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Volumn , Issue 11, 2008, Pages 1603-1617

Esterification of carboxylic acids and etherification of phenols with amide acetals

Author keywords

Amide acetals; Carboxylic acids; Esterification; Ethers; Phenols

Indexed keywords

4 NITROBENZOIC ACID; ACETAL DERIVATIVE; AMIDE; CARBOXYLIC ACID; DIOXANE; N,N DIMETHYLFORMAMIDE DIMETHYL ACETAL; PHENOL DERIVATIVE; TETRAHYDROFURAN;

EID: 48249138499     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2008-1077882     Document Type: Article
Times cited : (14)

References (127)
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    • While at Stanford in 1962 as a postdoc with C. Djerassi, I read with great interest the seminal publication of H. Meerwein et al, see ref. 14 on the syntheses and reactions of new amide acetals and I was intrigued by the observation that on addition of water to cyclic DMF ethylene acetal 7g, heat was evolved. To test whether 7g might be an interesting new reagent for mild selective ketalizations of carbonyl groups, I prepared DMF diethyl acetal 7b and converted it with ethylene glycol into DMF ethylene acetal 7g. Yet, cholestan-3-one only reacted with 7g in boiling CH 2C12 after adding acetic acid as a catalyst, whereupon the desired crystalline cholestan-3-one ethylene ketal was obtained in 83% yield, see: Vorbrüggen, H. Steroids 1963, 1, 45. On chromatography of the crude reaction mixture using deactivated alumina, the O-monoacetate of ethylene glycol was isolated alongside the desired ethylen
    • 2 after adding acetic acid as a catalyst, whereupon the desired crystalline cholestan-3-one ethylene ketal was obtained in 83% yield, see: Vorbrüggen, H. Steroids 1963, 1, 45. On chromatography of the crude reaction mixture using deactivated alumina, the O-monoacetate of ethylene glycol was isolated alongside the desired ethylene ketal. Because amide acetals, such as 7g, seemed to transform carboxylic acids into their corresponding esters, I reacted compounds such as benzoic and nicotinic acid, as well as phenol and 2,4,6-trichlorophenol, with diethyl acetal 7b and dibenzyl acetal 7c and, indeed, obtained the corresponding esters and phenyl ethers. While wondering about the possible scope of these new esterifications, I contacted Dr. John G. Moffatt at the neighboring Syntex Laboratories in Palo Alto and asked him whether he might be interested in trying to synthesize esters from nucleotides using diethyl acetal 7b. A few days later, John called and told me that a new postdoc of his, who had just completed his Ph.D. with A. Eschenmoser at ETH in Zürich, had informed him that A. Eschenmoser was also working on the esterifications of carboxylic acids with amide acetals. When I discussed this work with C. Djerassi, who had generously supported my little additional research project, he only commented, 'Write him!'. This I did although with some trepidation as a completely unknown scientist, but I received an immediate reply in which A. Eschenmoser suggested that we should publish our results in two adjacent communications in Angewandte Chemie (see refs. 38 and 39). I later met A. Eschenmoser on a number of occasions and exchanged information with him on various aspects of the field of nucleic acids. I learnt to admire A. Eschenmoser not only for his intellectual brilliance, but also, in particular, as a scientist and colleague, who has always been absolutely fair to other scientists in his publications and lectures by giving credit to whom ever credit was due, which unfortunately is not as common nowadays.
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    • 3β-(4-Nitrophenoxy)-5α-androstan-17-one (82) To a boiling solution of 3α-hydroxy-5α-androstan-17-one (80, 0.249 g, 1 mmol) in abs benzene (15 mL) was added a third of a suspension of DMF dineopentyl acetal 7d (4.3 mL, 15 mmol) and 4-nitrophenol (81, 2.087 g, 15 mmol) in abs benzene (15 mL, After heating at 80 °C for 24 h, the rest of the suspension was added in small portions over a period of 48 h. The mixture was heated at 80 °C for a further 14 h and then was cooled. Ice (20 g) was added to the mixture, which was then extracted with 2 M NaOH (2×35 mL, The extracts were dried (MgSO4) and benzene was evaporated off to give the crude crystalline product (1.618 g, which on recrystallization (MeOH) gave slightly impure 3β(4-nitrophenoxy)-5α- androstan-17-one (82, 0.188 g, Filtration of the product in CH 2C12 over a small column of neutral alumina 7.5 g, activity II
    • 3). The combined mother liquors were column chromatographed [silica gel (70 g), cyclohexane]. Elution [cyclohexane-toluene, 2:3 (200 mL), then 3:7 (400 mL)] afforded homogeneous 5α-androst-2-en-17-one, which was recrystallized (pentane) to give the pure side product. Yield: 0.056 g (24%); mp 106.5-107 °C. Further elution (toluene, 1 L) gave additional pure 82 (0.051 g). Combined yield: 0.239 g (68%).
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    • Methyl 4-Nitrobenzoate (88)Using 7a and DCE: To a suspension of 4-nitrobenzoic acid (87, 3.342 g, 20 mmol) in DCE (25 mL) was added a solution of DMF dimethyl acetal 7a (8.2 mL, 62 mmol) in DCE (25 mL) over a period of 5 h at 24 °C with stirring. Stirring was continued for a further 66 h, whereupon a clear yellowish solution resulted. After evaporation at 35 °C/0.5 Torr, the crystalline residue was extracted with boiling Et2O (3 × 70 mL) resulting in, after further evaporation, crude methyl 4-nitrobenzoate (88, Yield: 3.265 g (90, mp 92-94 °C. Recrystallization from boiling hexane resulted in pure 88; mp 95-96 °C (Lit. mp 96 °C; see also ref. 108, The crystalline yellowish residue (0.480 g) that remained after the extraction with Et 2O was recrystallized (abs EtOH, 5 mL) to give acidic tetramethylammonium salt 89 0.063 g, mp 278-281 °C. On acidification of the mother liquor with
    • 3 gave crystalline 88; Yield: 2.712 g (100%) (see also ref. 20) Using 7a and THF: To a stirred boiling solution of 4-nitrobenzoic acid (87) (0.84 g, 5 mmol) in abs THF (30 mL) in a 100-mL three-necked round-bottom flask, connected to a reflux condenser and an addition funnel and in an oil bath at 80 °C, was added dropwise a solution of DMF dimethyl acetal 7a (1.8 mL, 15 mmol) in abs THF (20 mL), where-upon a colorless precipitate formed. After the addition of about 10 mL (7.5 mmol) of the THF solution of 7a, a clear yellowish solution resulted, indicating the completion of the reaction. Evaporation of the mixture afforded the crude crystalline product (1.33 g), which was dissolved in tert-butyl methyl ether (20 mL) and filtered over a layer of silica gel (18 g) to give crystalline methyl 4-nitrobenzoate (88). Yield: 0.94 g (100%); mp 94-96 °C. Recrystallization (boiling hexane, 40 mL) resulted in the first crop of pure 88 (0.69 g); mp 96 °C. Concentration of the mother liquor afforded another crop of pure 88 (0.16 g). Combined yield: 0.85 g (90%). The remaining hexane mother liquor still contained, according to TLC (hexane-EtOAc, 4:1), methyl 4-nitrobenzoate (88).
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    • Dimethyl Fumarate (94) To a stirred boiling solution of fumaric acid (92, 1.16 g, 10 mmol) in abs THF (30 mL) in a 100-mL three-necked round-bottom flask, connected to a reflux condenser and an addition funnel and in an oil bath at 80 °C, was added dropwise a solution of DMF dimethyl acetal 7a (4 mL, 30 mmol) in abs THF (20 mL) over a period of 1 h, whereupon salt 93 formed as a colorless precipitate. Because the solution was still somewhat turbid, additional 7a (1.3 mL, 10 mmol) in abs THF (10 mL) was added over a period of 0.5 h, and the mixture was heated for another 0.5 h and stirred overnight at r.t. for 16 h. The resulting yellowish solution was decanted from a small amount of colorless precipitate (0.03 g, which was washed with tert-butyl methyl ether and the extracts were filtered. On evaporation, the filtrate gave a crude yellowish crystalline substance (1.63 g) that was dissolved in tert-butyl methyl ether (125 mL) and fi
    • f= 0.35 (hexane-EtOAc, 9:1).
  • 127
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    • E, and (Z)-3-(Dimethylamino)acrylonitrile (111) and (112) In a 100-mL three-necked round-bottom flask, connected to a reflux condenser and an addition funnel and in an oil bath at 80 °C, was stirred a solution of cyanoacetic acid (104, 1.70 g, 20 mmol) in 1,4-dioxane (30 mL, previously dried over 4 Å MS, To this solution was added DMF dimethyl acetal 7a (4 mL, 30 mmol) in 1,4-dioxane (20 mL) with vigorous stirring over a period of 1 h. Heating was continued for a further 1 h. After cooling the mixture and evaporating off the solvent, the crude dark oily product (3.16 g) was extracted with tert-butyl methyl ether and the extracts were filtered over a layer of silica gel (ca. 16 g, On evaporation of the yellow filtrate, homogeneous 3-(dimethylamino)acrylonitrile (111/112) was obtained. Yield: 1.92 g (100, Rf= 0.72 tert-butyl methyl ether
    • f= 0.72 (tert-butyl methyl ether).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.