cas 10599-90-3, Chloramide | Articles data

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Rate constants for quenching and self-annihilation of NCl(a1Δ)
Quenching and self-annihilation rate constants for NCl(a) have been determined using pulsed 248 nm photolysis of ClN3 to generate the metastable. Previous quenching measurements that employed different sources for NCl(a) yielded dramatically different rate constants. The present study provided quenching rate constants for Cl2, HCl, and H2 that are in good agreement with the discharge flow measurements of Hewett et al. (J. Phys. Chem. A 2000, 104, 539). Determination of the self-annihilation rate constant required knowledge of the branching fraction for NCl(a) formation for 248 nm photolysis of ClN3. This information was obtained from time-resolved measurements of NCl(X) formation and decay. A lower bound for the branching fraction of 0.7 was determined. Self-annihilation of NCl(a) was studied by using intense photolysis pulses to generate high concentrations of NCl(a). Analysis of the second-order decay component yielded a rate constant of (7.0 ± 1.5) × 10-13 cm3 s-1. This value is an order of magnitude smaller than the previous estimate (Henshaw et al. J. Phys. Chem. A 1997, 101, 4048).
Komissarov, Anatoly V.,Manke II, Gerald C.,Davis,Heaven, Michael C.
p. 8427 - 8434
(2002)
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Theoretical and experimental studies of the all gas-phase iodine laser
All gas-phase iodine laser (AGIL) powered by the decomposition of nitrogen trichloride (NCl3) is studied. This reaction scheme uses commonly available reagents and reaction paths are milder than the previously studied azide-based AGIL. Theoreti
Endo,Nakamura,Masuda,Uchiyama
p. 1452 - 1456
(2009)
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Kinetics and Mechanism of the Reaction of NFCl2 with Hydrogen Atoms
The reaction of gaseous NFCl2 with excess H atoms has been observed in a continuous flow reactor.The reaction produces excited singlet states (a1Δ, b1Σ+) of NF and NCl and is thougth to proceed by a two-step mechanism in which H atoms react with NFCl2 to produce primarily HCl and NFCl, followed by the H + NFCl reaction which proceeds to both HCl + NF and HF + NCl.The rate constant of the first step, H + NFCl2, is (2.6 +/- 0.2) * 10-12 cm3 s-1 at 298 K.The rate constant of the second step, H + NFCl, was too great to be accurately measured with our apparatus.Overall, the two-step process shows a roughly 10-fold preference for the production of NF(a1Δ) over NCl(a1Δ).The generation of both NF(a1Δ) and NCl(a1Δ) in this system results in energy pooling among these species which produces NF(b1Σ+).This process is significantly enhanced by the admission of HI to the reaction medium.
Exton, D. B.,Gilbert, J. V.,Coombe, R. D.
p. 7758 - 7762
(1991)
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Conjugate addition from the excited state
Conjugate addition occurs efficiently from excited hydrazide based acrylanilides under both UV and metal free visible light irradiations. The reaction proceeds via an excited state encounter complex that bifurcates either via an electron or energy transfer pathway. The generality of excited state conjugate addition is demonstrated using chloromethylation and by thiol addition.
Iyer, Akila,Ahuja, Sapna,Jockusch, Steffen,Ugrinov, Angel,Sivaguru, Jayaraman
p. 11021 - 11024
(2018)
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Photodissociation of chlorine isocyanate
Gaseous ClNCO exhibits a continuous ultraviolet absorption feature peaked near 250 nm.Photolysis of this compound at 249 nm produces bright blue emission identified as the A2Σ+ -> X2Π transition in NCO.The excited NCO arises from a collisional process in which N(2D) atoms, produced directly by the photodissociation, react with the parent ClNCO.The rate constant for this process is k = (2.1 +/- 0.2)*10-11 cm3 s-1. From production of N(2D) by the 249 nm photolysis, the heat of formation of gaseous ClNCO is inferred to be ΔHf(ClNCO) >= 52.9 kcal mol-1. ClNCO is metastable with respect to the ground electronic states of NCl and CO by 8.2 kcal mol-1.
Bell, D. D.,Coombe, R. D.
p. 1317 - 1322
(1985)
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Photodissociation dynamics of C1N3 at 203 nm: The NC1 (a1Δ/X3∑-) product branching ratio
Velocity map imaging was applied to study the photodissociation dynamics of ClN3 near 203 nm under collision free conditions. Images of state-selected N2(X1∑g+, v = 0. J = 68) characterize the interna
Hansen,Wodtke,Komissarov,Heaven
p. 568 - 573
(2003)
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Quenching Rate Constants for NCl(b1Σ+) and PCl(b1Σ+) and Radiative Lifetimes of NCl(b1Σ+), PCl(b1Σ+) and PBr(b1Σ+)
NCl(b1Σ+), PCl(b1Σ+) and PBr(b1Σ+) molecules have been generated in a flow reactor by passing dilute flows of NFCl2, PCl3 and PBr3 in He through a dc discharge, and the total rate constants for quenching of NCl(b1Σ+) and PCl(b1Σ+) by several diatomic and small polyatomic molecules have been measured at 300 K.Except for O2, NO2 and molecular halogenes, the rate constants are in the 1E-13 - 1E-14 cm3 molecule-1 s-1 range.The dependence of the rate constants on the properties of the reagent suggests that the dominant quenching mechanism for PCl(b) and NCl(b) is electronic-to-vibrational (E-V) energy transfer with the a1Δ state as the product, just as for the reactions of NF(b1Σ+) and PF(b1Σ+).The rate constants for quenching of NCl(b1Σ+) and PCl(b1Σ+) by O2 are 1.0E-12 and 3 molecule-1 s-1, respectively, and are in accord with an electronic-to-electronic (E-E) energy transfer with the final states being O2(b1Σ+) + NCl(X3Σ+) or PCl(X3Σ-).Formation of PBr(b1Σ+) from the PCl(b1Σ+) + Br2 reaction was observed, and quenching of PCl(b1Σ+) by F2, Cl2 and Br2 proceeds by a chemical mechanism with rate constants of 2.3E-12, 0.79E-12 and 16E-12 cm3 molecule-1 a-1, respectively.The radiative lifetimes for NCl(b1Σ+), PCl(b1Σ+) and PBr(b1Σ+) are 2.0 +/- 0.4, 4.9 +/- 0.8 and 0.8 +/- 0.2 ms, respectively, as determined from the decay of the respective b1Σ+ -> X1Σ- emission intensities along the flow reactor.
Zhao, Yao,Setser, D. W.
p. 2979 - 2988
(1995)
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Synthesis and antiproliferative assessments of new derivatives of isothiazolo[3,4-d]pyrimidine
Various derivatives of 5-aryl-4-imino-3-(phenylamino)-4,5-dihydroisothiazolo[3,4-d]pyrimidines (3a-f) were synthesized. The synthesis has been done through treatment of 3-amino-4-cyano-5-(phenylamino)isothiazole with various aryl isothiocyanates. The isothiazole skeleton was obtained by the reaction of malononitrile and phenyl isothiocyanate followed by chloramine treatment. Some of the synthesized dihydroisothiazolo[3,4-d]pyrimidines were tested against different cancer cell lines, including ACHN, HeLa, HL-60, MCF-7, and PC3. Malignant cells were cultured in RPMI medium and incubated with different concentrations of the mentioned compounds. Cell viability was assessed using the MTS assay. The cytotoxicities of the synthesized compounds are not significant and are probably safe for other biological use.
Khoshniazi, Hamideh,Eshghi, Hossein,Tayarani-Najjaran, Mona,Tayarani-Najaran, Zahra,Saadat, Kayvan,Shiri, Ali
p. 193 - 201
(2021)
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The Cl to NCl branching ratio in 248-nm photolysis of chlorine azide
The primary reaction products from 248-nm chlorine azide photolysis are identified in a collision-free experiment. In contrast to all previous reports, the radical channel producing Cl+N3 (95±3%) is seen to dominate the photochemistry. The molecular channel producing NCl+N2 (5±3%) was also observed.
Wodtke, Alec M.,Hansen, Nils,Robinson, Jason C.,Sveum, Niels E.,Goncher, Scott J.,Neumark, Daniel M.
p. 334 - 337
(2004)
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The microwave spectrum of the NCI radical in the electronically excited (a1Δ) state
The pure rotational spectrum of the 14N35Cl radical in the first electronically excited a 1Δ state was detected by microwave spectroscopy. The NCl radical was produced by a de-glow discharge of an N2 and Cl2 mixture between 175-210 K. Seven rotational transitions for ν=0 and five for ν=l, showing hyperfine structures due to the nitrogen and chlorine nuclei, were observed in the 162-404 GHz region. The rotational, centrifugal distortion, and hyperfine coupling constants including nuclear spin-rotation coupling constant of the chlorine nucleus were determined accurately by a least-squares analysis of the measured frequencies. The equilibrium structural parameters were derived and discussed.
Kobayashi, Kaori,Goto, Masahiro,Yamamoto, Satoshi,Saito, Shuji
p. 8865 - 8870
(1996)
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The measurement of gain on the 1.315 μm transition of atomic iodine in a subsonic flow of chemically generated NCl(a 1Δ )
Gain is measured on the electronic I(2P3/2)-I*(2P1/2) transition of atomic iodine at 1.315 μm when hydrazoic acid HN3 is injected into a flow of iodine and chlorine atoms. The inversion was generated in a transverse subsonic flow device that produced electronically excited I*(2P1/2) atoms from the efficient energy transfer reaction between NCl(a 1Δ) metastable and ground state I(2P3/2) atoms. The population inversion was directly observed using a 1.315 μm tunable diode laser that scanned the entire line shape of the (3,4) hyperfine transition of iodine.
Herbelin, John M.,Henshaw, Thomas L.,D. Rafferty, Brent,Anderson, Brian T.,Tate, Ralph F.,Madden, Timothy J.,Manke II, Gerald C.,Hager, Gordon D.
p. 583 - 588
(1999)
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Microwave spectrum of NCl in the second electronically excited state (b 1∑+)
The pure rotational transitions of N35Cl in the second electronically excited state, b 1∑+, were detected together with those of the isotopic species N37Cl by microwave spectroscopy. The NCl radical in the b 1∑+ state was generated by de-glow discharge of a N2/Cl2 mixture. The rotational constant, centrifugal distortion constant, and quadrupole coupling constants of the Cl nucleus were determined. The observation of rotational transitions in the vibrationally excited v = 1 state made it possible to derive equilibrium structural parameters. A discussion on the internuclear potential of the three low-lying electronic states of NCl is given.
Kobayashi, Kaori,Saito, Shuji
p. 1068 - 1071
(1997)
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Production of NCl(a) by Thermal Decomposition of ClN3
Thermal decomposition of ClN3 by pulsed CO2 laser pyrolysis has been investigated by using SF6 as a sensitizer.The electronically excited decomposition products, NCl(a) and NCl(b), were monitored by absolute time-resolved emission spectroscopy while ClN3 was followed by ultraviolet absorption.The results indicate a higher barrier to dissociation of ClN3 than FN3, consistent with ab initio calculations, and an NCl(a) yield of order unity, based on a nominal 0.7/s radiative rate for the NCl(a-X) transition.Studies of simultaneous dissociation of FN3 and ClN3 have also revealed that NCl(a), when coproduced with NF(a), upconverts the latter species to NF(b) efficiently (in the presence pf trace I2) and cooperatively pumps the IF(B) state (upon addition of CF3I) by an energy pooling mechanism that does not involve NF(b) as an intermediate.These results indicate a potential for development of chemical lasers that operate on either the NF(b->X) or IF(B->X) transitions at visible wavelength.
Benard, D. J.,Chowdhury, M. A.,Winker, B. K.,Seder, T. A.,Michels, H. H.
p. 7507 - 7514
(1990)
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Chlorine-atom transfer reactions between chloramine (= chloramide) and piperidine: Kinetic reactivity and characterization in a Raschig medium
The kinetics of the Cl-transfer reaction between chloramine (1) and piperidine (2)in a Raschig medium (8 1H- and 13C-NMR, and MS. Their thermal stabilities were evaluated by differential scanning calorimetry (DSC), and their absorption coefficients at various wavelengths were determined experimentally by UV spectrophotometry.
Darwich, Chaza,Elkhatib, Mazen,Steinhauser, Georg,Delalu, Henri
p. 98 - 111
(2009)
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The microwave spectrum of the N 35Cl radical in the X3Σ- state
The microwave spectrum of the N 35Cl radical in the ground vibronic state has been observed by using a source frequency modulation spectrometr with a 3.5 m long free space absorption cell.The NCl radical was generated directly in the cell by a dc discharge in a mixture of N2 and Cl2 flowing through the cell.The electric-dipole allowed rotational transitions of N up to 4 a few spin components, were observed in the frequency region 41.5-155 GHz.Each transition was found to consist of many hyperfine components.To analyze the observedspectrum, the matrix elements of magnetic hyperfine and electric quadropole hyperfine Hamiltonians were derived for a diatomic molecule in the triplet state of which both nuclei have nonzero spins.The rotational spin-spin interaction, and spin-rotation interaction constants were determined to be B = 19 383.4655(42) MHz, λ = 56 390.850(16) MHz, and γ = -208.6306(96) MHz, with three standard erros in parentheses.The hyperfine parameters b, c, and eQq for both the nitrogen and chlorine atoms were precisely determined together with the nuclear-spin rotation interaction constant for the chlorine atom.The spin density of the unpaired electrons was estimated to be 76percent and 22percent, respectively, on the nitrogen and chlorine atoms from the observed hyperfine coupling constants.
Yamada, Chikashi,Endo, Yasuki,Hirota, Eizi
p. 4159 - 4166
(1983)
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Generation of Excited NCl by the Reaction of Hydrogen Atoms with NCl3
Discharge-flow methods were used to study the reaction of gaseous NCl3 with excess hydrogen atoms.The system produces electronically excited NCl(a1Δ,b1Σ+) by a two-step mechanism in which the hydrogen atoms first react with NCl3 to produce HCl and NCl2 and then with NCl2 to produce HCl and excited NCl.From measurements of the time-dependence of NCl b1Σ+ -> X3Σ- chemiluminescence in the system, the two rate constants were found to be (9 +/- 4)*10-11 cm3 s-1 and (4.0 +/- 0.4)*10-12 cm3 s-1, both at 300 K.Based on the rates of analogous reactions with NF3 and NF2, the larger rate is tentatively assigned to the H + NCl2 reaction.The branching fraction for production of NCl(a1Δ) by H + NCl has a lower limit of 0.15.The propensity for production of NCl(a1Δ) by H + NCl2 is considered in terms of an addition-elimination mechanism similar to that operative in the analogous H + NF2 reaction.
Exton, D. B.,Gilbert, J. V.,Coombe, R. D.
p. 2692 - 2696
(1991)
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Facile and Scalable Methodology for the Pyrrolo[2,1-f][1,2,4]triazine of Remdesivir
Pyrrolo[2,1-f][1,2,4]triazine (1) is an important regulatory starting material in the production of the antiviral drug remdesivir. Compound 1 was produced through a newly developed synthetic methodology utilizing simple building blocks such as pyrrole, chloramine, and formamidine acetate by examining the mechanistic pathway for the process optimization exercise. Triazine 1 was obtained in 55% overall yield in a two-vessel-operated process. This work describes the safety of the process, impurity profiles and control, and efforts toward the scale-up of triazine for the preparation of kilogram quantity.
Roy, Sarabindu,Yadaw, Ajay,Roy, Subho,Sirasani, Gopal,Gangu, Aravind,Brown, Jack D.,Armstrong, Joseph D.,Stringham, Rodger W.,Gupton, B. Frank,Senanayake, Chris H.,Snead, David R.
p. 82 - 90
(2022/01/28)

Pyrrolotriazine compounds and applications thereof
The invention belongs to the field of medical chemistry, and particularly relates to a class of lactam-based histone deacetylase inhibitors and a preparation method thereof, a pharmaceutical composition containing the histone deacetylase inhibitor, and applications of the inhibitors in drugs for preventing and/or treating diseases related to histone deacetylase activity out-of-control.
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Paragraph 0094-0098

(2020/05/01)

Discovery of a JAK1/3 Inhibitor and Use of a Prodrug to Demonstrate Efficacy in a Model of Rheumatoid Arthritis
The four members of the Janus family of nonreceptor tyrosine kinases play a significant role in immune function. The JAK family kinase inhibitor, tofacitinib 1, has been approved in the United States for use in rheumatoid arthritis (RA) patients. A number
Spergel, Steven H.,Mertzman, Michael E.,Kempson, James,Guo, Junqing,Stachura, Sylwia,Haque, Lauren,Lippy, Jonathan S.,Zhang, Rosemary F.,Galella, Michael,Pitt, Sidney,Shen, Guoxiang,Fura, Aberra,Gillooly, Kathleen,McIntyre, Kim W.,Tang, Vicky,Tokarski, John,Sack, John S.,Khan, Javed,Carter, Percy H.,Barrish, Joel C.,Nadler, Steven G.,Salter-Cid, Luisa M.,Schieven, Gary L.,Wrobleski, Stephen T.,Pitts, William J.
supporting information
p. 306 - 311
(2019/03/19)

A simple and efficient approach to the N-amination of oxazolidinones using monochloroamine
Chiral nonracemic N-amino cyclic carbamates (ACCs) are important auxiliaries for certain asymmetric transformations. In the past they have been synthesized from oxazolidinones using methods that require the preparation and use of non-atom economical aminating agents that can be difficult to prepare, and often strong bases. In what follows we describe a mild and operationally simple method for the direct N-amination of oxazolidinones that use NH2Cl derived from commercial bleach.
Huynh, Uyen,Uddin, Md. Nasir,Wengryniuk, Sarah E.,McDonald, Stacey L.,Coltart, Don M.
supporting information
p. 4799 - 4802
(2016/10/05)

PYRROLO[2,1-F][1,2,4]TRIAZINE COMPOUND, AND PREPARATION METHOD AND APPLICATION THEREOF
The present invention relates to a pyrrolo[2,1-f][1,2,4]triazine compound, an isomer thereof or a pharmaceutically acceptable salt, ester or hydrate thereof, and a preparation method and application thereof. The pyrrolo[2,1-f][1,2,4]triazine compound has a structure expressed in general formula (I). The pyrrolo[2,1-f][1,2,4]triazine compound expressed in general formula (I) can inhibit a phosphatidylinositol-3 kinase (PI3K) signal pathway, thereby being used to prepare medicine for treating phosphatidylinositol-3 kinase related diseases such as cancer.
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Paragraph 0021-0024

(2015/04/15)

PYRROLOPYRIDAZINES AS POTASSIUM ION CHANNEL INHIBITORS
A compound of formula (I) wherein A, R1, R3, and R24 are described herein. The compounds are useful as inhibitors of potassium channel function and in the treatment of arrhythmia, IKur-associated disorders, and other disorders mediated by ion channel function.
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Page/Page column 38

(2014/09/29)

AGENTS FOR TREATING NEURODEGENERATIVE DISORDERS
The present invention relates to compounds of formula I, use of these compounds to treat mental and neurological disorders, especially depressions and psychoses of different etiology and methods for their preparation. The compounds provided for the treatm
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Page/Page column 24

(2013/08/28)

NOVEL FUSED PYRIDAZINE DERIVATIVES
The present invention relates to novel fused pyridazine compounds, their pharmaceutically acceptable salts, and their isomers, stereoisomers, conformers, tautomers, polymorphs, hydrates and solvates. The present invention also encompasses pharmaceutically acceptable compositions of said compounds and process for preparing novel compounds. The invention further relates to the use of the above-mentioned compounds for the preparation of medicament for use as pharmaceuticals.
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Page/Page column 45-46

(2011/05/06)

AZOLOTRIAZINONE MELANIN CONCENTRATING HORMONE RECEPTOR-1 ANTAGONISTS
The present application provides compounds that are useful as MCHR1 antagonists, especially for the treatment of obesity, including all stereoisomers, solvates, prodrugs and pharmaceutically acceptable forms thereof according to Formula I, wherein R1, is selected from the group consisting of monocyclic aryl or monocyclic heteroaryl; W is selected from the group consisting of a direct bond, -O-, and -N(R6)-; provided that if W is a direct bond, D is a cyclic amine that is attached to A via the nitrogen atom of the cyclic amine; D is selected from the group consisting of a direct bond, substituted or unsubstituted C1 to C4 alkyl, substituted or unsubstituted C3 to C7 cycloalkyl, cycloalkylalkyl, and 4- to 6-membered cyclic amines, provided that if D is a direct bond, R2a, R2b, and R2c must be selected from H, alkyl, or cycloalkyl; E and G are independently N or CH provided that both are not N; R1 is substituted or unsubstituted phenyl or substituted or unsubstituted monocyclic heteroaryl; R2a, R2b, and R2c are independently selected from the group consisting of hydrogen, halo, cyano, hydroxyl, -NR5R5a, -SO2R34, -CO2R35 -NR5CO2R21, -NR5COR21, substituted or unsubstituted C1 to C4 alkyl, substituted or unsubstituted C3 to C7 cycloalkyl, substituted or unsubstituted 4- to 6-membered cyclic amines wherein said cyclic amine is optionally substituted with -OH, carbonylamino, alkoxycarbonylamino, or at least one of R2a, R2b, and R2c is a prodrug moiety selected from amino acid esters or phosphoric acid esters wherein said amino acid ester has the formula -OC(O)CH(NH2)R31, wherein R31 is H or C1 to C4 alkyl; or any two of R2a, Rb, or R2c, may be taken together to form a ring; R3 and R3a are each independently selected from the group consisting of hydrogen, hydroxyl, lower alkoxy, halo, CN, substituted or unsubstituted C1 to C4 alkyl, perfluoroalkyl, substituted or unsubstituted C3 to C7 cycloalkyl, cycloalkoxy, amino, alkylamino, dialkylamino, and aminoalkyl, wherein R3 or R3a and D may optionally be taken together with the atoms to which they are attached to form a 5- to 7-membered ring; R5 and R5a are the same or different and are independently selected from the group consisting of hydrogen, substituted or unsubstituted lower alkyl, hydroxyalkyl, hydroxyalkylcycloalkyl, substituted or unsubstituted heterocycloalkyl, acyl, alkoxycarbonyl, carboxyalkyl, substituted or unsubstituted cycloalkyl, and substituted or unsubstituted cycloalkylalkyl, wherein the R5 and R5a groups and the N atom to which they are attached may form a ring; R21 and R31 are each H or C1 to C4 alkyl; R34 is alkyl; R35 is H or alkyl; and R6 is selected from the group consisting of H, C1 to C4 alkyl and C3 to C7 cycloalkyl.
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Page/Page column 51

(2010/04/28)

JAK KINASE MODULATING COMPOUNDS AND METHODS OF USE THEREOF
Provided herein are pyrrolotriazine compounds for treatment of JAK kinase, including JAK2 kinase mediated diseases. Also provided are pharmaceutical compositions comprising the compounds and methods of using the compounds and compositions.
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Page/Page column 168

(2010/04/03)

Process for the production of pyrazoles
The present invention relates to novel processes for the production of compounds of formula I
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Page/Page column 17

(2009/01/24)

METHODS AND COMPOSITIONS FOR THE TREATMENT OF PAIN
The invention features methods, kits, and compositions for the treatment of pain.
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Page/Page column 25

(2008/12/07)

AQUEOUS SOLUTIONS CONTAINING CHLORAMINE WHICH ARE FREE FROM DI-AND TRICHLOROAMINE, AS WELL AS FROM AMMONIA
The combination of N-chlorotaurine, preferably in the form of sodium salt, and ammonium chloride in aqueous solution absent a buffer is a powerful antiseptic preparation sufficiently stable for use in topical treatment of infections, inflammation and oozing tissue deficiencies. The outstanding microbicidal properties of the preparation are founded in the formation of monochloramine, which is distinguished by the absence, or substantial absence, of dichloramine and trichloramine.
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Page/Page column 3-4

(2008/12/04)

Method and apparatus for producing synergistic biocide
An apparatus and methods to produce synergistic mixtures (or combinations) of haloamines to control growth of microorganisms in aqueous systems are disclosed. The apparatus and methods to produce synergistic mixtures entails producing a batch quantity of a haloamine and converting part of the haloamine to a second haloamine species to form the synergistic mixture.
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Page/Page column 6-7

(2008/06/13)

Method for the continuous synthesis of monoalkyl-hydrazines with a functionalised alkyl group
The invention relates to a method for the continuous synthesis of monoalkyl-hydrazines with a functionalised alkyl group. The inventive method is characterised in that it comprises a step consisting in demixing a solution containing the synthesised monoalkyl hydrazine, by reacting an anhydrous amine with monochloramine, in an organic phase and an aqueous phase with the addition of anhydrous sodium hydroxide. The invention can he used to obtain perfect selectivity in relation to monoalkyl-hydrazine without the presence of the di- and tri-substituted forms thereof. According to the invention, the starting amine which has not reacted is collected and reused directly without any additional treatment.
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Page/Page column 3-4

(2008/06/13)

Method for the Synthesis of Exocyclic Derivatives of Cycloalkyl-Hydrazines and Exocyclic Derivatives of Heterocycloalkyl-Hydrazines
The invention relates to a method for the synthesis of exocyclic derivatives of cycloalkyl-hydrazines and exocyclic derivatives of heterocycloalkyl-hydrazines. The invention is characterised in that the method comprises a step consisting in demixing a solution containing said synthesised derivative, by reacting a heterocyclic amine with monochloramine, in an organic phase and an aqueous phase with the addition of anhydrous sodium hydroxide. According to the invention, the starting amine which has not reacted is collected and reused directly without any additional treatment. The inventive method can also be used to obtain the corresponding exocyclic heterocycloalkyl-hydrazine or cycloalkyl-hydrazinederivative derivative at a low cost compared to that of other known methods.
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Page/Page column 4-5

(2008/06/13)

PYRROLOTRIAZINE KINASE INHIBITORS
The present invention provides compounds of formula I and pharmaceutically acceptable salts thereof. The formula I compounds inhibit tyrosine kinase activity of Trk receptors such as TrkA, TrkB, TrkC or Flt-3 thereby making them useful as antiproliferative agents.
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Page/Page column 11

(2008/06/13)

Biocides and apparatus
There are provided methods for controlling microbial or bioflim growth, comprising mixing a hypochlorite oxidant and at least one nitrogen-containing compound or salt thereof selected from a particular group of nitrogen-containing compounds and salts to form a biocide, and applying the biocide. Apparatus for practicing the methods are also provided.
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Page/Page column 28-29

(2008/06/13)

Process for preparing salts of 4-[[5-[(cyclopropylamino)carbonyl]-2-methylphenyl]amino]-5-methyl-N-propylpyrrolo[2,1-f][1,2,4]triazine-6-carboxamide and novel stable forms produced therein
Processes are provided for selectively preparing novel stable crystalline salt forms, selectively and consistently, namely, preparing Form N-1 of the methanesulfonic acid salt, and Form N-1 and Form N-4 of the hydrochloric acid salt of the p38 kinase inhibitor 4-[[5-[(cyclopropylamino)carbonyl]-2-methylphenyl]amino]-5-methyl-N-propylpyrrolo[2,1-f][1,2,4]triazine-6-carboxamide. The processes preferably employ solvent systems including formic acid/acetone and formic acid/methylethyl ketone which produce crystals having suitable flow properties and desired particle size, and solvents such as N,N-dimethylformamide and N,N-dimethylacetamide may be employed as well. Novel Form N-1 crystals of the Form N-1 and Form N-4 crystals of the hydrochloride salt and Form N-1 crystals of the methanesulfonic acid salt of the above free base, pharmaceutical compositions containing such novel forms and a method of treating p38 kinase associated conditions, including rheumatoid arthritis are also provided.
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(2010/11/24)

The [NH3Cl]+ ion
Stable! The first stable salts containing a simple, inorganic cation with an N-Cl bond are prepared (see picture). They are [NH3Cl] +[BF4]-, [NH3Cl] +[AsF6]-, and [NH3Cl] +[SbF6]- and can be safely prepared from (Me3Si)2NCl in mixtures of HF and the corresponding Lewis acids and could be used as storable generators for monochloramine gas.
Schneider, Stefan,Haiges, Ralf,Schroer, Thorsten,Boatz, Jerry,Christe, Karl O.
p. 5213 - 5217
(2007/10/03)

Radiolytic Reactions of Monochloramine in Aqueous Solutions
Monochloramine reacts with hydrated electrons very rapidly, k(NH 2Cl+eaq-) = (2.2 ± 0.3) × 10 10 L mol-1 s-1, to produce .NH 2 radicals. It reacts with .OH radicals more slowly, k(NH2Cl+.OH) = (5.2 ± 0.6) × 108 L mol-1 s-1, to produce .NHCl radicals. While .NH2 exhibits an absorption peak at 530 nm, with a molar absorption coefficient ε530 = 80 L mol-1 cm -1, .NHCl exhibits two peaks at 330 and 580 nm, ε330 = (85 ± 30) L mol-1 cm-1 and ε580 = (56 ± 30) L mol-1 cm-1. The .NHCl radical undergoes self-decay and can react also with O 2 to form a peroxyl radical. It is suggested that the peroxyl radical exists in equilibrium NHClO2? NHCl + O2 with an estimated equilibrium constant of (3 ± 2) × 10 -3 mol L-1. The reaction of chloramine with the carbonate radical is suggested to form a complex [CO3NH2Cl] .- with kf = 2.5 × 105 L mol-1 s -1 and kr = 4 × 102 s-1, and this complex decomposes with k = 7 × 102 s-1 to form .NHCl.
Poskrebyshev,Huie,Neta
p. 7423 - 7428
(2007/10/03)

Electrochemical behavior of chloramines on the rotating platinum and gold electrodes
Electroreduction of chloramines (mono-, di-, and trichloramine) in 1 M NH4Cl solutions of different pH was investigated at the rotating platinum and gold electrodes. It was found that all chloramines are present in the solution in nonprotonated forms and give well-formed one-step or two-step current-potential waves. The final products of reduction are ammonium (or ammonia) and chloride ions. Monochloramine is reduced in a single two-electron irreversible wave. Hydrazine is not an intermediate in monochloramine reduction. Dichloramine reduction generally proceeds in two two-electron steps (via monochloramine). Below pH 4.3 a kinetic current due to the protonated dichloramine reduction (single four-electron wave) is in force, appearing as an increase of the height of the first step on lowering pH. Due to this process below pH 2.5 only one four-electron reduction wave is observed. Trichloramine reduction occurs in two steps: two-electron trichloramine to dichloramine reduction and four-electron dichloramine reduction. In strong acidic solutions the kinetic current due to the protonated trichloramine reduction has to be taken into account. A reaction mechanism common for all chloramines was proposed with [NXCl·] as an intermediate (X = H2, HCl, and Cl2 for mono-, di-, and trichloramine, respectively). The rate-determining step does not involve proton transfer.
Piela, Barbara,Wrona, Piotr K.
p. E255-E265
(2008/10/08)

Photodissociation of gaseous NCl3 at 193 and 249 nm
The optical absorption spectrum of gaseous NCl3 was measured from 170 to 350 nm, and experiments were performed in which this molecule was irradiated with a pulsed laser at 193 nm and 249 nm. Photodissociation channels accessible at these wavelengths can produce fragments in singlet, doublet, or triplet manifolds of states. Photodissociation at 249 nm produces prompt banded emission in the visible and near-IR spectral regions that is tentatively ascribed to transitions in NCl2, suggesting that the dissociation channel leading to doublet fragments (NCl2 and Cl) is operative at this photolysis wavelength. The absence of emission from excited singlet states of NCl or excited triplet states of Cl2 suggests that the singlet and triplet dissociation channels are not important at 249 nm. For photolysis at 193 nm, prompt emission is observed from both the a1Δ and b1Σ+ excited states of NCl. No emission is observed from either NCl2 or excited triplet states of Cl2. A measure of the quantum yield for NCl(a1Δ) production by the 193 nm photodissociation of NCl3 was determined by observing the transfer of energy from excited NC1 to iodine atoms in the pulsed photolysis system. This method suggests that the yield has a value of 0.8 ± 0.2.
Coombe,Gilbert,Beaton,Mateljevic
p. 8422 - 8426
(2007/10/03)

Temperature dependence of the Cl+HN3 reaction from 300 to 480 K
The rate constant for Cl+HN3 over the temperature range 300-480 K has been studied in a flow reactor. Based on the rate of loss of HN3 and the rate of NCl(a1Δ) generation, the temperature dependence of this reaction is des
Manke II, Gerald C.,Henshaw, Thomas L.,Madden, Timothy J.,Hager, Gordon D.
p. 111 - 120
(2008/10/08)

Non-metal redox kinetics: Oxidation of bromide ion by nitrogen trichloride
Bromide ion reacts with NCl3 to generate NBrCl2 with the rate expression d[NCl3]/dt = 12[Br-][NCl3] (M s-1 at 25.0°C, μ = 0.50 M). The NBrCl2 intermediate subsequently reacts with Br- to give N2, Br2, and Cl- with the rate expression -d[NBrCl2]/dt = (0.05 + 5.3[Br-])[NBrCl2]. The overall stoichiometry from pH 3.2 to 6.5 corresponds to 2NCl3 + 6Br- → N2 + 3Br2 + 6Cl-. Rate constants for NCl3 reactions show extreme sensitivity to nucleophilic strength with SO32- > CN- > I- ? Br-. Aqueous absorption spectra are determined for NCl3 with maxima at 336 nm (∈ 190 M-1 cm-1) and 220 nm (∈ 5320 M-1 cm-1) and for NBrCl2 with a maximum at 228 nm (∈ 4800 M-1 cm-1). Spectral bands for NCl3, NBrCl2, NBr2Cl, and NBr3 shift systematically with the number of bromine atoms from 220 to 256 nm. The rate constants for the reactions of NHCl2 with Br2, HOBr, and Br- are much larger than that for the reaction of NCl3 with Br-.
Gazda, Michael,Kumar, Krishan,Margerum, Dale W.
p. 3536 - 3542
(2008/10/08)

Infrared Chemiluminescence Studies of the H + NFCl2 and H + NFCl Reactions
The primary and secondary reactions in the H + NFCl2 system have been studied by infrared chemiluminescence in a fast flow reactor at 300 K.The primary reaction is exclusively Cl atom abstraction to give HCl(ν=0-4) + NFCl with a total rate constant of (1.9 +/- 0.4) X 10-11 cm3 molecule-1 s-1 and an inverted vibrational distribution of Ρo-Ρ4 = 9:20:32:27:12.The rate constant for HF formation from H + NFCl was estimated as (0.9 +/- 0.4) X 10-11 cm3 molecule-1 s-1, and the HF vibrational distribution, Ρo-Ρ3 = 42:34:18:6, is characteristic of unimolecular HF elimination reactions.These data for the HF + NCl(a) product channel from the H + NFCl reaction are compared to earlier studies, which provided information about the HCl + NF(a) product channel.The latter seems to be the more important, and the total rate constant for H + NFCl is about 4 X 10-11 cm3 molecule-1 s-1 at 300 K.The dynamics of the H + NFCl reaction are discussed and compared to the H + NF2 reaction.A small number of experiments also were done with the H + NF2Cl reaction system.
Arunan, E.,Liu, C. P.,Setser, D. W.,Gilbert, J. V.,Coombe, R. D.
p. 494 - 501
(2007/10/02)

Formation of mono N-chloramine by electrolysis of ammonium chloride in aqueous ammoniacal solutions
The formation of mono N-chloramine by electrolysis of ammonium chloride in aqueous ammoniacal solution was studied versus the concentrations of , , , current density and time at 273.1 K.The cells, with or without porous diaphragm, were provided with platinum electrodes.According to experimental conditions a current yield in chloramine between 50 and 78percent was obtained.With high ammonia concentration the formation of hydrazine was observed.A mechanism is proposed where hypochlorite ions are formed by an electrochemical process and react with ammonia to give monochloramine.A cathodic reduction of monochloramine occurs at -0.35 V/SCE.Keywords: mono N-chloramine / electrolysis / ammonium chloride
Tremblay, C.,Cohen-Adad, M. T.
p. 79 - 90
(2007/10/02)

Dynamics of the O(1D) + ClNCO Reaction
The reaction of excited O(1D) atoms with ClNCO was studied by pulsed photolysis of O3/ClNCO mixtures with the 249-nm output of a KrF laser.The rate constant for O(1D) quenching by ClNCO was determined to be k = (1.3 -+/- 0.3) * 10-10 cm3 s-1.Investigation of the possible products of this reaction indicated that production of ClO + NCO is a major channel, with a branching fraction greater than 0.20.No evidence was found for the production of NCl in its X3Σ-, a1Δ, or b1Σ+ states.An upper limit for the branching fraction to NCl + CO2 is 0.005.
Singleton, Steven M.,Coombe, Robert D.
p. 9865 - 9870
(2007/10/02)

Photolysis of NCl3 in Low-Temperature Argon Matrices
NCl3 has been photolyzed in low-temperature argon matrices and the products identified via the IR spectra of the matrices.For matrices in which the NCl3 was not aggregated with Cl2, NCl was produced at all photolysis wavelengths used (220, 248, 280, and 3
Gilbert, Julanna V.,Smith, Londa J.
p. 7278 - 7281
(2007/10/02)

?*-Radicals R3Nhal: Electron Paramagnetic Resonance Studies of the Radiolysis of Alkylammonium Halides
Exposure of various ammonium and alkylammonium salts to 60Co γ-rays at 77 K gives a range of paramagnetic products including several R3Nhal radicals (R = H, alkyl; hal = Cl, Br, I) characterized by their EPR spectra.These showed large hyperfine couplin
Raynor, J. Barrie,Rowland, Ian J.,Symons, Martyn C. R.
p. 571 - 577
(2007/10/02)

Non-metal redox kinetics: Reactions of sulfite with dichloramines and trichloramine
Pulsed-accelerated-flow (PAF) and stopped-flow techniques are used to study the kinetics of HNCl2 and CH3NCl2 reactions with sulfite. Pseudo-first-order rate constants with excess sulfite at p[H+] 3.7-6.4 are measured from 35-45000 s-1 (25.0°C, μ = 0.50). Acid suppresses the rate because SO3H- is much less reactive than SO32-. The rate expression is -d[RNCl2]/dt = k1[RNCl2][SO32-], where k1 (M-1 s-1) is 5.8 × 106 for HNCl2 and 2.4 × 107 for CH3NCl2. The initial nitrogen product is RNHCl, which reacts further with sulfite. Trichloramine reactions with sulfite are measured by the PAF method under second-order conditions with unequal concentrations (25.0°C, μ = 0.50) from p[H+] 3.8 to 4.6. The rate expression is -d[NCl3]/dt = (k1[SO32-] + k2[SO3H-])[NCl3], where k1 is 4.5 × 109 M-1 s-1 and k2 is 1.4 × 107 M-1 s-1. The initial nitrogen product is HNCl2, which reacts further with sulfite. A Cl+-transfer mechanism is proposed for all the reactions with sulfite to give ClSO3- as an initial product that hydrolyzes to give Cl- and SO42-. The relative reactivities of active chlorine species with SO32- are NCl3 ? HNCl2 ? NH2Cl ? OCl-, where the NCl3 and HNCl2 reactions are suppressed by acid whereas the NH2Cl and OCl- reactions are acid assisted.
Yiin, Boudin S.,Margerum, Dale W.
p. 1942 - 1948
(2008/10/08)

Non-metal redox kinetics: Reactions of trichloramine with ammonia and with dichloramine
Trichloramine reacts with excess NH3 and base (B) with the rate expression -d[NCl3]/dt = 2kB[B][NH3][NCl3], based on the overall stoichiometry 2NCl3 + 3NH3 + 3OH- → 3NH2Cl + N2 + 3Cl- + 3H2O. The reaction is general-base assisted with kB values (M-2 s-1, 25.0°C, μ = 0.50 M) of 4.46 × 103 for OH-, 3.3 × 103 for PO43-, and 22 for NH3. A water path with kH2O = 2.2 M-1 s-1 and an acidic phosphate path for H2PO4- (kHB = 450 M-2 s-1) are also found. The rate-determining step in the proposed mechanism is a Cl+ transfer between NCl3 and NH3 to give HNCl2 and NH2Cl. This is followed by N2 formation in a rapid base-assisted reaction between NCl3 and HNCl2 with the rate expression -d[NCl3]/dt = kB′[B][HNCl2][NCl3], based on the stoichiometry NCl3 + HNCl2 + 3OH- → N2 + 2HOCl + 3Cl- + H2O. Values of kB′ (M-2 s-1, 25.0°C, μ = 0.50 M) are 2.92 × 104 for HPO42- and greater than 4 × 107 for OH-. The HOCl released in the formation of N2 reacts with excess NH3 to give more NH2Cl, which accounts for the overall stoichiometry of 1.5 NH2Cl formed per NCl3. The reaction between NCl3 and HNCl2 is of critical importance in the explanation of breakpoint chlorination processes.
Yiin, Boudin S.,Margerum, Dale W.
p. 2135 - 2141
(2008/10/08)

Kinetics and Mechanism of X + ClNO -> XCl + NO (X = Cl, F, Br, OH, O, N) from 220 to 450 K. Correlation of Reactivity and Activation Energy with Electron Affinity of X
The rate constants for a series of radical reactions with ClNO, X + ClNO -> products where X = Cl, F, Br, OH, O, N, have been measured as a function of temperature in discharge flow systems at pressures between 1 and 2 Torr of helium buffer gas.Radicals were detected by resonance fluorescence (X = Cl, Br, OH, O), laser magnetic resonance (X = OH), and chemical conversion/resonance fluorescence (X = F, N).The rate constants, with units of cm3 molecule-1 s-1 and to 95 percent confidence level, are for Cl + ClNO -> Cl2 + NO, e(-128+/-46)/T; for F + ClNO -> FCl + NO, e(-28+/-84)/T; for Br + ClNO -> BrCl + NO, e(-52+/-43)/T; for OH + ClNO -> ClOH + NO, e(-1130+/-170)/T; for OH + ClNO -> HONO + Cl, e(240+/-130)/T; for O + ClNO -> ClO + NO, e(-1520+/-36)/T; and for N + ClNO -> NCl + NO, e(-2250+/-90)/T.Both the reaction activation energies and the logarithms of the room temperature rate constants are found to correlate strongly with the affinity of the radical in such a way that high electron affinity leads to enhanced reactivity.The reactivity trend is rationalized by a frontier orbital interaction dominated by the ease with which electron transfer from the CINO molecule to the X radical can occur to stabilize a polar transition state, a mechanism shown to be widely prevalent in radical-molecule systems.The propensity for this type of interaction is determined by the energy required for electron transfer which, in this case, is given by IPCINO - EAX, where IP refers to ionization potemtial and EA to electron affinity.In addition, the A factors for the X/CINO reactions are found to increase as the electron affinity of the radical increases, indicating that the tightness of the reansition state is directly related to the height of the activation barrier.
Abbatt, J. P. D.,Toohey, D. W.,Fenter, F. F.,Stevens, P. S.,Brune, Wm. H.,Anderson, J. G.
p. 1022 - 1029
(2007/10/02)

Contribution a l'etude de la reaction d' oxydation de l'ammoniaque par l'hypochlorite de sodium :reactions de formation et de degradation des chloramines
Reactions of sodium hypochlorite (OCl(1-)) with ammonia in aqueous solution have been studied at 20 deg C.Depending upon the conditions of solution pH, reactant concentrations, temperature and initial reactant ratios R = 0/0, chloramines (mono, di or trichloramine) together with a variety of degradation products (N2 or oxides of nitrogen) were produced.With an adjusted excess of ammonia, the reaction conditions were sufficiently stationnary to permit the determination of equilibrium constants for the hydrolysis of the different chloramines and for the disproportionation of NH2Cl and NHCl2.For reactions in basic medium and with an excess of oCl(1-), a comparison of observed reaction behavior with equilibrium theory leads to the assumption that the degradation of NHCl2 produced OCl(1-).The degradation process appeared very complex; one product detected by HPLC gave a UV spectrum in the same wave length range as that of NH2Cl.
Rizk-Ouaini, Rosette,Ferriol, Michel,Gazet, Josette,Saugier-Cohen Adad, Marie-Therese
p. 512 - 521
(2007/10/02)