105-40-8Relevant articles and documents
1,3-Dialkyl-3-acyltriazenes: Products and Rates of Decomposition in Acidic and Neutral Solutions
Smith, Richard H.,Wladkowski, Brian D.,Herling, Julie A.,Pfalzgraff, Timothy D.,Pruski, Brunon,et al.
, p. 654 - 661 (1992)
The products and mechanism of hydrolytic decomposition of a series of 1,,3-dialkyl-3-acyltriazenes were studied in both acidic and neutral buffers.In the acidic region, the products are alkyl alcohols derived from the N(1) alkyl group and amides derived from the intact N(3) portion of the molecule.The solvent deuterium isotope effect (kH2O/kD2O)) is less than 1.0.The mechanism is specific acid catalyzed, involving rapid reversible protonation of the 3-acyl group followed by scision of the N(2)-N(3) bond to generate an amide and an alkyl diazonium ion.The (2-hydroxyethyl)diazonium ion gives ethylene glycol and acetaldehyde, while the (2-chloroethyl)diazonium ion yields 2-chloroethanol.In the neutral region, the products are similar to those found in acidic buffers, alkyl alcohols, and amides.At this pH the (2-chloroethyl)diazonium ion produces ethylene glycol and acetaldehyde in addition to 2-chloroethanol.The solvent deuterium isotope effect (kH2O/kD2O) is greater than 1.0.The mechanism involves unimolecular heterolylsis of the N(2)-N(3) bond to form an amide anion and an alkyldiazonium ion.The methyldiazonium ion leads to incorporation of deuterium in the methyl group of the products, indicating the existence of an equilibrium between the metastable methyldiazonium ion and diazomethane.
Base sequence selectivity in the alkylation of DNA by 1,3-dialkyl-3- acyltriazenes
Smith,Taneyhill,Michejda,Smith Jr.
, p. 341 - 348 (1996)
The base sequence selectivity of DNA alkylation for a series of structurally related 1,3-dialkyl-3-acyltriazenes was examined with calf thymus DNA or polymers containing the sequences GGG, CGC, TGT, and AGA. The reaction products at the N7 and the O6 positions of guanine were identified, quantitated, and then correlated with the decomposition rates of the triazenes, 1-(2-chloroethyl)-3-methyl-3-carbethoxy- (CMC), 1-(2-chloroethyl)- 3-methyl-3-acetyl- (CMA), 1-(2-hydroxyethyl)-3-methyl-3-carbethoxy- (HMC), 1- (2-hydroxyethyl)-3-methyl-3-acetyl-(HMA), and 1,3-dimethyl-3-acetyl- (DMA). The results of these studies revealed that DNA sequences with runs of purines were more reactive toward alkylation by all of the triazenes tested, irrespective of whether the alkylation was measured by N7, O6, or total guanine adducts. Within this generalization, the (hydroxyethyl)triazenes showed a preference for the AGA sequence, while the (chloroethyl)triazenes favored the GGG sequence. The structure of the 3-acyl group of the triazene also played a role in the extent of alkylation of a particular sequence of DNA. Both the (chloroethyl)- and the (hydroxyethyl)triazenes produced higher alkylation product yields for the 3-carbethoxytriazenes as compared with the 3-acetyl derivatives for most of the sequences examined. These overall patterns correlated well with the order of decomposition of the triazenes at 37 °C: HMC > DMA > HMA > CMC > CMA. This study has demonstrated how varying the structure of 1,3-dialkyl-3-acyltriazenes can modulate DNA alkylation, a finding which may be important in the design of new triazene antitumor agents.
A Class of N-O-Type Oxidants to Access High-Valent Palladium Species
Nappi, Manuel,Gaunt, Matthew J.
, p. 143 - 148 (2018/12/11)
This article presents a new class of mild reagents that is capable of oxidizing palladacycle(II) complexes to high-valent palladium species, promoting the formation of C-N bonds in stoichiometric and catalytic conditions. The weak N-O bond and the extremely electron-withdrawing benzenesulfonate group on the oxygen atom of the oxidant are crucial moieties to ensure the desired activity. The oxidation mechanism could involve outer-sphere single-electron transfer processes, opening the possibility for a complementary reactivity of Pd(IV) species.
Capture-Collapse Heterocyclization: 1,3-Diazepanes by C-N Reductive Elimination from Rhodacyclopentanones
McCreanor, Niall G.,Stanton, Steven,Bower, John F.
supporting information, p. 11465 - 11468 (2016/10/06)
Rhodacyclopentanones derived from carbonylative C-C activation of cyclopropyl ureas can be "captured" by pendant nucleophiles prior to "collapse" to 1,3-diazepanes. The choice of N-substituent on the cyclopropane unit controls the oxidation level of the product, such that C4-C5 unsaturated or saturated systems can be accessed selectively.
COMPOSITIONS AND METHODS FOR THE TREATMENT OF RESTLESS LEG SYNDROME AND FIBROMYALGIA
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Paragraph 0122; 0123, (2015/05/26)
The invention relates to the compounds of formula I or its pharmaceutical acceptable salts, as well as polymorphs, solvates, enantiomers, stereoisomers and hydrates thereof. The pharmaceutical compositions comprising an effective amount of compounds of formula I, and methods for the treatment of fibromyalgia, restless leg syndrome may be formulated for oral, buccal, rectal, topical, transdermal, transmucosal, intravenous, parenteral administration, syrup, or injection. Such compositions may be used to treatment of motor neurone disease, diabetic neuropathy, postherpetic neuralgia, acute opioid withdrawal management, obsessive-compulsive disorder, premature ejaculation, PTSD, injury, post-operative pain, osteoarthritis, rheumatoid arthritis, multiple sclerosis, spinal cord injury, migraine, HIV related neuropathic pain, bipolar depression, depression, stress, cancer pain and lower back pain.
COMPOSITIONS AND METHODS FOR THE TREATMENT OF CHRONIC PAIN
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Paragraph 00176-00177, (2013/03/28)
The disclosures herein provide compounds of formula (I) or its pharmaceutical acceptable salts, as well as polymorphs, enantiomers, stereoisomers, solvates, and hydrates thereof. These salts may be formulated as pharmaceutical compositions. The pharmaceutical compositions may be formulated for peroral administration, transdermal administration, transmucosal, syrups, topical, extended release, sustained release, or injection. Such compositions may be used to treatment of neurological disorders or conditions such as pain or its associated complications.
Dibutyltin oxide catalyzed aminolysis of oxalate to carbamate, oxamate and derivatives of imidazolidine trione
Kunde, Lalita B.,Kalyani, Vishwanath S.,Gupte, Sunil P.
experimental part, p. 402 - 407 (2010/08/06)
Catalytic aminolysis of oxalates by simple and substituted ureas has been shown to give carbamates, oxamates and derivatives of imidazolidine trione. Various substituted ureas and oxalates were screened to verify the applicability of the protocol. The rol
Process for the preparation of alkyl carbamates
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, (2008/06/13)
The invention relates to an efficient process for the preparation of methyl methyl carbamate by reacting methyl amine or N,N'-dimethyl urea with carbon monoxide, an oxidizing agent and a monoalcohol in the presence of a catalyst system including (i) a precursor selected from the group consisting of platinum group metals and soluble compounds of platinum group metals, and (ii) a promoter comprising at least one halogen containing compound selected from the group consisting of alkali metal halides, alkaline earth metal halides, quaternary ammonium halides, oxo acids of halogen atoms and their salts, and complex compounds containing halogen ions, organic halides and halogen molecules.
Specificity of DNA alkylation by 1-(2-chloroethyl)-3-alkyl-3- acyltriazenes depends on the structure of the acyl group: Kinetic and product studies
Smith,Schmidt,Czerwinski,Taneyhill,Snyder,Kline,Michejda,Smith Jr.
, p. 466 - 475 (2007/10/03)
The reactions of calf thymus DNA with ten 1-(2-chloroethyl)-3-alkyl-3- acyltriazenes of varying acyl side chain structure were studied alone, or in the presence of porcine liver esterase in pH 7.0 phosphate buffer. In several of the key triazenes, the acyl substituent contained a free carboxylic acid group. With esterase present in the reaction mixture, the resultant levels of DNA alkylation could be correlated with the kinetic rates of decomposition of the triazenes. Under these conditions, the predominant pathway of decomposition involved deacylation of the parent triazene and eventual production of an alkanediazonium ion. This intermediate subsequently alkylated DNA-guanine to give 7-alkylguanine as the principal reaction product. In the absence of esterase, the order of DNA alkylation for all of the acyltriazenes did not correlate with their respective rates of decomposition, leading to the conclusion that the triazenes did not decompose by the expected mode of uncatalyzed N(2)-N(3) heterolyic cleavage. The major DNA alkylation product from the N(3)-methyltriazenes was 7-methylguanine, instead of the expected 7-(chloroethyl)- and 7-(hydroxyethyl)guanine products, which suggested that the acyl group was being hydrolyzed. However, acyltriazenes with an N(3)-benzyl group rather than a methyl in this position produced very little 7-benzylguanine product, contrary to prediction. An alternative mechanism involving internally assisted hydrolysis of the side chain ester is proposed to explain these results. NMR product analysis and computational studies were carried out to lend support to the postulated mechanism.
DICHLORONITROACETIC ACID DERIVATIVES AS ACYLATING AGENTS FOR PRIMARY AMINES, AMMONIA, AND PHENYLHYDRAZINE
Yurtanov, A. I.,Adkhamova, Z. M.,Baidildaeva, S. K.
, p. 891 - 894 (2007/10/02)
The corresponding carbamic acid derivatives were obtained (28-91percent) yields) as a result of the reaction of dichloronitroacetic acid derivatives, O2NCCl2COR, (1a-c, R=OEt, OCH2Ph, NH2) with ammonia, methylamine, benzylamine, glycine, phenylhydrazine, and aniline. The probable mechanism of the process and factors that affect the nature of the departing group were discussed. Keywords: dichloronitroacetic acid derivatives, aminolysis, intermediate states, mechanisms of reactions.
