, J’=6 Hz, 1H), 1940 (m, 2H), 2038 (tt, J=7 Hz, J’=2 Hz, 1H), 2513 (m, 2H); 13C NMR: 14.2, 22.7, 27.3, 28.7, 32.0, 39.6, 124.0, 124.1, 137.4, 148.7, 149.2.
Di-i-butyl hex-1-enyl aluminum-pyridine complex and tosyl chloride
1H NMR: 117 (d, J=7 Hz, 4H), 265 (t, J=7 Hz, 3H), 364 (s, 12H), 390-465 (m, 4H), 522 (s, 3H), 636 (m, 2H), 699 (m, 2H), 1884 (dt, J=20 Hz, J’=1.5 Hz, 1H), 1929 (dt, J=20 Hz, J’=6 Hz, 1H), 1950 (m, 2H), 1959 (d, J=8 Hz, 2H), 2061 (tt, J=7 Hz, J’=2 Hz, 1H), 2263 (d, J=8 Hz, 2H), 2514 (m, 2H); 13C NMR: 14.2, 21.1, 22.7, 27.3, 28.7, 28.7, 32.0, 39.6, 124.3, 126.9, 130.0, 137.9, 141.9, 146.3, 148.5, 149.1. Al Bu-n i-Bu i-Bu Al Bu-n N i-Bu 2 Ar S N O O (i-Bu)2Al Bu-n Cl
