Showing papers on "Morpholine published in 1978"

Structural Studies of Crystalline Enamines

Abstract: Crystal structure analyses of five crystalline enamines together with recently published structural data for two other enamines reveal varying degree of pyramidality at the enamine nitrogen atom. The pyramidality appears to be most pronounced in enamines from piperidine and morpholine, less so in enamines derived from prolinoid amines. A pyrolidine enamine obtained from a derivative of cyclohexane-1,4-dione seems to have a virtually planar enamine group. The implications of these findings for current stereochemical problems in enamine chemistry are discussed.

Organic stripping compositions and method for using same

Abstract: Improved organic stripping compositions useful in removing polymeric organic substances, such as photoresists, from aluminized inorganic substrates, which comprise one or more organic sulfonic acids, such as linear dodecylbenzene-sulfonic acid, toluenesulfonic acid and phenolsulfonic acid, one or more organic solvents and, optionally, phenol. A hydrogen fluoride complex is incorporated into the composition comprising HF at about 5 to 300 pm by weight of fluoride per weight of composition and at least about 0.1 mols per mol of HF of a complexing agent, such as morpholine or dimethyl formamide, having a nitrogen with an unshared electron pair. The hydrogen fluoride complex reduces aluminum corrosion during stripping even after repeated use at high temperature as is common in industrial semiconductor photoresist stripping.

Tryptophan derivatives having an increased effect on the central nervous system

Abstract: Tryptophan derivatives represented by the general formula: ##STR1## in which R denotes an acetyl group, M denotes an alkali metal or alkaline-earth metal (more particularly lithium or magnesium) having the value n or the quaternary ammonium cation of one of the following nitrogenous organic bases: morpholine and monoethanolamine; n is an integer equal to 1 or 2, and the formula (I) derivatives can be in the racemic DL form or the optically active L(+) form, the drugs being useful inter alia as agents having an increased effect on the central nervous system.

Mobile phase for liquid chromatography

Abstract: A mobile phase for use in reversed phase high performance liquid chromatography The mobile phase is a mixture of a polar organic solvent selected from acetonitrile and methanol and an aqueous solution of a salt of a tertiary amine and phosphoric acid or formic acid The tertiary amines are selected from the group consisting of trialkyl amines and cyclic tertiary amines such as N-methyl morpholine, wherein the alkyl moiety is selected from methyl, ethyl, propyl, butyl and mixtures thereof

Some effects of phenol- and thiol-nitrosation reactions on N-nitrosamine formation.

Abstract: C-Nitrosophenols, produced by the nitrosation of phenols, catalyse N-nitrosamine formation. The rate of N-nitrosation of pyrrolidine, catalysed by p-nitroso-o-cresol, is fastest at about pH 5. The catalytic species is thought to be the quinone monoxime tautomer of the nitrosophenol. A possible mechanism for the catalysis is proposed. A reaction of pyrrolidine with nitrite at pH 5.0 is described, which gives enhanced N-nitrosation in the presence of p-cresol. The yield of N-nitrosopyrrolidine (NPYR) is further enhanced when this reaction is carried out under anaerobic conditions. Nitrosocysteine hydrochloride reacts with N-methylaniline at pH 2.65, 5.5 and 9.75 in the absence of nitrite to give N-nitroso N-methylaniline. The N-nitrosation of morpholine and pyrrolidine at pH 9.75 is also effected by nitrosocysteine hydrochloride. The rate of N-nitrosation at this pH decreases with increasing amine basicity. The reaction of nitrosocysteine with N-methylaniline at pH 9.75 under anaerobic conditions leads to a significant reduction in the yield of N-nitroso-N-methylaniline.

Oligomerisation and telomerisation of buta-1,3-diene catalysed by bis-(η-cyclo-octa-1,5-diene)-palladium and -platinum

Abstract: The [Pd(cod)2]-catalysed reaction of buta-1,3-diene with secondary amines (morpholine, piperidine, diethylamine, or dimethylamine) affords octa-2,7-dienylamines, the highest yields being obtained with the cyclic amines. However, treatment of buta-1,3-diene with acetic acid-diethylamine in the presence of [Pd(cod)2](cod = cyclo-octa-1,5-diene) affords an improved yield of the diethylamine C8 adduct. The addition of 1 mol of PPh3 per mol of Pd has only a small effect on the above reactions. The addition of acetic acid to buta-1,3-diene is catalysed by [Pd(cod)2] to give octa-2,7-dienyl acetate and 1-vinylhex-5-enyl acetate in the ratio of 4 : 1. The [Pd(cod)2]-catalysed reaction of isoprene with morpholine affords as the major product the tail-to-tail amine adduct. The specificity of this reaction is improved by the addition of 1 mol of PPh3. The system [Pd(cod)2]–PPh3 catalyses the addition of acetaldehyde to buta-1,3-diene to form 2-methyl-3,6-divinyltetrahydropyran. With phenyl isocyanate, piperidones are formed. Reaction of buta-1,3-diene with morpholine in the presence of [Pt(cod)2] gives only octa-1,3,6-triene; however, addition of the co-catalyst Al(OPrt)3 or Al(OBut)3 leads to the formation of the octadienylamine adducts. Telomerisation of buta-1,3-diene with acetic acid catalysed by [Pt(cod)2] gives selectively octa-2,7-dienyl acetate. Possible mechanisms for these reactions are discussed.

The kinetics and mechanism of the aminolysis of phenethyl nitrite

Abstract: Kinetic studies on the ammonolysis and aminolysis of phenethyl nitrite were carried out in 61% dioxan–water. Good second-order rate constants were obtained for the reactions except that with trimethylamine which is autocatalysed by the trimethylammonium ion formed. The rate of the trimethylammonium ion catalysed reaction was obtained from the slope of the plots of apparent second-order rate constants against concentration of trimethylammonium ion. There was no general base catalysis in any of the reactions. Solvent kinetic deuterium isotope effects were found to be 1.96 and 2.21 for the reactions with methylamine and morpholine, respectively, and 2.44 for the trimethylammonium ion catalysed reaction with trimethylamine. Bronsted plots are scattered, since substitution of hydrogen by a methyl group on NH3 markedly increases the nucleophilicity, e.g. the relative rates NH3 : MeNH2 : Me2NH : Me3N were 1 : 5.5 × 102 : 5.1 × 105 : 5.3 × 106. However, logarithms of the rate constants are correlated linearly with the vertical ionization potentials of these amines. All these results suggest that the reaction is ‘orbital controlled’ and proceeds via concerted displacement of alkoxide by amine rather than addition–elimination. The results are rationalized in terms of the high electronegativity of nitrogen and the presence of a lone pair of electrons on nitrogen.

Quinones and quinone methides. III. A novel side-chain amination reaction of 2-(1-Phenylethyl)-1,4-benzoquinones

Abstract: 2-Benzyl-5-methoxy-1,4-benzoquinones react as expected with morpholine to yield 2-phenylmorpholinomethylhydroquinones. However, 5-methoxy-2-(1-phenylethyl)-1,4-benzoquinones undergo a novel amination reaction at the β-carbon atom of the alkyl group with the formation of 2- morpholino-3-phenylbenzofurans.

Excretion and Distribution of Morpholine Salts in Rats

Abstract: Elimination, distribution and metabolism of morpholine salts in rats were investigated by means of chemical analysis and/or radioassay. Gas-liquid chromatography was used for chemical analysis of morpholine in the rat urine and faeces. The analytical results of the excreta accorded with those made by the tracer technique.When rats were given morpholine-HCl or -palmitate, it was found that about 90% of the dose was excreted in the urine over a period of 3 days and the remaining in the faeces. The faecal excretion of morpholine palmitate appeared to be a little more than that of morpholine-HCl after an oral dose of each labelled compound.Morpholine was largely excreted unchanged in the urine. The elimination of morpholine from organs, tissues and blood was generally rapid and specific organ-affinity was not observed in other organs except the intestine. The lowest affinity was found for adipose regardless of routes of administration.

Volatility of amines used for water treatment in steam generating systems

Abstract: The relative volatilities of cyclohexylamine and morpholine in dilute aqueous solution have been measured in the temperature range 150 to 300 °C at the corresponding equilibrium vapour pressure of the solution. Cyclohexylamine strongly prefers the steam phase while morpholine has a relatively volatility close to that of water. In both cases an azeotrope of the amine and water, with a vapour pressure higher than that of either component, must exist; however, with morpholine and water azeotrope formation only occurs above 175 °C. The concentration dependence of the distribution between the steam and solution phases of both amines is explained in terms of their partial ionization in solution.

Reaction between 2′,3′,5′-tri-O-acetyladenosine and aryl chloroformates. 2′,3′,5′-Tri-O-acetyl-N(6)-phenoxycarbonyladenosine as an intermediate in the synthesis of 6-ureidopurine ribosides

Abstract: Reaction between 2′,3′,5′-tri-O-acetyladenosine (6) and p-nitrophenyl chloroformate in pyridine solution at 20 °C or between (6) and phenyl chloroformate in pyridine solution at 70 °C gives the protected symmetrical urea derivative (7b) in moderate or high yield Deacetylation of (7b) gives the corresponding unprotected urea (7a) Treatment of (6) with an excess of phenyl chloroformate in pyridine solution at 20 °C gives the bisphenoxycarbonyl derivative (10) which, on reaction with morpholine in dioxan solution, is rapidly converted into 2′,3′,5′-tri-O-acetyl-N(6)-phenoxycarbonyladenosine (3c) Compound (3c) readily reacts with cyclohexylamine, ammonia, and glycine methyl ester at 20 °C to give, after deacetylation, the corresponding 6-ureidopurine riboside derivatives (9b, c, and d; R1= H) in high yields

The Oxidative Animation of Tropone and Tropolone

Abstract: The reaction of tropone with aniline, p-toluidine, p-anisidine, and p-chloroaniline in the presence of copper(II) acetate gave 2-arylaminotropones and 2-arylamino-N-aryltroponeimines. However, when o-toluidine and o-anisidine were used, only the corresponding 2-arylaminotropones were obtained. The reaction of tropolone with methylamine, ethylamine, and isopropylamine afforded 3-aminotropolone derivatives, while the reaction with dimethylamine, pyrrolidine, and morpholine gave 3- and 5-aminotropolone derivatives, the latter being minor products.

Imino containing morpholine compounds

Abstract: Compounds having the formula ##STR1## or a pharmaceutically acceptable salt thereof, wherein R1 is alkyl, cycloalkyl or aryl; R2 is acyl or sulfonyl; R3 is alkylamino, dialkylamino or a nitrogen containing heterocyclic group; R4 is alkoxy; A1 is a saturated bond or an alkylene group having 1 to 4 carbon atoms; and A2 is an alkylene group having 2 to 5 carbon atoms; have antiinflammatory activity.

Aminophenoxymethyl-2-morpholine derivatives, the preparation thereof and pharmaceuticals containing them

Abstract: 1. Aminophenoxymethyl-2-morpholine derivatives of formula see diagramm : EP0000693,P18,F1 in which R1 represents a hydrogen or halogen atom or the methyl group, R2 represents a hydrogen or halogen atom, R3 represents a hydrogen atom or the nitro group and R4 represents a hydrogen atom, a lower alkyl group, a carbalkoxy group, the phenyl or benzyl group, and their physiologically compatible acid addition salts.

Swelling behavior of cotton fibers in morpholine and piperidine

Abstract: Solution properties (conductivity and refractometry) of aqueous solutions of morpholine and piperidine as well as their aqueous mixtures with model compounds (glucose, cellobiose, xylose, and cellobiose octaacetate) in varying molar ratios were studied. The possible mechanism of the unique swelling action of morpholine on cotton cellulose and the total inaction of piperidine was investigated. It was shown that the solubility parameter (δ) may not fully indicate the swelling ability of a reagent, but the H-bonding portion (δH) and polar part (δp) of δ are of importance. Morpholine possesses a higher value of δH + δp than does piperidine; hence it is a powerful swelling agent for cellulose. It produces over 200% swelling at the interfibrillar level and has the ability to decrystallize cellulose under certain favorable conditions.

Cholesteryl phosphite and related compounds

Abstract: The preparation of cholesteryl phosphorodichloridite (2) is described; this compound with aniline (2 mol. equiv.) gave the N-phenylphosphoramidochloridite (5) and the latter by condensation with water afforded the N-phenyl-amidophosphite (6). Similarly the N-phenylphosphoramidochloridite (5) with morpholine gave the morpholidite (7); phenylhydrazine gave the hydrazinophosphite (8) and ethanol the amidoethyl phosphite (9). Cholesteryl phosphorodichloridite (2) by reaction with aniline (4 mol. equiv.) gave the N,N 1−diphenylphosphorodiamidite (10). The reaction of cholesteryl phosphorodichloridite (2) with methanol and ethanol are discussed in relation to the analogous reactions with cholesteryl phosphorodichloridate. Boiling ethanol gave cholesterol as the only isolatable product but at room temperature a low yield of the diethylphosphite (11; R=Et) was obtained. The yield of the phosphite was greatly increased in the presence of base. Similarly the dichloridite 2 with boiling water gave cholester...

Reaction of cyclohexanone enamines with diacyldi-imides

Abstract: Cyclohexanone morpholine and piperidine-enamines react with diacyldi-imides to give only monocycloaddition products, while pyrrolidine enamines also give bisaddition products in the 2,2- and 2,6-positions. The results of hydrolysis in D2O form the basis of a reaction scheme which takes the experimental findings into account. Dibenzoyldi-imide reacts with 2-methylcyclohexanone enamines giving two stereoisomeric cycloadducts, which are different in the orientatation of the methyl group, while bisaddition products could not be isolated. The stereochemistry of the reaction is discussed.

The thermal decomposition of quaternary ammonium hydroxides. Part 5. The importance of conformational factors in β-eliminations from quaternary hydroxides derived from piperidines, morpholines, and decahydroquinolines

Abstract: Classical work on the thermal decomposition of the 1-methylmethohydroxides of piperidine and C-methyl-piperidines has been confirmed, although the elimination products from 2- and 3-methylpiperidines contain small proportions of isomeric alkenes. The products of thermal decomposition of 3-oxa-6-azoniaspiro[5,5]undecane hydroxide show that β-elimination occurs several times faster in a morpholine ring than in a piperidine ring. The requirement for easy elimination in six-membered rings is the anti-coplanarity of the four centres Hβ, Cβ, Cα and N+. Strikingly, molecules which lack this requirement, such as the 1-methylmethohydroxide of cis-2,6-dimethylmorpholine gave no elimination whatever on thermal decomposition. On the other hand, thermal decomposition of the 1-methylmethohydroxide of trans-3,5-dimethylpiperidine gave ca. 50%β-elimination. Elimination of the β-hydrogens of an α-attached methyl group are strongly preferred to elimination of ring β-hydrogens, as in the degradation of cis-2,6-dimethylpiperidine, but a β-attached oxygen atom allows the corresponding morpholine compound to undergo 16% elimination of a ring hydrogen. The 1-methylmethohydroxides of substituted trans- and cis-decahydroquinolines (type 1) undergo elimination of a β-hydrogen in a 2-alkyl group, as expected from conformational considerations. However, a cis-molecule in which the type 2 conformation is dominant such as the 1-methylmethohydroxide of cis(4H,4aH), cis(4aH,8aH)-decahydro-2,2,4-trimethylquinoline, undergoes an appreciable proportion of elimination of the correctly oriented 8ax-H in the cyclohexane ring. In all cases reported, the direction of elimination is readily explained by reference to stereochemical considerations and to the steric and inductive effects of β-attached substituents.

Purification of acrylonitrile

Abstract: PURPOSE:To obtain a starting material of, e.g. acrylamide polymers which are excellent polymeric flocculants, easily by removing a small amount of impurities, e.g. acrolein, from acrylonitrile completely, using an aqueous solution of amine salt having a specific pH (alkali). CONSTITUTION:Acrylonitrile containing a small amount of impurities, e.g. acrolein, is purified by treating with an aqueous solution of pH 7.0-9.0 containing an amine salt, comprising a salt of an amine (e.g. aliphatic amines having amino-group and imino-group; alicyclic amines; heterocyclic amines, e.g. morpholine; aromatic amines, e.g. aniline) and an inorganic acid (e.g. carbonic acid, hydrochloric acid) or an organic acid (e.g. acetic acid, oxalic acid). USE:Starting material of acrylic synthetic fibers, acrylonitrile-butadiene-styrene synthetic resins, acrylonitrile-butadiene rubber, etc.

Bis-triazinylaminostilbene compounds and their use as fluorescent brightening agents

Abstract: Bis-triazinylaminostilbene compounds of the formula ##STR1## in which R 1 is alkyl, alkenyl, cyclohexyl or phenylalkyl, R 2 is hydrogen, alkyl, cyclohexyl, benzyl, alkyl which is substituted by hydroxyl, cyano, sulpho or carbamoyl, alkoxyalkyl or hydroxyalkoxyalkyl or alkoxyalkoxyalkyl or mono- or di-alkylaminoalkyl, and R 3 is hydrogen, alkyl, alkyl which is substituted by hydroxyl, cyano or sulpho, or alkoxyalkyl or hydroxyalkoxyalkyl or R 2 and R 3 together with the nitrogen atom to which they are bonded are a morpholine ring or a pyrrolidine, piperidine, hexamethyleneimine or piperazine ring which is unsubstituted or substituted by 1 or 2 alkyl groups, and M is hydrogen or an alkali metal, ammonium or amine ion, and, if R 2 or R 3 is hydroxyalkyl, R 1 is methyl, cyclohexyl or alkenyl only, and their use as fluorescent brightening agents for organic material of high molecular weight are disclosed.

Stabilization of magnetite pigments with heterocyclic nitrogen compounds

Abstract: of the Disclosure A finely divided magnetite pigment such as is used in magnetic tapes is stabilized against oxidation by contact with a heterocyclic nitrogen compound such as morpholine, triazole, piperazine or substitution products thereof. The heterocyclic compound can be applied as a solution or in vapor form.

Reactions of 3-alkoxy- and 3-alkylthio-benzo[b]thiophen 1,1-dioxides with morpholine, piperidine, and pyrrolidine

Abstract: 2-Phenyl-(1a) and 2-methyl-3-methoxybenzo[b]thiophen 1,1-dioxide (1b) undergo ring opening to form amides on treatment with morpholine and with piperidine, but react with pyrrolidine to yield enamines; the 2-unsubstituted analogue (1c) undergoes ring-cleavage to amides with all three amines. 3-Benzyloxy- 6(a) and 3-benzylthio-2-phenylbenzo[b]thiophen 1,1-dioxide (8a) also yield the corresponding amide or thioamide with morpholine and piperidine but the enamine with pyrrolidine.

Improved Syntheses for CIS- BIS (Amino) Tetrachlorocyclotriphosphazenes

Abstract: Methods for the preparation of cis-bis (alkylamino) tetrachloro-cyclotriphosphazenes (amines: methylamine, dimethylamine, diethylamine, piperidine, morpholine, pyrrolidine) in yields 5-30-fold greater than previously reported, are presented and discussed.

The Synthesis Of 2,4-Bis(dialkylamino)-2,4-dichloro-6,6-difluorocyclotriphosphazenes

Abstract: Five pairs of isomeric cis- and trans- 2,4-bis(dialkylamino) -2,4-dichloro-6,6-difluorocyclotriphosphazenes (amines: dimethylamine, diethylamine, piperidine, morpholine, pyrrolidine) were prepared by fluorination, using KSO2F, of the corresponding 2,4-bis(dialkylamino) tetrachlorocyclotriphosphazenes. Mechanistic and other aspects of the reaction are discussed.