MacMillan, J. et al. published their research in Journal of the Chemical Society in 1959 |CAS: 53724-96-2

Ethyl 6-methoxy-3-methylbenzofuran-2-carboxylate(cas:53724-96-2) belongs to benzofuran. Benzofuran is the “parent” of many related compounds with more complex structures. For example, psoralen is a benzofuran derivative that occurs in several plants. Product Details of 53724-96-2

MacMillan, J. published an article in 1959, the title of the article was Griseofulvin. XVII. Synthesis of 7-chloro-4,6-dimethoxy-2′-methylgrisan-3,4′-dione.Product Details of 53724-96-2 And the article contains the following content:

The synthesis is described of grisan and 3-coumaranone spirocyclopentane analogs of some griseofulvin (I) derivatives and of racemates of some I degradation products. (All m.ps. are corrected; absorption spectra determined in EtOH.) Et 6-hydroxy-3-methylcoumarone-2-carboxylate (II), m. 179° (EtOH), ν 1700 cm.-1, λ 313, 282, 241, 210 mμ (log ε 4.30, 4.07, 3.90, 4.24), was prepared in 60% yield by the method of Hantzsch [Ber. 19, 292(1886)]. Treatment of II with Me2SO4 gave 30% 6-methoxy-3-methylcoumarone-2-carboxylic acid (III), m. 184°, and 25% III Et ester (IV), m. 74-5°, ν 1700 cm.-1, λ 312, 285, 243 mμ (log ε 4.44, 4.13, 3.97); esterification of III gave IV. 6-Methoxy-3-methylcoumarone-2-acetic acid (V) chloride and AcCH(MgOEt)CO2Et (VI) gave Et α-acetyl-β-oxo-6-methoxy-3-methylcoumarone-2-γ-butyrate (VII), oil, ν 1714, 1623, and 1587 cm.-1; Cu derivative (VIII), m. 175° (MeOH), ν 1715, 1692, 1671, 1587 cm.-1 VII (7 g.) and 15 mL. concentrated H2SO4 kept 3 days at -5°, diluted with 50 mL. H2O, extracted with Et2O, the Et2O solution extracted with aqueous NaHCO3, and the alk. extract acidified gave 200 mg. V, m. 139-40°; recovery from the Et2O solution gave a pale yellow oil (IX). IX in EtOH passed through a C column, the resulting material triturated for a long time under petr. ether (X) at -50°, and the solid further recrystallized at room temperature gave 2.8 g. Et 6-methoxy-3-methylenecoumaran-2-spiro-1′-(2′-methyl-4′-oxocyclopent-2′-en-3′-carboxylate) (XI), m. 122°, ν 1745, 1707, 1649, 1615, 1595 cm.-1, λ 327, 263, 231, 214 mμ (log ε 3.98, 4.12, 4.35, 4.31); 2,4-dinitrophenylhydrazone, m. 175-6° (C6H6-X). Cyclization of VIII with H2SO4 gave 45% XI. XI (150 mg.) hydrogenated at room temperature and pressure with a catalyst prepared in situ from 7 mg. PdCl2 and 75 mg. C in 10 mL. AcOH (1 mol H absorbed), the recovered gum chromatographed in Et2O on Al2O3, eluted with Et2O, and the product repeatedly triturated with X at 0° gave 105 mg. corresponding 3-Me analog, m. 77-8°, ν 1738, 1698, 1610 cm.-1, λ 320, 302, 281, ∼263,228 mμ (log ε 2.78, 3.45, 3.59, 3.72, 4.25); 2,4-dinitrophenylhydrazone, m. 160° (C6H6-petr. ether). A stream of O3-O passed into 500 mg. XI in 30 mL. CCl4 until the solution became opaque, the filtered solution evaporated, the residual gum mixed with 25 mL. H2O, kept 24 h., and the aqueous phase distilled into saturated dimedon (XII) solution in 10% aqueous alc. gave XII derivative of CH2O, m. 191-2°; an Et2O solution of the residual gum chromatographed on Al2O3, the lowest bright-blue fluorescent band eluted with Et2O and the recovered product boiled with X (110 mg. solid obtained); the solid combined with 100 mg. slightly impure material from the following band fluorescing greenish-blue and recrystallized (petr. ether) gave 200 mg. corresponding 3-oxo compound (XIII), m. 115-17°, ν 1751, 1715, and 1701 cm.-1, λ 321, 275, 232 mμ (log ε 3.98, 4.21, 4.23); mono-2,4-dinitrophenylhydrazone, m. 243° (decomposition) (C6H6-petr. ether). Oxidation of 100 mg. XIII with Fehling’s solution gave 25 mg. 2,4-HO(MeO)C6H3CO2H, m. 154-5°. XIII (70 mg.) and 17.5 mL. 2N HCl and 14 mL. EtOH refluxed 6 h. under N cooled (15 mg. solid separated), EtOH removed in vacuo (15 mg. solid and 30 mg. XIII separated), the combined product purified through the Na salt, and recrystallized (EtOH) gave 23 mg. corresponding acid (XIV), m. 175-7°, ν 1716 and 1697 cm.-1, λ 318, 273, 232, 210 mμ (log ε 4.05, 4.25, 4.30, 4.45). XIV (70 mg.) heated 10 min. at 190-200° in an N atm., the residue sublimed in situ in vacuo, and the sublimate recrystallized (aqueous Me2CO) gave 40 mg. 6-methoxy-3-oxocoumaran-2-spiro-1′-(2′-methylcyclopent-2′-en-4′-one) (XV), m. 193-5°, ν 1713 cm.-1, λ 320, 273, 232, 209 mμ (log ε 3.92, 4.07, 4.16, 4.40); mono-2,4-dinitrophenylhydrazone, m. 238-40° (EtOAc). XV (15 mg.) in 1.5 mL. EtOAc added to a previously catalyst prepared from 10 mg. PdCl2 and 40 mg. C in 1 mL H2O, the mixture shaken with H at room temperature and pressure until absorption ceased (2.4 mol H absorbed in 5 min.), and the product (XVI) (13 mg.) recovered; XVI (13 mg.) chromatographed in C6H6 on Al2O3, a bright-blue fluorescent band eluted with C6H6, the product (2 mg.) recovered, sublimed, and crystallized (petr. ether) gave 0.8 mg. 6-methoxy-3-oxocoumaran-2-spiro-1′-(2′-methylcyclopentane), m. 167-8°, identical with the product from condensation of 6-methoxycoumaran-3-one and CH2Br(CH2)2CHBrMe (cf. preceding abstract). β-Propiolactone (XVII) (8.64 g.) and 19.44 g. 6-methoxy-3-methylcoumarone refluxed 6 h. at 200°, the cooled residue ground with aqueous Na2CO3, the mixture filtered, the Et2O-washed filtrate acidified, the precipitate filtered off, sublimed in vacuo, and the sublimate crystallized (dilute EtOH) gave 4.9 g. 6-methoxy-3-methyl-coumarone-2-β-propionic acid (XVIII), m. 137°, ν 1707 cm.-1, λ 292 and 253 mμ (log ε 3.80, 4.16). 6-Methoxy-3-methylcoumarone-2-acetic acid (440 mg.) and 1 mL. SOCl2 was warmed gently until a clear solution was obtained, volatiles removed in vacuo below 30°, the residual oil in 10 mL. Et2O added at 0° to a 3-fold excess CH2N2 in 15 mL. Et2O, the solution kept 24 h. at 0°, and the Et2O removed in vacuo; the residual crude diazo ketone (m. 118-23°) in 10 mL. dioxane added dropwise with stirring to 2 g. Ag2O in 1 g. Na2S2O3 and 1 g. K2CO3 in 20 mL. H2O at 50-60° (N evolved), after 20 min. the mixture heated 10 min. at 70° and 5 min. at 90°, filtered, the filtrate acidified with dilute HNO3, the oil triturated with H2O, the resulting semisolid sublimed in vacuo, and the sublimate crystallized (dilute EtOH) gave 60 mg. XVIII, m. 137-8°. XVIII treated with PCl5 gave the acid chloride (XIX), green oil; amide, plates (C6H6-petr. ether). XIX in 500 mL. Et2O mixed with a suspension of VI [from 2.7 g. AcCH2CO2Et (XX), 1.2 mL. EtOH, and 0.48 g. Mg in 50 mL. Et2O], the mixture refluxed 24 h., excess dilute AcOH added, the separated Et2O layer washed with aqueous NaHCO3 (from the alk. wash 200 mg. XVIII was isolated on acidification), concentrated, the oil (4.2 g.) chromatographed in C6H6 on Al2O3 and eluted with C6H6 gave, from a narrow fluorescent band, 90 mg. oil, which, on crystallization (petr. ether), afforded 60 mg. XVIII Et ester (XXI), m. 51-2°, ν 1737, 1624, 1594 cm.-1, identical with material obtained by esterifying XVIII, and, from a greenish-red band, 3.1 g. oil, which, heated 4 h. at 100-10°/10-4 mm., yield 2.2 g. crude oxo ester (XXII), giving an intense Fe+++ reaction in EtOH and forming a Cu chelate. Crude XXII (12 g.) in 25 mL. concentrated H2SO4 kept 8 days at 0°, worked up as described above for the lower homolog, and the alk. extract acidified gave a yellow precipitate which decomposed on filtration; the unfiltered mixture extracted with C6H6, the extract passed through silica, and eluted with C6H6 gave 600 mg. XVIII, m. 133-5°; the Et2O solution concentrated, the oil (4.5 g.) chromatographed in Et2O on Al2O3, and eluted with Et2O gave, from a narrow band, 20 mg. XXI, and, from a pale blue band, 4.1 g. oil, which, crystallized (EtOH) and recrystallized (aqueous EtOH), afforded 3.8 g. Et 6-methoxy-2′-methyl-3-methylene-4′-oxogris-2′-ene-3′-carboxylate (XXIII), m. 97-8°, ν 1728, 1668, 1641, 1614 cm.-1, λ 326, 316, 273, 260, 233, 215 mμ (log ε 4.05, 4.09, 4.18, 4.43, 4.37); 2,4-dinitrophenylhydrazone, m. 182° (decomposition). Crude XXII (1.5 g.) mixed with 20 g. polyphosphoric acid (XXIV), kept 4 days at room temperature, and worked up gave 700 mg. XXIII, 30 mg. XXI, and no acidic product. XXIII (1.0 g.) in 30 mL. CCl4 ozonized as above (CH2O isolated with XII), the product chromatographed in Et2O on Al2O3, the yellow gum (510 mg.) treated with EtOH, seeded, and the solid recrystallized (dilute EtOH) gave Et 6-methoxy-2′-methyl-3,4′-dioxogris-2′-ene-3′-carboxylate (XXV), m. 110-11°, ν 1735, 1704, 1686 cm.-1, λ 320, 272, 231, 208 mμ (log ε 3.95, 4.12, 4.17, 4.42), giving an intractable precipitate with Brady reagent. XXV (3 g.) refluxed 4 h. in an N atm. with 300 mL. EtOH and 350 mL. 2N HCl (0.6 mol CO2 evolved), the solution concentrated in vacuo, the aqueous residue extracted with Et2O, the extract washed with aqueous NaHCO3 (recovery gave only a trace of acidic gum), concentrated, the residual oil (1.6 g.) chromatographed in Et2O on Al2O3, and eluted with Et2O gave, from a blue band, 1.5 g. 6-methoxy-2′-methylgris-2′-ene-3,4′-dione, gum, ν 1713 and 1667 cm.-1, λ, 318, 272, 232, 209 mμ (log ε 3.98, 4.13, 4.22, 4.45) [2,4-dinitrophenylhydrazone, m. 230° (EtOAc)], and, from a dark blue band, 20 mg. XXV. 3,2,4,6-Cl(HO)(MeO)2C6HAc (XXVa) (46.0 g.), 66.4 g. CH2BrCO2Et, and 56.0 g. anhydrous K2CO3 in 700 mL. Me2CO refluxed 72 h., filtered, the filtrate evaporated in vacuo, the oil dissolved in 200 mL. EtOH, the solution treated with Et2O, and the precipitate recrystallized (EtOH) gave 56.6 g. 2,6,3,5-Ac(Cl)-(MeO)2C6HOCH2CO2Et (XXVI), m. 72°, ν 1763, 1735, 1684 cm.-1, λ 305, 292, 258, 223 mμ (log ε 3.35, 3.43, 3.70, 4.21); 2,4-dinitrophenylhydrazone m. 136° (EtOAc). With CH2-BrCO2Me in the above experiment, there was obtained the corresponding Me ester (XXVII), m. 103-4° (MeOH), ν 1760 and 1680 cm.-1, λ 305, 293, 268, 233 mμ (log ε 3.35, 3.42, 3.66, 4.20). XXVI (47.4 g.) in 200 mL. EtOH, 300 mL. H2O, and 14 mL. H2SO4 refluxed 4 h., diluted with H2O until cloudy, kept overnight at 5%, the precipitate filtered off, washed with aqueous Na2CO3 (19.7 g. XXVI remained), and the alk. extract acidified gave 19.1 g. acid (XXVIII), m. 144° (C5H6 or H2O), ν 1751 and 1659 cm.-1, λ 301, 292, 258, 224 mμ (log ε 3.42, 3.39, 3.66, 4.19). XXVII (500 mg.) and 20 mL. 3N HCl refluxed 6.5 h., the solid filtered off, dissolved in warm aqueous Na2CO3, the solution treated with C, filtered, and the filtrate acidified at 0° gave 311 mg. XXVIII cyclic form (XXIX) (R = H) (XXX), m. 143-4° (dilute EtOH), ν 1746 cm.-1, λ 275 and 240 mμ (log ε 3.09, 3.95); mixtures of XXVIII and XXX m. 115-40°; a 1:1 mixture (XXXI), m. 119-20°, behaved as a pure compound (see below). XXVII (1.5 g.) and 75 mL. N HCl refluxed 4 h. and worked up gave 1.1 g. XXX, m. 119-20° (C6H6), ν 1749 and 1659 cm.-1, identical with a 1:1 mixture XXVIII and XXX. XXX (29 mg.) in 5 mL. Et2O treated overnight with 1 mol CH2N2 in 5 mL. Et2O and worked up gave 24 mg. XXIX (R = Me) (XXXII), m. 97° (MeOH), ν 1742 cm.-1, λ ∼275 and 235 mμ (log ε 3.07, 3.98). XXVIII treated similarly gave the isomeric open-chain acid (XXXIII), m. 103-4°, mixed m.p. with XXXII 78-85°. XXXIII or XXXII (17.3 g.), 34 g. fused NaOAc, and 100 mL. Ac2O heated under reflux until CO2 evolution ceased (30 min.), the cooled solution diluted with H2O, made alk. with Na2CO3, the product filtered off, passed through a column of Al2O3 in 3 l. C6H6 recovered, and crystallized (EtOH) gave 14 g. 7-chloro-4,6-dimethoxy-3-methylcoumarone (XXXIV), m. 148°, ν 1626, 1611, 1591 cm.-1, λ 320, ∼275, 263, 220, 216 mμ (log ε 2.42, 4.00, 4.19, 4.56, 4.56). XXVI (15.8 g.) refluxed 1 h. with 1 g. Na in 50 mL. EtOH, the cooled solution diluted with 750 mL. H2O, the precipitate (2.7 g.) filtered off, and crystallized (EtOH) gave Et 7-chloro-4,6-dimethoxy-3-methylcoumarone-2-carboxylate (XXXV), m. 172-3°, ν 1712 cm.-1, λ 312, 298, 245, 230 mμ (log ε 4.32, 4.37, 4.34, 4.30); acidification of the filtrate with dilute HCl gave 11.2 g. XXVIII, m. 143°. XXXV (895 mg.) warmed 10 min. at 40° with 6 g. NaOH in 100 mL. 50% aqueous EtOH, diluted with ice and H2O, the solution acidified, and the precipitate (790 mg.) sublimed in vacuo gave the corresponding acid (XXXVI), m. 310° (decomposition), ν, 1671 cm.-1, λ 293 and 238 mμ (log ε 4.26, 4.31); Me ester, m. 196° (MeOH). XXXVI converted to the acid chloride (SOCl2 plus C5H5N) and the latter treated with CH2N2-Et2O gave the diazo ketone (XXXVII), m. 118-20° (Et2O). Attempted Wolff rearrangement of 600 mg. XXXVII as above gave 530 mg. XXXVI, m. 250-60° (decomposition). XXXVI (200 mg.) in 0.5 mL. quinoline heated 5 min. at 190-5° with 100 mg. Cu bronze and worked up gave 150 mg. XXXIV, m. 143°. Anhydrous HCN (200 mL.) added to 142 g. XXXIV in 6 1. Et2O at 0°, a fast stream of dry HCl passed in at 0-5° until absorption ceased (6 h.), the solution kept overnight at 0°, the aldimine-HCl (XXXVIII) filtered off, washed with Et2O, heated with 10 1. H2O at 100%, and the product (XXXIX) (110 g.) filtered off (after 24 h. a second crop XXXVIII separated from the Et2O mother liquor which yielded 27 g. addnl. XXXIX on hydrolysis); XXXIX in C6H6 passed through Al2O3, crystallized (C6H6, EtOH, or Me2CO), sublimed, and the sublimate recrystallized (Me2CO) gave the 2-OHC derivative (XL) m. 183°, μ 1662 cm.-1, λ 341, 312, 253 mμ (log ε 4.24, 4.16, 4.28) [2,4-dinitrophenylhydrazone m. 312°(Me2CO); azlactone m. 235°(EtOAc), giving on alk. hydrolysis 7-chloro-4,6-dimethoxy-2,3-dimethylcoumarone (XLI), m. 290° (MOH), μ and 1596 cm.-1]. XL oxidized with KMn-O4 in aqueous Me2CO gave XXXVI, m. 310° (decomposition). XL (2.26 g.) and 720 mg. XVII refluxed 4 h., cooled, the melt dissolved in 200 mL. Et2O, the solution filtered, the filtrate extracted with aqueous Na2CO3, and the alk. extract acidified gave 720 mg. 7-chloro-4,6-dimethoxy-3-methylcoumarone-2-β-propionic acid (XLII), m. 123-30° (chromatog. followed by recovery from the Ag salt); a sample of XLII was converted by Et2O-CH2N2 to the Me ester (XLIII), m. 102° (MeOH), ν 1739 cm.-1, λ 320, 294, 278, 265, 226, 223 mμ (log ε 2.61, 3.30, 4.05, 4.27, 4.53, 4.52, 4.52). The remaining XLII (500 mg.) methylated as above, the product chromatographed in C6H6 on Al2O3, a pale-blue band eluted with Et2O, the recovered ester (350 mg.) hydrolyzed with N alc. HCl, the compound sublimed in vacuo, and recrystallized (aqueous EtOH) gave XLII, m. 134-5°, ν (Nujol mull) 1722 and 1706 cm.-1, (in CHCl3) 1716 cm.-1 XXXIX (4 g.), 6.7 g. CH2(CO2H)2, 330 mg. piperidine, and 17 mL. C5H5N heated 1 h. at 100° and then 10 min. at 120°, The cooled solution was acidified, the precipitate (6.1 g.) extracted with aqueous Na2CO3 (1.3 g. XXXIV remained), and the alk. extract acidified gave 4.75 g. 7-chloro-4,6-dimethoxy-3-methylcoumarone-2-acrylic acid (XLIV), m. 252° (C6H6), ν 1692 and 1676 cm.-1, λ 329 and 255 mν (log ε 4.44, 4.04); Me ester, m. 179° (MeOH), ν 1709 cm.-1 (a) XLIV (102 mg.) in 50 mL. AcOH added to 0.2 g. Raney Ni in 2 mL. EtOH, hydrogenated at room temperature and pressure until absorption ceased (1 mol H absorbed in 8 h.), the mixture filtered, the filtrate concentrated to 5 mL. in vacuo, 100 mL. H2O added, stored overnight at 5°, the solid (60 mg.) collected, stirred 1 h. with cold dilute HCl, the mixture filtered, the precipitate (35 mg.) purified through the Na salt, and crystallized (petr. ether) gave XLII, identical with XLII as prepared above. (b) Crude XLIV (93 g.) in 3.5 1. 0.1N NaOH hydrogenated at room temperature and pressure in the presence of 50 g. 5% Pd-SrCO3 (absorption ceased after 8 h. when 0.64 mol H was absorbed), 10 g. C added, the filtered solution acidified (38 g. solid obtained and an addnl. 5 g. by repptg. the sticky material from aqueous NaOH), and the product chromatographed in C6H6 on silica gave 39 g. XLII, m. 133-5°, identical with XLII prepared in a. (c) XLIV (56 g., m. 252°) in 2.3 1. 0.1N NaOH hydrogenated as in b (2 mol H absorbed in 1 h.), the acidified solution extracted with Et2O, the extracts concentrated, the combined solids therefrom treated with CH2N2-Et2O, the resulting oil (50.7 g.) chromatographed in C6H6 on Al2O3, and a single bright blue band eluted with C6H6 gave 6.3 g. product (XLV), needles, m. 104-6° (C6H6-petr. ether), and 3.6 g. product (XLVI), prisms, m. 98-100° (MeOH), and, on further elution, 37 g. gum (XLVII). XLV crystallized (MeOH) gave Me 7-chloro-4,6-dimethoxy-3-methylcoumaran-2-β-propionate, prisms, m. 107-8°, ν 1731 cm.-1, hydrolyzed with boiling N NaOH to the corresponding acid, m. 147-8°, ν 1716 cm.-1 XLVI recrystallized (MeOH) gave 2.7 g. XLIII, m. 102°, alk. hydrolysis giving 1.9 g. XLII. XLVII rechromatographed, the single band eluted in 10 equal fractions with C6H6, and fractions 2 and 8 rechromatographed; fraction 2 gave essentially Me 4,6-dimethoxy-3-methylcoumaran-2-β-propionate (XLVIII), uncrystallizable gum, ν 1728 cm.-1, alk. hydrolysis yielding the acid (XLIX), m. 114° (1:1 Et2O-petr. ether); fraction 8 hydrolyzed with NaOH, the product crystallized (1:1 C6H6-petr. ether), the crystals hand-picked, and recrystallized gave 4,6-dimethoxy-3-methylcoumarone-2-β-propionic acid (L), m. 124°. XLIX (2 g.) and 200 mg. S heated 20 min. at 220° and 5 min. at 280°, the product continuously extracted with X, and the resulting crystallized extract hand-picked gave 320 mg. recovered XLIX and 540 mg. L, m. 124°. XLVIII (157 mg.) and 135 mg. ο-chloranil in 5 mL. CHCl3 stored 1.5 h. in the dark, the recovered product chromatographed in C6H6 on Al2O3, the pale blue band eluted with C6H6, and the product (135 mg.) crystallized (1:1 Et2O-petr. ether and then MeOH) gave the coumarone-tetrachloropyrocatechol complex (LI), m. 117°. LI hydrolyzed by alkali and the product crystallized (1:1 Et2OX) gave L, m. 122-4°. XLII (23.5 g.) in 500 mL. dry CHCl3 treated with 20 g. PCl5, the mixture refluxed 0.5 h., volatile products removed at 30° in vacuo, and the residue (LII) kept 4 h. at 12 mm., LII dissolved in 1.5 l. Et2O, 12 g. VI added, the mixture refluxed 24 h., 250 mL. 40% AcOH added, the Et2O layer separated, extracted with Na2CO3 solution (the extract afforded 5.9 g. XLII), and concentrated; the residual oil (25 g.) chromatographed in Et2O on Al2O3 and eluted gave, from a bright-blue band, 800 mg. XLII Et ester (LIII), m. 74-6° (EtOH), and, from an orange-red band, 18 g. orange oil (LIV). LIV heated 2 h. at 110°/10-4 mm. (excess XX removed) gave 14 g. gum (LV), giving a red color with alc. FeCl3 and forming no stable ketonic derivatives LV (12 g.) in 100 mL. Et2O shaken with saturated aqueous Cu(OAc)2 deposited 2.8 g. blue crystals (LVI); the Et2O layer evaporated and the residual gum fractionally crystallized gave 6 g. product (LVII) and 1.8 g. Et α-acetyl-β-oxo-7-chloro-4,6-dimethoxy-3-methylcoumarone-2-γ-carboxylate (LVIII) β-Cu chelate (LIX), m. 98-100° (EtOH), converted to the α-Cu isomer (LX) on continued heating at 120-30°; LVI and LVII combined and crystallized (CHCl3) gave LX, m. 164°. (a) LIX (1.4 g.) and 20 g. XXIV kept 10 days at room temperature, diluted with 50 mL. ice and H2O, extracted with Et2O, the extract washed with aqueous Na2CO3, dried, evaporated, the residual gum (1.18 g.) chromatographed in C6H6 on Al2O3, and the column eluted with C6H6 gave (1) from a narrow blue band, 5 mg. LIII, m. 72-3°, (2) from a greenish-blue band, a gum, which, kept in EtOH, deposited 175 mg. product (LXI), m. 137° and (3) from a blue band, a gum, which, kept in X, deposited 278 mg. product (LXII), m. 129-31°. LXI and LXII combined, recrystallized (EtOH), the crystals (410 mg.) sublimed in vacuo, and the sublimate recrystallized (MeOH) gave Et 7-chloro-4,6-dimethoxy-2′-methyl-3-methylene-4′-oxogris-2′-ene-3′-carboxylate (LXIII), m. 137°, ν 1731, 1680, 1638, 1610 cm.-1, λ282, ∼275, and 253 mμ (log ε 4.30, 4.28, 4.57). (b) LX (500 mg.) and 20 g. XXIV heated 1 h. at 70-80° and worked up as above gave 210 mg. LXIII, m. 137°. (c) LX (1.8 g.) and 30 g. XXIV kept 10 days at room temperature, worked up as above, and the alk. extract acidified gave 600 mg. XLII; some Cu derivative (600 mg.) was regenerated by shaking the acid with aqueous Cu(OAc)2; the remaining gum (320 mg.) chromatographed gave 120 mg. LIII and 5 mg. unidentified compound, m. 181-2° (MeOH). LXIII (248 mg.) in 15 mL. CCl4 ozonized 8 min. at room temperature, CCl4 removed in vacuo, the residue in 20 mL. Et2O and 10 mL. AcOH cooled in ice, treated with 2 mL. H2O and 100 mg. Zn dust, after 12 h. 20 mL. H2O added, the Et2O layer separated, combined with Et2O-washings of the aqueous layer, and worked up gave 5% LXIII, 40% XXVa, 30% Cl-free acidic fraction, and 4% 7-chloro-4,6-dimethoxy-2′-methylgris-2′-ene-3,4′-dione (LXIV), m. 167-8°, ν 1718 and 1683 cm.-1, λ 323, 291, 235, 213 mμ (log ε 3.70, 4.30, 4.19, 4.42). LXIII (137 mg.) in CCl4 ozonized 0.5 h. and worked up gave 10 mg. Cl-free solid, 30 mg. XXVa, 6 mg. LXIII, 1.2 mg. unidentified product, m. 143-9°, and 13 mg. Et 7-chloro-4,6-dimethoxy-3,4′-dioxogris-2′-ene-3′-carboxylate, m. 174° (EtOH), ν 1739, 1705, 1684, 1623, 1593 cm.-1, not hydrolyzed by boiling 1-10N HCl, alk. hydrolysis causing degradation LXIV (10 mg.) in 1 mL. EtOAc added to a previously reduced catalyst prepared from 5 mg. PdCl2 and 20 mg. C in 1 mL. H2O, shaken 6 h. with H at room temperature and pressure (absorption complete in 3 h.), the recovered gum chromatographed in C6H6 on Al2O3, and the recovered gums from each eluate chromatographed on circular paper gave an alc. fraction (not investigated) and the racemate of l,d-7-chloro-4,6-dimethoxy-2′-methylgrisan-3-one, d,d-7-chloro-4,6-dimethoxy-2′-methylgrisan-3,4′-dione, m. 170-5°. The experimental process involved the reaction of Ethyl 6-methoxy-3-methylbenzofuran-2-carboxylate(cas: 53724-96-2).Product Details of 53724-96-2

Ethyl 6-methoxy-3-methylbenzofuran-2-carboxylate(cas:53724-96-2) belongs to benzofuran. Benzofuran is the “parent” of many related compounds with more complex structures. For example, psoralen is a benzofuran derivative that occurs in several plants. Product Details of 53724-96-2

Referemce:
Benzofuran – Wikipedia,
Benzofuran | C8H6O – PubChem

Macmillan, J. et al. published their research in Journal of the Chemical Society in 1959 |CAS: 53724-96-2

Ethyl 6-methoxy-3-methylbenzofuran-2-carboxylate(cas:53724-96-2) belongs to benzofuran. Benzofuran is the “parent” of many related compounds with more complex structures. For example, psoralen is a benzofuran derivative that occurs in several plants. Related Products of 53724-96-2

Macmillan, J. published an article in 1959, the title of the article was Griseofulvin. XVI. Synthesis of compounds related to griseofulvin.Related Products of 53724-96-2 And the article contains the following content:

Racemic spirans related to griseofulvin (I) were prepared by condensation between coumarones and dibromoalkanes (II). The presence of the grisan ring synthesis in I was confirmed by synthesis of 7-chloro-4,6-dimethoxy-2′-methylgrisan-3-one (III), which was shown to be the racemate of the l,d-stereoisomer, obtained by degrading the l,d-diastereoisomer of I (the prefixes denote the configuration of the 2 asym. centers, the spiran center preceding; I is the d,d-stereoisomer, inversion of the spiran center giving the l,d-diastereoisomer). The synthesis of racemates of some non-spiran oxidation products, and improved preparations of some II, were also described. (All m.ps. are corrected; ultraviolet spectra determined in EtOH solution) NaBr (109 g.) and 137 ml. concentrated H2SO4 in 125 ml. H2O kept at 30° during the gradual addition of 43 g. tetrahydro-2-methylfuran, the mixture boiled 2 hrs., steam distilled, the distillate extracted with Et2O, and the extract fractionated gave 103 g. CH2Br(CH2)2CHBrMe (IV), b25 98-9°, n15D 1.516. (a) CH2Br(CH2)3CHBrMe (V), b100 153-5°, was prepared in 1.2% over-all yield according to Perkin [J. Chem. Soc. 51, 702(1887)]. (b) PBr3 (182 g.) and then 120 g. Br added in portions to 140 g. 1-benzoyl-2-methylpiperidine, m. 46°, at 0° with shaking, the product distilled in vacuo until the distillate became yellow, the distillate shaken with 500 g. ice, the mixture extracted with petr. ether (VI), the extract washed with aqueous Na2CO3, H2O, and concentrated H2SO4 until the washings were colorless, concentrated, and the residue distilled gave 103 g. V, b23 121-4°. Dry HCl passed into a solution of 72.0 g. m-C6H4(OH)2, 48 g. CH2ClCN, and 48 g. ZnCl2 in dry Et2O 2 hrs. at room temperature, after 1 hr. the precipitate filtered off, washed with Et2O, hydrolyzed 1 hr. at 70° with 5 l. H2O, the mixture cooled, and the product crystallized (PhMe) gave 85 g. 2,4-(HO)2C6H3COCH2Cl (VII), in. 132-3°. (a) VII (30 g.) in 300 ml. Et2O treated with CH2N2-Et2O and the precipitate crystallized (EtOH) gave 31 g. 5,2-MeO(ClCH2CO)C6H3OH (VIII), m. 116-17°. (b) Powd. AlCl3 (9 g.) added to 8.0 g. m-C6H4(OMe)2 and 6.5 g. CH2ClCOCl in 30 ml. CS2, after 1 hr. CS2 decanted from a red oil, the oil treated with 30 ml. ice-cold H2O and 20 ml. concentrated HCl, steam distilled, and the steam distillate worked up gave 3.9 g. VIII, m. 116-17°. (a) 6-Hydroxy-3-coumaranone (5.0 g.) in 2 l. C6H6 and excess CH2N2-Et2O kept 18 hrs. and the neutral product recovered gave 4.2 g. 6-methoxy compound (IX), m. 124-5°, ν 1710 cm.-1, λ 318, 268, 233, 208 mμ (log ε 4.00, 4.12, 4.05, 4.29). (b) VIII (3.0 g.) and 3.0 g. NaOAc in 150 ml. EtOH heated 2 hrs. and the product crystallized gave 2.2 g. IX, m. 124-5°. IX (0.82 g.) in 50 ml. C6H6 added (during 30 min.) simultaneously with 1.15 g. IV in 50 ml. C6H6 to a stirred and refluxing suspension of 1.4 g. Me3COK (X) in 50 ml. C6H6, the mixture refluxed 3 hrs., cooled, the filtered solution washed with aqueous NaOH and H2O, evaporated, the residue chromatographed in C6H6 on Al2O3, a blue band eluted with C6H6, the recovered oil (300 mg.) rechromatographed in VI, eluted with 20:1 Et2O-VI, and the gum crystallized from petr. ether gave 36 mg. 6-methoxy-3-oxocoumaran-2-spiro-1′-(2′-methylcylopentane), m. 167-8° (sublimation in vacuo and recrystallization from EtOH), ν 1712 cm.-1, λ 318, 267, 233, 208 mμ (log ε 4.01, 4.12, 4.05, 4.29). 7-Chloro-4,6-dimethoxy-3-coumaranone (XI) (2.29 g.) in 50 ml. C6H6 treated as above with 2.8 g. X in 50 ml. C6H6, refluxed 5 hrs., cooled, filtered, the filtrate extracted with aqueous NaOH, and the extract acidified gave 60 mg. 3,2,4,6-Cl(HO)(MeO)2C6HAc, m. 189-91°; the semisolid (recovered from the neutral fraction) repeatedly extracted with VI, the solid (400 mg.) recovered from the extract sublimed at 110°/10-4 mm., and the sublimate crystallized (EtOH) gave 7-chloro-4,6-dimethoxy-3-oxocoumaran-2-spirocydopentane, m. 192-3°, ν 1717 cm.-1, λ 331, 322, 289, 238, 213 mμ (log ε 3.68, 3.69, 4.30, 4.20, 4.37); the VI-insoluble material chromatographed and sublimed gave 1.08 g. XI, m. 212-14°. XI (2.29 g.) in 50 ml. C6H6 condensed with 2.31 g. Br(CH2)5Br in 50 ml. C6H6 in the presence of 2.8 g. X in 50 ml. C6H6 as above, the residual gum treated with C6H6-VI, the precipitated solid (120 mg.) sublimed at 130°/10-4 mm., and the sublimate recrystallized (EtOH) gave 70 mg. 7-chloro-4,6-dimethoxygrisan-3-one, m. 176-7°, ν 1715 cm.-1; 1.20 g. XI was recovered from the C6H6-VI mother liquor. XI (2.90 g.) condensed as above with 2.44 g. V in the presence of 2.80 g. X (identical volumes C6H6 used), refluxed 1.5 hrs., cooled, the filtered solution washed with aqueous NaOH, concentrated to 5 ml., diluted with 5 ml. VI, and the solution kept at 0° deposited 112 mg. precipitate (XII); the gum recovered from the mother liquor chromatographed in C6H6 on Al2O3 and eluted with C6H6 gave, from a yellow band, 40 mg. gum, which, sublimed (120-30°/10-4 mm.) and crystallized (EtOH), afforded 25 mg. compound (XIII), and, from a blue band, 340 mg. gum, which, crystallized (C6H6-VI), yielded 295 mg. compound (XIV); XII, XIII, and XIV combined, sublimed (110-20°/10-4 mm.), and crystallized (EtOH) gave 405 mg. III, m. 157-8°, λ 331, 322, 289, 238, 212 mμ (log ε 3.67, 3.70, 4.33, 4.20, 4.41). XI (11.45 g.) in 200 ml. C6H6 condensed with 12.25 g. MeCHBr(CH2)2COBr in 100 ml. C6H6 in the presence of 14 g. X in 100 ml. C6H6 as above, the C6H6 solution extracted with aqueous NaOH, evaporated, and chromatographed gave 1.3 g. 7-chloro-4,6-dimethoxycoumaron-3-yl- γ-bromovalerate, m. 124°, ν 1760, 1623, 1609 cm.-1, λ 265 and 219 mμ (log ε 4.18, 4.62). XI (4.2 g.) in 200 ml. dioxane treated at 46° with 2.1 g. MeCH:CHCO2Me (XV) and 8.0 ml. N MeONaMeOH, kept 6 hrs. at 55-60° and 2 days at room temperature, the filtered solution treated with 5 ml. AcOH and C, filtered, and the filtrate evaporated in vacuo; the residue dissolved in 150 ml. C6H6, the solution washed with H2O, dried, chromatographed on Al2O3, eluted with 100:1 C6H6-MeOH, the recovered product distilled (170-200°/10-4 mm.) on to a cold finger, and the material crystallized gave 1.0 g. product (XVI); the material recovered from the mother liquor extracted with Me2CO gave 0.5 g. product (XVII); XVI and XVII combined and washed with Me2CO gave 1.00 g. α-ester (XVIII), Me 7-chloro-4,6-dimethoxy-3-oxocoumaran-2-β-butyrate, m. 152-4° (C6H6-VI); the gum recovered from the mother liquors fractionally crystallized (Et2O) gave 0.8 g. impure material and 0.90 g. β-XVIII, m. 83-6°, m.p. not depressed with (-)-β-XVIII prepared from I (see below). β-XVIII (100 mg.), 0.5 g. anhydrous K2CO3, and 10 ml. Me2CO refluxed 7 hrs. and the product fractionally crystallized (C6H6-VI) gave 36 mg. α-XVIII, m. 150-2°; crystallization of the more soluble fractions from Et2O gave 41 mg. β-XVIII, m. 83-5°. Similar results were obtained with α-XVIII. (1) α-XVIII (561 mg.) and 25 ml. N HCl boiled 3 hrs. (20 ml. H2O added after 2.5 hrs.), the precipitate (495 mg.) filtered off, and washed with H2O gave (-)-7-chloro-4,6-dimethoxy-3-oxocoumaran-2-β-butyric acid (XIX), m. 154-62° (decomposition). (2) Hydrolysis of 500 mg. β-XVIII in the same way gave 460 mg. XIX. XIX treated with CH2N2 gave a mixture separated by crystallization into 47 mg. α-XVIII, m. 142-50°, and 38 mg. β-XVIII, m. 82-5°. XIX (234 mg.) and 10 ml. N NaOH boiled 4 hrs., cooled, filtered, the filtrate acidified, the precipitate (123 mg.) collected, and crystallized (EtOAc) gave 7-chloro-6-hydroxy-4-methoxy-3-oxocoumaran-2-β-butyric acid, m. 212-14° (decomposition), ν (CHCl3) 1701 and 1737 cm.-1 XIX (134 mg.) in 10 ml. N Na2CO3 treated at 1-2° during 1.5 hrs. with 3.0 ml. 4.5% aqueous KMnO4, the mixture kept 1.5 hrs. at 0°, excess decomposed with SO2, the filtered solution acidified with HCl, the gummy product (isolated with Et2O) treated with a little Et2O, and the resultant solid (85 mg.) crystallized from EtAc-petr. ether gave the 2-OH derivative (XX), m. 189-90° (decomposition). XX (85 mg.), 0.3 ml. Ac2O, and 0.7 ml. C5H5N kept 3 days at 35°, diluted with H2O at 0°, and the product washed with aqueous NaHCO3 and H2O gave the lactone (XXI), m. 223-4° (EtOAc). XXI was also obtained by subliming XX at 190-210°/10-4 mm. N MeONa-MeOH (2.0 ml.) added to 1.94 g. 4,6-dimethoxy-3-coumaranone (XXII) and 1.00 g. XV in 40 ml. dioxane at 24°, after 24 hrs. the mixture acidified with AcOH, evaporated in vacuo, the residue taken up in Et2O, the solution washed with aqueous NaHCO3, and H2O, evaporated, the oily product chromatographed in Et2O on Al2O3, and a blue band eluted with 100:1 Et2O-MeOH gave 1.7 g. sirup (XXIII); 2.3 g. XXIII from several experiments kept with Et2O gave 1.0 g. α-ester, Me 4,6-dimethoxy-3-oxocoumaran-2-β-butyric acid (XXIV) Me ester (XXV), m. 88-9° (C6H6Et2O); the sirup from the Et2O mother liquor distilled (180-210°/10-3 mm.) gave essentially β-XXV, sirup. 2N EtONa-EtOH (0.43 ml.) added to 1.00 g. XXII and 0.59 g. MeCH:CHCO2Et in 18 ml. dioxane at 20° after 48 hrs. the mixture filtered, the filtrate acidified with AcOH, the product recovered, chromatographed, eluted like XXV, and the oil (1.00 g.) distilled (190°/10-3 mm.) gave XXIV Et ester (XXVI), oil. XXVI (1.9 g.) and 20 ml. 3N HCl boiled 5 hrs., the cooled mixture made alk., washed with Et2O, acidified, the product (1.19 g.) extracted with Et2O, and the extract distilled (200°/10-3 mm.) gave XXIV, containing a phenolic impurity. XXIV (350 mg.) in 22 ml. N Na2CO3 treated at 1-2° during 2 hrs. with 7.6 ml. 4.5% aqueous KMnO4 and worked up gave 70 mg. 2-OH derivative (XXVII), m. 169-73° (decomposition). Dehydration of XXVII as above gave the lactone (XXVIII), m. 150-1° (EtOAc-petr. ether). An ice-cold suspension of 525 mg. XXVI in 30 ml. N Na2CO3 treated dropwise with 5% aqueous KMnO4 (only a few drops decolorized), 25 ml. dioxane added, 10.0 ml. 5% aqueous KMnO4, added in 1 hr., the mixture kept overnight at 0°, decolorized with SO2, filtered, the filtrate and Me2CO washings of the filter cake evaporated in vacuo, aqueous NaOH added to the residue, the mixture extracted with Et2O (0.2 g. XXVI recovered from the extract), acidified, the product extracted with Et2O, and crystallized (Et2O and then EtAc) gave 34 mg. XXVIII, m. 150-1°. (-)-XIX from I gave (-)-β-XVIII, m. 96-8° (Et2O), [α]22D -19° ± 3° (c 0.84, Me2CO). The experimental process involved the reaction of Ethyl 6-methoxy-3-methylbenzofuran-2-carboxylate(cas: 53724-96-2).Related Products of 53724-96-2

Ethyl 6-methoxy-3-methylbenzofuran-2-carboxylate(cas:53724-96-2) belongs to benzofuran. Benzofuran is the “parent” of many related compounds with more complex structures. For example, psoralen is a benzofuran derivative that occurs in several plants. Related Products of 53724-96-2

Referemce:
Benzofuran – Wikipedia,
Benzofuran | C8H6O – PubChem

Nakanishi, Teruo et al. published their research in Seikagaku in 1970 |CAS: 29735-85-1

The Article related to benzofurans inhibition deaminases, deaminases inhibition benzofurans, inhibition deaminases benzofurans, amp deaminase inhibition benzofurans, and other aspects.Quality Control of 5-Hydroxybenzofuran-3-carboxylic acid

Nakanishi, Teruo; Saeki, Toru published an article in 1970, the title of the article was Inhibitory action of benzofuran compounds on 5′-AMP deaminase and adenosine deaminase.Quality Control of 5-Hydroxybenzofuran-3-carboxylic acid And the article contains the following content:

The inhibitory action of benzofuran derivatives on 5′-AMP deaminase (I) and adenosine deaminase (II) was investigated by using a number of synthetic compounds Introduction of carboxyl or hydroxyl groups increased the inhibitory action on I, but no pronounced effect of the substituent was observed on II. No common feature in structure seems to exist for the inhibition of these 2 deaminases. The experimental process involved the reaction of 5-Hydroxybenzofuran-3-carboxylic acid(cas: 29735-85-1).Quality Control of 5-Hydroxybenzofuran-3-carboxylic acid

The Article related to benzofurans inhibition deaminases, deaminases inhibition benzofurans, inhibition deaminases benzofurans, amp deaminase inhibition benzofurans, and other aspects.Quality Control of 5-Hydroxybenzofuran-3-carboxylic acid

Referemce:
Benzofuran – Wikipedia,
Benzofuran | C8H6O – PubChem

Enz, Albert et al. published their research in Bioorganic & Medicinal Chemistry Letters in 2009 |CAS: 60770-67-4

The Article related to nicotinic receptor a7 agonist mol modeling nachr, gamma lactam derivative sar preparation, Pharmacology: Structure-Activity and other aspects.Name: 5-Iodobenzofuran

On March 1, 2009, Enz, Albert; Feuerbach, Dominik; Frederiksen, Mathias U.; Gentsch, Conrad; Hurth, Konstanze; Muller, Werner; Nozulak, Joachim; Roy, Bernard L. published an article.Name: 5-Iodobenzofuran The title of the article was Gamma-lactams-A novel scaffold for highly potent and selective α7 nicotinic acetylcholine receptor agonists. And the article contained the following:

A novel class of α7 nicotinic acetylcholine receptor (nAChR) agonists has been discovered through high-throughput screening. The cis γ-lactam scaffold has been optimized to reveal highly potent and selective α7 nAChR agonists with in vitro activity and selectivity and with good brain penetration in mice. The experimental process involved the reaction of 5-Iodobenzofuran(cas: 60770-67-4).Name: 5-Iodobenzofuran

The Article related to nicotinic receptor a7 agonist mol modeling nachr, gamma lactam derivative sar preparation, Pharmacology: Structure-Activity and other aspects.Name: 5-Iodobenzofuran

Referemce:
Benzofuran – Wikipedia,
Benzofuran | C8H6O – PubChem

Shao, Xinxin et al. published their patent in 2022 |CAS: 60770-67-4

The Article related to preparation deuterated methyl phenyl sulfide thiomethylation reagent thioetherification coupling, Placeholder for records without volume info and other aspects.Application of 60770-67-4

On September 16, 2022, Shao, Xinxin; Zhang, Yan; Liu, Wen published a patent.Application of 60770-67-4 The title of the patent was Preparation of S-(methyl-d3)phenyl sulfide as deuterated thiomethylation reagents. And the patent contained the following:

The invention discloses a preparation of S-(methyl-d3)phenyl sulfide shown in general formula I [R2=2-naphthyl, 1-quinolinyl or substituted phenyl] as deuterated thiomethylation reagents, which has the advantages of low cost, simple preparation and good structure controllability. For example, S-(methyl-d3) 4-methylbenzenesulfonothioate was prepared by thioetherification of methyl-d3 4-methylbenzenesulfonate and sodium 4-methylbenzenesulfonothioate. The title compound is used as an electrophilic tri-deuterium methylation reagent for reductive coupling reaction with aryl iodine derivatives or cross coupling reaction with terminal alkyne derivatives The experimental process involved the reaction of 5-Iodobenzofuran(cas: 60770-67-4).Application of 60770-67-4

The Article related to preparation deuterated methyl phenyl sulfide thiomethylation reagent thioetherification coupling, Placeholder for records without volume info and other aspects.Application of 60770-67-4

Referemce:
Benzofuran – Wikipedia,
Benzofuran | C8H6O – PubChem

Rochette, Elise M. et al. published their research in Chemical Communications (Cambridge, United Kingdom) in 2013 |CAS: 1459793-02-2

The Article related to chiral sulfinimide radical stereoselective cyclization, General Organic Chemistry: Synthetic Methods and other aspects.Formula: C8H10ClNO

Rochette, Elise M.; Lewis, William; Dossetter, Al G.; Stockman, Robert A. published an article in 2013, the title of the article was Highly diastereoselective radical cyclisations of chiral sulfinimines.Formula: C8H10ClNO And the article contains the following content:

Chiral amines are formed by the highly diastereoselective intramol. addition of alkyl and aryl radicals onto chiral mesityl sulfinimines. The experimental process involved the reaction of (S)-2,3-Dihydrobenzofuran-3-amine hydrochloride(cas: 1459793-02-2).Formula: C8H10ClNO

The Article related to chiral sulfinimide radical stereoselective cyclization, General Organic Chemistry: Synthetic Methods and other aspects.Formula: C8H10ClNO

Referemce:
Benzofuran – Wikipedia,
Benzofuran | C8H6O – PubChem

Holt, Connor et al. published their research in Journal of the American Chemical Society in 2019 |CAS: 60770-67-4

The Article related to chemodivergent haloindene indanone preparation, halo prins aryl halo nazarov cyclization computational study, General Organic Chemistry: Synthetic Methods and other aspects.Quality Control of 5-Iodobenzofuran

On April 3, 2019, Holt, Connor; Alachouzos, Georgios; Frontier, Alison J. published an article.Quality Control of 5-Iodobenzofuran The title of the article was Leveraging the Halo-Nazarov Cyclization for the Chemodivergent Assembly of Functionalized Haloindenes and Indanones. And the article contained the following:

In this report, we describe a halo-Prins/aryl halo-Nazarov cyclization strategy that employs readily available starting materials, inexpensive reagents, and convenient reaction procedures to generate functionalized haloindenes and indanones. The scope and limitations of the method are outlined, demonstrating that aromatic systems readily react under mild, catalytic conditions when this strategy is implemented. Furthermore, we present both exptl. and computational data supporting the notion that cyclizations of 3-halopentadienyl cationic intermediates are more kinetically accessible, as well as more thermodynamically favorable, than cyclizations of the analogous 3-oxypentadienyl cationic systems. The energetic advantage imparted by the halo-Nazarov cyclization design was found to be especially valuable in the cyclizations of arylallyl cationic intermediates, which require disruption of aromaticity. The experimental process involved the reaction of 5-Iodobenzofuran(cas: 60770-67-4).Quality Control of 5-Iodobenzofuran

The Article related to chemodivergent haloindene indanone preparation, halo prins aryl halo nazarov cyclization computational study, General Organic Chemistry: Synthetic Methods and other aspects.Quality Control of 5-Iodobenzofuran

Referemce:
Benzofuran – Wikipedia,
Benzofuran | C8H6O – PubChem

Gravatt, Christopher S. et al. published their research in ChemRxiv in 2021 |CAS: 60770-67-4

The Article related to trifluoro arene preparation, aryl iodide silver trifluoromethanethiolate trifluoromethylthiolation nickel catalyst, General Organic Chemistry: Synthetic Methods and other aspects.Electric Literature of 60770-67-4

Gravatt, Christopher S.; Johannes, Jeffrey W.; Ghosh, Avipsa published an article in 2021, the title of the article was Photoredox-mediated, nickel-catalyzed trifluoromethylthiolation of aryl and heteroaryl iodides.Electric Literature of 60770-67-4 And the article contains the following content:

The area of trifluoromethylthiolation of aryl halides RI (R = 4-CH3C6H4, 9H-fluoren-2-yl, 4-phenylmorpholine, etc.) has been extensively explored, the current methods require complex and/or air-sensitive catalysts. A method employing a bench-stable nickel(II) salt and an iridium photocatalyst that can mediate the trifluoromethylthiolation of a wide range of electronically diverse aryl and heteroaryl iodides, likely via a Ni(I)/Ni(III) catalytic cycle is reported. The reaction has broad functional group tolerance and potential for application in medicinal chem., as demonstrated by a latestage functionalization approach to access (racemic)-Monepantel. The experimental process involved the reaction of 5-Iodobenzofuran(cas: 60770-67-4).Electric Literature of 60770-67-4

The Article related to trifluoro arene preparation, aryl iodide silver trifluoromethanethiolate trifluoromethylthiolation nickel catalyst, General Organic Chemistry: Synthetic Methods and other aspects.Electric Literature of 60770-67-4

Referemce:
Benzofuran – Wikipedia,
Benzofuran | C8H6O – PubChem

Emmett, Edward J. et al. published their research in Angewandte Chemie, International Edition in 2014 |CAS: 60770-67-4

The Article related to aryl halide dabso butyl bromoacetate sulfonylation palladium catalyst, bytylacetate sulfone preparation, alcohols, arenes, palladium, sulfonamides, synthetic methods, General Organic Chemistry: Synthetic Methods and other aspects.SDS of cas: 60770-67-4

Emmett, Edward J.; Hayter, Barry R.; Willis, Michael C. published an article in 2014, the title of the article was Palladium-catalyzed synthesis of ammonium sulfinates from aryl halides and a sulfur dioxide surrogate. A gas- and reductant-free process.SDS of cas: 60770-67-4 And the article contains the following content:

Described herein is a simple reaction system consisting of the sulfur dioxide surrogate DABSO, triethylamine, and a palladium(0) catalyst for effective conversion of a broad range of aryl and heteroaryl halides into the corresponding ammonium sulfinates. Key features of this gas- and reductant-free reaction include the low loadings of palladium (1 mol%) and ligand (1.5 mol%) which can be employed, and the use of iso-Pr alc. as both a solvent and formal reductant. The ammonium sulfinate products are converted in situ into a variety of sulfonyl-containing functional groups, including sulfones, sulfonyl chlorides, and sulfonamides. © Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. The experimental process involved the reaction of 5-Iodobenzofuran(cas: 60770-67-4).SDS of cas: 60770-67-4

The Article related to aryl halide dabso butyl bromoacetate sulfonylation palladium catalyst, bytylacetate sulfone preparation, alcohols, arenes, palladium, sulfonamides, synthetic methods, General Organic Chemistry: Synthetic Methods and other aspects.SDS of cas: 60770-67-4

Referemce:
Benzofuran – Wikipedia,
Benzofuran | C8H6O – PubChem

Deng, Yong et al. published their patent in 2010 |CAS: 60770-67-4

The Article related to benzofuranylacrylic acid ester preparation substitution friedel crafts heck, Heterocyclic Compounds (One Hetero Atom): Furans and other aspects.Application of 60770-67-4

On March 10, 2010, Deng, Yong; Wu, Chenglong; Shen, Yi; Wan, Jie published a patent.Application of 60770-67-4 The title of the patent was Simple and green method for synthesis of (E)-3-(benzofuran-5-yl)acrylic acid ester. And the patent contained the following:

A process for preparation of (E)-3-(benzofuran-5-yl)acrylic acid ester from p-halophenol and 2-haloacetaldehyde or 2-haloacetal is disclosed. The claimed (E)-3-(benzofuran-5-yl)acrylic acid ester is shown in structure I (R = C1-12 alkyl or cycloalkyl, (un)substituted benzyl, allyl, (un)substituted C6-10 aryl). (E)-3-(benzofuran-5-yl)acrylic acid ester is prepared from p-halophenol and 2-haloacetaldehyde or 2-haloacetal via substitution reaction, Bronsted acid or Lewis acid catalyzed Friedel-Crafts reaction to form 5-halobenzofuran, further Heck reaction with acrylic acid ester to provide the title compound The obtained (E)-3-(benzofuran-5-yl)acrylic acid ester can be further reduced, hydrolyzed, or hydrogenized for give the corresponding derivatives The experimental process involved the reaction of 5-Iodobenzofuran(cas: 60770-67-4).Application of 60770-67-4

The Article related to benzofuranylacrylic acid ester preparation substitution friedel crafts heck, Heterocyclic Compounds (One Hetero Atom): Furans and other aspects.Application of 60770-67-4

Referemce:
Benzofuran – Wikipedia,
Benzofuran | C8H6O – PubChem