ChemInform Abstract: BOND SCISSION PROCESSES IN SULPHUR COMPOUNDS PART 9, NUCLEOPHILIC CATALYSIS IN THE METHANOLYSIS OF METHYL P‐NITROPHENYL SULPHATE

Buncel, Erwin; Chuaqui, Claudio; Forsythe, P. P.; MAHONEY, SUSAN; Raoult, A.; Wiltshire, J. F.

doi:10.1002/chin.197525106

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“…In conclusion, it has been shown in this study that the nucleophiles H2NNH3+ and H2NNH2 react with methyl p-nitrophenyl sulfate by displacement at the aliphatic carbon with p-nitrophenyl sulfate ion as the leaving group.This is analogous to the alkaline methanolysis (2) and the reaction with some common anions (1).…”

Section: Reactions With the Hznnh3+/+h3nnh3+mentioning

confidence: 93%

Bond Scission in Sulfur Compounds. Part X. The Hydrazinolysis of Methyl p-Nitrophenyl Sulfate

Buncel¹,

Chuaqui²

1975

Can. J. Chem.

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ERWIN BUNCEL and CLAUDIO CHUAQUI. Can. J. Chem. 53, 1275Chem. 53, (1975. Reaction of methyl p-nitrophenyl sulfate with the hydrazine-hydrazine hydrochloride system in methanol gives rise to different types of behavior depending on the state of ionization of the reagent. For the H2NNH2/H2NNH3+ combination the observed reaction is conversion of methyl p-nitrophenyl sulfate to p-nitrophenyl sulfate ion (alkyl-oxygen scission). For the H2NNH3+/+H3NNH3+ combination, or with +H3NNH3+ alone, one observes the consecutive processes methyl p-nitrophenyl sulfate + p-nitrophenyl sulfate ion + p-nitrophenol (alkyl-oxygen followed by sulfur-oxygen scission). For the alkyl-oxygen scission process, i.e. nucleophilic displacement on the alkyl carbon, the observed pseudo first-order rate constant is given by the contributions of several nucleophilic species; k,,,. A method for the dissection of k,,, into the constituent terms is given. The sulfur-oxygen scission process is an acid catalyzed reaction and the measured kinetic data have been utilized for the derivation of the pK. of +H3NNH3+ in methanol. Rate data for the conversion of sodium p-nitrophenyl sulfate to p-nitrophenol in methanol containing HCI have also been determined in this connection.ERWIN BUNCEL et CLAUDIO CHUAQUI. Can. J. Chem. 53, 1275Chem. 53, (1975. La riaction du p-nitrophinyl sulfate de methyle avec le systime hydrazine -chlorhydrate d'hydrazine dans le mkthanol donne lieu a differents types de reaction dependant de I'Ctat d'ionisation du reactif. Pour la cornbinaison H2NNH2/H2NNH3 +, la reaction observte est la transformation du p-nitrophknyl sulfate de mkthyle en ion p-nitrophenyl sulfate (scission alkyle-oxygene). Pour la combinaison H 2 N N H 3 + / + H 3 N N H 3 + ou avec +H3NNH3+ seul, on observe des rkactions consecutives allant du p-nitrophknyl sulfate de methyle + I'ion p-nitrophknyl sulfate + p-nitrophenol (scission alkyle-oxygene suivie par une scission soufreoxygene). Pour le processus de scission alkyle-oxygene, i.e. le deplacement nuclCophile sur le carbone de la chaine alkyle, la constante de vitesse du pseudo premier ordre qui est observee est obtenue a partir des contributions de plusieurs espkes nucleophiles; k,,, = k,,, + kc,-IC1-1 + ~H~N N~~+ [ H~N N H~+ ] + ~H~N N H~[ H~N N H~] .Ondonne une methode pour ladissection du k,,, en ses termes constituants. Le processus de scission soufre-oxygene est une rkction acido catalyske et on a pu utiliser les valeurs cinetiques mesurkes pour dtterminer les valeurs de pK, du +H3NNH3+ dans le mkthanol. A cet effet on a aussi determine la vitesse de transformation (dans du methanol contenant du HCI) du p-nitrophknyl sulfate de sodium en p-nitrophenol.[Traduit par le journal]Methyl p-nitrophenyl sulfate is the first member of the family of mixed alkyl aryl sulfates to be subjected to intensive investigation. This particular substrate offers several possible electrophilic centers in its reactions with nucleophiles: the alkyl carbon, the sulfonyl sulfur, and the aryl carbon. So far we have reported on ...

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Section: Reactions With the Hznnh3+/+h3nnh3+mentioning

confidence: 93%