Preparation of Arylimidobis(sulfates)

Kanetani, Fujio

doi:10.1246/bcsj.59.952

Cited by 5 publications

(8 citation statements)

References 4 publications

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“…2), which was included because it had not been prepared by Kanetani when he prepared a series of aryldisulfamates. 15 Of the 29 compounds prepared in this work only three compounds (1-3) have been previously prepared. 1,14 These were resynthesized as standards and also because their taste data was needed for comparison with their monosulfamates, two of which are sweet.…”

Section: Resultsmentioning

confidence: 99%

“…The synthesis of the disulfamates was based on Kanetani's procedures. 14, 15 Typically, chlorosulfonic acid (0.1 mol, 6.7 ml) was added dropwise to stirred 2-picoline (1.0 mol, 81 ml) at 0 ЊC under anhydrous conditions. The solution was maintained at 0 ЊC using an icebath with the aid of salt-acetone.…”

Section: Preparation Of Disulfamatesmentioning

confidence: 99%

“…Various hydrazine tri-and tetrasulfonates have been synthesized 11 and in two papers 12, 13 Baumgarten describes the preparation of some tetra potassium and barium sulfonate salts of urea, 12 a series of aminoacid disulfonates and one trisulfonate, N,NЈ,NЉ-histidylhistidine trisulfonate. 13 Few reports have focused on the syntheses of disulfamates per se apart from the work of Baumgarten, 13 who synthesized seven di-/tri-amino acid sulfonates using pyridine-sulfur trioxide, and Kanetani, 14, 15 who used amine-SO 3 adducts and amines to synthesize over 20 disulfamates including 1-3 (Fig. 2).…”

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confidence: 99%

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Synthesis and tastant properties of disulfamates. Multisulfamation studies

Spillane

Ryder

Concagh

et al. 2001

J. Chem. Soc., Perkin Trans. 2

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Twenty four disulfamates, one trisulfamate, two tetrasulfamates and two monosulfamates have been made. The disulfamates are of two types: RN(SO 3 Na) 2 (Type A, compounds 1-20) and NaO 3 S(H)NRЈN(H)SO 3 Na (Type B, compounds 21-24) and all except three (which had not been tasted) are new materials. The positions of the -SO 3 Na groups in compounds 21-23 have been established by the use of model compounds (e.g. parent amines, appropriate monosulfamates) and 13 C-NMR. Some multisulfamation synthesis leading to compounds 25-27 has been carried out. Taste data have been obtained for almost all the sulfamates made and the significance of these in relation to structure-taste studies for sulfamate sweeteners is discussed. In particular, the possibility that the entity CHN(R)SO 3 Ϫ might function as a hydrogen source in the Shallenberger-Acree, multicomponent attachment and α-helical protein receptor mechanisms has been examined.

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Section: Resultsmentioning

confidence: 99%

Section: Preparation Of Disulfamatesmentioning

confidence: 99%

mentioning

confidence: 99%

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Synthesis and tastant properties of disulfamates. Multisulfamation studies

Spillane

Ryder

Concagh

et al. 2001

J. Chem. Soc., Perkin Trans. 2

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“…Examples of bioactive C(sp 2 )-sulfonates include (D) suramin, a medication for treating river blindness and African sleeping sickness [6]; (E) an inhibitor against the coenzyme A binding site of choline acetyltransferase [7]; and (F) an indole derivative possessing PGD2 receptor antagonist activity [8]. In turn, methods to prepare these N(sp 2 )-aryl sulfamate precursors under mild, noncorrosive conditions are limited [9][10][11][12][13][14][15], and C(sp 2 )-sulfonated compounds are only achievable under more forcing conditions (Scheme 1) [16][17][18][19][20].…”

Section: Introductionmentioning

confidence: 99%

Rearrangement of Arylsulfamates and Sulfates to Para-Sulfonyl Anilines and Phenols

Zhou,

Jones

2024

Molecules

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The C(sp2)-aryl sulfonate functional group is found in bioactive molecules, but their synthesis can involve extreme temperatures (>190 °C or flash vacuum pyrolysis) and strongly acidic reaction conditions. Inspired by the 1917 Tyrer industrial process for a sulfa dye that involved an aniline N(sp2)-SO3 intermediate en route to a C(sp2)-SO3 rearranged product, we investigated tributylsulfoammonium betaine (TBSAB) as a milder N-sulfamation to C-sulfonate relay reagent. Initial investigations of a stepwise route involving TBSAB on selected anilines at room temperature enabled the isolation of N(sp2)-sulfamate. Subsequent thermal rearrangement demonstrated the intermediary of a sulfamate en route to the sulfonate; however, it was low-yielding. Investigation of the N-sulfamate to C--sulfonate mechanism through control experiments with variation at the heteroatom positions and kinetic isotope experiments (KIEH/D) confirmed the formation of a key N(sp2)-SO3 intermediate and further confirmed an intermolecular mechanism. Furthermore, compounds without an accessible nitrogen (or oxygen) lone pair did not undergo sulfamation- (or sulfation) -to-sulfonation under these conditions. A one-pot sulfamation and thermal sulfonation reaction was ultimately developed and explored on a range of aniline and heterocyclic scaffolds with high conversions, including N(sp2)-sulfamates (O(sp2)-sulfates) and C(sp2)-sulfonates, in up to 99 and 80% (and 88% for a phenolic example) isolated yield, respectively. Encouragingly, the ability to modulate the ortho-para selectivity of the products obtained was observed under thermal control. A sulfonated analog of the intravenous anesthetic propofol was isolated (88% yield), demonstrating a proof-of-concept modification of a licensed drug alongside a range of nitrogen- and sulfur-containing heterocyclic fragments used in drug discovery.

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“…[7][8][9][10][11][12][13][14][15][16][17][18][19] In turn, methods to prepare these N(sp 2 )-sulfamated precursors are limited [20][21][22][23][24] and C(sp 2 )-sulfonated compounds are often only achievable under more forcing conditions (Chart 1). [25][26][27][28][29] An ortho-selective aminative rearrangement of (arenesulfonyl)hydroxylamines has recently been revealed. [30] Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

A Sulfonative rearrangement of N-Aryl Sulfamates to para-Sulfonyl Anilines

Zhou

Jones

2022

Preprint

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The C(sp2)-aryl sulfonate functional group is widely found in bioactive scaffolds but can often only be accessed under forcing temperatures (>190 °C) and corrosive reaction conditions. Inspired by the Tyrer process to sulfa dyes that involves an aniline N(sp2)-SO3 intermediate en route to a C(sp2)-SO3 rearranged product - we deployed tributylsulfoammonium betaine (TBSAB) as an initiating mild sulfamating agent to sulfonate relay reagent. A range of aniline and heterocyclic scaffolds were sulfonated in high conversions (6 examples of N(sp2)-sulfamates up to 99% isolated yield and 16 examples of C(sp2)-sulfonate in up to 80% isolated yield) with the ability to change the ortho-para selectivity of the products obtained under thermal control. Isolation of the N(sp2)-SO3 intermediates for a two-step procedure was significantly lower yielding than a direct one-pot procedure. Furthermore, we explore counterion effects on the N- to C- sulfate rearrangement and discovered the reversibility of the TBSAB reagent. Investigation of the N- to C- mechanism through designed examples with variation at the heteroatom position, and kinetic isotope experiments (KIEH/D) confirmed the formation of a key N(sp2)-SO3 intermediate and further supporting evidence of an intermolecular mechanism. Compounds without an accessible nitrogen (or hydroxyl) lone pair did not undergo sulfonation under these reaction conditions.

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Preparation of Arylimidobis(sulfates)

Abstract: Seven arylimidobis(sulfates), six of which are new compounds, have been prepared by the N-sulfonation of the corresponding primary aromatic amines with 2-methylpyridine-sulfur trioxide in 60–92% yields.

Cited by 5 publications

References 4 publications

Synthesis and tastant properties of disulfamates. Multisulfamation studies

Synthesis and tastant properties of disulfamates. Multisulfamation studies

Rearrangement of Arylsulfamates and Sulfates to Para-Sulfonyl Anilines and Phenols

A Sulfonative rearrangement of N-Aryl Sulfamates to para-Sulfonyl Anilines

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