Buchta, Emil published the artcilePolycyclic compounds. IX. 20-Methylcholanthrene and cholanthrene, Related Products of catalysis-chemistry, the publication is Chemische Berichte (1962), 213-21, database is CAplus.
cf. CA 54, 457b. -Methyl-3-(2-bromoethyl)acenaphthene (I) was converted by a modification of the previously described method (loc. cit.) to 20-methylcholanthrene (II). 3-(2-Bromoethyl)acenaphthene (III) was prepared in 8 steps from naphthalene-1,2-dicarboxylic acid anhydride (IV) and converted in an analogous manner to cholanthrene (V). Granulated K (4 g.) in 100 cc. PhMe refluxed 1 hr. with 16 g. CH2(CO2Et)2 in 20 cc. dry PhMe, cooled slightly, treated with stirring dropwise during 0.5 hr. with 16 g. I in 100 cc. PhMe, refluxed 40 hrs., cooled, and poured into H2O, the aqueous phase extracted with Et2O, the combined organic phase and Et2O extract worked up, the resulting viscous brown oil refluxed 3 hrs. with 18 g. KOH in 300 cc. MeOH, concentrated, and filtered, the residue refluxed 2 hrs. with 400 cc. H2O, filtered, and added dropwise to dilute H2SO4, and the product isolated with Et2O and heated 1 hr. at 180¡ã gave 10.5 g. 4-(8-methyl-3-acenaphthenyl)butyric acid (VI), yellow, m. 116-17¡ã (ligroine). VI (8 g.) and 80 cc. anhydrous HF kept 2 hrs. at room temperature and evaporated with a stream of air, and the residue neutralized with 30% aqueous K2CO3 and extracted with C6H6 yielded 6 g. 6-methyl-1-oxo-1,2,3,4-tetrahydro-5,10-aceanthrene (VII), m. 118¡ã (sublimed at 180-90¡ã/0.2 mm.). Com. NaOMe (5 g.) in 20 cc. C6H6 stirred 15 min., treated dropwise during 15 min. with 5 g. HCO2Et in 50 cc. dry C6H6 with cooling under N, the mixture treated dropwise during 45 min. with cooling and stirring with 5 g. VII in 100 cc. dry C6H6, stirred 5 hrs. with cooling, diluted with 50 cc. H2O, and treated with 100 cc. dilute H2SO4, and the C6H6 layer worked up gave 5.3 g. 2-hydroxymethylene derivative (VIII) of VII, yellow needles, m. 127-8¡ã (EtOH). VIII (4 g.) in 30 cc. dry C6H6, 3 g. AcCH:CH2, and 10 drops Et3N kept 5 days and evaporated in vacuo, and the residue chromatographed on Al2O3 yielded 2.5 g. 2-formyl-2-(3-oxobutyl) derivative (IX) of VII, yellow, m. 123-4¡ã (EtOH). IX (2 g.) in 25 cc. dioxane refluxed 3 hrs. with 130 cc. 3% aqueous KOH, cooled, poured into H2O, and extracted with C6H6, and the extract filtered through Al2O3 and evaporated gave 1.5 g. 20-methyl-2-oxo-2,3,-4,5,6,7-hexahydrocholanthrene (X), light yellow, m. 174-5¡ã (EtOH). X (1 g.) in 100 cc. dry tetrahydrofuran added dropwise with stirring during 0.5 hr. to 1.5 g. powd. LiAlH4 in 50 cc. tetrahydrofuran, refluxed 2 hrs. with stirring, and worked up, and the viscous, red-brown product heated during 3 hrs. with 0.5 g. 30% Pd-C under N gradually to 300-20¡ã, cooled, diluted with C6H6, filtered, and evaporated, and the viscous brown residue sublimed at 180-200¡ã/0.01 mm. yielded 18 mg. II, pale yellow, m. 175-6.5¡ã (PrOH). IV (45 g.) in 400 cc. dry tetrahydrofuran added dropwise during 1 hr. to 15 g. powd. LiAlH4 in 200 cc. dry tetrahydrofuran, refluxed 1.5 hrs., and worked up yielded 29 g. 1,2-C10H6(CH2OH)2 (XI), m. 122-3¡ã (EtOAc). XI (28 g.) in 250 cc. 1:1 C6H6-PhMe stirred about 15 min. at room temperature, treated with stirring with 45 g. PBr3 in 150 cc. C6H6, stirred 2 hrs. at room temperature and 2 hrs. at 50¡ã, cooled, and poured into iced H2O, and the product isolated with 1:1 PhMe-C6H6 yielded 38.5 g. 1,2-C10H6(CH2Br)2 (XII), leaflets, m. 148.5-9.5¡ã (CHCl3). KCN (15 g.) in 35 cc. H2O and 125 cc. 96% EtOH treated with stirring during 1 hr. with 28 g. XII in portions, stirred 3 hrs., refluxed 1 hr. with stirring, concentrated in vacuo, added hot to 225 cc. H2O, cooled, and filtered yielded 14.5 g. 1,2-C10H6(CH2CN)2 (XIII), needles, m. 188¡ã (EtOAc). XIII (18 g.), 200 cc. 40% H2SO4, and 20 cc. AcOH refluxed 2 hrs., cooled, diluted with 100 cc. H2O, and filtered, and the residue reprecipitated from 20% aqueous Na2CO3 with dilute H2SO4 yielded 14 g. 1,2-C10H6CH2CO2H)2 (XIV), m. 214¡ã (30% AcOH). XIV (15 g.), 60 g. SOCl2, 75 cc. Et2O, and a few drops C5H5N kept 0.5 hr. at room temperature, concentrated, diluted with CS2, evaporated again, dissolved in 300 cc. dry CS2, treated with stirring during 1 hr. with 30 g. powd. AlCl3, stirred 3 hrs. with cooling, and worked up gave 7.5 g. acenaphthen-1-one-3-acetic acid (XV), leaflets, m. 168¡ã (hot H2O). XV (12 g.) and 120 g. amalgamated Zn, 50 cc. H2O, 75 cc. concentrated HCl, and 40 cc. PhMe refluxed 34 hrs. while adding at 8-hr. intervals four 25-cc. portions concentrated HCl and cooled, the PhMe layer and Zn residues extracted with 20% aqueous Na2CO3, and the extract acidified gave 12 g. acenaphthene-3-acetic acid (XVI), leaflets, m. 164¡ã. XVI (10 g.) in 50 cc. dry tetrahydrofuran added dropwise during 0.5 hr. to 2 g. powd. LiAlH4 in 100 cc. refluxing dry tetrahydrofuran, refluxed 2 hrs. with stirring, and worked up gave 8 g. 3-(2-hydroxyethyl)acenaphthene (XVII), needles, m. 96¡ã (ligroine). XVII (10 g.) in 50 cc. dry CCl4 treated dropwise during 0.5 hr. at 60¡ã with 10 g. PBr3 in 10 cc. CCl4, heated 0.5 hr. at 70¡ã, and worked up gave 7 g. III, leaflets, m. 66¡ã (ligroine). CH2(CO2Et)2 (20 g.) in 50 cc. drytetrahydrofuran added dropwise with stirring to 3 g. powd. Na in 100 cc. dry PhMe, refluxed 1 hr., cooled to about 50¡ã, treated dropwise with stirring during 0.5 hr. with 20 g. III in 50 cc. dry PhMe, refluxed 36 hrs., and worked up gave 19 g. di-Et 2-(3-acenaphthyl)ethylmalonate (XVIII), b0.03 180¡ã. XVIII (6 g.) and 6 g. KOH in 100 cc. MeOH refluxed 6 hrs. gave 4.8 g. 2-(3-acenaphthenyl)ethylmalonic acid (XIX), leaflets, m. 180¡ã (decomposition). XIX (7 g.) heated 1.5 hrs. at 180-90¡ã yielded 5.2 g. 4-(3-acenaphthenyl)butyric acid (XX), leaflets, m. 154¡ã, b0.1 212¡ã. XX (5 g.) treated with 50 cc. anhydrous HF during 36 hrs. yielded 3.8 g. 1-oxo-1,2,3,4-tetrahydro-5,10-aceanthrene (XXI), needles, m. 145¡ã (EtOH). XXI (1 g.) in 50 cc. dry tetra hydrofuran added dropwise with stirring to 1.5 g. powd. Li-AlH4 in 100 cc. dry tetrahydrofuran, the mixture worked up, and the resulting viscous, yellow oil heated with 150 mg. 10% Pd-C at 320-30¡ã and then sublimed at 120¡ã/0.2 mm. yielded 0.48 g. aceanthrene (XXII), pale yellow leaflets, m. 117¡ã. Com. NaOMe (7 g.) in 20 cc. dry C6H6 treated during 15 min. with stirring with 7 g. HCO2Et in 50 cc. dry C6H6 and then during 45 min. with 7 g. XXI gave 7.5 g. 2-hydroxymethylene derivative (XXIII) of XXI, yellow needles, m. 120¡ã (EtOH). XXIII (6 g.) in 60 cc. dry C6H6 treated with 10 drops Et3N and 4 g. AcCH:CH2 and kept 4 days yielded 4 g. 2-formyl-2-(3-oxobutyl) derivative (XXIV) of XXI, needles, m. 146 7¡ã (EtOH). XXIV (4 g.) in 50 cc. dioxane refluxed 2 hrs. with 250 cc. 2% aqueous KOH yielded 3.1 g. 2-oxo-2,3,4,5,6,7-hexahydrocholanthrene (XXV), yellow leaflets, m. 180¡ã (EtOH). XXV (1 g.) in 50 cc. dry tetrahydrofuran reduced in the usual manner with 1.5 g. LiAlH4 in 50 cc. tetrahydrofuran, and the crude product heated 5 hrs. with 0.5 g. 10% Pd.C at 320-30¡ã gave 80 mg. V, pale yellow leaflets, m. 169-70¡ã (PrOH). MeCH(CO2Et)2 (40 g.) added dropwise with stirring to 4 g. powd. Na in 150 cc. dry PhMe, refluxed 1 hr., cooled, treated dropwise with 40 g. PhCH2CH2Br, refluxed 7 hrs., and worked up yielded 37.3 g. PhCH2CH2CMe(CO2Et)2 (XXVI), b10 176-9¡ã. XXVI (67 g.) and 40 g. KOH in 200 cc. MeOH refluxed 4 hrs. yielded 53 g. PhCH2-CH2CMe(CO2H)2, m. 166-7¡ã (decomposition); the acid heated 0.5 hr. at 180-90¡ã and then fractionated yielded 34 g. PhCH2CH2CHMeCO2H (XXVII), b9 161-4¡ã. XXVII (105 g.) cyclized by the method of Alexander and Mudrak (J. Am. Chem. Soc. 72, 3194(1950)) gave 89 g. 2-methyl-1-tetralone (XXVIII), b9 126-7¡ã. MeMgI from 6.25 g. Mg and 35.5 g. MeI in 100 cc. dry Et2O treated dropwise with stirring with 32.5 g. XXVIII in 50 cc. Et2O, refluxed 1 hr., and worked up, and the resulting oil refluxed 0.5 hr. with 20 g. AcCl gave 23 g. 1,2-dimethyl-3,4-dihydronaphthalene (XXIX), b12 123-6¡ã. XXIX (10.6 g.) and 2.1 g. powd. S heated 0.5 hr. at 180¡ã and 15 min. at 220-30¡ã and distilled yielded 9.5 g. 1,2-C10H6Me2, b12 132-3¡ã.
Chemische Berichte published new progress about 1949-41-3. 1949-41-3 belongs to catalysis-chemistry, auxiliary class Carboxylic acid,Benzene, name is 2-Methyl-4-phenylbutanoic acid, and the molecular formula is C11H14O2, Related Products of catalysis-chemistry.
Referemce:
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