- Kinetic model for reactivity in quaternary water-in-oil microemulsions
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A study was carried out on the nitrosation of piperazine (PIP) and N-methylbenzylamine (MeBzAm) by N-methyl-N-nitroso-p-toluenesulfonamide (MNTS) in quaternary microemulsions of tetradecyltrimethylammonium bromide (TTABr)/isooctane/alcohol/water, varying the nature and the concentration of the following alcohols: 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol and 1-decanol keeping the [1-alcohol]/[TTABr] = 4 relationship constant. In addition a study was carried out on the influence of the alcohol concentration, working with molar relationships [1-hexanol]/[TTABr] = 3, 4 and 5. On the basis of the molar volumes of the alcohol and surfactant and the concentration of alcohol at the interface it was possible to calculate the change in its volume with as varying compositions of the microemulsion. In order to interpret the experimental results a kinetic model was devised which takes into account the distribution of the reactants between the different pseudophases and the change in the volume of the interface. The rate constants at the interface of the microemulsion are lower than in pure water and are independent of the nature of the alcohol used as a cosurfactant and the molar relationship [alcohol]/[TTABr]. This independence indicates that the main role of the cosurfactant is to increase the volume of the interface with the consequent dilution of the reactants.
- Garcia-Rio, Luis,Hervella, Pablo
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Read Online
- Facile N-nitrosation of secondary amines using poly(N,N'-dibromo-Nethylene- benzene-1,3-disulfonamide) and N,N,N′,N′-tetrabromobenzene-1,3- disulfonamide/NaNO2 under mild conditions
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In this research project, a combination of poly(N,N′-dibromo-N- ethylene-benzene-1,3-disulfonamide) [PBBS] and/or (N,N,N′,N′- tetrabromobenzene-1,3-disulfonamide) [TBBDA] with sodium nitrite in the presence of wet SiO2 (50% w/w) was used as an efficient nitrosating agent for the conversion of secondary amines to their corresponding nitroso compounds. N-Nitrosation reaction has been performed in dichloromethane at room temperature under mild and heterogeneous conditions. The reaction is operationally simple and corresponding products were achieved in good to excellent yields.
- Ghorbani-Vaghei, Ramin,Shiri, Lotfi,Ghorbani-Choghamarani, Arash
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Read Online
- Electrochemical Nonacidic N-Nitrosation/N-Nitration of Secondary Amines through a Biradical Coupling Reaction
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An acid-free N-nitrosation/nitration of the N?H bonds in secondary amines with Fe(NO3)3 ? 9H2O as the nitroso/nitro source through an electrocatalyzed radical coupling reaction was developed. Cyclic aliphatic amines and N-heteroaromatic compounds were N-nitrosated and N-nitrated, respectively, under mild conditions. Control and competition experiments, as well as kinetic studies, demonstrate that N-nitrosation and N-nitration involve two different radical reaction pathways involving N+ and N. radicals. Moreover, the electrocatalysis method enables the preferential activation of the N?H bond over the electrode and thus provides high selectivity for specific N atoms. Finally, this strategy exhibits a broad scope and provides a green and straightforward approach to generate useful N-nitroso/nitro compounds in good yields. (Figure presented.).
- Zhao, Ji-Ping,Ding, Lu-jia,Wang, Peng-Cheng,Liu, Ying,Huang, Min-Jun,Zhou, Xin-Li,Lu, Ming
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supporting information
p. 5036 - 5043
(2020/07/13)
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- Deuterated diphenylaminopyrimidine compound
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The invention belongs to the field of medicine, and relates to a deuterated diphenylaminopyrimidine compound or a pharmaceutically acceptable salt thereof, and more particularly to a compound of the formula (I) or a pharmaceutically acceptable salt thereof, a preparation process thereof, a pharmaceutical composition thereof and application thereof in the treatment of a cell proliferative disease.
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Paragraph 0109; 0110; 0111; 0112; 0113; 0114
(2017/05/10)
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- Deuterium-modified Abemaciclib derivative
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The invention belongs to the field of medicinal chemistry and specifically relates to a deuterium-modified Abemaciclib derivative, a preparation method of the derivative, a pharmaceutical composition containing the deuterium-modified Abemaciclib derivative, and application of the deuterium-modified Abemaciclib derivative and the pharmaceutical composition in the preparation of a medicine for treating cell proliferative diseases. In comparison with Abemaciclib, some compounds of the invention (especially compounds in the embodiment) have more excellent pharmacokinetic properties. It is expected that clinical dosage will be reduced. Thus, treatment cost is reduced so as to benefit more patients.
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Paragraph 0218; 0219; 0220; 0221; 0222; 0223
(2017/08/02)
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- N-nitrosation of secondary amines using supported perchloric acid on silica gel and stereoselectivity study of nitrosated products
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N-Nitrosation of different types of secondary amines has been proceeded using supported perchloric acid on silica gel and sodiume nitrite under heterogeneous conditions. The operational system is simple and high pure products can be easily isolated with good to high yields.
- Goudarziafshar, Hamid,Ghorbani-Choghamarani, Arash,Hadian, Laila
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p. 1272 - 1276
(2014/04/03)
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- N-nitrosation of secondary amines using p-TSA-NaNO2 as a novel nitrosating agent under mild conditions
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A combination of p-toluenesulfonic acid (p-TSA) and sodium nitrite was used as a novel effective nitrosating agent for the N-nitrosation of secondary amines to their corresponding nitroso derivatives under mild and heterogeneous conditions in moderate to excellent yields.
- Borikar, Sanjay P.,Paul, Vincent
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experimental part
p. 654 - 660
(2011/02/27)
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- Ph3P/Br2/n-Bu4NNO2 as an efficient system for the preparation of N-nitrosamines and azides
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The combination PPh3/Br2/n-Bu4NNO2 was developed as a new reagent system for the efficient preparation of N-nitrosamines and azides from the corresponding amines and hydrazine derivatives, respectively, at 0 °C to room temperature, in excellent yields.
- Iranpoor, Nasser,Firouzabadi, Habib,Nowrouzi, Najmeh
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p. 4242 - 4244
(2008/09/20)
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- Efficient procedure for chemoselective N-nitrosation of secondary amines with trichloromelamine-NaNO2
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A combination of trichloromelamine and sodium nitrite in the presence of wet silica gel was used as an effective nitrosating agent for the transformation of secondary amines into the corresponding N-nitroso derivatives under mild and heterogeneous conditions in good to excellent yields.
- Bamoniri,Zolfigol,Mirjalili,Fallah
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p. 1393 - 1396
(2008/03/27)
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- Molybdate sulfuric acid/NaNO2: A novel heterogeneous system for the N-nitrosation of secondary amines under mild conditions
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Wet molybdate sulfuric acid (=dioxo[bis(sulfato-κO)]molybdenum; MSA), a new solid acid, can be used in combination with sodium nitrite (NaNO 2) to transform a variety of secondary amines to the corresponding N-nitroso compounds under mild, heterogeneous conditions (Table). The process has several advantages: the reagents are inexpensive and non-hazardous, the reaction is clean, fast, and high-yielding, and MSA can be readily removed by filtration and re-used (after treatment with HCl) without loss of activity. Further, only N-nitrosation was observed, but no C- or O-nitrosation.
- Montazerozohori, Morteza,Karami, Bahador
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p. 2922 - 2926
(2007/10/03)
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- Alumina-methanesulfonic acid (AMA)/NaNO2 as an efficient procedure for the chemoselectivite N-nitrosation of secondary amines
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A combination of alumina/methanesulfonic acid (AMA) and sodium nitrite was used as an effective nitrosating agent for the nitrosation of secondary amines under mild and heterogeneous conditions in good to excellent yields. Copyright Taylor & Francis Group, LLC.
- Niknam, Khodabakhsh,Zolfigol, Mohammad Ali
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p. 2311 - 2319
(2007/10/03)
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- Dinitrogen tetroxide-impregnated charcoal (N2O 4/charcoal): Selective nitrosation of amines, amides, ureas, and thiols
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Efficient N-nitrosation of amines, amides, and ureas, and also S-nitrosation of thiols were performed with dinitrogen tetroxide impregnated on activated charcoal (N2O4/charcoal) in CH 2Cl2 at room temperature. High selectivity was observed for N-nitrosation of dialkyl amines, N-alkylamides and N-alkylureas. Dealkylation and N-nitrosation of trialkylamines were also performed by this reagent. Copyright Taylor & Francis, Inc.
- Iranpoor, Nasser,Firouzabadi, Habib,Pourali, Ali Reza
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p. 1517 - 1526
(2007/10/03)
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- Selective N-nitrosation of amines, N-alkylamides and N-alkylureas by N2O4 supported on cross-linked polyvinylpyrrolidone (PVP-N2O4)
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N2O4 was supported on the cross-linked polyvinylpyrrolidone (PVP) to afford a solid, stable and recyclable nitrosating agent. This reagent shows excellent selectivity for N-nitrosation of dialkyl amines in the presence of diaryl-, arylalkyl-, trialkylamines and also for secondary amides in dichloromethane at room temperature under mild and heterogeneous conditions. Also N-nitroso-N-alkyl amides can be selectively prepared in the presence of primary amides and N-phenylamides under similar reaction conditions. Selective N-nitrosation or dealkylation and N-nitrosation of tertiary amines can also be performed by this reagent.
- Iranpoor, Nasser,Firouzabadi, Habib,Pourali, Ali-Reza
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p. 1591 - 1597
(2007/10/03)
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- The use of Nafion-H/NaNO2 as an efficient procedure for the chemoselective N-nitrosation of secondary amines under mild and heterogeneous conditions
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A combination of Nafion-H and sodium nitrite in the presence of wet SiO2 was used as an effective agent for the N-nitrosation of secondary amines under mild and heterogeneous conditions in good to excellent yields.
- Zolfigol, Mohammad Ali,Habibi, Davood,Mirjalili, BiBi Fatemeh,Bamoniri, Abdolhamid
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p. 3345 - 3349
(2007/10/03)
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- Silica sulfuric acid/NaNO2 as a novel heterogeneous system for the chemoselective N-nitrosation of secondary amines under mild conditions
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Neat chlorosulfonic acid reacts with silica gel to give silica sulfuric acid in which sulfuric acid is immobilized on the surface of silica gel via a covalent bond. A combination of silica sulfuric acid and sodium nitrite in the presence of wet SiO2 was used as an effective nitrosating agent for the nitrosation of secondary amines to their corresponding nitroso derivatives under mild and heterogeneous conditions in excellent yields.
- Zolfigol, Mohammad Ali,Bamoniri, Abdolhamid
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p. 1621 - 1624
(2007/10/03)
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- Trichloroisocyanuric acid/NaNo2 as a novel heterogeneous system for the N-nitrosation of N,N-dialkylamines under mild conditions
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A combination of trichloroisocyanuric acid and sodium nitrite in the presence of wet SiO2 was used as an effective nitrosating agent for the nitrosation of N,N-dialkyl amines to their corresponding nitroso derivatives under mild and heterogeneous conditions in moderate to excellent yields.
- Zolfigol, Mohammad Ali,Choghamarani, Arash Ghorbani,Hazarkhani, Hassan
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p. 1002 - 1004
(2007/10/03)
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- A comparison of the thermal decomposition of nitramines and difluoramines
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The decomposition rates and product distributions of a number of nitro- and difluoramino-substituted six-membered rings were compared: nitrocyclohexane (I); 1,1-dinitro-cyclohexane (II); 1,1,4,4-tetranitrocyclohexane (III), 1,1,4,4-tetrakis(difluoramino)cyclohexane (IV); 1,4-dinitropiperazine (V); 1,4,4-trinitropiperidine (VI), and 4,4-bis(difluoramino)-1-nitropiperidine (VII). The study suggested the following order for susceptibility to decomposition: N-NO2 > C-(NO2)2 > C-(NF2)2 The difference in bond energies among the compounds is small. Geminal bis(difluoramino) compounds appeared to be somewhat more stable than the corresponding gem-dinitro compounds though they released more heat during decomposition. Where a nitramine functionality was present, the nitroso analogue was observed as a major decomposition product. The decomposition of gem-bis(difluoramino) and gem-dinitro compounds exhibited similarities. Both experienced loss of one geminal NX2 group followed by the rearrangement of the remaining NX2. Where X was oxygen, loss of the initial nitro by homolysis was favored; rearrangement of the remaining nitro followed by homolysis of NO resulted in a C=O bond. Where X was fluorine, the initial difluoramino may have been lost as HNF2. The remaining difluoramino reacted by losing fluorine, leaving C=NF or by losing HNF, resulting in =C-F; the latter was mainly observed.
- Oxley,Smith,Zhang,Bedford
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p. 579 - 590
(2007/10/03)
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- Reactivity of nitrogen nucleophiles towards S-nitrosopenicillamine
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We report the results of a kinetic study of the reactions of a number of nitrogen nucleophiles with the nitrosothiol S-nitrosopenicillamine (SPEN). The range of nucleophiles includes primary, secondary and tertiary aliphatic amines, together with hydrazine, hydroxylamine, azide ion, ammonia, semicarbazide, thiomorpholine and S-methylcysteine. Secondary amines form N-nitrosamines quantitatively. As expected, reaction occurs via the free base forms of the nucleophiles and consequently most of the reactions take place readily only at relatively high pH. Experiments were carried out with [nucleophile] ? [RSNO], and for many reactions, plots of the first order rate constant vs. [nucleophile] were linear. For ammonia and the primary amines, however, this plot tended to level off at high [nucleophile] and an explanation is offered involving the reversible formation of an inactive RSNO-amine complex, for which there is spectral evidence, in parallel with the main reaction. For the secondary amines there is a reasonably good Broensted plot with a β value of ~0.2. The much greater reactivities of S-methylcysteine and thiomorpholine, compared to those of primary amines and morpholine respectively are consistent with initial attack at the sulfur atom, followed by an internal rearrangement. Over the whole range of nucleophiles studied there is a reasonable correlation with the Ritchie N+ parameter, and not with the Pearson n scale. Comparisons are made with the corresponding reactions of alkyl nitrites and N-methyl-N-nitrosotoluene-p-sulfonamide (MNTS).
- Munro, Andrew P.,Williams, D. Lyn H.
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p. 1989 - 1993
(2007/10/03)
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- Mechanisms of Nitramine Thermolysis
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The thermal decomposition of a number of nitramines was studied in dilute solution and in the melt.The nitramines included acyclic mononitramines , cyclic mononitramines , cyclic dinitramines , and 1,3,5-trinitro-1,3,5-triazocyclohexane (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), hexanitrohexaazaisowurtzitane (HNIW), and 1,3,3-trinitroazetidine (TNAZ).For the acyclic and cyclic mono- and dinitramines, the corresponding nitrosamines were the only or major condensed-phase product.Kinetics and activation parameters were determined for the thermolysis of dilute solutions (0.01-1.0 wtpercent) over the range 200-300 deg C.The thermolyses were found to be first-order with the rate constants unaffected by the use of deuterated solvent.As the nitramines became more complex than dimethylnitramine (DMN), the rate of decomposition increased and the product distribution became more complex.As the length of the aliphatic chain increased (DMN DEN DPN), the rate of thermolysis increased, yet nitrosamine remained the only observed condensed-phase product.When a secondary carbon was attached to the N-nitramine (DIPN) rather than the primary (DPN), the rate of decomposition increased and a new condensed-phase product was observed.Among the cyclic nitramines, the rate of decomposition increased as the number of NNO2 groups increased (NPIP pDNP; NPyr DNI; mDMP RDX).The position of the nitramine groups affected the decomposition: meta NNO2 groups (mDNP) decomposed faster than para (pDNP).Ring strain decreased stability: mDNP DNI; HMX RDX.In complex nitramines, the increase in decomposition rate, the appearance of new products, and the change in the relative importance of nitrosamine and of N2 and N2O are attributed to new decomposition routes available to them.However, since complex nitramines (e.g.RDX) maintain first-order kinetics and since most have activation energies in the range of 40-50 kcal/mol, it is belived that the triggering mechanism remains N-NO2 homolysis.Intramolecular hydrogen transfer is also considered an important mode of nitramine decomposition.
- Oxley, J. C.,Kooh, A. B.,Szekeres, R.,Zheng, W.
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p. 7004 - 7008
(2007/10/02)
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- N-NITROSATION OF SECONDARY AMINES EFFECTED BY ELECTROCHEMICAL OXIDATION OF NITRITE ION IN WEAKLY BASIC MEDIA
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Constant current electrolysis of sodium nitrite in aqueous acetonitrile containing secondary amines at ambient temperature resulted in the formation of the corresponding N-nitrosamines in good yields.KEYWORDS - N-nirosation; secondary amine; sodium nitrite; electrochemical oxidation; constant current electrolysis
- Masui, Masaichiro,Yamawaki, Norihiko,Ohmori, Hidenobu
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p. 459 - 461
(2007/10/02)
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- Nitrolysis of Tertiary Amines: Piperidines, Piperazines, Bisdimethylaminoalkanes, and Functionalized Methyldialkylamines
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Preparative amounts of mono- and di-nitrosamines were obtained from aliphatic cyclic and acyclic tertiary monamines and diamines by treatment with dinitrogen tetraoxide in carbon tetrachloride at 0 - 45 deg C.N-Methyl- and N-ethyl-piperidines (1) and (2) gave N-nitrosopiperidine (15), but N-isopropyl- and N-t-butyl-piperidines (3) and (4) did not.N-Methyl-, N-ethyl-, N-isopropyl- and N-t-butyl-N'-methylpiperazines (5) - (8) gave N,N'-dinitrosopiperazine (22) (in 90 percent, 81 percent, 55 percent, and 8 percent yields, respectively) and the diamine (8) also gave N-t-butyl-N'-dinitrosopiperazine (23) (45 percent).The N'-nitroso and the N'-nitro derivatives of N-methylpiperazine were similarly converted into N,N'-dinitroso- and N-nitroso-N'-nitropiperazines (22) (45 percent) and (30) (53 percent).Bisdimethylaminoalkanes (Me2N)2(CH2)n (10) - (14) gave bismethylnitrosaminoalkanes 2(CH2)n (24) - (27) and dimethylnitrosamine (28): n=1 (0 percent, 90 percent); n=2 (68 percent, 0 percent); n=3 (48 percent, 43 percent); n=4 (41 percent, 38 percent); n=6 (58 percent, 35 percent). β-Dimethylaminopropionitrile (18), 1-methylnitrosamino-2-dimethylaminoethane (17), and α-dimethylaminoacetic acid (19) gave the corresponding nitrosoamines by replacement of an N-methyl group.
- Boyer, Joseph H.,Kumar, Govindarajulu,Pillai, T. Perumal
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p. 1751 - 1754
(2007/10/02)
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- Nitrosamines from Tertiary Amines and Dinitrogen Tetraoxide
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A preparative nitrosolysis of aliphatic acyclic and cyclic tertiary monoamines to nitrosoamines was brought about by treatment with dinitrogen tetraoxide in carbon tetrachloride at 0-40 deg C.Dealkylation was restricted, where applicable, to demethylation.Competitive oxidation to an amide was observed in the formation of dibutylformamide from tributylamine.Diamine dinitrate salts, without nitrosamine formation, were obtained from 1,4-dimethylpiperazine and 1,4-diazabicyclo-octane; however, each dinitrate salt thermolysed at 180-200 deg C to give a small amount of 1,4-dinitrosopiperazine.In acetic anhydride dinitrogen tetraoxide converted amines less efficiently, gave lower yield of nitrosoamines, was less selective in dealkylation, and introduced the formation of by-products.
- Boyer, Joseph H.,Pillai, T. Perumal
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p. 1661 - 1664
(2007/10/02)
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