Dehydration of Alcohols, Diols, and Related Compounds in Dimethyl Sulfoxide<sup>1</sup>

Traynelis, Vincent J.; Hergenrother, William L.; Hanson, Harry T.; Valicenti, John A.

doi:10.1021/jo01024a028

Cited by 105 publications

(23 citation statements)

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“…Bulb-to-bulb distillation 30-33 "C (15 Torr) gave 0.46 g 4-fluoro-4-methylpentan-Zone, which was 95% pure according to GC with a retention time of 4 min; initial column temperature 50 "C for 4 min, then ramp at 10 "C min-' to 180 "C. d(300 MHz; CDCl,) 1.43 (d, J = 22.0 Hz, 6 H), 2.21 (s, 3 H) and 2.76 (d, J = 17.7 Hz, 2 H); dF(282 MHz; CDC1,) -133.7 (m); J = 22.8 Hz), 93.8 (J = 166 Hz) and 202.6 (br s); m/z (rel. intensity) 103 (2), 98 (9), 61 (30), 58 (1 I), 56 (12) and 43 (100); vmax/cm-' 299Om, 2941w, 1730s, 1369m, 1214m, 1138w, 884w and 747m.…”

Section: Synthesis Of 24difluoro-2-methylpentane (3)mentioning

confidence: 96%

Reaction of diethylaminosulfur trifluoride with diols

Shellhamer¹,

Anstine²,

Gallego³

et al. 1995

J. Chem. Soc., Perkin Trans. 2

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Diethylaminosulfur trifluoride (DAST) reacts with dialcohols to give difluorides, sulfite esters or cyclic ethers depending on the number of carbons separating the two alcohol groups. Vicinal and 1,3-diols give large amounts of sulfite ester products while butane-1,4-diol gives almost exclusively the cyclic ether tetrahydro furan. Terminal dialcohols longer than four carbons give primarily difluoride products. Semiempirical calculations indicate a preference for cyclic intermediates when four or less carbons separate the two alcohol moieties. These cyclic intermediates lead directly to the cyclic ethers and sulfite ester products.Aminosulfur trifluorides such as diethy laminosulfur trifluoride (DAST) react with alcohols to replace the hydroxy group with a fluorine.In polyhydroxy compounds such as sugars only one hydroxy group is usually replaced by fluorine.1b,2 Replacement of two hydroxy groups by fluorine has been observed in a few instances.2c For example, Middleton reported a 70% yield of 1,2-difluoroethane (1) for the reaction of DAST with ethylene glycol. lo Results and discussionWe investigated the reaction of DAST with ethylene glycol and found that ethylene sulfite (2) was also produced in 20% yield. 1 2 3.5 1 .o 90% overall yield Reaction of DAST with 2-methylpentane-2,4-diol gave primarily difluoride 3 and the sulfite esters 4a, b in 80% yield. + DAST -+yF + 3 11 .o 4a 2.2 4b 1 .o Paper 41032836

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Section: Synthesis Of 24difluoro-2-methylpentane (3)mentioning

confidence: 96%

Reaction of diethylaminosulfur trifluoride with diols

Shellhamer¹,

Anstine²,

Gallego³

et al. 1995

J. Chem. Soc., Perkin Trans. 2

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“…pinacol leads to 3,3-dimethy1-2-butanone in good yield. The yield is much better than in the transformations in a large excess of DMSO [3], where, depending on the temperature, it is only 20-30%. 1,2-Elimination occurs in similar ease with 2,4-dimethy1-2,4-pentanediol, to give unsaturated alcohol and diene.…”

Section: R = H Mementioning

confidence: 83%

“…-During the past twenty years a number of publications have appeared on the transformations of diols on the action of dimethylsulfoxide (DMSO) (see, for example, review [2]). The transformations of 1,2-and 1,3-diols lead not only to the formation of dienes, 0x0 compounds and unsaturated alcohols [3], but in certain cases to dioxacycloalkanes [4] [5]. For the higher diol homologues the main reaction is cyclodehydration to the cyclic ether [3] [6-101, generally with good yield, but side-reactions (diene formation) sometimes accompany this process.…”

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confidence: 99%

“…The transformations of 1,2-and 1,3-diols lead not only to the formation of dienes, 0x0 compounds and unsaturated alcohols [3], but in certain cases to dioxacycloalkanes [4] [5]. For the higher diol homologues the main reaction is cyclodehydration to the cyclic ether [3] [6-101, generally with good yield, but side-reactions (diene formation) sometimes accompany this process. It is a common feature of these investigations that the reagent was used in large excess, the diol: DMSO ratio usually lying in the range 1 : 4-1 : 19.…”

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confidence: 99%

See 1 more Smart Citation

Studies on the Conversions of Diols and Cyclic Ethers. Part 48. Dehydration of alcohols and diols on the action of dimethylsulfoxide

Molnár¹,

Bartók²

1981

Helvetica Chimica Acta

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SummaryThe transformations of 13 alcohols and 13 diols in the presence of a small amount dimethylsulfoxide (1/ 16 mol) were studied. Relationships were found between the type of the hydroxy compound and the selectivity of the transformation, and conclusions were drawn regarding the transformation mechanism. The ether formation observed with certain alcohols proceeds via a carbenium cation. The reaction conditions applied were found suitable for inducing water elimination from the ditertiary 1,2-and 1,3-diols (pinacol rearrangement, 1,2-elimination). From the 1,4-and 1,5-diols the corresponding oxacycloalkanes can be obtained in good yield. Cyclodehydration occurs by intramolecular nucleophilic substitution, via a concerted mechanism. The effect of DMSO is exerted directly, and protoncatalysis occurs simultaneously. It has recently been demonstrated in the transformations of various benzyl alcohols [ l l ] that at very high alcohol: DMSO ratios (16:l) the olefin formation and certain oxidation reactions to be observed when the reagent is in high excess over the alcohol can be totally suppressed, and ethers can be obtained in excellent yields.

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“…The acid-catalyzed synthesis of furans from 1,4-diketones has been known for more than a century, 10 however, the heterocyclization of the hexane-2,5-dione required the continuous removal of the produced furan, 11 or harsh reaction conditions. 12 After investigation of the most powerful conditions for conversion of the 3-alkylated hexane-2,5-diones 5 into the furan derivatives 6, we found that this cyclization can be easily accomplished using half equivalent of p-toluenesulfonic acid in refluxing diethyl ether (Scheme).…”

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confidence: 99%