- METHOD FOR MAKING N-(FLUOROSULFONYL) DIMETHYLAMINE
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Dimethylamine (Me2NH) is reacted with sulfuryl fluoride (SO2F2) to form at least a first phase comprising N-(fluoro sulfonyl) dimethylamine (FSO2NMe2), tetramethylsulfamide (SO2(NMe2)2), or a combination thereof. A second phase, which may include dimethylamine hydrofluoride (Me2NH2F), may be also formed and separated from the first phase. FSO2NMe2 or SO2(NMe2)2 is then isolated from the first phase. For example, the first phase may be a liquid phase, and FSO2NMe2 and SO2(NMe2)2 are separated by distillation, optionally under reduced pressure.
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Paragraph 0073; 0077
(2018/06/04)
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- Enantioselective enolate protonation: Matching chiral aniline and substrate acidity
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A comparison of chiral anilines 1a-f in the asymmetric protonation of enolate 15 shows that the optimum ΔpK(a) value (chiral acid vs protonated enolate) for the highest enantioselectivity is ca. 3 (Table 2). An extension of this concept to amino acid enolates was possible, and 1e was found to give the best enantioselectivity (85% ee) with the alanine-derived N-lithioenolate 5a (Table 3). Changes in aniline pK(a) due to variation of substituents at the aniline nitrogen were evaluated briefly, but these changes did not show consistent trends in the enantioselectivity vs pK(a).
- Vedejs,Kruger,Suna
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p. 7863 - 7870
(2007/10/03)
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- Betylates. 1. Synthesis and reactions of an isolable betylate, N,N-dimethyl-N-(phenoxysulfonyl)methanaminium fluorosulfate
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Phenyl betylate fluorosulfate (2), the first example of a "betylate" (trialkylammoniosulfate ester), has been prepared by methylation of phenyl N,N-dimethylsulfamate with methyl fluorosulfate.Nucleophiles react with 2 either by attack on the sulfur or methyl carbon atoms, but with no sign of any products derived from benzyne or the phenyl cation.A synthesis of enol N,N-dimethylsulfamates has been devised using a reagent, Me2NSO2N(1+)Me3 FSO3(1-), prepared from tetramethylsulfamide and methyl fluorosulfate, but no satisfactory method was found for converting the sulfamic ester to the betylate.Evidence is presented that phenyl chlorosulfate reacts with trimethylamine to give the phenylbetylate which then undergoes further reaction.
- King, James Frederick,Lee, Teresa Mee-Ling
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p. 356 - 361
(2007/10/02)
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