Organic sulfur mechanisms. 24. Preparation and reactions of 2-hydroxyethanesulfonyl chloride, the first hydroxyalkanesulfonyl chloride

1983 ◽  
Vol 61 (7) ◽  
pp. 1583-1593 ◽  
Author(s):  
James Frederick King ◽  
John Henry Hillhouse
Keyword(s):  
Aqueous Solution ◽  
Hydroxy Group ◽  
Intramolecular Cyclization ◽  
Ring Opening ◽  
Sulfonyl Chloride ◽  
Tertiary Amines ◽  
Deuterium Labelling ◽  
Chlorination Process ◽  
Principal Reaction ◽  
A Minor

2-Hydroxyethanesulfonyl chloride (1a) is readily made by reaction of an aqueous solution of 2-mercaptoethanol (4a) with chlorine. This is the first clearly proved preparation of a compound which is both an alcohol and a sulfonyl chloride. Reactions of 1a with water and alcohols evidently proceed largely by intramolecular cyclization to the transient β-sultone (2a), which then undergoes nuclcophilic ring opening to form the products. In the presence of tertiary amines a minor but significant part of the reaction is shown by deuterium labelling to proceed via hydroxymethylsulfene (14). the principal reaction of which is simply to add the alcohol or water; only a small part, if any, of the sulfene (14) loses the hydroxy¡ group to give the ethenesulfonate derivatives (13 or 22). Aqueous chlorination of 3-mercapto-1-propanol gave 3-chloro-1-propanesulfonyl chloride (5a) and 1,3-propane sultone (2b) with no sign of any 3-hydroxy-1-propanesulfonyl chloride (1b). A mechanism for the aqueous chlorination process invoking a cyclic chlorooxasulfoxoniuin ion (27) is discussed.

Vinylogous nucleophilic catalysis. The tertiary amine promoted reaction of ethenesulfonyl chloride with alcohols

1989 ◽  
Vol 67 (2) ◽  
pp. 330-334
Author(s):  
James Frederick King ◽  
Sheena May Loosmore ◽  
John Henry Hillhouse ◽  
Kishan Chand Khemani
Keyword(s):  
Tertiary Amine ◽  
Reaction Pathway ◽  
Sulfonyl Chloride ◽  
Side Reactions ◽  
Tertiary Amines ◽  
Nucleophilic Catalysis ◽  
Product Composition ◽  
Major Process ◽  
A Minor ◽  
Transfer Mechanisms

Ethenesulfonyl chloride (1) reacts with alcohols in the presence of tertiary amines to give a mixture of the alkyl ethenesulfonate (5) and the alkyl betylate (R3′N+CH2CH2SO2OR Cl−). With pyridine and neopentyl alcohol the product composition from the reaction of 1 is identical to that from the pyridinio-sulfonyl chloride (9). These results, when taken with experiments with deuterium labelled reagents, lead to the conclusion that the major (~80%) reaction pathway involves conversion of 1 or 9 to the sulfene 8, which reacts with the alcohol to form 5 or the betylate, and hence vinylogous nucleophilic catalysis is the major process leading to 5. The labelling experiments disclosed a minor pathway, evidently involving interconversion of 1 and 9. Examination of possible mechanisms leads to the suggestion that the sulfene is formed from 1 or 9 by way of the carbanion (14), i.e., that 9 reacts by an E1cB process, and that the minor pathway is simply the result of side reactions of the carbanion (14). Keywords: sulfenes, sulfonyl transfer mechanisms, vinylogous nucleophilic catalysis.

Lubrication Properties of Aqueous Solutions with Polyethoxylated Ether (PEOE) Added

2011 ◽  
Vol 239-242 ◽  
pp. 1359-1363
Author(s):  
Chao Hui Zhang ◽  
Si Si Liu ◽  
Yue Tao Sun ◽  
Jun Ming Liu
Keyword(s):  
Aqueous Solution ◽  
Aqueous Solutions ◽  
Metal Working ◽  
Functional Additives ◽  
Film Forming ◽  
Minor Influence ◽  
Forming Characteristics ◽  
Aqueous Surfactants ◽  
A Minor ◽  
Lubrication Properties

Aqueous solutions have found broad usages as lubricants, in conjunction with other possible utilizations, such as in metal working and other industries. Due to the inferior lubricity, functional additives are needed to improve their tribological performances among which aqueous surfactants are exclusively included. The film forming property of aqueous solution with polyethoxylated ether added (PEOE) is measured, taking consideration of the influences of the temperature and the concentration. The addition of PEOEs into aqueous solutions will largely increase the film forming capacity. But the concentration has only a minor influence on the lubrication property of the aqueous solutions with PEOEs. The cloud point will strongly alter the film forming characteristics.

scholarly journals Identification of rare Lewis oligosaccharide conformers in aqueous solution using enhanced sampling molecular dynamics

2017 ◽  
Author(s):  
Irfan Alibay ◽  
Kepa K. Burusco ◽  
Neil J. Bruce ◽  
Richard A. Bryce
Keyword(s):  
Molecular Dynamics ◽  
Aqueous Solution ◽  
Md Simulations ◽  
Umbrella Sampling ◽  
Biological Action ◽  
Sialyl Lewis X ◽  
Enhanced Sampling ◽  
Sialyl Lewis ◽  
Aqueous Solvent ◽  
A Minor

<p>Determining the conformations accessible to carbohydrate ligands in aqueous solution is important for understanding their biological action. In this work, we evaluate the conformational free energy surfaces of Lewis oligosaccharides in explicit aqueous solvent using a multidimensional variant of the swarm-enhanced sampling molecular dynamics (msesMD) method; we compare with multi-microsecond unbiased MD simulations, umbrella sampling and accelerated MD approaches. For the sialyl Lewis A tetrasaccharide, msesMD simulations in aqueous solution predict conformer landscapes in general agreement with the other biased methods and with triplicate unbiased 10 ms trajectories; these simulations find a predominance of closed conformer and a range of low occupancy open forms. The msesMD simulations also suggest closed-to-open transitions in the tetrasaccharide are facilitated by changes in ring puckering of its GlcNAc residue away from the <sup>4</sup>C<sub>1</sub> form, in line with previous work. For sialyl Lewis X tetrasaccharide, msesMD simulations predict a minor population of an open form in solution, corresponding to a rare lectin-bound pose observed crystallographically. Overall, from comparison with biased MD calculations, we find that triplicate 10 ms unbiased MD simulations may not be enough to fully sample glycan conformations in aqueous solution. However, the computational efficiency and intuitive approach of the msesMD method suggest potential for its application in glycomics as a tool for analysis of oligosaccharide conformation.</p>

A Novel Photosensitive Polyimide: A Polyimide Containing the Hydroxytriphenylamine Structure with Diazonaphthoquinone

2000 ◽  
Vol 12 (1) ◽  
pp. 177-184 ◽  
Author(s):  
Satoshi Akimoto ◽  
Mitsutoshi Jikei ◽  
Masa-aki Kakimoto
Keyword(s):  
Aqueous Solution ◽  
Phthalic Anhydride ◽  
Ring Opening ◽  
Polyimide Film ◽  
Tetramethylammonium Hydroxide ◽  
Thermal Cyclization

A novel photosensitive polyimide based on a polyimide containing the hydroxytriphenylamine structure (HTA-PI) and 2, 3, 4-tris[1-oxo-2-diazonaphthoquinone-4-sulfonyloxy] benzophenone (D4SB) as a photoreactive compound has been developed. The HTAPI was prepared by the ring-opening polyaddition of 4, 4′-hexafluoroisopropylidenebis(phthalic anhydride) (6FDA) and 4,4′-diamino-4″-hydroxytriphenylamine (DHTA), followed by thermal cyclization in refluxing N-methyl-2-pyrrolidone (NMP). The resulting polyimide film showed excellent transparency to 436 nm light. Photosensitive polyimide containing 30 wt% of D4SB showed a sensitivity of 800 mJ cm−2 and a contrast of 0.8 when it was exposed to 436 nm light followed by development with 5% tetramethylammonium hydroxide (TMAH) aqueous solution at 45°C.

scholarly journals Metal Ion-Binding Properties of the Diphosphate Ester Analogue, Methylphosphonylphosphate, in Aqueous Solution

1999 ◽  
Vol 6 (6) ◽  
pp. 321-328 ◽  
Author(s):  
Bin Song ◽  
Jing Zhao ◽  
Fridrich Gregáň ◽  
Nadja Prónayová ◽  
S. Ali A. Sajadi ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Metal Ion ◽  
Minor Role ◽  
Ion Binding ◽  
Metal Ion Binding ◽  
Ph Titration ◽  
Role Based ◽  
The Stability ◽  
A Minor ◽  
Complex Stabilities

The stability constants of the 1:1 complexes formed between methylphosphonylphosphate (MePP3-), CH3P(O)2--O-PO32- , and Mg2+, Ca2+, Sr2+, Ba2+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+,​ or Cd2+ (M2+) were determined by potentiometric pH titration in aqueous solution (25 C° ; l = 0.1 M, NaNO3 ). Monoprotonated M(H;MePP) complexes play only a minor role. Based on previously established correlations for M2+ -diphosphate monoester complex-stabilities and diphosphate monoester β-group. basicities, it is shown that the M(Mepp)- complexes for Mg2+ and the ions of the second half of the 3d series, including Zn2+ and Cd2+, are on average by about 0.15 log unit more stable than is expected based on the basicity of the terminal phosphate group in MePP3-. In contrast, Ba(Mepp)- and Sr(Mepp)- are slightly less stable, whereas the stability for Ca(Mepp)- is as expected, based on the mentioned correlation. The indicated increased stabilities are explained by an increased basicity of the phosphonyl group compared to that of a phosphoryl one. For the complexes of the alkaline earth ions, especially for Ba2+, it is suggested that outersphere complexation occurs to some extent. However, overall the M(Mepp)- complexes behave rather as expected for a diphosphate monoester ligand.

Biopatterned Reorganization of Alkaloids Enabled by Ring-Opening Functionalization of Tertiary Amines

2021 ◽  
Author(s):  
Hyeonggeun Lim ◽  
Sikwang Seong ◽  
Youyoung Kim ◽  
Sangwon Seo ◽  
Sunkyu Han
Keyword(s):  
Ring Opening ◽  
Tertiary Amines

ChemInform Abstract: 2-HYDROXYETHANESULFONYL CHLORIDE: A SULFONYL CHLORIDE WITH A PRIMARY HYDROXY-GROUP

1981 ◽  
Vol 12 (29) ◽  
Author(s):  
J. F. KING ◽  
J. H. HILLHOUSE
Keyword(s):  
Hydroxy Group ◽  
Sulfonyl Chloride ◽  
Primary Hydroxy Group

scholarly journals Solution structures of nisin A and its two major degradation products determined by n.m.r

1992 ◽  
Vol 283 (2) ◽  
pp. 413-420 ◽  
Author(s):  
L Y Lian ◽  
W C Chan ◽  
S D Morley ◽  
G C Roberts ◽  
B W Bycroft ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Ring Opening ◽  
Polypeptide Chain ◽  
Degradation Products ◽  
Correlation Spectroscopy ◽  
Solution Structures ◽  
Stimulated Annealing ◽  
Nuclear Overhauser Enhancement ◽  
Stereospecific Assignments ◽  
Nuclear Overhauser

The conformations of nisin and two major degradation products, nisin-(1-32)-peptide (nisin1-32) and des-delta Ala5-nisin1-32 (where delta Ala is alpha beta-didehydroalanine), in aqueous solution have been determined from n.m.r. data. Sequential assignments of the peptides using correlation spectroscopy (‘COSY‘), homonuclear Hartmann-Hahn spectroscopy (‘HOHAHA’), nuclear Overhauser enhancement spectroscopy (NOESY), relayed NOESY and rotating-frame nuclear Overhauser spectroscopy (ROESY) experiments are presented, including stereospecific assignments of beta-methylene protons of the lanthionine residues. ROESY experiments are also used to detect flexible regions in the polypeptide chain. A dynamic-stimulated-annealing approach is used for structural determination. It can be concluded that all these peptides are flexible in aqueous solution, with no experimental evidence of preferred overall conformations; the only defined conformational features are imposed by the presence of the lanthionine residues. Low-temperature studies also reveal that des-delta Ala5-nisin1-32 adopts conformations similar to those when the ring is intact, suggesting that the loss of activity of this degradation product is due to the absence of the delta Ala5 residue rather than to the conformational consequences of ring-opening.

Oxidative reaction of 2-aminopyridine-3-sulfonyl chlorides with tertiary amines

2016 ◽  
Vol 22 (6) ◽  
Author(s):  
Huiping Wei ◽  
Gaigai Wang ◽  
Binbin Li ◽  
Jianjun Huang ◽  
Haiyan Li ◽  
...  
Keyword(s):  
Aerobic Oxidation ◽  
Sulfonyl Chloride ◽  
Dual Role ◽  
Tertiary Amines ◽  
Oxidative Reaction ◽  
Sulfonyl Chlorides

Abstract2-Aminopyridine-3-sulfonyl chlorides undergo a reaction with tertiary amines in the presence of air to produce sulfonylethenamines. The 2-aminopyridine-3-sulfonyl chloride apparently plays a dual role in the process promoting the aerobic oxidation of the amine and electrophilically trapping the resulting enamine.

Condensation de la poly-L-lysine et de la poly- L-ornithine avec des dérivés de bases puriques et de sulfamides

1969 ◽  
Vol 47 (19) ◽  
pp. 3641-3646 ◽  
Author(s):  
Louis Berlinguet ◽  
Jacky Gautier
Keyword(s):  
Aqueous Solution ◽  
Amino Acids ◽  
Free Amino ◽  
Sulfonyl Chloride ◽  
Amino Groups ◽  
Carbodiimide Method

Free ε-amino groups of poly-L-lysine and poly-L-ornithine were alkylated in aqueous solution with 6-chloropurine and 6-chloropurine-riboside, were acylated with 4-acetylamino benzene sulfonyl chloride, and were condensed with N-(4-acetylamino benzene sulfonyl)-glycine using carbodiimide method. Approximately 50% of the free amino groups of the basic polypetides were substituted. The same method was used to prepare poly-α-amino acids bearing radioactive substituants.

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