16641-71-7

Usage

InChI:InChI=1/C12H15NO2/c14-12(13-9-5-2-6-10-13)15-11-7-3-1-4-8-11/h1,3-4,7-8H,2,5-6,9-10H2

Upstream product

• 110-89-4 piperidine 
• 102-09-0 bis(phenyl) carbonate 
• 157892-15-4 dichloromethyl phenyl carbonate 
• 1885-14-9 phenyl chloroformate 
• 501411-82-1 1-(2-methoxy-benzenesulfonyl)-piperidine 
• 10130-87-7 o-Methoxybenzenesulfonyl chloride 
• 108-95-2 phenol 
• 124-38-9 carbon dioxide 
• 98-80-6 phenylboronic acid 
• 128337-08-6 phenyl-(2-pyridyl)carbonate 
• 17175-11-0 phenyl O‐(4‐nitrophenyl) carbonate 
• 1268380-12-6 C₁₅H₁₂O₄ 
• 1268380-10-4 C₁₄H₁₀O₄ 
• 1268380-09-1 phenyl 4-ethoxycarbonyl phenyl 

Downstream Products

• 2890-83-7 (2-hydroxyphenyl)(piperidin-1-yl)methanone 
• 1092074-87-7 C₁₂H₁₂N₂O₃ 
• 1092074-41-3 4-(N-(phenoxycarbonyl)formamido)butanoic acid 
• 164732-66-5 3,4-dihydro-2H-pyridine-1-carboxylic acid phenyl ester 
• 98-67-9 p-hydoroxybenzenesulfonic acid 
• 72962-46-0 piperidinium hydrogen sulfate 

Relevant academic research and scientific papers

Kinetics and mechanism of the aminolysis of phenyl and 4-nitrophenyl chloroformates in aqueous solution

The reactions of secondary alicyclic amines with phenyl and 4- nitrophenyl chloroformates (PClF and NPClF, respectively) are subjected to a kinetic investigation in aqueous solution, 25.0 °C, ionic strength 0.2 (KCl). The reactions are followed spectropho

A copper-catalyzed oxidative coupling reaction of arylboronic acids, amines and carbon dioxide using molecular oxygen as the oxidant

A Cu-catalyzed oxidative coupling reaction of arylboronic acids, amines and carbon dioxide is described for the first time in this paper. The reaction tolerates a wide range of functional groups, providing a convenient protocol for the synthesis of various O-aryl carbamates. The successful development of the transformation was enabled by the use of BF3·OEt2 as the promoter and molecular oxygen as the oxidant. Mechanistic studies suggested that the CuII carbamato complex is involved in the catalytic transformation.

A facile synthesis of sulfonylureas: Via water assisted preparation of carbamates

A novel and simple approach to the synthesis of sulfonylureas has been reported. It involved the reaction of various amines with diphenyl carbonate to yield the corresponding carbamates, which subsequently reacted with different sulphonamides to produce different sulfonylureas in excellent yields. The first reaction of diphenyl carbonate with amines was carried out in aqueous:organic (H2O:THF, 90:10) medium at room temperature to produce carbamates that paved a straightforward route to sulfonylureas after reaction with sulfonamides. The above process avoided traditional multistep protocols and the use of hazardous, irritant, toxic and moisture sensitive reagents such as phosgene, isocyanates and/or chloroformates.

Kinetic study on aminolysis of phenyl 2-pyridyl carbonate in acetonitrile: Effect of intramolecular h-bonding interaction on reactivity and reaction mechanism

Second-order rate constants (kN) have been measured spectrophotometrically for the reactions of phenyl 2- pyridyl carbonate (6) with a series of cyclic secondary amines in MeCN at 25.0 ± 0.1 °C. The Bronsted-type plot for the reaction of 6 is linear with βnuc = 0.54, which is typical for reactions reported previously to proceed through a concerted mechanism. Substrate 6 is over 103 times more reactive than 2-pyridyl benzoate (5), although the reactions of 6 and 5 proceed through the same mechanism. A combination of steric hindrance, inductive effect and resonance contribution is responsible for the kinetic results. The reactions of 6 and 5 proceed through a cyclic transition state (TS) in which H-bonding interactions increase the nucleofugality of the leaving group (i.e., 2-pyridiniumoxide). The enhanced nucleofugality forces the reactions of 6 and 5 to proceed through a concerted mechanism. In contrast, the corresponding reaction of 4-nitrophenyl 2-pyridyl carbonate (7) proceeds through a stepwise mechanism with quantitative liberation of 4-nitrophenoxide ion as the leaving group, indicating that replacement of the 4-nitrophenoxy group in 7 by the PhO group in 6 changes the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway) as well as the leaving group (i.e., from 4-nitrophenoxide to 2-pyridiniumoxide). The strong electron-withdrawing ability of the 4- nitrophenoxy group in 7 inhibits formation of a H-bonded cyclic TS. The presence or absence of a H-bonded cyclic TS governs the reaction mechanism (i.e., a concerted or stepwise mechanism) as well as the leaving group (i.e., 2-pyridiniumoxide or 4-nitrophenoxide).

Leaving-group substituent controls reactivity and reaction mechanism in aminolysis of phenyl y-substituted-phenyl carbonates

A kinetic study is reported for the nucleophilic substitution reactions of phenyl Y-substituted-phenyl carbonates (5a-5k) with piperidine in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 °C. The plots of k obsd vs. [piperidine] for the reactions of substrates possessing a strong electron-withdrawing group (EWG) in the leaving group (i.e., 5a-5i) are linear and pass through the origin. In contrast, the plots for the reactions of substrates bearing a weak EWG or no substituent (i.e., 5j or 5k) curve upward, indicating that the electronic nature of the substituent Y in the leaving group governs the reaction mechanism. Thus, it has been suggested that the reactions of 5a-5i proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate (i.e., T±) while those of 5j and 5k proceed through a stepwise mechanism with two intermediates (i.e., T± and its deprotonated form T-). The slope of the Bronsted-type plot for the second-order rate constants (i.e., kN or Kk2) changes from -0.41 to -1.89 as the leaving-group basicity increases, indicating that a change in the rate-determining step (RDS) occurs. The reactions of 5a-5k with piperidine result in larger k1 values than the corresponding reactions with ethylamine. Copyright

Phenyl 4,5-dichloro-6-oxopyridazine-1(6H)-carboxylate as carbonyl source: Facile and selective synthesis of carbamates and ureas under mild conditions

The selective syntheses of carbamates, symmetric -ureas, and unsymmetrical ureas have been accomplished by the -reaction of amines with phenyl 4,5-dichloro-6-oxopyridazine-1(6H)-carboxylate as a carbonyl source under mild conditions. It is noteworthy that this process is mild, economic, and convenient.

Anionic ortho-fries rearrangement, a facile route to arenol-based mannich bases

Phenol and 1-naphthol-based carbamates undergo the anionic ortho-Fries rearrangement to their corresponding amides. Bulky substitution at position 8 of 1-naphthol-based carbamates makes the rearrangement an exclusive reaction, even at -90 C, under a variety of conditions. The amides can be efficiently reduced to the corresponding Mannich bases. A novel route to 7-[(dialkylamino)methyl]-8- hydroxy-1-naphthaldehydes is presented.

ortho-anisylsulfonyl as a protecting group for secondary amines: Mild Ni0-catalyzed hydrodesulfonylation

A potentially good alternative to the tosyl group (Ts) as a protecting group for amines is N-ortho-anisylsulfonyl (Ans), which is readily cleaved under mild, Ni0-catalyzed reductive conditions (see scheme, acac = acetylacetonate). N-Anisylation of primary amines followed by alkylation and deprotection provides a route to a range of secondary amines.

Practical Syntheses of N-Substituted 3-Hydroxyazetidines and 4-Hydroxypiperidines by Hydroxylation with Sphingomonas sp. HXN-200

(Equation Presented) Hydroxylation of N-substituted azetidines 11 and 12 and piperidines 15-19 with Sphingomonas sp. HXN-200 gave 91-98% of the corresponding 3-hydroxyazetidines 13 and 14 and 4-hydroxypiperidines 20-24, respectively, with high activity and excellent regioselectivity. High yields and high product concentrations (2 g/L) were achieved with frozen/thawed cells as biocatalyst. For the first time, rehydrated lyophilized cells were successfully used for the biohydroxylation.

Kinetics and mechanism of the aminolysis of methyl 4-nitrophenyl, methyl 2,4-dinitrophenyl, and phenyl 2,4-dinitrophenyl carbonates

The reactions of methyl 4-nitrophenyl carbonate (MNPC) with a series of secondary alicyclic amines (SAA) and quinuclidines (QUIN), methyl 2,4-dinitrophenyl carbonate (MDNPC) with QUIN and 1-(2-hydroxyethyl)piperazinium ion (HPA), and phenyl 2,4-dinitrophenyl carbonate (PDNPC) with SAA are subjected to a kinetic investigation in aqueous solution, at 25.0°C and an ionic strength of 0.2 M. By following spectrophotometrically the nucleofuge release (330-400 nm) under amine excess, pseudo-first-order rate coefficients (kobsd) are obtained. Plots of kobsd VS [amine] at constant pH are linear, with the slope (kN) being pH independent. The Broensted-type plot (log kN vs amine pKa) for the reactions of SAA with MNPC is biphasic with slopes β1 = 0.3 (high pKa region) and β2 = 1.0 (low pKa region) and a curvature center at pKa0 = 9.3. This plot is consistent with a stepwise mechanism through a zwitterionic tetrahedral intermediate (T±) and a change in the rate-determining step with SAA basicity. The Broensted plot for the quinuclidinolysis of MNPC is linear with slope βN = 0.86, in line with a stepwise process where breakdown of T± to products is rate limiting. A previous work on the reactions of SAA with MDNPC was revised by including the reaction of HPA. The Broensted plots for the reactions of QUIN and SAA with MDNPC and SAA with PDNPC are linear with slopes β = 0.51, 0.48, and 0.39, respectively, consistent with concerted mechanisms. Since quinuclidines are better leaving groups from T± than isobasic SAA, yielding a less stable T±, it seems doubtful that the quinuclidinolysis of PDNPC is stepwise, as reported.