55665-95-7

Upstream product

• 67-56-1 methanol 
• 127903-02-0 N-methyl-N-phenylsulfuric diamide 
• 127903-06-4 N-(2-methoxycarbonylphenyl)sulfuric diamide 
• 127903-07-5 N-methyl-N-(2,4-dibromophenyl)sulfuric diamide 
• 127903-04-2 N-(4-methoxycarbonylphenyl)sulfuric diamide 
• 127903-03-1 N-methyl-N-(4-methoxycarbonylphenyl)sulfuric diamide 
• 127903-05-3 N-methyl-N-(2-methoxycarbonylphenyl)sulfuric diamide 

Downstream Products

• 1306748-23-1 (E)-methyl N-(1,3-diphenylallyl)sulfamate 
• 1306748-30-0 (E)-methyl N-(4-phenylbut-3-en-2-yl)sulfamate 
• 1306748-12-8 methyl cyclohex-2-en-1-ylsulfamate 
• 120-14-9 3,4-dimethoxy-benzaldehyde 

Relevant academic research and scientific papers

Competition between SN2 and (general acid-catalysed) E1cB reactions in the aqueous decomposition of methyl N-(substituted phenoxycarbonyl)sulfamate esters

The aqueous reaction mechanisms of methyl N-(substituted phenoxycarbonyl)sulfamates 4a-d were examined in the entire pH range 0-14 at 50 °C. The pH-rate profiles indicate a rate law that includes two pH-independent terms. ka (s-1) in acid and kp (s-1) around neutral pH, with ka > kp, and a hydroxide-ion dependent term, kOH (dm3 mol-1 s-1), at high pH. In acid, product analysis reveals that two competitive reactions are involved for hydrolysis with ka = kCO + kMe: a general acid-catalysed acyl-oxygen bond cleavage reaction of anions 4- (kCO) and a methyl-oxygen bond cleavage reaction resulting from water attack at the methyl carbon of neutral compounds 4 (kMe). For all compounds 4 investigated the kMe reaction is the dominant pathway (i.e., > 79%) in 1.0 mol dm-3 HCl solution. In contrast to ka, the spontaneous hydrolysis reaction of 4-, kp, takes place exclusively by acyl-oxygen bond cleavage and leads to the formation of methoxysulfonyl isocyanate as free intermediate. As observed in acid for the kMe reaction, the kOH reaction of 4- is best rationalized by a SN2Al mechanism in which hydroxide ion attacks anions 4- at the saturated methyl carbon leading to methyl-oxygen bond cleavage.

KINETICS AND MECHANISM OF SOLVOLYSIS OF N-ARYL SULFURIC DIAMIDES

The methanolysis and hydrolysis kinetics have been studied with the following sulfuric diamide derivatives: N-methyl-N-phenyl- (IIIa), N-methyl-N-(4-methoxycarbonylphenyl)- (IIIb), N-(4-methoxycarbonylphenyl)- (IIIc), N-methyl-N-(2-methoxycarbonylphenyl)- (IIId), N-(2-methoxycarbonylphenyl)- (IIIe), and N-methyl-N-(2,4-dibromophenyl)- (IIIf).The solvolyses of the neutral substrates IIIa and IIIb proceed by the addition-elimination mechanism.In the presence of the solvent lyate ions the solvolyses go by the E1cb mechanism.The solvolyses of the conjugated bases ofcompounds IIIa and IIIb are subject to general acid catalysis, the effects of the ring substituents being opposite to those in the addition-elimination mechanism.The solvolyses of compounds IIId and IIIf exhibit a distinct catalytic effect of neighbouring group; the reaction goes via a reactive intermediate, the transformation of the intermediate into the solvolysis product being subject to general acid and base catalysis.