Organic Syntheses with Sulfuryl Chloride

Binkley, W. W.; Degering, Ed. F.

doi:10.1021/ja01267a004

Cited by 20 publications

(10 citation statements)

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“…The boiling points, comparable with those reported in the literature (21,22) and the characteristics of n.m.r. spectra for these chlorides are summarized in Table 7.…”

Section: Ma Rerialssupporting

confidence: 91%

Hydrolysis of Sulfamoyl Chlorides. II. Hydrogen Participation in the Hydrolysis of Diethyl and Methylethylsulfamoyl Chlorides

Ko¹,

Robertson²

1972

Can. J. Chem.

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Diethylsulfamoyl chloride (2) hydrolyzes eight times faster than dimethylsulfamoyl chloride (1). In 2 the secondary deuterium isotope effect was found to be about 2, hence hydrogen participation is important in the hydrolysis of this compound. The temperature coefficient of the enthalpy of activation ( A c t ) is exceptional (-39 cal mol-' deg-') for a reaction presumably following an SNI mechanism. The kinetic solvent isotope effect was normal for such a mechanism. The corresponding value of AC: for the hydrolysis of piperidylsulfamoyl chloride (4) was about the same as found for 2 while the value for the methylethyl isomer (3) was -66 cal deg-' mol-', an intermediate value supporting an explanation based on solvent exclusion. Experiments in mixed solvents support the hypothesis that solvent reorganization is the major factor in determining the value of AC: for 2 but not for 4.Le chlorure de dii.thylsulfamoyle (2) hydrolyse huit fois plus vite que le chlorure de dimCthylsulfamoyle (1). Dans 2, l'effet isotopique secondaire du deuterium est trouve a peu prts egal a 2, par suite la participation de I'hydrogtne est importante dans I'hydrolyse de ce composC. Le coefficient de temptrature de l'enthalpie d'activation (AC:) est exceptionnel (-39 cal mol-' deg-') pour une reaction suivant probablement un mecanisme SN1. L'effet isotopique cinetique du solvant ttait normal pour un tel mtcanisme. La valeur correspondante de AC: pour I'hydrolyse du chlorure de pipi.ridylsulfamoyle (4) a ttC environ la meme que celle trouvte pour 2 tandis que la valeur de I'isomere methyltthyl (3) etait de -66 cal deg-' mol-', valeur intermediaire ktayant une explication fondke sur I'exclusion de solvant. Des exptriences dans des solvants melanges ttayent I'hypothtse que la reorganisation du solvant est le facteur principal dans la determination de la valeur de AC: pour 2 mais non pas pour 4.

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“…The boiling points, comparable with those reported in the literature (21,22) and the characteristics of n.m.r. spectra for these chlorides are summarized in Table 7.…”

Section: Ma Rerialssupporting

confidence: 91%

Hydrolysis of Sulfamoyl Chlorides. II. Hydrogen Participation in the Hydrolysis of Diethyl and Methylethylsulfamoyl Chlorides

Ko¹,

Robertson²

1972

Can. J. Chem.

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“…This situation is reminiscent of the behaviour of aniline towards ethyl chlorosulfate where products of displacement of chlorosulfate, monoand di-ethylanilines, and products attributable to chloride displacement from sulfur, phenylsulfamic acids, have been reported. 19 Interestingly attack at sulfur seems to be favoured by tertiary bases such as pyridine. 20 Finally, the trimethyl borate catalysed procedure for CMCS preparation, although rapid and clean, produces a substantial amount of MBCS; this is hydrolysed and the hydrolysis product discarded.…”

Section: Reactions Of Cmcs Mcs and Mbcs With Nucleophilesmentioning

confidence: 99%

Chloromethyl chlorosulfate: a new, catalytic method of preparation and reactions with some nucleophiles

Power

Bethell

Proctor³

et al. 2004

Org. Biomol. Chem.

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The reaction of liquid (gamma-) SO3 with CH2Cl2 at room temperature leads to SO3 insertion into the C-Cl bonds, giving the useful chloromethylating agent chloromethyl chlorosulfate (CMCS). The process is very slow but becomes rapid on addition of catalytic quantities of trimethyl borate. The product mixture consists almost entirely of CMCS and the product of further sulfation, methylene bis(chlorosulfate)(MBCS), in a ratio of ca. 2 : 1, but typical yields of CMCS, isolated by distillation, are only 30-35%. The catalysed reaction in the homogeneous liquid phase at -45 degrees C has been followed as a function of time and of reactant concentration by 1H nmr spectroscopy. It is observed that, besides CMCS and MBCS, three additional, transient products (designated A, B and C) are formed. Products A, B and C decompose slowly at -45 degrees C but much more rapidly if the reaction mixture is raised to room temperature, giving additional CMCS and MBCS. From an analysis of the SO3 balance, it is inferred that products A, B and C arise from the reaction of one molecule of CH2Cl2 with respectively two, three and four molecules of SO3; they are suggested to be chloromethyl chloropolysulfates. By measuring initial rates of CMCS formation or total CH2Cl2 consumption, it is shown that the reaction is first order in the catalyst and roughly third order in SO3. A mechanistic scheme is proposed in which SO3 forms equilibrating zwitterionic molecular complexes with CH2Cl2. of 1 : 1, 2 : 1 and higher stoichiometries. The boron-containing catalyst can activate these complexes towards nucleophilic attack at carbon by the negatively charged oxygen of another zwitterion. An analogous mechanism can be written for the conversion of CMCS into MBCS by SO3 in the presence of trimethyl borate. CMCS reacts rapidly with anionic nucleophiles, such as halide or acetate ions (X-), in homogeneous solution of their tetrabutylammonium salts in CD3CN, or in a two-phase system (CDCl3/H2O) using alkali-metal salts in conjunction with a phase-transfer catalyst. In both situations the products (ClCH2X) arise by rapid nucleophilic displacement of the chlorosulfate moiety; this then more slowly liberates chloride ion, which converts further CMCS into CH2Cl2. The reactivity of CMCS has been compared with that of MBCS and methyl chlorosulfate (MCS) in competitive experiments; the reactivity order is MCS > MBCS > CMCS >> CH2Cl2. Evidence is also presented suggesting that, in contrast to the halide nucleophiles, reaction of CMCS with sodium phenoxide in tetrahydrofuran solution leads to nucleophilic displacement of the sulfur-bound chloride.

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“…Other workers have encountered a similar failure to detect either phenyl cations or benzyne with so-called "super sulfonate" esters (10 The first problem appeared in the preparation of en01 N,N-dimethylsulfamate esters. Whereas the procedure of Binkley and Degering (12), involving reaction of a sodium alkoxide or aryloxide with N,N-dimethylsulfamoyl chloride, had worked well for aryl and alkyl N,N-dimethylsulfamates (see Table 1 and the accompanying paper), the corresponding reaction of sodium or lithium cyclohexenoxide, for example, gave no sign of the sulfamate ester. The only identified product from this reaction was tetramethylsulfamide (5).…”

Section: Resultsmentioning

confidence: 99%

Betylates. 1. Synthesis and reactions of an isolable [0]betylate, N,N-dimethyl-N-(phenoxysulfonyl)methanaminium fluorosulfate

King¹,

Lee²

1981

Can. J. Chem.

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Phenyl [0]betylate fluorosulfate (2), the first example of a "[0]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, [Formula: see text], prepared from tetramethylsulfamide and methyl fluorosulfate, but no satisfactory method was found for converting the sulfamic ester to the [0]betylate. Evidence is presented that phenyl chlorosulfate reacts with trimethylamine to give the phenyl [0]betylate which then undergoes further reaction.

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Organic Syntheses with Sulfuryl Chloride

Cited by 20 publications

References 0 publications

Hydrolysis of Sulfamoyl Chlorides. II. Hydrogen Participation in the Hydrolysis of Diethyl and Methylethylsulfamoyl Chlorides

Hydrolysis of Sulfamoyl Chlorides. II. Hydrogen Participation in the Hydrolysis of Diethyl and Methylethylsulfamoyl Chlorides

Chloromethyl chlorosulfate: a new, catalytic method of preparation and reactions with some nucleophiles

Betylates. 1. Synthesis and reactions of an isolable [0]betylate, N,N-dimethyl-N-(phenoxysulfonyl)methanaminium fluorosulfate

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