Freudenberg, Karl published the artcileSynthetic experiments connected with lignin, Application In Synthesis of 70110-65-5, the publication is Annalen der Chemie, Justus Liebigs (1953), 40-53, database is CAplus.
The following model substances are in part related to the dimers obtained by F. in experiments with coniferyl alc. (C.A. 47, 12296g), which are considered “secondary building stones” in lignin formation. Veratraldehyde condensed with CH2(CO2H)2 gave quant. yields of 3,4-(MeO)2C6H3CH:CHCO2H, whose Et ester (obtained in 94% yield) with Br in CHCl3 in artificial light yielded the dibromide, m. 110°; this was refluxed 7-8 hrs. with 3 moles KOH in alc., cooled, filtered, neutralized gradually (at about 0°) with concentrated HCl, refiltered, and concentrated in vacuo. Any salts that had been filtered, combined with those separating on concentration, were dissolved in H2O and acidified with 20% H2SO4, giving 20-30% 3,4-(MeO)2C6H3CCCO 2H (I), m. 156° (Fulton and Robinson, J. Chem. Soc. 1903, 1463). Carefully purified 4,3-Me(MeO)C6H3OH (13.8 g.) and 50 cc. MeOH containing 2.3 g. Na, evaporated in vacuo, heated 5 hrs. at 100° with 22 g. I Me ester, 50 cc. PhMe, and 13.8 g. creosol, allowed to stand 12 hrs. at room temperature, extracted with Et2O, shaken repeatedly with aqueous H2SO4, and the excess creosol extracted from the Et2O with aqueous NaOH, followed by washing, drying, evaporation, and fractionation, gave 17 g. Me β-(3-methoxy-4-methylphenoxy)-3,4-dimethoxycinnamate (II), prisms, m. 107-8°. At -70 to -80°, 5 g. crude II in 100 cc. dry Et2O with 0.3 g. LiAlH4 in 26 cc. Et2O gave a precipitate which, when decomposed with H2SO4, yielded a mixture of creosol, dimethoxycinnamyl alc. (III), and α-(2-methoxy-4-methylphenoxy)-3,4-dimethoxycinnamyl alcohol (IV). III and IV could not be separated by distillation, or by adsorption in C6H6 on Al2O3 but the separation was effected on a paper chromatogram with C6H6 (Rf of III and IV being 0 and 0.9, resp.). IV was noncrystalline, but gave a red, crystalline p-PhN2C6H4CO derivative, m. 118-19°; and a crystalline phenyl-urethan, m. 134-5°. The phenylurethan of III m. 107-8°. PhOCH2CO2Me (22 g.) and 14 g. BzH reacted vigorously with 3 g. Na wire and 40 cc. dry Et2O. After 12 hrs. 8.2 g. glacial AcOH, 60 cc. H2O, and 20 cc. Et2O were added successively, giving 38% PhCH(OH)CH(OPh)CO2Na (V), the Et2O and alc. washings from which, when concentrated and esterified, yielded 48% PhCH:C(OPh)CO2Me (VI), b11 210°, m. 60-1°. The free acid from V, oil (not characterized) gave the Me ester (VII), m. 61° (from petr. ether); Ac derivative of VII, m. 69-70°; S-benzylthiuronium salt (corresponding to V), m. 188°. VI in Et2O, under N at -70° with LiAlH4, gradually warmed to -20° with aqueous H2SO4 gave PhCH:C(OPh)CH2OH, viscous oil; phenyl urethan, m. 104°. VII, similarly reduced (at -20°) gave PhCH(OH)CH(OPh)CH2OH, b1 197°, m. 74-5°. Using Giacosa’s technique [J. prakt. Chem. 19, 396(1879)] but with longer initial heating, creosol, ClCH2CO2H, and NaOH gave 67% 4,2-Me(MeO)C6H3OCH2CO2H, m. 115°; Me ester (VIII), b11 167°; amide, m. 134-5°. Veratraldehyde (15.8 g.), 20 g. VIII, and 2.2 g. powd. Na under Et2O, first cooled, then heated several hrs. on a steam bath and acidified with AcOH, gave 3,4-(MeO)2C6H3CH:CRCO2Me (IX) [R in this and other compounds = 4,2-Me(MeO)C6H3O], which, reduced with LiAlH4 at -70° yielded the alc., C19H22O5 (isolated by treating the intermediate salt, under Et2O, with Dry Ice), oil, setting to a resin; 3,5-dinitrobenzoale, yellow needles, m. 158-9° (from BuOH). When 15.8 g. veratraldehyde, 20 g. VIII, 2.2 g. Na, and 50 cc. Et2O were kept at about 0° and then acidified with aqueous AcOH, the product was a mixture, b0.01 225°, of IX and 3,4-(MeO)2C6H3(OH)CHRCO2Me, m. 137° (from aqueous MeOH). To 8 g. Na (powdered under 100 cc. absolute PhMe) were added successively 25 g. abs EtOH and 50 g. vanillin, and the resulting Na derivative was filtered, triturated with and suspended in PhMe, well-cooled, and treated with freshly distilled ClCH2OMe; this kept at least 6 hrs. at room temperature, washed with 2% NaOH, and fractionated gave 41 g. methoxymethylvanillin (X), b1.5 145-7°, m. 39-40°. Freshly prepared X (9.8 g.) fused with 10.5 g. VIII, the product cooled, treated with 1.15 g. Na wire and 40 cc. Et2O, allowed to stand overnight, 3.1 g. AcOH in 40 cc. H2O added, and the mixture extracted with Et2O gave 9 g. 4,3-(MeOCH2O)(MeO)C6H3CH(OH)CHRCO2Me, b0.05 175-7°. With 30 g. 14-day-old X (or with fresh X containing small amounts of vanillin), the reaction was sluggish and required heating for completion, giving as the principal product 3,4-MeO(MeOCH2O)C6H3CH: CRCO2Me (XI), m. 112-13° (from aqueous MeOH). With a drop of H2SO4, AcOH, and Ac2O, 2 g. XI at 0° gave, after 1.5 hrs., 1.3 g. 3,4-MeO(AcO)C6H3CH:CRCO2Me (XII), m. 80° (from aqueous EtOH); when cooling was omitted, but the reaction continued for 8 hrs., the yield of XII was 87%. XII reduced with LiAlH4 under N at -20°, followed by a fully described extensive purification, including chromatographic fractionation on powd. cellulose, gave 3,4-MeO(HO)C6H3CH:CRCH2OH (XIII), b0.0001 140° (bath temperature), prisms, m. 90-1° (from CH2Cl2-petr. ether). Hydrogenated in MeOH with 5% Pd-BaSO4, XII gave the dihydro derivative, C21H24C7, b0.01 197°, which, reduced with LiAlH4, yielded the dihydro derivative of XIII, C18H22O5, b0.01 150°. Vanillin (10 g.), 6.25 g. CH2ClCO2H, 8.5 g. KOH, and 30 cc. H2O heated 4 hrs. at 100° and acidified with aqueous HCl gave quantitatively 2,4-MeO(OHC)C6H3OCH2CO2H, m. 188-9° [Elkan, Ber. 19, 3045(1886)], 8 g. of which with 10 g. CH2(CO2H)2 in 50 cc. pyridine containing small amounts of piperidine heated 2 hrs. at 100° yielded quantitatively 3,4-MeO(HO2CCH2O)C6H3CH:CHCO2H, m. 234° (also formed in 73% yield from ferulic acid, CH2ClCO2H and NaOH); di-Me ester (XIV), m. 104-5°. Veratraldehyde, (3 g.), 5 g. XIV, 0.41 g. Na powder, 20 cc. Et2O, and several drops absolute MeOH, heated several hrs. and acidified with aqueous AcOH, gave 2 g. Me α-[2-methoxy-4-(β-carbomethoxyvinyl)phenoxy]-3,4-dimethoxycinnamate, b0.01 260°, m. 129°. XIV and X refluxed with Na in Et2O gave, after acidification and fractionation of the Et2O extract, 31% Me O-methoxymethyl-α-[2-methoxy-4-(β-carbomethoxyvinyl)phenoxy]ferulate (XV), b0.01 275°, m. 100-1° (from MeOH). By replacing the MeOCH2 group in XV by Ac, the O-Ac analog (XVI), C24H24O9, b0.0001 180° (bath temperature), m. 117-18°, was formed. XVI (18 g.) in Et2O reduced by stepwise addition of LiAlH4 at room temperature, followed by adding moist Et2O, Na2S2O4, and Dry Ice to the aqueous phase, and fractionation in high vacuum of the Et2O extract, gave about 100 mg. resinous. 3,4-MeO[3,4-MeO(HO)C6H3CH:C(CH2OH)O] C6H3CH:CHCH2OH (XVII). The tetrahydro derivative of XVI, sirup, b0.001 160° (bath temperature); the tetrahydro derivative of XVII, colorless sirup, b0.001 150° (bath temperature). Inasmuch as both acetone-lignin and the dehydrogenation polymers of coniferyl alc. yielded 1.5-2% HCHO when distilled with H2SO4, a similar treatment was applied to a number of the synthetic compounds listed above. None of these gave more than faint traces of HCHO, with the single exception of PhCH(OH)CH(OPh)CH2OH, which yielded 1.3% HCHO. From this and previous studies (C.A. 42, 882a). F. and M. have indicated what types of structure, in O-containing derivatives of PhPr, are capable of giving rise to HCHO. 19 references.
Annalen der Chemie, Justus Liebigs published new progress about 70110-65-5. 70110-65-5 belongs to alcohols-buliding-blocks, auxiliary class Benzene,Alcohol,Ether,Benzene Compounds, name is 2-Phenoxy-1-phenylpropane-1,3-diol, and the molecular formula is C15H16O3, Application In Synthesis of 70110-65-5.
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