- Synthesis and complexation of N,N-Bis(O-diethylhydroxyphosphorylmethyl)-N-butylamine
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The acid-base and complexing properties of N,N-bis(O-diethylhydroxyphosphorylmethyl)-N-butylamine (H3L) with divalent metals were investigated in aqueous solution via the potentiometric titration method. The formation of 1:1 species has been established. The structure of complex N,N-bis(O-diethylhydroxyphosphorylmethyl)-N-butylamine with copper(II) was determined using an X-ray diffraction method.
- Cherkasov, Rafael A.,Shurygin, Igor D.,Garifzyanov, Airat R.,Mirzayanov, Ildar I.,Gaynullin, Aynaz Z.,Ivshin, Kamil A.,Kataeva, Olga N.
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- A new and efficient procedure for the synthesis of hexahydropyrimidine-fused 1,4-naphthoquinones
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A new and efficient method for the synthesis of hexahydropyrimidine-fused 1,4-naphthoquinones in one step with high yields from the reaction of lawsone with 1,3,5-triazinanes was developed.
- Reis, Marcelo Isidoro P.,Campos, Vinícius R.,Resende, Jackson A. L. C.,Silva, Fernando C.,Ferreira, Vitor F.
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- Synthesis and Crystal Structure of Dipotassium Salts of N-Alkyl-N-{[O-alkoxy(hydroxy)phosphoryl]methyl}ditiocarbamic Acids
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Abstract: A one-pot method for the synthesis of dipotassium salts of N-alkyl-N-{[O-alkoxy(hydroxy)phosphoryl]methyl}dithiocarbamic acids has been elaborated. Dipotassium salts of N-isopropyl-, N-butyl-, and N-cyclohexyl-N-{[hydroxy(O-ethoxy)phosphoryl]methyl}dithiocarbamic acids as well as N-{[O-butoxy(hydroxy)phosphoryl]methyl}-N-(2-methoxyethyl)dithiocarbamic acid have been synthesized and isolated. Crystal and molecular structure of the latter compound have been elucidated.
- Garifzyanov, A. R.,Islamov, D. R.,Mirzayanov, I. I.,Shtyrlin, V. G.
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p. 381 - 384
(2020/04/27)
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- Hydroheteroarylation of Unactivated Alkenes Using N-Methoxyheteroarenium Salts
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We report the first reductive coupling of unactivated alkenes with N-methoxy pyridazinium, imidazolium, quinolinium, and isoquinolinium salts under hydrogen atom transfer (HAT) conditions, and an expanded scope for the coupling of alkenes with N-methoxy pyridinium salts. N-Methoxy pyridazinium, imidazolium, quinolinium, and isoquinolinium salts are accessible in 1-2 steps from the commercial arenes or arene N-oxides (25-99%). N-Methoxy imidazolium salts are accessible in three steps from commercial amines (50-85%). In total 36 discrete methoxyheteroarenium salts bearing electron-donating, electron-withdrawing, alkyl, aryl, halogen, and haloalkyl substituents were prepared (several in multigram quantities) and coupled with 38 different alkenes. The transformations proceed under neutral conditions at ambient temperature, provide monoalkylation products exclusively, and form a single alkene addition regioisomer. Preparatively useful and complementary site selectivities in the addition of secondary and tertiary radicals to pyidinium salts are documented: harder secondary radicals favor C-2 addition (2->10:1), while softer tertiary radicals favor bond formation to C-4 (4.7->29:1). A diene possessing a 1,2-disubstituted and 2,2-disubstituted alkene undergoes hydropyridylation at the latter exclusively (61%) suggesting useful site selectivities can be obtained in polyene substrates. The methoxypyridinium salts can also be employed in dehydrogenative arylation, borono-Minisci, and tandem arylation processes. Mechanistic studies support the involvement of a radical process.
- Ma, Xiaoshen,Dang, Hester,Rose, John A.,Rablen, Paul,Herzon, Seth B.
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supporting information
p. 5998 - 6007
(2017/05/04)
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- REACTIONS OF DICHLOROMETHANE WITH THIOANIONS. 2. FORMATION OF 5-ALKYL-1,3,5-DITHIAZINANES, 3,5-DIALKYL-1,3,5-THIADIAZINANES, AND 1,3,5-TRIALKYL-1,3,5-TRIAZINANES BY REACTION OF DICHLOROMETHANE WITH SODIUM SULFIDE AND MONOALKYLAMINES
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The reaction of dichloromethane with sodium sulfide and monoalkylamines, catalyzed by polyethyleneglycol 1,500, is studied.A mixture of 5-alkyl-1,3,5-dithiazinane, 3,5-dialkyl-1,3,5-thiadiazinane, and 1,3,5-trialkyl-1,3,5-triazinane is obtained.The proportion of these heterocycles depends on the amine structure and the presence of sodium hydroxide. - Key words: 5-Alkyl-1,3,5-dithiazinanes; 3,5-dialkyl-1,3,5-thiadiazinanes; dichloromethane double substitution; polyethyleneglycol as catalyst
- Torres, Martin,Vega, Juan C.
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p. 125 - 130
(2007/10/03)
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- Alkylation of 6-mercaptopurine (6-MP) with N-alkyl-N-alkoxycarbonylaminomethyl chlorides: S6-(N-alkyl-N-alkoxycarbonyl)aminomethyl-6-MP prodrug structure effect on the dermal delivery of 6-MP
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The S6-(N-alkyl-N-alkoxycarbonyl)aminomethyl-6-MP (6-CARB-6-MP) prodrugs 5-20 were synthesized from the reaction of 6-MP weith N-alkyl-N-alkyoxycarbonylaminomethyl chlorides (4) in dimethyl sulfoxide in overall yields of 5-62%, depending on the N-alkyl and the alkoxy groups involved. The derivatives were fully characterized by spectral and micranalyses. The assignment of the substitution pattern as S6-alkyl was based on comparisons of the UV, 1H NMR and 13C NMR spectra with model compounds. A S6,9-bis-alkyl derivative was obtained from the reaction of 2 equivalents of 4 with 6-MP but the product was unstable and decomposed on standing to a 9-alkyl derivative. The 6-CARB-6-MP prodrugs reverted to 6-MP in water by an S(N)1-type mechanism involving unimolecular charge separation in the transition state of the rate determining step. There was no effect of dermal enzymes on the rate of hydrolysis. The solubilities in isopropyl myristate (IPM) for all of the 6-CARB-6-MP prodrugs were significantly greater than the solubility of 6-MP in IPM but only one prodrug (5) was apparently even as soluble as 6-MP in water. Selected 6-CARB-6-MP prodrugs were examined in diffusion cell experiments. Only the N-methyl-N-methoxycarbonyl derivative 5 gave a steady-state rate of delivery of 6-MP from IPM that was significantly greater than the steady-state rate of delivery of 6-MP from 6-MP in IPM. All the other derivatives gave steady-state rates of delivery of 6-MP from IPM that were either not significantly different, or were significantly lower than the rate obtained from 6-MP in IPM. In all cases, the effect of the 6-CARB-6-MP:IPM suspensions on the permeability of the skin, as determined by the second application flux of theophylline:propylene glycol, was of the same magnitude as the effect of IPM alone.
- Siver,Sloan
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- SYNTHESE D'IMINES LINEAIRES NON-STABILISEES PAR REACTIONS GAZ-SOLIDE SOUS VIDE(1).
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Unstabilized imines are synthetized in gram-scale by vacuum dehydrochlorination of N-chloroalkylamines and by vacuum dehydrocyanation of α-aminonitriles on solid base.All the new compounds are characterized at low temperature by 1H, 13C NMR and IR spectroscopy.
- Guillemin, Jean-Claude,Denis, Jean-Marc
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p. 4431 - 4446
(2007/10/02)
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- Preparation of N,O-Aminals as Synthetic Equivalents of H2C=NAr and (H2C=NHAr)+ ions: Neutral- and Acid-promoted Transformations
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A general method for the synthesis of N, O-aminals derived from primary aromatic amines is described.The reactivity of these compounds under neutral and acidic conditions has been studied and the title compounds can be envisaged as general purpose H2C=NAr or (H2C=NAr)+ equivalents.N,O-Aminals have been converted into perhydrotriazines by moderate heating and into bis(4-aminoaryl)methane derivatives or N-benzylarylamines, respectively, when heated in acidid media with pH control.Reduction od N,O-acetals with sodium cyanoborohydride has revealed that the C-O bond is broken exclusively in acidic media.
- Barluenga, Jose,Bayon, Ana M.,Campos, Pedro,Asensio, Gregorio,Gonzalez-Nunez, Elena,Molina, Yolanda
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p. 1631 - 1636
(2007/10/02)
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- Flash Vacuum Thermolysis of α-Aminonitriles and Subsequent HCN Removal on Solid Base, a 'One Line' Multistep Sequence to Reactive N-Methyleneamines
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Reactive methyleneamines bearing alkyl or functional groups are isolated at low temperature in the condensate state by flash vacuum thermolysis of α-aminonitriles and subsequent vapour phase HCN removal on solid base.
- Guillemin, J. C.,Denis, J. M.
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p. 951 - 952
(2007/10/02)
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- Monoalkylation of Primary Aliphatic Amines via N-Alkyl-N-(alkylthiomethyl)ammonium Chlorides. Evidence for the Formation of Stable N-Methylenealkylamines
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Monomeric N-methylenealkylamines (3), formed from N-alkyl-N-(alkylthiomethyl)ammonium chlorides (5) are stable at -60 deg C and may be trapped with organometallic reagents to provide the N,N-dialkylamines (8).
- Barluenga, Jose,Bayon, Ana M.,Asensio, Gregorio
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p. 427 - 428
(2007/10/02)
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