Iodomethaneboronic esters and aminomethaneboronic esters

An efficient preparation of pinacol iodomethaneboronate and dibutyl iodomethaneboronate from the respective (phenylthio)methaneboronic esters has been devised, using the reaction with methyl iodide. Pinacol iodomethaneboronate reacts efficiently wit tertiary amines to form the crystalline quaternary ammonium salts. Dibutyl iodomethaneboronate reacts with excess piperidine or morpholine in ether to precipitate piperidine or morpholine hydriodide and yield the distillable piperidino- or morpholinomethaneboronic ester. Benzylamine failed to yield a stable product.     

Synthesis and Transformations of Two Types of 4-Phosphorylated Aldehydes of the Oxazole Series

Available N-(1,2,2,2-tetrachloroethyl)dichloroacetamide selectively reacts with trialkyl phosphites and triphenylphosphine, which was used for preparing polycentered electrophilic agents unusually reacting with piperidine and morpholine in the presence of water to give in high yields 4-dialkoxyphosphoryl- or 4-triphenylphosphonio-substituted oxazole-2-carbaldehydes containing piperidine or morpholine moiety in the 5-position. Their structure was determined by spectroscopy and also by chemical transformations into phenylhydrazones, thiosemicarbazones, aminals, and other functional derivatives of these two types of phosphorus-containing aldehydes of the oxazole series.     

Surface active properties of simple cyclic and heterocyclic amines in water

The surface tension of aqueous solutions of simple cyclic, heterocyclic and aromatic amines was measured with a Du N?uy tensiometer at 25 degrees C and the results discussed in terms of structure-aggregation relationships. The simple compounds used in this study were piperazine, piperidine, morpholine, 3-methylpyridine, cyclohexylamine and benzylamine, with carbon numbers ranging from four to seven. Piperazine, piperidine and morpholine did not form micellar associations but cyclohexylamine, benzylamine and 3-methylpyridine did, indicating that more than six carbons are necessary to form micellar associations, at least for compounds having a six-membered ring.     

Spectroscopic and kinetic evidence for an accumulating intermediate in an SNV reaction with amine nucleophiles. Reaction of methyl beta-methylthio-alpha-nitrocinnamate with piperidine and morpholine

A spectroscopic and kinetic study of the reaction of methyl beta-methylthio-alpha-nitrocinnamate (4-SMe) with morpholine, piperidine, and hydroxide ion in 50% DMSO/50% water (v/v) at 20 degrees C is reported. The reactions of 4-SMe with piperidine in a pH range from 10.12 to 11.66 and those with morpholine at pH 12.0 are characterized by two kinetic processes when monitored at lambdamax (364 nm) of the substrate, but by only one process when monitored at lambdamax (388) nm of the product. The rate constants obtained at 388 nm were the same as those determined for the slower of the two processes at 364 nm. These rate constants refer to product formation, whereas the faster process observed at 364 nm is associated with the loss of reactant to form an intermediate. In contrast, for the reaction of 4-SMe with morpholine at pH 8.62 the rates of product formation and disappearance of the substrate were the same, i.e., there is no accumulation of an intermediate. Likewise, the reaction of 4-SMe with OH- did not yield a detectable intermediate. The factors that allow the accumulation of intermediates in certain SNV reactions but not in others are discussed in detail, and structure-reactivity comparisons are made with reactions of piperidine and morpholine with other highly activated vinylic substrates.     

Transformations of dibenzo(γ-oxopiperidino)aza-14-crowns-4 upon acylation. Molecular structure of dibenzo-16-crown-3

The result of acylation of dibenzoaza-14-crowns-4 containing a 4-oxopiperidine fragment with acetic anhydride depends on the substituent on the nitrogen atom. The NH-substrates initially undergo acylation at the piperidine nitrogen atom, followed by enolization and O-acylation. The acylation of N-methyl derivatives is accompanied by cleavage of the piperidine ring at the C-N bond with formation of acetylamino-substituted dibenzo-16-crowns-3. The structure of the latter was determined by X-ray analysis.     

Thioamides from 5-arylfurfural and monosubstituted piperazine derivatives (Wilgerodt-Kindler reaction)

Interaction of 5-arylfurfurals or arylaldehydes with secondary amines (monosubstituted piperazines, morpholine, piperidine) and sulfur under conditions of Wilgerodt-Kindler reaction provided N-substituted thioamides of 5-arylfuran-2-carboxylic and benzoic acids.     

Complex hydrogen bonded cations - VI cations involving aliphatic bases

Hydrogen bond complexing between aliphatic bases and their cations has been examined by infrared spectroscopy. The results are: Morpholinium/morpholine - strong complex - asymmetric single minimum bond (a.s.m.). Piperidinium/piperidine - strong complex (a.s.m.). Piperidinium/NMe morpholine - complex (a.s.m.). NMe piperidinium/morpholine - weaker complex (a.s.m.). NMe piperidinium/NMe piperidine - no complexing. NMe morpholinium/NMe morpholine - no complexing. Triethylenediamine (TED). Complexes of type (TEDH⁺)_n, and TEDH⁺/TED have been distinguished.Models indicate the Me group retains the equatorial position in the tertiary bases on complexing, and the N β N distance is ? 2.5 Å.     

Intercalation of non-aromatic heterocyclic amines into layered zirconium glycine-<Emphasis Type="Italic">N,N</Emphasis>-dimethylphosphonate

New materials were prepared by intercalation reactions between layered zirconium glycine-N,N-dimethylphosphonate (ZGDMP) and non-aromatic heterocyclic amines: piperazine, piperidine, and morpholine. X-ray powder diffraction patterns showed that the entrance of piperazine, piperidine, and morpholine caused an interlayer expansion of 0.40 nm, 0.66 nm, and 0.67 nm, respectively. The infrared spectra were in agreement with an acid-base reaction, involving layered acid host COOH of ZGDMP and basic center atoms of guest molecules. Thermogravimetric curves revealed thermal stability of the intercalation compounds and content of the inserted amine molecules. These results indicate that non-aromatic heterocyclic amines were intercalated into the galleries of host ZGDMP.     

几个烯胺的邻硝基苯甲酰化和在酸水解中发生的重排

为了了解芳酰基化的效率和双酰基衍生物的形成, 对几个典型醛和酮的吗啉烯胺进行了邻硝基苯甲酰化的探索。丁醛和异丁醛吗啉烯胺的酰化正常, 水解分别生成55%的2-(邻硝基苯甲酰基)丁醛(2)和40%的2-(邻硝基苯甲酰基)异丁醛(3)。3-戊酮和1, 3-二甲氧基丙酮的吗啉烯胺在酰化和水解时分别生成37%和14.8%相应的β-二酮的烯醇邻硝基苯甲酸酯(4)和(5)。4和5的酸水解发生意外的1, 5-和1,3-酰基转位, 分别生成3, 5-二甲基-2, 6-双(邻硝基苯基)吡喃-4-酮(6)和2-甲氧基-2-甲氧乙酰基-1, 3-双(邻硝基苯基)-1, 3-丙二酮(7)。环戊酮和环已酮吗啉烯胺的酰化分别产生9%和34%的双酰基烯胺(9a)和(9b),逐次酸水解得到2-(邻硝基苯甲酰基)环戊酮(11a)和-环已酮(11b)。在总酰化产物的直接水解中, 11a的产率可以达到81%, 而11b只有35%。对双酰化进行了一些讨论。     

Three-Component Reaction of Dimethyl Malonate with α,β-Acetylenic Aldehydes and Amines. Synthesis of Push–Pull Buta-1,3-dienes

Russian Journal of Organic Chemistry - Three-component reaction of dimethyl malonate with α,β-acetylenic aldehydes and cyclic secondary amines (pyrrolidine, piperidine, morpholine, and...     

Effect of a Nitrogen-Containing Base on the Kinetics of Formation of the Zinc–Octa(m-trifluoromethylphenyl)porphyrazine Complex in Benzene

Russian Journal of Physical Chemistry A - The effect additions of n-butylamine, tert-butylamine, piperidine, and morpholine have on the kinetics of the complexation of zinc acetate with...     

Equilibres liquide-vapeur isothermes de melanges binaires formes de composes heterocycliques tels que: Morpholine,tetrahydropyranne, piperidine et 1,4-dioxane

The authors have measured the vapour pressure of four binary systems, morpholine+piperidine, morpholine+1,4-dioxane, morpholine+tetrahydropyrane and 1,4-dioxane+tetrahydropyrane. The measurements were carried out using an isoteniscope built by J. Jose [1]. The vapour pressure, excess Gibbs free energies at 298.15, 303.15, 313.15, 323.15, 333.15 and 343.15 K are reported for these mixtures. The excess Gibbs free energies have been fitted to the Redlich-Kister equation.     

取代邻苯二酚Mannich反应研究I:

把3-[N,N-双(羧甲基)氨甲基]邻苯二酚和哌啶,吡咯,二乙胺,吗啉和哌嗪在加热可得到相应的5-取位Mannich碱.研究了Mannich反应的机理,理解了这一Mannich反应的定位是由于反应物的分子内氢键.但是在与亚胺基二乙酸反应时或3-吗啉甲基邻苯二酚与吗啉反应,得到正常的6-取代Mannich碱.     

A convenient and high yield synthesis of tertiary (amino) phosphines by transamination route

Tris (diethylamino)phosphine affords tertiary (amino) phosphines of pyrrolidine, piperidine, hexamethyleneimine, morpholine and N-methylpiperazine in nearly quantitative yields by transamination route - an easy and convenient synthesis occuring under mild conditions.     

Adsorption of oligooxypropylenated amines at the aqueous solution—air interface: Homologous series of piperidine and morpholine derivatives

The surface tension isotherms for pure oligooxypropylenated piperidine and morpholine at the aqueous solution—air interface were determined and interpreted. The surface excess concentration, Γ, the surface area per molecule, A, and the standard free energy of adsorption, ΔG°, were calculated according to a new empirical adsorption equation. The standard free energy contribution for the oxypropylene group (PO) in morpholine derivatives,ΔG° (PO) = −3.34 kJ mol⁻¹, is substantially lower than that for the PO group located in the piperidine derivatives, i.e. ΔG° (PO)= −3.12 kJ mol⁻¹.     

N-Aryl-2-dialkylaminosuccinimides

Reaction of N-arylmaleimides with an equimolar amount of diethylamine, piperidine, and morpholine afforded the corresponding N-aryl-2-dialkylaminosuccinimides as mixtures of stereoisomers.     

Kinetics of Proton Transfer from Octa(m-trifluoromethylphenyl)porphyrazine to Nitrogen-Containing Bases in the Benzene–Dimethylsulfoxide System

Russian Journal of Physical Chemistry A - The acid–base interaction between octa(m-trifluoromethylphenyl)porphyrazine and pyridine, 2‑methylpyridine, morpholine, and piperidine in the...     

Mannich base derivatives of bioactive benzyl-1,3-benzodioxo-5-ols

3,4-Methylenedioxyphenol (sesamol) reacts with equimolecular quantities of an aromatic aldehyde and morpholine or piperidine in methanol to give Mannich bases 7 and 8 , related to insect growth regulators and anti-leukemic and antimitotic benzyl-1,3-benzodioxole derivatives.     

Synthesis and steric structure of [2-(3-pyridyl)piperidino](2-vinyloxyethylamino)methanethione

Thioureas derivatives were synthesized on the basis of anabasine, piperidine, and morpholine, and 2-vinyloxyethyl isothiocyanate. X-Ray diffraction was used to determine the steric structure of [2-(3-pyridyl)piperidino](2-vinyloxyethylamino)methanethione.     

A Convenient Synthesis of N-(α-Aminobenzyl)formamides

Three-component condensation of benzaldehyde, formamide, and morpholine or piperidine, results in an expeditious synthesis of the N-(α-dialkylaminobenzyl)-formamides.