Synthesis of Mono- And Polysulfur-Bridged Bisphenols and Their Application to New Type Lewis Acids

Ohba, Yusuke; K, Ito; Nagasawa, Tomomi

doi:10.1515/hc.1998.4.6.529

Cited by 5 publications

(3 citation statements)

References 5 publications

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“…The dependence of activity upon the oxidation state of sulfur is not easy to predict on the basis of known chemistry. Ohba and co-workers, studying the Lewisacid-catalyzed rearrangement of aromatic epoxides to ketones by aluminum complexes, found that sulfoxide-, sulfone-, 11 and trisulfido-bridged 12 biphenol ligands all support high activity for this reaction.…”

Section: Resultsmentioning

confidence: 99%

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Ethylene Oxide Polymerization Catalyzed by Aluminum Complexes of Sulfur-Bridged Polyphenols

et al. 2004

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The products derived from the reaction of sterically hindered sulfur-bridged bisphenols with aluminum trialkyls enable the efficient polymerization of ethylene oxide. The activity of the catalyst is largely determined by the structure of the bisphenol ligand and the size of the aluminum alkyl groups. Bonds of sulfur to aluminum are a common feature of the solid-state structures of compounds examined to this point. In solution, precatalysts of the formula (3-t-Bu-5-Me-2-OAlEt2−C6H2)2S are fluxional, and two processes appear to contribute to the equilibration of all ethyl substituents. The addition of a hindered monomer, 1,2-epoxyhexane, causes the initial formation of solvation complexes with the aluminum precatalysts and effects the disproportionation of the initial dialuminum complex of the bisphenol. One of the polymer end groups appears to be easily replaced by a halide atom during acid workup.

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Section: Resultsmentioning

confidence: 99%

“…The crystal structure of this compound lacked this solvent, however. 1 (12). To a solution of 2.018 g of 4a in 40 mL of dry diethyl ether was slowly added 3.65 mL of triethylaluminum solution (5.62 mmol) at ambient temperature.…”

Section: 4-di-t-butyl-6-[(35-di-t-butyl-2-methoxyphenyl)thio]phenol (5d)mentioning

confidence: 99%

Ethylene Oxide Polymerization Catalyzed by Aluminum Complexes of Sulfur-Bridged Polyphenols

et al. 2004

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“…However, the coordination chemistry of trisulfide-containing molecules is far less investigated, which is surprising in view of the high abundance of metals in biological systems. − A Cambridge database search revealed only four crystallographically characterized examples of a metal complex with a directly coordinated S 3 unit. ,,, Some of them were prepared by the solvo- and hydrothermal synthesis of mercaptopyrimidine disulfide and a metal precursor. ,, While this gives some insight into the coordination properties of the biologically active class of compounds, the thermal synthesis is usually nonselective because several sulfur-containing products were detected. ,, Thus, there is a high need for a better understanding of the coordination chemistry of S 3 units, as well as for their formation from sulfur precursors in the presence of metal salts.…”

Section: Introductionmentioning

confidence: 99%

Unusual C–N Coupling Reactivity of Thiopyridazines: Efficient Synthesis of Iron Diorganotrisulfide Complexes

et al. 2017

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The reaction of iron(II) triflate with 6-tert-butyl-3-thiopyridazine (PnH) and 4-methyl-6-tert-butyl-3-thiopyridazine (PnH) respectively led to iron bis(diorganotrisulfide) complexes [Fe(PnSPn)](OTf) [R = H (1a) and Me (2a)]. The corresponding perchlorate complexes were prepared by using the iron(II) chloride precursor and the subsequent addition of 2 equiv of NaClO, giving [Fe(PnSPn)](ClO) [R = H (1b) and Me (2b)]. The compounds were fully characterized including single-crystal X-ray diffraction analysis. All four compounds exhibit nearly perfect octahedral geometries with an iron center coordinated by four nitrogen atoms from two PnSPn ligands and by two sulfur atoms of the central atom in the S unit. The diamagnetic complexes exhibit unusually high redox potentials for the Fe couple at E = 1.15 V (for 1a and 1b) and 1.08 V (for 2a and 2b) versus Fc/Fc, respectively, as determined by cyclic voltammetry. Furthermore, the source of the extra sulfur atom within the S unit was elucidated by isolation of C-N-coupled pyridazinylthiopyridazine products.

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Synthesis and properties of new types of sulfoxide‐ or sulfone‐bridged lewis acids

Ohba¹,

K²,

Nagasawa³

et al. 2000

Journal of Heterocyclic Chem

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A series of new types of sulfur‐bridged Lewis acids were synthesized. The ligands that contained the sulfoxide or sulfone as the joint moieties of two phenols were found to quantitatively give Lewis acids. These obtained Lewis acids also have good discrimination properties of some epoxides. The reaction prop erties of the Lewis acids were studied using the rearrangement of the epoxides to carbonyl compounds.

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Synthesis of Mono- And Polysulfur-Bridged Bisphenols and Their Application to New Type Lewis Acids

Abstract: Several bisphenoles which contain sulfur (s) as bridge moiety were synthesized by the reaction of sulfur monochloride with phenols and the reaction of the trisulfur-bridged bisphenols with trimethylalumininum quantitatively gave new type of Lewis acids.

Cited by 5 publications

References 5 publications

Ethylene Oxide Polymerization Catalyzed by Aluminum Complexes of Sulfur-Bridged Polyphenols

Ethylene Oxide Polymerization Catalyzed by Aluminum Complexes of Sulfur-Bridged Polyphenols

Unusual C–N Coupling Reactivity of Thiopyridazines: Efficient Synthesis of Iron Diorganotrisulfide Complexes

Synthesis and properties of new types of sulfoxide‐ or sulfone‐bridged lewis acids

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