Relative Oxidizabilities of 2,4-Pentanedithiol, 2,5-Hexanedithiol, and Hydrolyzed Poly(vinyl thiolacetate)<sup>1</sup>

Overberger, C. G.; Ferraro, J. J.; Orttung, F. W.

doi:10.1021/jo01067a104

Cited by 21 publications

(6 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Preparation of the dimers, {ReO(dt)(SPh)}2, where H2dt represents 2-(mercaptomethyl)thiophenol, 1,2-ethanedithiol, 1,3-propanedithiol, and 1,3-butanedithiol, has been reported elsewhere. 5 2-(Diphenylphosphino)benzenethiol, 24 [Cl3ReO- (PPh3)2], 25 and 2,4-pentanedithiol (H2pdtMe2) 26 were synthesized according literature procedures. Infrared spectra were collected with a Bruker IFS66V FT-IR spectrometer as KBr pellets.…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Studies of C−S Bond Cleavage Reactions of Re(V) Dithiolates: Synthesis, Reactivity, and Mechanism

Ellern

Espenson

2005

J. Am. Chem. Soc.

View full text Add to dashboard Cite

A series of rhenium(V) complexes, [(X)(ReO)(dt)(PPh(3))] and [(o-SC(6)H(4)PPh(2))(ReO)(mtp)], were prepared to explore electronic effects on the C-S cleavage reaction that occurs upon reaction with PAr(3) at ambient temperature [where X = S(C(6)H(4)-p-Z) (Z = OMe, Me, H, F, Cl), OPh, Cl, and SC(2)H(5), and dt is the chelating dithiolate ligand derived from 2-(mercaptomethyl)thiophenol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,3-butanedithiol, and 2,4-pentanedithiol]. The scope and selectivity of the C-S activation were examined. The C-S bond cleavage to form metallacyclic Re(V) complexes with a ReS core occurs only for the complexes with mtp and pdt frameworks and X = SAr and SC(2)H(5). The difference in reactivity is due to the different donating abilities of ancillary and dithiolate ligands, especially their pi-donating ability, which plays a critical role in C-S activation. The kinetics of the C-S activation process was determined; nucleophilic attack of PPh(3) on the oxo group of the Re(V)O core appears to be the rate-controlling step. The reaction is accelerated by electron-poor ArS ligands, but is unaffected by the substituents on phosphines. A detailed mechanistic study is presented. The results represent a rare example of migration of alkanethiolate leading to the formation of alkylthiolato complexes.

show abstract

Section: Methodsmentioning

confidence: 99%

“…Preparation of the dimers, {ReO(dt)(SPh)} 2 , where H 2 dt represents 2-(mercaptomethyl)thiophenol, 1,2-ethanedithiol, 1,3-propanedithiol, and 1,3-butanedithiol, has been reported elsewhere . 2-(Diphenylphosphino)benzenethiol, [Cl 3 ReO(PPh 3 ) 2 ], and 2,4-pentanedithiol (H 2 pdtMe 2 ) were synthesized according literature procedures.…”

Section: Methodsmentioning

confidence: 99%

Studies of C−S Bond Cleavage Reactions of Re(V) Dithiolates: Synthesis, Reactivity, and Mechanism

Ellern

Espenson

2005

J. Am. Chem. Soc.

View full text Add to dashboard Cite

show abstract

“…Similar to the preparation of polyvinyl alcohol (PVA), a possibility is the polymerization of thioacetates, which after hydrolysis leads to the equivalent polyvinyl thiol. 32,[76][77][78] The polymerization rate is lower for radical homopolymerizations than for vinyl acetates. 79 However the stabilization of the radicals is greater for copolymerizations due to the inclusion of the 3d-orbitals of sulfur.…”

Section: Vinyl Thioacetatesmentioning

confidence: 99%

“…Similar to the thioacetates, they can be polymerized with radical azo-initiators, but in addition also peroxides result in the formation of polymers. 76,[89][90][91][92][93] The resulting polymers can be converted into poly thiols as in the case of thioacetates, although this occurs more slowly. For example, free radical polymerization of S-vinyl-O-t-butyl thiocarbonate leads to the corresponding polythiocarbonate.…”

Section: Other Electron Rich S-vinyl Groupsmentioning

confidence: 99%

Polymers fromS-vinyl monomers: reactivities and properties

et al. 2022

View full text Add to dashboard Cite

show abstract

“…The method of converting an epoxide (commercially available) to a trithiocarbonate followed by lithium aluminum hydride reduction to the corresponding 1,2-dithiol (Iqbal and Owen, 1960;Hauptmann and Bobbio, 1960) was employed to obtain 2-phenyl-l,2-ethanedithiol, 2-methyl-l,2-propanedithiol, 3-methoxy-l,2-propanedithiol, 1,2-cyclohexanedithiol, and 3,4-sulfolanedithiol. The conversion of , -dibromoalkanes to the corresponding a,7-dithiols by way of diisothiuronium salts (Overberger et al, 1961) was used to prepare 1.3-butanedithiol and 2,4-pentanedithiol.…”

mentioning

confidence: 99%

Synthesis and biological activity of .alpha.-mercaptol O-(carbamoyl)oximes

Fridinger¹,

Mutsch²,

Matteson³

1971

J. Agric. Food Chem.

View full text Add to dashboard Cite

The selective condensation of a-dicarbonyl comlane-2-carboxaldehyde 0-(methylcarbamoy1)oxime pounds with one equivalent of a dithiol followed by has exhibited especially outstanding greenhouse and oxime formation and subsequent carbamoylation field control of nematodes with no phytotoxicity. has afforded a series of novel a-mercaptol 0-Structure us. activity relationships appear to be (carbamoyl)oximes, some of which possess good consistent with previously studied cholinesteraseto excellent insecticidal, acaricidal, and nematicidal inhibiting carbamates. Toxicological aspects are activity. The compound 2,4-dimethyl-1,3-dithiodiscussed.he continuing search for improved carbamate insecticides has led, in the last decade, to a class of potent T acetylcholinesterase inhibitors derived from a variety of oxime precursors. For example, significant pesticidal activity has been reported for 0-(carbamoy1)oximes of cycloaliphatic and bicyclic ketones (Kilsheimer and Manning, 1963;Weiden, 1968), 2-keto-1,3-dithiolanes (Addor, 1965), 5-keto-l,3-dithianes (Addor, 1968), alkoxy and alkylthio esters (Felton, 1968), and trisubstituted acetaldehydes (Payne et al., 1966;Weiden, 1968). Detailed structure ES. activity studies of the latter class of compounds, exemplified by 2-methyl-2-(methylthio)propionaldehyde 0-(methylcarbamoy1)-oxime (aldicarb, Temik, UC 21149), have defined certain important criteria for high or optimum acetylcholinesterase inhibition. These include a conformational similarity to acetylcholine, the presence of an a-alkylthio (or electronegative) substituent, and monomethylation of the carbamate nitrogen. The special role of sulfide sulfur is also apparent in other 0-(methylcarbamoy1)oximes ; for example, Smethyl N-[(methylcarbamoyl)oxy]thioacetimidate (methomyl, Lannate, DuPont 1179), in substituted thiophenyl carbamates (Mahfouz ef a/., 1969), and in the case of certain (methylcarbamoy1oxy)benzaldehyde mercaptals (Durden and Weiden, 1969;Nikles, 1969). The present work describes a new series of insecticidalnematicidal a-mercaptol 0-(carbamoy1)oximes of general structure I. The compound 2,4-dimethyl-1,3-dithiolane-2-carboxaldehyde 0-(methylcarbamoy1)oxime (MBR 6168, Tirpate) has demonstrated especially outstanding greenhouse and field nematode control with no phytotoxicity, and is currently under development by 3M Company. 0 0 II RIS -C I -CR3 II R,S NOCNReRs ii CH 3 < ? \OCNHCH3

show abstract

Relative Oxidizabilities of 2,4-Pentanedithiol, 2,5-Hexanedithiol, and Hydrolyzed Poly(vinyl thiolacetate)¹

Cited by 21 publications

References 0 publications

Studies of C−S Bond Cleavage Reactions of Re(V) Dithiolates: Synthesis, Reactivity, and Mechanism

Studies of C−S Bond Cleavage Reactions of Re(V) Dithiolates: Synthesis, Reactivity, and Mechanism

Polymers fromS-vinyl monomers: reactivities and properties

Synthesis and biological activity of .alpha.-mercaptol O-(carbamoyl)oximes

Contact Info

Product

Resources

About

Relative Oxidizabilities of 2,4-Pentanedithiol, 2,5-Hexanedithiol, and Hydrolyzed Poly(vinyl thiolacetate)1

Cited by 21 publications

References 0 publications

Studies of C−S Bond Cleavage Reactions of Re(V) Dithiolates: Synthesis, Reactivity, and Mechanism

Studies of C−S Bond Cleavage Reactions of Re(V) Dithiolates: Synthesis, Reactivity, and Mechanism

Polymers fromS-vinyl monomers: reactivities and properties

Synthesis and biological activity of .alpha.-mercaptol O-(carbamoyl)oximes

Contact Info

Product

Resources

About

Relative Oxidizabilities of 2,4-Pentanedithiol, 2,5-Hexanedithiol, and Hydrolyzed Poly(vinyl thiolacetate)¹