- Synthetic method for drug intermediate nicotinamide-N-oxide
-
The invention discloses a synthetic method for the drug intermediate nicotinamide-N-oxide. The synthetic method comprises the following steps: adding 3-methylpyridine and a potassium chloride solutioninto a reaction vessel, controlling a stirring speed to be 150-180 rpm, controlling a solution temperature to be 40-45 DEG C, adding a diethyl fumarate solution and a 1,3-propanediamine solution, adding N-chloroacetamide in batches within 30-50 min, and continuing a reaction for 80-100 min; and adding manganese chloride powder, controlling the stirring speed to be 230-250 rpm, continuing the reaction for 3-5 h, adding a sodium sulfate solution, subjecting the obtained solution to layering, separating an oil layer, washing the oil layer with a potassium bromide solution for 30-50 min, then washing the oil layer with a chloroprene solution for 20-40 min, carrying out recrystallization in a glycol monomethyl ether solution and then carrying out dehydration with a dehydrating agent so as to obtain the finished nicotinamide-N-oxide.
- -
-
Paragraph 0014; 0017-0028
(2018/07/30)
-
- Catalyst-free and selective oxidation of pyridine derivatives and tertiary amines to corresponding N-oxides with 1,2-diphenyl-1,1,2,2-tetrahydroperoxyethane
-
The catalyst-free oxidation of various pyridine derivatives and tertiary amines to their corresponding N-oxides with 1,1,2,2-tetrahydroperoxy-1,2-diphenylethane as an efficient oxidant has been developed. The methodology proved to tolerate a number of functional groups. The reactions proceeded smoothly under solvent-free and mild conditions at room temperature. All the products were easily extracted from the reaction mixtures in excellent yields. Graphical abstract: The catalyst-free oxidation of various pyridine derivatives and tertiary amines to their corresponding N-oxides with 1,1,2,2-tetrahydroperoxy-1,2-diphenylethane as an efficient oxidant has been developed. The methodology proved to tolerate a number of functional groups. The reactions proceeded smoothly under solvent-free and mild conditions at room temperature. All the products were easily extracted from the reaction mixtures in excellent yields.
- Azarifar, Davood,Mahmoudi, Boshra
-
p. 645 - 651
(2016/02/19)
-
- Renewable waste rice husk grafted oxo-vanadium catalyst for oxidation of tertiary amines to N-oxides
-
Low cost renewable waste rice husks (RH) have been used as a support for grafting of an oxo-vanadium Schiff base via covalent attachment for the oxidation of tertiary amines to N-oxide. The synthesis of the desired RH grafted oxo-vanadium complex involves prior functionalization of the RH support with amino-propyltrimethoxysilane (APTMS) followed by its reaction with salicylaldehyde to get an RH-functionalized Schiff base which subsequently reacted with vanadyl sulphate to get the targeted oxo-vanadium catalyst. The synthesized catalyst was found to be an efficient heterogeneous catalyst and afforded an excellent yield of corresponding N-oxides via oxidation of tertiary amines with hydrogen peroxide as an oxidant. Furthermore, the synthesized catalyst was found to be quite stable and showed consistent activity for five runs without any loss in activity.
- Panwar, Vineeta,Bansal, Ankushi,Ray, Siddharth S.,Jain, Suman L.
-
p. 71550 - 71556
(2016/08/05)
-
- 2,2,2-Trifluoroacetophenone as an organocatalyst for the oxidation of tertiary amines and azines to N-oxides
-
A cheap, mild and environmentally friendly oxidation of tertiary amines and azines to the corresponding Noxides is reported by using polyfluoroalkyl ketones as efficient organocatalysts. 2,2,2-Trifluoroacetophenone was identified as the optimum catalyst for the oxidation of aliphatic tertiary amines and azines. This oxidation is chemoselective and proceeds in high-to-quantitative yields utilizing 10 mol% of the catalyst and H2O2 as the oxidant.
- Limnios, Dimitris,Kokotos, Christoforos G.
-
supporting information
p. 559 - 563
(2014/04/03)
-
- Trichloroacetonitrile-hydrogen peroxide: A simple and efficient system for the selective oxidation of tertiary and secondary amines
-
A variety of tertiary and secondary amines were efficiently oxidized to their corresponding N-oxides and nitrones, respectively, using the trichloroacetonitrile-hydrogen peroxide system. The in situ generated trichloromethylperoxyimidic acid is the active reagent for the oxidation processes.
- Nikbakht, Fatemeh,Heydari, Akbar
-
p. 2513 - 2516
(2014/05/06)
-
- A chemoselective deoxygenation of N-oxides by sodium borohydride-Raney nickel in water
-
A simple and convenient protocol for deoxygenation of aliphatic and aromatic N-oxides to the corresponding amines in good to excellent yield using sodium borohydride-Raney nickel in water is reported. Other functional moieties such as alkenes, halides, ethers, and amides are unaffected under the present reaction condition.
- Gowda, Narendra B.,Rao, Gopal Krishna,Ramakrishna, Ramesha A.
-
supporting information; experimental part
p. 5690 - 5693
(2010/11/05)
-
- Comparative rate study on the oxidation of nicotinamide and isonicotinamide by permanganate in acidic medium
-
A comparative rate study on the oxidation of nicotinamide and isonicotinamide by potassium permanganate has been carried out in acidic solutions over an extended [H+]·range (1 × 10 -5-1.0 mol L-1). Under the similar reaction conditions, the oxidation of pyridine is imperceptible. Further, In the absence of acid none of the two amides is oxidised and in both cases, the N-protonated amide species appears to be reactive. For nicotinamide, the results are in agreement with the two-term rate law (A). The oxidation product was corresponding N oxide. -d[MnO4 -Ydt = (k0K + k1KK 1 [H+]) [S]0, [MnO4 -]t [H+Y(1 + K [H+)]) (A) On the other hand, the oxidation of isonicotinamide follows a simpler rate law (B). -d[MnO4-Ydt = k0K [S]0 [MnO 4-]1 [H+Y(1 + K. [H+]) (B) The values of k0, K. and k1K1 for nicotinamide were round to be 5.5 × 10-3 L. mol-1 s-1, 1.8 × 104 and 1.0 × 10-2 L. mol-1 s-1, respectively at 35 °C. And for isonicotinamide, the k0, and K. values were 4.4 × 10 -3 L. mol-1 s-1 and 5.6 × 103 respectively at 35 °C. The oxidation of nicotinamide is faster than the oxidation of isonicotinamide. It appears that the presence of -CONH2 group at position 3 activates the ring nitrogen more for oxidation than the presence of this group at position 4.
- Sharma, Ashok,Mudgal, Punit K.,Gupta
-
experimental part
p. 920 - 925
(2009/12/03)
-
- Rhenium-catalyzed highly efficient oxidations of tertiary nitrogen compounds to N-oxides using sodium percarbonate as oxygen source
-
Sodium percarbonate was found to be an ideal and efficient oxygen source for the oxidation of tertiary nitrogen compounds to N-oxides in excellent yields in presence of various rhenium-based catalysts under mild reaction conditions. Georg Thieme Verlag Stuttgart.
- Jain, Suman L.,Joseph, Jomy K.,Sain, Bir
-
p. 2661 - 2663
(2008/09/16)
-
- Silica-supported vanadium-catalyzed N-oxidation of tertiary amines with aqueous hydrogen peroxide
-
A recyclable silica supported vanadium 1 catalyzes the oxidation of tertiray amines to the corresponding N-oxides with 30% H2O 2 in high yield.
- Rout, Laxmidhar,Punniyamurthy, Tharmalingam
-
p. 1958 - 1960
(2007/10/03)
-
- Bromamine-T/RuCl3 as an efficient system for the oxidation of tertiary amines to N-oxides
-
A variety of tertiary amines were efficiently and selectively oxidized to the corresponding N-oxides by bromamine-T using ruthenium trichloride as catalyst in alkaline (pH8.4) acetonitrile/water (1:1) at 80°C.
- Sharma, Vishal B.,Jain, Suman L.,Sain, Bir
-
p. 4281 - 4283
(2007/10/03)
-
- An unconventional cobalt-catalyzed aerobic oxidation of tertiary nitrogen compounds to N-oxides
-
A simple system, simple workup, and excellent yields make the new method for the oxidation of tertiary nitrogen compounds described in Equation (1) an attractive, environmentally acceptable synthetic tool. Molecular oxygen serves as the oxygen source and no sacrificial agents are required.
- Jain, Suman L.,Sain, Bir
-
p. 1265 - 1267
(2007/10/03)
-
- Ring cleavage of N-arylpyridinium salts by nucleophiles - Regioselectivity and stereochemistry of the products - Part 2
-
The reaction of quaternary 3-pyridinecarboxamide compounds 2, 7 and 14 with alkali does not - contrary to literature result in regiospecific ring opening, but yields mixtures of position isomer penta-2,4-dienal derivatives. With increasing steric hindrance by the 3-substituent, the hydroxide ion prefers the attack at 6-position. Usually products with all trans configuration are obtained. Only the 2-substituted aldehydes from 2 and 14 additionally occur in the 2,3-cis configuration as 5b and 2lb, explainable by a hydrogen bond between the formyl and carbamoyl group. Surprisingly the "ring opened" 5-aminopenta-2,4-dienals 5 and 6 resp. 21 and 22 in acetone solution show an equilibrium of the positional isomers in each case, which must be generated by recyclization via the intermediates 24 resp. 25. With hydroxylamine 2, 7 and 14 only react to the 4-substituted pentadienal derivatives, which represent E,Z oxime mixtures. This is proved by dehydration to uniform nitriles and the synthesis from the corresponding aldehydes by oximation.
- Moehrle,Niessen
-
p. 448 - 457
(2007/10/03)
-
- Reaction of N-alkylpyridinium salts with hydroxylamine
-
1-Methylpyridinium salts showed no reaction with excessive hydroxylamine, but nicotinic acid derivatives in HMPT gave the corresponding N-oxides. 3-Acetyl-1-methylpyridinium iodide generated the hydroximino-pyridine 1-oxide 13 and the isoxazoles 14, 15E,
- M?hrle, Hans,Nie?en, Robert
-
p. 434 - 442
(2007/10/03)
-
- A simple and efficient method for the preparation of N- heteroaromatic N-oxides
-
Urea-hydrogen peroxide/formic acid system has shown utility for mild and safe N-oxidation of N-heteroaromatic compounds.
- Balicki, Roman,Golinski, Jerzy
-
p. 1529 - 1534
(2007/10/03)
-
- A comparison of methods for N-oxidation of some 3-substituted pyridines
-
The results from the N-oxidation of four 3-substituted pyridines using five different reagents are reported. The best yields are obtained with m-chloroperoxybenzoic acid.
- Bremner, David H.,Sturrock, Keith R.,Wishart, Grant,Mitchell, Stewart R.,Nicoll, Stuart M.,Jones, Gareth
-
p. 1535 - 1542
(2007/10/03)
-
- An Excellent Method for the Mild and Safe Oxidation of N-Heteroaromatic Compounds and Tertiary Amines
-
Selective, mild and safe N-oxidation of N-heteroaromatic compounds and tertiary amines affording high product yields was achieved by using the H2O2-urea/phthalic anhydride system. Key Words: N-Oxidation / Hydrogen peroxide / Urea / Phthalic anhydride
- Kaczmarek, Lukasz,Balicki, Roman,Nantka-Namirski, Pawel
-
p. 1965 - 1966
(2007/10/02)
-
- KINETICS OF THE N OXIDATION OF SOME COMPOUNDS OF THE PYRIDINE SERIES WITH PERBENZOIC ACID IN CHLOROFORM AND AQUEOUS DIOXANE
-
A comparative study of the kinetics of the N oxidation of 19 derivatives of the pyridine series with perbenzoic acid in choroform and aqueous dioxane at 20, 25, 30, and 35 deg C was made.The rate constants, the parameters of the Arrhenius equation, and the activation energies of the N oxidation of the indicated monoazines were determined.The scale of the reactivities of the derivatives of the pyridine series was calculated within the framework of the Pearson hard-soft acid-base concept.
- Lohkov, R.E.
-
p. 264 - 271
(2007/10/02)
-
