85599-62-8Relevant academic research and scientific papers
O-(Aminosulfonylation) of phenols and an example of slow hydrolytic release
Yang, Baocheng,Sun, Zhexun,Liu, Changzhi,Cui, Yan,Guo, Zhilei,Ren, Yuwei,Lu, Zhijian,Knapp, Spencer
supporting information, p. 6658 - 6661 (2014/12/11)
Sequential replacement of imidazole from sulfonyldiimidazole by phenols and then amines leads to O-arylsulfamate esters. Application of this coupling method to 19 phenols and 6 amines generates a library of 114 sulfamate esters, Ar-OSO2-NR2. A sulfamate based conjugate of ethinyl estradiol was prepared by using the steroid 3-hydroxyl as the phenol component, and an amino amide derived from linoleic acid as the amine. Hydrolysis of this conjugate was studied in aqueous buffer at pH values 2, 5, and 7.4, and (essentially identical) respective half-lives of 6.8, 6.6, and 6.7 days were observed.
AMINOLYSIS AND HYDROLYSIS OF SULPHAMATE ESTERS: SUBSTANTIAL N=S BONDING IN THE TRANSITION STATE LEADING TO N=SULFONYLAMINES
Spillane, William J.,Hogan, Geraldine,McGrath, Paul
, p. 610 - 616 (2007/10/02)
The aminolysis and hydrolysis of several sulphamate esters, RNHSO2ONp (R = PhCH2, Ph, 4-MeC6H4, 3-MeC6H4, 4-FC6H4, 4-ClC6H4, 3-ClC6H4, H; Np = 4-NO2C6H4) were been studied in 50 percent (v/v) aqueous acetonitrile at various temperatures.Reaction of the esters with an amine (R1NH2) gives -ONp and both sulphamide, (RNHSO2NHR1) and sulphamate (RNHSO2O-R1NH3+) products.First-order rates were determined by the appearance of -ONp and sometimes also by the disappearance of ester.The reaction was found to be independent of amine type and concentration and at the high pHs that obtain the substrate esters are fully ionized.A Hammett ρacyl of -1.8 was obtained for the decomposition of the sulphamate anions and this is consistent with substantial N=S bonding in the transition state leading to N-sulphonylamine, RN=SO2.This intermediate then partitions very rapidly, reacting with R1NH2 and H2O respectively. ΔH*, ΔS* and a deuterium solvent isotope effect were determined and were also interpreted in favour of the proposed mechanism.The dimethyl sulphamate ester (Me2NSO2ONp) does not react under the conditions used.
