Showing papers on "Piperidine published in 1969"

Catalytic synthesis of organic halogen compounds from an ethylenically unsaturated compound and a halogenated organic compound

Abstract: Method for forming a chemical adduct of an ethylenically unsaturated compound with a halogenated organic compound having on a single carbon atom thereof at least two halogen atoms at least one of which is chlorine, bromine or iodine, characterized by employing a catalyst of which the essential members are copper and an amine selected from piperidine, substituted piperidines, cyclohexylamines and secondary amines on which the hydrocarbyl substituents are allyl, benzyl or lower alkyl radicals.

Studies on Stable Free Radicals. II. Reactivity of Stable Nitroxide Radicals and NMR Spectra of Reaction Products

Abstract: We have isolated coupled products of such stable free radicals as 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl (II), cyclohexane-1-spiro-2′-(4′-oxoimidazolidine-l′-oxyl)-5′-spiro-l″-cyclohexane (IV) and 2,2,6,6-tetramethyl-4-oxopiperidine-1-thiyl derived from bis-[2,2,6,6-tetramethyl-4-oxopiperidyl-(1)]disulfide (VII) with a C-radical derived from α,α′-azo-bis(isobutyronitrile). The reactive site in these stable free radicals was studied from the structure of the coupled products. The homolysis of the disulfide (VII) appeared to be accelerated by an attack of the C-radical, 1-methyl-1-cyanoethyl. The NMR spectra of the products suggested a slow inversion of the nitrogen atom in piperidine derivatives.

Synthetic Reactions by Complex Catalysts. XIV. Reaction of Isocyanide with Amine Catalyzed by Group IB and IIB Metal Compounds

Abstract: Group IB and IIB metal compounds catalyze the reaction of isocyanides (1) with amines (2) producing formamidines (3). In the reaction of cyclohexyl isocyanide with piperidine, the accelerating effect of catalyst was in the order AgCl>CuCl>>ZnCl2, Cd(OAc)2, HAuCl4·4H2O. The AgCl catalyzed reaction proceeded almost quantitatively in 2.5 hr at 17°C. The reaction of aliphatic isocyanide with aromatic amine, e.g., N-methylaniline, required higher reaction temperatures (160°C) even in the presence of catalyst, in which the order of catalytic activity was HAuCl4·4H2O>ZnCl2>AgCl>>CuCl. A ternary complex of (CuCl)2 (cyclohexyl isocyanide)2 (piperidine) was isolated, which was unstable and decomposed gradually at room temperature to give N-cyclohexyl-N,N′-pentamethylene formamidine. A mechanism through a mixed ligand complex has been proposed, in which both isocyanide and amine are coordinated with the same metal ion and the reaction takes place in the sphere of complex ligand.

Process for the preparation of 3-indolyl aliphatic acid derivatives

Abstract: WHEREIN R1 IS AN UNSUBSTITUTED OR C1-C3 ALKYL-, C1-C3 ALKOXY-, C1-C3 ALKYLTHIO- OR HALOGEN-SUBSTITUTED PHENYL OR NAPHTHYL GROUP, OR AN UNSUBSTITUTED OR HALOGEN- OR C1-C2 ALKYL-SUBSTITUTED, PYRIDINE, THIOPHENE, FURAN OR PIPERIDINE RING, R2 AND R3 ARE HYDROGE ATOMS OR C1-C2 ALKYL GROUPS R4 IS A HYDROGEN ATOM OR A CARBOXY OR C1-C4 ALKOXYCARBONYL GROUP, R5 IS AN ALKOXY HAVING 4 OR LESS CARBON ATOMS, BENZYLOXY, AMINO OR HYDROXY GROUP, R6 IS A C1-C3 ALKOXY, COR C1-C3 ALKYLTHIO OR NITRO GROUP OR A HALOGEN ATOM AT THE POSTION OF 4, 5 OR 6, M AND P ARE O OR 1 AND N IS O OR AN INTEGER OF FROM 1 TO 3, AND ARE PRODUCED IN GOOD YIELDS. TYPICAL EXAMPLES INCLUDE NNICOTINOYL-2-METHYL-5-METHOXY-3-INDOLYLACETIC ACID, $-(1CP - CHLOROBENZOYL) - 2,5-DIMETHYL-3-INDOLY)-BUTYRIC ACID AND N-(P-METHYLBENZOYL)-2-METHYL-5-METHOXY-3-INDOLYLACETIC ACID, ALL OF WHICH EXHIBIT EXCELLENT ANTI-INFLAMMATORY PROPERTIES WITH LOW TOXICITY ON THE BASIS OF STANDARD LABORATORY ANIMAL TESTS. R6-INDOLE 1-(R1-CO-),2-R2,3-(R5-CO-(CH(-R4))P-(CH2)N-(CH(-R3))M-), N-ACYL 3-INDOLYALIPHATIC ACID COMPOUNDS ARE PREPARED BY (1) REACTING A PHENYLHYDRAZONE COMPOUNDS WITH AN ACYLATING AGENT TO GIVE N1-ACYLATED PHENYLHYDRAZONE COMPOUND, (2) DECOMPOSING THE RESULTANT COMPOUND WITH A MINERAL ACID TO YIELD AN N1-ACYLATED PHENYLHYDRAZINE, (3) AND THEN REACTING THE RESULTANT PRODUCT WITH AN ALIPHATIC ACID COMPOUND. THE FINAL PRODCUTS HAVE THE FORMULA

Heterocyclic polyfluoro-compounds. Part XV. Synthesis of tetrafluoropyridine-4-sulphonic acid and related sulphur-containing derivatives of pentafluoropyridine

Abstract: Pentafluoropyridine reacts with potassium hydrosulphide, potassium thiophenoxide, sodium benzenesulphinate, or sodium sulphite in aprotic solvents to yield 2,3,5,6-tetrafluoropyridine-4-thiol, phenyl 2,3,5,6-tetrafluoropyridyl sulphide, phenyl 2,3,5,6-tetrafluoropyridyl sulphone, and 2,3,5,6-tetrafluoropyridine-4-sulphonic acid, respectively Reaction of sodium 2,3,5,6-tetrafluoropyridine-4-sulphonate with sodium cyanide in dimethylformamide gives 4-cyano-2,3,5,6-tetrafluoropyridine Treatment of 2,3,5,6-tetrafluoropyridine-4-thiol with pentafluoropyridine, cyanuric chloride, or performic acid yields bis-(2,3,5,6-tetrafluoropyridyl) sulphide, dichloro-s-triazinyl 2,3,5,6-tetrafluoropyridyl sulphide, and 2,3,5,6-tetrafluoropyridine-4-sulphonic acid, respectively Oxidation of phenyl 2,3,5,6-tetrafluoropyridyl sulphide with hydrogen peroxide yields phenyl 2,3,5,6-tetrafluoropyridyl sulphone and the corresponding sulphoxide; bis-(2,3,5,6-tetrafluoropyridyl) sulphoxide and sulphone are formed when the corresponding sulphide is treated with peroxytrifluoroacetic acid Chlorination of bis(2,3,5,6-tetrafluoropyridyl)disulphide, obtained by oxidation of the parent thiol with bromine, yields 2,3,5,6-tetrafluoropyridine-sulphenyl chloride, which reacts with piperidine to give the corresponding sulphenamide

Der FISCHER'sche Indolringschluss mit 1, 3-disubstituierten 4-Piperidonen. 7. Mitteilung über synthetische Indolverbindungen [1]†

Abstract: Treatment of the arylhydrazones of 1, 3-disubstituted 4-piperidones with ethanolic hydrogen chloride (FISCHER reaction conditions) affords 1, 2, 3, 4-tetrahydropyrimido [3, 4-a]-indoles in good yields. During catalytic hydrogenation in the presence of protons these tetrahydropyrimido-indoles are split into 2-(2-methylamino-ethyl)-indoles. The formation of these tricyclic products can be explained by rearrangement immediately following the normal FISCHER reaction. If the substituent at the piperidine nitrogen is an acyl group, normal or rearranged products are formed, depending on the nature of the 3-substituent.

Diphenyl amine urea derivatives

Abstract: DIPHENYL AMINE DERIVATIVES OF THE FORMULA 1-((R1-PHENYL)-NH-),R2,4-(R3-CO-NH-)BENZENE WHEREIN EACH OF R1 AND R2 CAN BE HYDROGEN, HALOGEN, HYDROXY, LOWER ALKYL OR LOWER ALKOXY AND R3 IS LOWER ALKYL OR ALKENYL OF UP TO6 CARBON ATOMS; PYRIDYL; PHENYL OR PYRIDYL SUBSTITUTED WITH HALOGEN, HYDROXY, AMINO, LOWER ALKOXY OR LOWER ALKYL; LOWER ALKOXY WITH 1 TO 6 CARBON ATOMS; MONO AND DIALKYL AMINO GROUPS WHEREIN ALKYL IS OF 1 TO 6 CARBON ATOMS IN WHICH THE ALKYL GROUPS CAN BE CLOSED, IF DESIRED, WITH ANOTHER HETEROATOM TO A 5,6 OR 7 MEMBERED RING AS IN PYRROLIDONE, PIPERIDINE MORPHOLINE, PIPERAZINE AND HOMOPIPERAZINE AND ANY PRIMARY AMINO GROUPS PRESENT CAN, IF DESIRED, BE ACYLATED WITH LOW MOLECULAR WEIGHT ORGANIC ACIDS SUCH AS THE ALKANOIC ACIDS OR DERIVATIVES OF CARBONIC ACID AND THEIR ACID ADDITION SALTS. THE COMPOUNDS HAVE GOOD ANTI-INFLAMMATORY, ANALGESTIC AND ANTI-PYRETIC ACTION.

Coordination of silicon tetrafluoride with pyridine and other nitrogen electron-pair donor molecules

Abstract: Silicon tetrafluoride reacts with pyridine, pyrrolidine, and piperidine forming solid 1:2 complexes. With ethylenediamine, the stable 1:1 complex results. These compounds are easily hydrolyzed and ...

Reactions of complexes of ruthenium and osmium halides with ammonia, amines, and hydrazine

Abstract: Ammonia and primary amines (am) react with [MX3(PR3)3](M = Ru or Os, X = Cl or Br, and PR3= tertiary phosphine) in ethanol at 20° to form M(II) complexes, mer-[MX2am(PR3)3], and acetaldehyde. Secondary and tertiary amines with [MX3(PMe2Ph)3] also cause reduction, but the product is an alcohol complex [MX2(C2H5OH)(PMe2Ph)3]. The reduction may occur through a hydride complex intermediate because some hydrogen is produced in all the above reactions. The alcohol complexes are probably formed for steric reasons because the least sterically hindered secondary amine, piperidine, forms a piperidine complex.When the alcohol contains a small amount of water di-n-alkylamines (CnH2n+ 1)2NH are dealkylated to form the corresponding primary amine complexes [MX2 am (PR3)3](cf. similar decarbonylation of alcohol and aldehydes). The cleaved alkyl group generally appears as Cn–1H2n and all the lower n-alkanes down to methane, but from dimethylamine higher hydrocarbons are obtained and from diethylamine a little propane.Hydrazine in limited amounts forms mononuclear complexes [MCl2(N2H4)(PMe2Ph)3] or more commonly hydrazine-bridged complexes [M2X4(N2H4)2(PR3)4]. Nitrogen, hydrogen, and hydrazine hydrochloride are also produced. Under more vigorous reaction conditions [Ru(NH3)5N2]2+ is formed.

Transmission of electronic effects in some substituted phenyl derivatives of cobalt(III) bis(acetylacetone)ethylenedi-imine complexes

Abstract: The 1H n.m.r. spectra of a series of para-substituted phenyl derivatives of bae-cobalt complexes ([H2bae = bis(acetylacetone)ethylenedi-imine] have been measured. The chemical shifts of all the hydrogens in the planar ligand are dependent on the axial ligand. It is concluded that through-space effects are mainly responsible for the dependence on the axial ligand of the difference in the chemical shifts of the A2 and B2 hydrogens of the ethylene-di-imine bridge system whilst changes in electron density transmitted by way of the bonding electrons are mainly responsible for the variations in the chemical shifts of the methene and methyl hydrogens which are related to the Hammett σ-para-functions of the para-substituent in the axial ligand. A similar correlation is observed with the formation constants of the six-co-ordinate pyridine and piperidine complexes.

The α Effect. Aminolysis on a Saturated Carbon Atom

Abstract: The rates of aminolyses of methyl, isopropyl, allyl and benzyl iodides have been determined in acetonitrile. Bases used were hydrazine, morpholine, imidazole and piperidine. The rates of all the aminolysis reactions can be correlated nicely with the basicities. Hydrazine also did not show any positive deviation from the Brφnsted plots. This fact suggests that the α-effect is not operative in these displacement reactions on the saturated carbon atom.

Polyhalogeno-aromatic compounds. Part VIII. Reactions of hexabromobenzene with nucleophiles

Abstract: Hexabromobenzene unlike its chloro- or fluro-analogues undergoes protodebromination when treated with sodium methoxide in methanol and ethyl methyl ketone to give a mixture of tetrabromobenzenes. With piperidine or ethanolic ammonia debromination and some nucleophilic substitution occurs. Hydrazine gives only 1,2,3,4-tetrabromobenzene while cyclohexyamine or sodium methoxide in pyridine give the corresponding substitution products. Attempts have been made to rationalise these result.

Piperidine spiro compounds

Abstract: THE PIPERIDINE SPIRO COMPOUNDS OF THE FORMULA: 1,2-(-Y-(1,2-PHENYLENE)-N(-ALK-(1,4,4-PIPERIDINE-TRIYL)< (-S-A-CO-N(-R)-))-),4-X-BENZENE WHEREIN X IS H, CL, CH3-, CF3-, CH3O-, CH3S- OR CH3CO-; Y IS -S- OR -CH2CH2-;ALK IS ALKYLENE OF 2 TO 4 CARBON ATOMS (E.G. ETHYLENE, PROPYLENE, TRIMETHYLENE OR 2-METHYLTRIMETHYLENE); A IS METHYLENE, ETHYLENE OR ETHYLIDENE: AND R IS H OR LOWER ALKYL OF AT MOST 4 CARBON ATOMS (E.G. METHYL, ETHYL, PROPYL OR BUTYL ARE USEFUL AS TRANQUILIZERS.

3-(2-(4-cyclohexanecarboxamido-1-piperidyl)ethyl)indole

Abstract: THE INVENTION RELATES TO THE FIELD OF SUBSTITUTED INDOLES, IN PARTICULAR TO INDO-3-YL-LOWER ALKYLPIPERIDINES SUBSTITUTED IN THE PIPERIDINE RING BY A CYCLOALKANOYLAMINO RESIDUE, THEIR ACID ADDITION AND QUATERNARY AMMONIUM SALTS, AND TO INTERMEDIATES AND PROCESS FOR THE PREPARATION THEREOF. THE COMPOUNDS OF THE INVENTION ARE PHARMACOLOGICALLY EFFICATIOUS AS HYPOTENSIVE AND ANTI-HISTAMINE AGENTS.

Proton magnetic resonance spectra of porphyrins. Part VI. Complex formation between nickel(II)–mesoporphyrin IX dimethyl ester and piperidine

Abstract: Complex formation between nickel(II)–mesoporphyrin IX dimethyl ester and piperidine has been studied by 1H n.m.r. resonance. The dependence of the chemical shifts of the porphyrin protons on the piperidine concentration indicates that only one ligand is added, and the alternation in the sign of the shifts of the meso- and β-CH protons suggests that delocalisation of the unpaired spin occurs mainly via a π-mechanism.In order to obtain a quantitative interpretation of the results it is necessary to correct for simultaneous formation of a chloroform–piperidine complex. A separate study on this system gave K ca. 0·2 l. mole–1 and a low-field complex shift of the chloroform proton of 2·08 p.p.m. The porphyrin shifts when combined with these results are consistent with a contact shift of the meso-protons of ca. 103 Hz and an equilibrium constant for the 1 : 1 complex of ca. 10–2 l. mole–1.

Benzoylamino substituted 1-benzoyl-piperidines

Abstract: AMINOPIPERIDINE DERIVATIVES OF THE FORMULA 1-((R''1,R''2-PHENYL)-CO-),((R1,R2,R3-PHENYL)-CO-NH-) PIPERIDINE WHEREIN SUBSTITUTED BENZAMIDE RADICAL ATTACHES TO 2,3,4POSITIONS IN THE PIPERIDINE NUCLEUS, AND EACH R1, R2 R3 IS HYDROGEN OR LOWER ALKOXY WHICH CAN BE CHANGED INDEPENDENTLY. R''1, R''2 OF SUBSTITUTED BENZOYL RADICAL WHICH ATTACHES TO NITROGEN OR PIPERIDINE NUCLEUS ARE HYDROGEN OR AMINO RADICAL AND AT LEAST ONE OF R''1, R''2 INDICATES AMINO RADICAL. THE NEW COMPOUNDS EXHIBITS THREPEUTIC EFFECT FOR EXPERIMENTAL GASTRIC ULCER.

β-Ferrocenyl-α,β-unsaturated Ketones. I. Condensation Reactions of Formylferrocene with Ketones

Abstract: The condensation reaction of formylferrocene with simple aliphatic and alicyclic ketones, as acetone, ethyl methyl ketone, isobutyl methyl ketone, and cyclohexanone, in the presence of piperidine as a condensing agent afforded seven kinds of β-ferrocenyl-α,β-unsaturated ketones. The geometric configurations of the unsaturated ketones were discussed on the basis of their NMR spectra, and the influences of the ferrocenyl group on the π-π* transition bands in their UV spectra were also discussed.

Intermediates and products in the catalytic vapour-phase dehydration and ammonolysis of 2-hydroxymethyltetrahydrofuran over alumina

Abstract: Reactions of 2-methylenetetrahydrofuran, 2,3-dihydro-4H-pyran and 2-hydroxymethyltetrahydrofuran in the presence and absence of ammonia over an alumina catalyst have been compared within the temperature range 300–480°. 2,3-Dihydro-4H-pyran and 2,3,4,5-tetrahydropyridine have been isolated as products at low contact times in the synthesis of pyridine and piperidine by the ammonolysis of 2-hydroxymethyltetrahydrofuran.

4-hydroxy-piperidine derivatives and their preparation

Abstract: 1. A COMPOUND OF THE FORMULA: 1-R"'',2-R",3-R'',4-(HO-)-PIPERIDINE WHEREIN R IS LOWER ALKYL, PHENYL OR METHOXYPHENYL, R'' IS LOWER ALKENYL, PHENYL OR BENZYL, R" IS HYDROGEN, LOWER ALKYL, PHENYL NITROPHENYL, MONOOR DI-LOWER ALKOXY PHENYL, HALOPHENYL, LOWER ALKOXY BENZYL OR PYRIDYL, AND R"'' IS HYDROGEN.

Synthesis of 1- and 2-Piperidinophenazine Derivatives

Abstract: A number of new piperidinophenazines have been prepared by the reactions of various halogenophenazines and their oxides, including several new compounds, with piperidine. The halogenactivating effect of the oxide groups in 1- or 2-halogenophenazine oxides, which had previously been known, was also observed in the present piperidination. It has been found that 1-chlorophenazine was considerably less reactive than 2-chlorophenazine in the piperidination, that but the 5-oxide group in 1-chlorophenazine-5-oxide enhanced the reactivity of chlorine.

Production of derivatives of omega-hydroxytiglaldehyde

Abstract: Production of 4-halogen-2-formylbutene-(2) or its lower alkyl acetals or lower fatty acid acylates by the action of certain halogenating agents on 2-formyl-2-hydroxybutene-(3) or its acetals or its acylates in the presence of tertiary amines such as trialkyl amines or N-alkyl derivatives of nitrogen containing heterocyclic compounds such as piperidine, morpholine, piperazine or similar compounds having 5 to 6 ring members.

Mechanism of nonactivated bimolecular aromatic nucleophilic substitution. Reaction of meta- and para-substituted fluorobenzenes with piperidine

Abstract: An excellent linear correlation is obtained for second-order rate coefficients in the displacement of fluoride ion by piperidine in triethylene glycol from fluorobenzenes containing a wide variety of activating and nonactivating meta- and para-substituents

Beta-(para-halo-phenyl)-glutaric acid imides

Abstract: COMPOUNDS OF THE FORMULAE 2,6-DI(O=),4-(4-R-PHENYL)PIPERIDINE AND 3-(4-P-PHENYL),5-(O=)PYRROLIDINE IN WHICH R IS HALOGEN OR TRIFLUOROMETHYL ARE VALUABLE INTERMEDIATES FOR THE PREPARATION OF NEW AMINO ACIDS WHICH ARE USEFUL AS CENTRAL INHIBITING AGENTS, E.G. MUSCLE RELAXANTS.