Heck, Richard; Winstein, S. published the artcile< Neighboring carbon and hydrogen. XXVII. Ar1-5 aryl participation and tetralin formation in solvolysis>, Related Products of 52244-70-9, the main research area is .
p-MeOC6H4CH:CHCO2H added by means of a Soxhlet apparatus to 1.5 mole equivalents LiAlH4 yielded 44% p-MeOC6H4(CH2)3OH. 2,4-(MeO)2C6H3CH:CHCO2H (46 g.) reduced similarly with 12 g. LiAlH4 during 2 days gave 39% 2,4-(MeO)2C6H3(CH2)3OH, b3.5, 144-5°, nD25 1.5320, m. 36-8°. Ph(CH2)3CO2H reduced with LiAlH4 yielded Ph(CH2)4OH (I). I heated 1 hr. on the steam bath with Ac2O and a few drops pyridine gave the acetate (II), b8.5 120 °, nD25 1.4948. p-MeOC6H4(CH2)3CO2H reduced with LiAlH4 yielded 91.5% p-MeOC6H4(CH2)4OH (III), b1.5 125-30°, nD25 1.5200. 2,4-(MeO)2C6H3(CH2)3CO2H (IV) gave similarly 100% 2,4-(MeO)2C6H3(CH2)4OH (V), b2.5 157-61°, nD25 1.5296; p-nitrobenzoate (VI), m. 52-3° (from MeOH). Ph(CH2)3MgCl and ethylene oxide gave Ph(CH2)5OH, b3 110-13°, nD25 1.5149. The various primary alcs. were converted to the corresponding p-bromobenzenesulfonates (m.p. given) by the method described previously (Bs is used throughout this abstract to designate the group p-BrC6H4SO2): Ph(CH2)3OBs (VII), 35.5-7.5°; p-MeOC6H4(CH2)3OBs (VIII), 62-4°; 2,4-(MeO)2C6H3(CH2)3OBs (IX), 56-7°; Ph(CH2)4OBs (X), 21-3.5° (nD25 1.5694); p-MeOC6H4(CH2)4OBs (XI), 43-5°; 2,4-(MeO)2C6H3(CH2)4OBs (XII), 54.5-6.5°; Ph(CH2)5OBs (XIII), 34-5.5°. Glutaric anhydride (40 g.) and 50 g. m-C6H4(OMe)2 in 450 cc. purified tetrachloroethane treated at 0° with stirring with 100 g. anhydrous AlCl3 in small portions, the mixture kept about 0.5 hr. at 0°, treated with ice and dilute HCl, and worked up in the usual manner, and the product recrystallized from aqueous MeOH yielded 18 g. 2,4-(MeO)2C6H3CO(CH2)3CO2H (XIV), m. 106-7°. XIV (17 g.) refluxed 2 days with 50 g. Hg-Zn, 30 cc. PhMe, 30 cc. H2O, and 70 cc. concentrated HCl while 10 cc. concentrated HCl was added every 6 hrs., the PhMe phase extracted with aqueous NaHCO3, and the aqueous extract acidified gave 5.5 g. 2,4-(MeO)2C6H3(CH2)4CO2H (XV), m. 97-8.5° (from aqueous MeOH). XV reduced with LiAlH4 gave 96% 2,4-(MeO)2C6H3(CH2)5OH, b2 144-5°, nD25 1.5247; it gave with p-BrC6H4SO2Cl 90%-pure p-bromobenzenesulfonate (XVa). Ph(CH2)3CH(OH)Me (XVI) (15 g.), b1 80-4°, nD25 1.5108, in 75 cc. dry pyridine treated with 25 g. p-MeC6H4SO2Cl below room temperature, kept 2 hrs. at room temperature, and the product isolated with Et2O gave an oil which chromatographed on Al2O3 and eluted with C6H6-pentane yielded 9.5 g. p-toluenesulfonate (XVII) of XVI, nD25 1.5382. IV (16 g.) in 50 cc. Et2O added dropwise with stirring to MeLi from 25 g. MeI and 2.5 g. Li in 200 cc. Et2O, the mixture stirred 0.5 hr. and treated with cold dilute HCl, the Et2O layer worked up, and the product, b2 120-50°, reduced with LiAlH4 yielded 3.5 g. 2,4-(MeO)2C6H3(CH2)3CH(OH)Me b2 135-9°, nD25 1.5219, which gave a 70%-pure p-toluenesulfonate (XVIII), nD25 1.5250. The rates of the acetolysis in AcOH were determined by the method described previously (C.A. 51, 2830d) for the following compounds (temperature, M × 102 concentration of ester, and k in sec.-1 given): VII, 75.00°, 3.18, (1.07 ± 0.00)10-6; VII, 100.05°, 2.71, (1.17 ± 0.01)10-5; VIII, 75.00°, 3.04, (1.15 ± 0.03)10-6; IX, 75.00°, 2.57, 3.95 × 10-6; X, 75.00°, 3.09, (1.45 ± 0.03)10-6; X, 75.00°, 3.02, (1.49 ± 0.05)10-6; X, 100.05°, 3.68, (1.62 ± 0.01)10-5; XI, 75.00°, 2.66, (1.90 ± 0.01)10-6; XI, 100.05°, 2.16, (2.16 ± 0.01)10-5; XII, 75.00°, 2.66, (6.26 ± 0.06)10-6; XII, 100.00°, 1.94, (7.56 ± 0.05)10-5; XII (AcOH 0.0300M in LiClO4), 75.00°, 2.89, (7.2 ± 0.1)10-6; XIII, 75.00°, 2.77, (1.54 ± 0.03)10-6; XIII, 100.00°, 2.64, (1.65 ± 0.01)10-5; XVa, 75.00°, 2.40, (1.61 ± 0.03)10-6; XVa, 100.10°, 2.40, (1.76 ± 0.01)10-5. Similarly were determined the rates of the formolysis of the following compounds in 0.03151M HCO2Na in HCO2H (same data given): VII, 50.00°, 2.75, (1.54 ± 0.08)10-6; VII, 75.00°, 2.75, (1.99 ± 0.03)10-5; X (without added HCO2Na), 75.00°, 2.70, (3.35 ± 0.01)10-5; X, 75.00°, 2.68, (3.43 ± 0.03)10-5; X, 100.20°, 2.68, (3.13 ± 0.07)10-4; XI, 50.00°, 2.70, (5.03 ± 0.18)10-6; XI, 75.00°, 2.70, (6.08 ± 0.11)10-5; XII, 50.00°, 2.24, (2.58 ± 0.02)10-5; XII, 75.00°, 2.24, (3.40 ± 0.06)10-4; XVII, 25.00°, 3.13, (5.43 ± 0.10)10-5; XVIII, 25.00°, 3.63, (1.36 ± 0.13)10-4; XIII, 50.00°, 2.70, (2.90 ± 0.08)10-8; XIII, 75.00°, 2.70, (3.39 ± 0.02)10-5; XVa, 75.00, 2.69, (3.63 ± 0.11)10-5. The enthalpy (in kcal./mole) and the entropy (in e.u.) of the acetolysis were: VII, 24.0, -17.5; X, 23.9, -16.8; XI, 24.4, -15.0; XII, 25.0, -10.7; XIII, 23.8, -17.1; XVa, 23.9, -16.7; the same values for the formolysis were: VII, 22.2, -16.6; X, 22.0, -16.2; XI, 21.6, -16.1; XII, 22.4, -10.4; XIII, 21.3, -18.2. IX (18.4 g.) and 3.40 g. HCO2Na in 900 cc. dry HCO2H heated 6 hrs. at 75.0°, diluted with H2O, and extracted with Et2O, the extract washed, dried, and reduced with 2 g. LiAlH4, and the Et2O solution worked up gave a crude product which chromatographed on 500 g. Al2O3 and eluted with 5 l. pentane yielded 5.5 g. 2,3-dimethoxytetrahydronaphthalene (XIX), b2 102-5°, nD25 1.5454 (this material crystallized after several months, m. 36.5-38°; it gave with Br a monobromide, m. 78-80°). An addnl. 0.8 g. XIX, b3 110°, nD25 1.5401, was obtained by further elution with 4 l. Et2O; the column then eluted with 3 l. MeOH gave 0.7 g. V, b3 130°, which was converted to 0.8 g. VI, m. 49-51° (2nd crop, 0.1 g., m. 48-51°). XIX (2 g.) and 6 g. chloranil refluxed 15 hrs. in 20 cc. xylene yielded 1,3-C10H6(OMe)2 (XX), isolated as 0.8 g. picrate, m. 141-2°. V (2 g.) in 150 cc. 98-100% HCO2H heated 15 hrs. at 75° and the mixture worked up as described for the solvolysis run yielded 1.65 g. unchanged V, b2 150-2°, nD25 1.5296. V (0.5 g.) in 30 cc. 0.0315M HCO2Na in HCO2H heated 10 hrs. at 75° gave 0.35 g. unchanged V which yielded 0.40 g. VI, m. 50-3°. 1,3,2-(HO)2C10H5CO2Et (13 g.) treated with CH2N2 [from 15 g. H2NCON(NO)Me] in 200 cc. Et2O, the mixture allowed to stand overnight, the Et2O evaporated, the residual oil distilled, the distillate (11 g.), b2 155-75°, refluxed with 10 g. NaOH in 15 cc. H2O and 15 cc. EtOH overnight, the dark solution and solid treated with H2O and extracted with Et2O, and the residue from the extract distilled gave 2.8 g. dark oil, b3 145-50°, which chromatographed on Al2O3 readily lost its color but soon became colored again on standing; the purified XX had nD25 1.6140; picrate, long orange-red needles, m. 140-1° (from Et2O). XI (8 g.) in 700 cc. 0.03022M HCO2Na in dry HCO2H heated 42 hrs. at 75°, diluted with H2O, and extracted with pentane, the extract evaporated, the residue reduced with 1 g. LiAlH4, and the product chromatographed on 100 g. Al2O3 and eluted with 700 cc. pentane gave 1.65 g. 7-methoxytetrahydronaphthalene, b1.5 76°, nD25 1.5414; further elution with 600 cc. Et2O gave 1.55 g. III, b1.5 118-19°, nD25 1.5239. Dry HCO2Na (3.4 g.) in 1000 cc. dry HCO2H treated at 75.0° with 18.5 g. purified X, kept 66 hrs. at 76.0°, cooled, poured into 3 l. H2O, and extracted with pentane, the residue from the extract reduced with 2 g. LiAlH4, and the product chromatographed on 500 g. Al2O3 yielded 1.10 g. tetrahydronaphthalene (XXI), b22 101-3°, nD25 1.5388, which dehydrogenated with chloranil gave 80% C10H8, m. 75-7°; further elution of the column with MeOH yielded 5.4 g. I, b1.5 87-90°, nD25 1.5191. I (2.0 g.) and 0.6 g. p-MeC6H4SO3H in 100 cc. dry HCO2H heated 67 hrs. at 75.0°, cooled, poured into H2O, and extracted with pentane, and the residue from the extract reduced with LiAlH4 yielded 1.7 g. unchanged I, b10 124-7°, nD25 1.5189. Pure X (20.0 g.) added to 1200 cc. dry AcOH at 100.0°, the solution kept 101 hrs. at 100.0°, cooled, poured into 3 l. H2O, and extracted with pentane, the residue from the extract reduced with LiAlH4, and the product chromatographed on Al2O3 yielded 0.35 g. XXI, b10 75°, nD25 1.5370, and 6.85 g. I, b2 about 100°, nD25 1.5205. II (11.0 g.), 11.4 g. p-MeC6H4SO3H, and 1 cc. Ac2O in 1200 cc. dry AcOH kept 140 hrs. at 100.0° and the mixture processed in the usual manner with LiAlH4 reduction gave 8.2 g. I, b8.5 120-3°, nD25 1.5202. XVII (9.2 g.) (93% pure) and 2.45 g. dry HCO2Na in 600 cc. dry HCO2H kept 43.5 hrs. at 25.0° and worked up in the usual way yielded 2.05 g. hydrocarbon fraction, b25 112-15°, nD25 1.5229, and 2.20 g. XVI, b1.5 95-100°, nD25 1.5107. A 0.75-g. sample of the hydrocarbon fraction (containing 30% olefin) added to 1.0 g. OsO4 in 20 cc. Et2O containing 2 drops pyridine, kept 0.5 hr., treated with 150 cc. CH2Cl2, 2.5 g. KOH, and 2.5 g. mannitol in 50 cc. H2O, and shaken 2 hrs., the aqueous phase extracted with CH2Cl2, and the combined CH2Cl2 solutions worked up gave 0.4 g. 1-C10H7Me 55°, nD25 1.5323. XVI (5.0 g.) and 0.35 g. HCO2Na in 500 cc. HCO2H kept 41 hrs. at 25.0°, the mixture processed in the usual manner, and the product reduced with 1.5 g. LiAlH4 yielded 5.0 g. unchanged XVI, b8 117-20°, nD25 1.5108. XVI (4.4 g.) in 500 cc. HCO2H kept 27 days at 25° gave 0.06 g. hydrocarbon fraction and 4.0 g. XVI, b30 145-8°, nD25 1.5106. Olefin-hydrocarbon mixture (1.0 g.) from the solvolysis of XVII kept 42.5 hrs. at 25.0° with 0.050 g. pure HCO2Na in 150 cc. 98-100% HCO2H gave 0.95 g. product, nD25 1.5231, containing 26% olefin. Ph(CH2)3CH:CH2 (4.4 g.), b. 77-8°, nD25 1.5019, in 500 cc. 98-100% HCO2H kept 27 days at 25.0°, poured into H2O, and extracted with pentane, the residue from the extract reduced with LiAlH4, and the product chromatographed yielded 3.2 g. hydrocarbon, b30 106-8°, nD25 1.5054, and 1.0 g. alc., b2 95°, nD25 1.5099.
Journal of the American Chemical Society published new progress about Acetolysis. 52244-70-9 belongs to class ethers-buliding-blocks, and the molecular formula is C11H16O2, Related Products of 52244-70-9.
Referemce:
Ether – Wikipedia,
Ether | (C2H5)2O – PubChem