Showing papers on "Morpholine published in 1974"

Process for producing polyamines

Abstract: Polymers or copolymers of diallylamine derivatives of the formula, CH2=CR1-CH2+R2 ANGLE N ANGLE CH2=CR1-CH2R3 Y wherein R1 is hydrogen or methyl: R2 and R3 are independently hydrogen, allyl, methallyl, straight-chain or branched-chain alkyl having 1-16 carbon atoms, phenylalkyl or hydroxyalkyl of the formula, HO-(-CH2-)m-, in which m ia an integer of 1-6 or R2 and R3 may form together with the adjacent N atom pyrrolidyl, piperidyl or morpholino; and Y is halogen or inorganic acid anion, are produced by conducting photopolymerization of a solution or slurry of at least one diallylamine derivative mentioned above with or without other comonomer such as maleic anhydride, maleic acid, or a vinyl compound, with irradiation of light having wavelengths of 150-500 m mu . The polymerization rate can be accelerated in the presence of a special sensitizer such as benzophenone or acetophenone together with hydroquinone, dioxane, morpholine or derivative thereof, or a charge-transfer complex of sulfur dioxide and a diallylamine derivative.

Reaction of amines with 1,3-dienes catalysed by nickel complexes

Abstract: Reactions of morpholine, piperidine, pyrrolidine, di-n-propylamine, n-butylamine, aniline, and p-anisidine with buta-1,3-diene in the presence of catalytic quantities of nickel acetylacetonate and di-isopropoxyphenylphosphine have been studied. Mixtures of 1 : 1 (butenyl) and 2 : 1 (octadienyl) amine products are produced and the reaction with morpholine has been studied in detail to examine the factors determining the product mixtures. Butenyl adduct formation is favoured by (a) a 3 : 1 ratio of phosphine–nickel salt concentration, (b) use of nickel halides with ethanol solvent, and (c) a low effective concentration of butadiene. A product mixture containing 86% octadienyl adduct was obtained by using a preformed Ni0 complex Ni[P(OPh)3]4. Reaction of morpholine and isoprene gave mainly a 1 : 1 adduct and small amounts of a 2 : 1 adduct; a similar reaction with trans-piperylene gave only a 1 : 1 adduct. The mechanism of the reactions is discussed in terms of formation of the butenyl and octadienyl adduct formation from π-allylnickel and bis-π-allylnickel complexes. The use of cocatalysts such as sodium borohydride in the reactions is discussed. Isomerisation of branched to linear butenyl adduct has been demonstrated to occur.

Preparation and Evaluation of a Water-Soluble Cholesterol Standard

Abstract: We synthesized some inorganic and organic salts of cholesteryl hemisuccinate. Aqueous solutions of the morpholine salt, at concentrations equivalent to 400 mg of cholesterol per deciliter, have been evaluated as aqueous cholesterol standards and compared to alcoholic cholesterol solutions in analyses for cholesterol in serum, as performed by two analytical reference procedures. No significant differences were found. The usefulness of solutions of this salt as additives for serum controls or recovery studies has been also demonstrated.

Preparation, Infrared Spectra, Electronic Spectra, and Magnetic Moments of Copper(II) Complexes of N-Acetylglycine and Their Amine Adducts

Abstract: Compounds of the type [CuA2•H2O]2 and [CuA2•4H2O]2 have been prepared, where A is N-acetylglycine (aceturic acid). Amine adducts of the type CuA2B (B = piperazine, 2,2′-bipyridine, and 1,10-phenantroline) and CuA2B2 (B = N-methylpiperazine, piperidine, morpholine, pyridine, and ethylenediamine) were obtained by reaction of the amines with CuA2•4H2O. Each complex was characterized by elemental analysis, infrared spectrum, electronic spectrum, and magnetic moment. For the piperazine and ethylenediamine adducts a square-planar pattern of coordination about copper(II) ion is probable, while for the other amine adducts a square-pyramidal structure is proposed. For all the complexes the coordination of the N-acetylglycine occurs only through the terminal carboxyl oxygen in a monodentate arrangement.

Ortho alkyl phenol and ortho alkyl phenol sulphide lubricating oil additives

Abstract: An additive mixture for lubricating oils and fuel oils having good antioxidant and anticorrosion properties comprising: (a) 45-75 wt.% of an ortho alkyl phenol, (b) 5-20 wt.% of an ortho alkyl phenol disulphide and (c) 15-40 wt.% of an ortho alkyl phenol trisulphide. Optionally the additive may also contain small amounts of the corresponding mono- and tetra-sulphide. Such additives may be made by reacting an alkyl phenol with sulphur in the presence of an organic amine having a pKb of between 2 and 12, e.g. morpholine.

Acetato‐ and Propionato‐(Saturated Heterocyclic) Amine Complexes of Cobalt(II), Nickel(II), and Copper(II)

Abstract: Die bis-Acetato- und Propionato-Metalladdukte von Piperidin-(pipd), Piperazin(pipz), N-Methylpiperazin(CH3-pipz) und Morpholin(morph) wurden in festem Zustande isoliert und optisch und magnetisch untersucht. Piperazin bildet 1:1-Komplexe, die anderen Amine bilden 1:2-Komplexe. Die IR-Spektren ergeben, das die Amine an das Metallatom uber das N-Atom koordiniert sind, Acetat und Propionat sind symmetrische oder asymmetrische zweizahnige Liganden. In Monopiperazin-Addukten verbruckt das Amin zwei Metallatome. Elektronenspektren und magnetische Momente weisen auf eine transoktaedrische Konfiguration der Addukte. Acetato- und Propionato-Komplexe gesattigter N-Heterozyclen mit CoII, NiII und CuII The bis acetato and propionatometal-adducts of piperidine (pipd), piperazine (pipz), N-methylpiperazine (CH3-pipz) and morpholine (morph) are isolated in the solid state and investigated by spectral and magnetic measurements. Piperazine forms 1:1 complexes, the other amines 1:2 complexes. The infrared spectra show that the amines are coordinated to the metal atom toward the nitrogen atom and that the acetate and propionate act as symmetrical or asymmetrical bidentate ligands. The i.r. spectra give also evidence that in monopiperazine adducts the amine “bridges” two metal atoms. Electronic spectra and magnetic moments suggest a tran-octahedral configuration of the adducts.

Aqueous dispersions of thermosettable synthetic addition polymers with 1,2-epoxy resin plasticizer

Abstract: A process for producing an aqueous dispersion of a thermosettable, solid, water insoluble, addition polymer which comprises polymerizing in water at least one α,β-ethylenically unsaturated main monomer, which is very slightly soluble in water, with at least one α,β-ethylenically unsaturated monomer containing a reactive group in the presence of a material selected from the group consisting of surface active agents, suspension agents and mixtures thereof and water soluble, polymerizable ionic monomers consisting of sulpho esters of the formula: R -- CO.sub.2 -- Q -- SO.sub.3 M wherein R is selected from the group consisting of vinyl and α-substituted vinyl groups, Q is a divalent hydrocarbon radical having its valence bonds on different carbon atoms and M is a cation selected from the group consisting of sodium, potassium, lithium, ammonium, substituted ammonium compounds of the formula NR' 4 wherein R' is alkyl (C 1 -C 4 ) or alkanolamine (C 1 -C 3 ), morpholine, substituted morpholine derivatives and water soluble salts of vinyl sulphonate and allyl sulphonate and of at least one modifier which is non-reactive or contains at least one complementary reactive group, and when the modifier is non-reactive, incorporating in the polymerization mixtures, at least one α,β-ethylenically unsaturated monomer containing a complementary reactive group. In addition, the resulting polymerized dispersion may be blended with a water soluble resin. The polymer particles may be formed with the complementary reactive groups located in different layers of the particles or with the groups substantially uniformly distributed throughout their depth. The dispersions may be in the form of suspensions or emulsions. The resulting aqueous dispersions have great utility as coating compositions for glass and steel substrates.

4-Acetyl-2,3-dimethyl-6-isopropenylmethyl-cyclohexene

Abstract: AND (III) AND A MIXTURE OF COMPOUNDS HAVING THE II. A mixture of compounds having the structure: A superatmospheric process for directly producing a Diels-Alder adduct which comprises admixing: I. A conjugated diene which can be either alpha-terpinene, alloocimene, cyclopentadiene or myrcene; with II. A carbonyl group-containing compound which can be either acetone, acetaldehyde propionaldehyde or methylethyl ketone; with III. An aldehyde source which can be either a formaldehyde source or an acetaldehyde source which aldehyde source will yield formaldehyde or acetaldehyde; in the presence of IV. A secondary amine catalyst such as a lower dialkyl amine or a cyclic amine such as morpholine, pyrrolidine or piperidine, AT A TEMPERATURE IN THE RANGE OF FROM ABOUT 120*C up to about 200*C for a period of time from about 2 hours up to about 8 hours, and novel products produced therefrom to wit: I. A mixture of compounds having the structures:

Inhibiting discoloration of aqueous compositions containing hexamethylenetetramine 1,3-dichloropropene salts

Abstract: Aqueous compositions of cis- and cis-, trans-1-(3-chloroally)-3,5,7-triaza-1-azoniaadamantane chloride mixtures, which normally discolor on aging, are stabilized against discoloration by adding thereto an amine of the group of morpholine, ethylamine, N-methylethanolamine, diethanolamine, dipropylamine, diisopropanolamine and di-sec.-butanolamine.

Mechanism of cyclisation of N-(1,2,4-triazol-3-yl)hydrazonyl bromides to mixtures of isomeric triazolotriazoles

Abstract: The reaction of N-(5-phenyl-1,2,4-triazol-3-yl)arenohydrazonyl bromides (2) in mixed aqueous, organic solvents may yield three products, dependent on the acidity of the medium. In strongly acidic solution, N-(5-phenyl-1,2,4-triazol-3-yl)arenohydrazides (4) are formed as major products; at pH 3–6, 3-aryl-5-phenyl-1H-s-triazolo-[3,4-c]-s-triazoles (5) were formed exclusively while in basic media the isomeric 3-aryl-6-phenyl-5H-s-triazolo-[4,3-b]-s-triazoles (6)[which are also formed by the action of lead tetra-acetate on the hydrazone (1)] predominate. Kinetic studies (in 85 : 15 dioxan–water at 25°) indicate that in neutral solution (5) is formed by intramolecular cyclisation of the neutral triazole on an azocarbonium ion centre (Hammett ρ for the variation of substituents in Ar is –1·32); when the triazole ring is protonated intermolecular attack by water [formation of (4) occurs]. The isomer (6) is formed by [1,5] dipolar cycloaddition involving the triazolyl anion as nucleophile. The isomer (6) was synthesised by an independent route. Under appropriate conditions intermolecular reactions of (2) with chloride ion, aniline, and morpholine yielded products in which bromide ion was replaced by the nucleophile.

A New Synthesis of 4-(4-Methyl-4-hydroxyamyl)-Δ3-cyclohexenecarboxaldehyde

Abstract: A new synthetic route of 4-(4-methyl-4-hydroxyamyl)-Δ3-cyclohexenecarboxaldehyde (Lyral) from myrcene (1) was investigated. It involves subjecting 1 first to the diene synthesis with acrolein (2) followed by hydration of the morpholine enamine of the adduct in 50% sulfuric acid at 0–5° and the subsequent hydrolysis in diluted sulfuric acid at 15–20°.The present method is superior in simplicity as well as productivity for the preparation of Lyral to any other methods hitherto reported.

Triazines and related products. Part XIII. Decomposition of 4-Arylamino-1,2,3-benzotriazines and their precursors in secondary amines

Abstract: 4-Arylamino-1,2,3-benzotriazines (1) decompose in piperidine and related secondary amines to afford NNN′-trisubstituted 2-aminobenzamidines (4) in excellent yields. 4-o-Aminoanilinobenzotriazine (1f) yields 2-(2-aminophenyl)benzimidazole (9) when heated in ethylene glycol or piperidine. Nucleophilic attack by the amines at C-4 of the triazine ring is implicated in these transformations. 1-o-Cyanophenyl-3-m-cyanophenyltriazene (13a) is unreactive in piperidine whereas the p-cyanophenyltriazene isomer (13b) yields 2-amino-N′-p-cyanophenyl-NN-pentamethylenebenzamidine (4b). 1,3-Bis-o-cyanophenyltriazene (13c) rearranges and decomposes in boiling piperidine, pyrrolidine, morpholine, diethylamine, di-n-propylamine, and piperazine to afford the triazenylquinazolines (19)–(24), respectively.

Synthese von 2-Methylen-2,3-dihydro- und 2-Methyl-5 H -thiazolo[3,2— a ]thieno[2,3— d ]pyrimidinen

Abstract: The title substances and their [1]benzothieno analogues were synthesized by reaction of 3-allyl-2-mercapto-([1]benzo)thieno-[2.3—d]pyrimidine-4(3H)-ones with Br2 to 2-bromomethyl-2.3-dihydro-thiazolo[3.2—a]([1]benzo-)thieno[2.3—d]pyrimidine-5-ones, which on treatment with morpholine did not give the corresponding morpholine derivatives but elimination to the exocyclic double bond. These 2-methylene-2.3-dihydro-products were isomerized by H2SO4 to the corresponding 2-methyl compounds.

Substituted morpholine guanidines for the treatment of arrhythmic conditions

Abstract: The pharmaceutical compositions and methods of using these compositions for anti-arrhythmic and diuretic uses are disclosed for the compounds below: ##EQU1##

N6 -Substituted-9-[3-(4-phenyl-piperazino)-propyl]-adenines

Abstract: A N 6 -substituted-9-[3-(4-phenyl-piperazino)-propyl]-adenine of the formula ##STR1## wherein R 1 is hydrogen or a lower alkyl radical, and R 2 is a lower alkyl radical, a lower alkyl radical substituted by at least one of phenyl and hydroxyl, a lower alkenyl radical, a cycloalkyl radical or an aryl radical, or R 1 and R 2 together with the nitrogen atom to which they are attached form a piperidine, pyrrolidine or morpholine ring, and R 3 is hydrogen, halogen, a lower alkyl radical or a lower alkoxy radical, Or a salt thereof with a pharmacologically compatible acid, which compounds are characterized by marked anti-edematous activity as well as by activity in reducing capillary permeability.

A New Synthesis of 3-Alkyl-2-hydroxy-2-cyclohexen-1-ones

Abstract: A New synthesis of 2-hydroxy-3-methyl-2-cyclohexen-1-one (Ia), a flavor component of coffee aroma, is described. The selenium dioxide oxidation of ethyl 1-methyl-2-oxocyclohexanecarboxylate (IIa) gave α-diketone (IIIa), which was then hydrolyzed and decarboxylated to afford Ia. The treatment of IIa with cupric chloride in 50% acetic acid also yielded Ia. The dimethyl sulfoxide oxidation of ethyl 3-bromo-1-methyl-2-oxocyclohexanecarboxylate (IV) afforded IIIa, along with 3-bromo-6-ethoxycarbonyl-2-hydroxy-6-methyl-2-cyclohexen-1-one (V). The halogenation of IIa produced dihalogeno ketoesters (VIa) (VIIa), which also yielded Ia in a pure state by means of a direct acidic hydrolysis or by a two-step hydrolysis using morpholine. Other allied compounds are also described.

Enamine chemistry. Part XIX. Stereochemistry of the transition state of the reaction of αβ-unsaturated acid chlorides with enamines: crystal structure of 1-methyl-7-exo-t-butylbicyclo[3.3.1]nonane-2,9-dione

Abstract: Treatment of the morpholine enamine of 2-methyl-4-t-butylcyclohexanone with acryolyl chloride in boiling benzene gives 1-methyl-7-t-butylbicyclo[3.3.1]nonane-2,9-dione (VIII) as a mixture of two isomers (4 : 1). X-Ray analysis of the major isomer indicates that initial carbon–carbon bond formation occurs predominantly from the axial side of the enamine double bond. The molecular conformation is boat-chair.

Polymerisable disubstd. carbamoyloxyalkyl carboxylic acid esters - prepd. from disubstd. carbamic acid beta-hydroxy-alkyl esters and mono-olefinically unsatd. carboxylic acids

Abstract: New polymerisable N,N-disubstd. carboxylic acid esters of general formula R1R2N-COO-CHR3-CH2OOC-CHR3-CHR5 (I) (where R1 and R2 are 1-4C alkyl, 5-6C cycloalkyl, or R1 and R2 form a morpholine-, a piperazine- or an N- 1-4C alkyl-piperazine ring together with N atom to which they are bonded; R3 is H, Me or Et; R4 is H or Me; R5 is H or Me or -COOH provided R4 is H). Starting materials for prodn. of homo- and copolymers which can be have mol. wt. 5000 - 107, for mfr. of moulded bodies, coatings, adhesives binders for fibre fleeces, paper coatings, finishing compsns. for textiles, leather and paper. Polymers have strong affinity to OH gp.-contg. polymers without having appreciable basicity.

Tautomerism of enamines derived from 2-tetralone. Difference in nucleophilic behaviour between morpholine and pyrrolidine enamines

Abstract: Phenyl isocyanate attacks both the morpholine and the pyrrolidine enamine derived from 2-tetralone at C-1, whereas β-nitrostyrene attacks the former 80% at C-1 and 20% at C-3 and the latter exclusively at C-3. These results confirm the existence of an equilibrium between the 3,4- and 1,4-dihydro-forms of the enamines.

N-Aminoalkyl-2-alkoxy-5-sulphamoyl-benzamides prepn - from 2-alkoxy-benzoic acids via 5-fluorosulphonyl cpds

Abstract: Benzamides of formula (I) (where X is H or halogen; R is H or alkyl, R1, R2 and R3 are H, is not >4C alkyl or benzyl, and may be linked with each other or with R so as to form a ring; R4 is alkyl, alkenyl, aralkyl, or alkoxyalkyl; and R5 and R6 are H, alkyl or alkenyl, and may be linked with each other so as to form a ring), e.g. N-(1-ethyl-2-pyrrolidinylmethyl)-2-methoxy-5-sulphamoylbenzamide, and their salts are prepd. by reacing a 2-halo-4-X-benzoic acid (II) with R4OH in the presence of Cu and a sec. aliphatic amine (e.g. dimethylamine) or a cycloaliphatic amine (e.g. dimethylamine) or a cycloaliphatic amine (e.g. morpholine, piperidine or pyrrolidine) to give a 2-OR4-4-X-benzoic acid (IV), chlorosulphonating this cpd. and reacting the prod. in water or a lower alcohol with a fluoride so as to give a 2-OR4-4-X-5-fluorosulphonylbenzoic acid (VI), converting this into the acid chloride (VII), reacting (VII) with a stoichiometric amt. of an amine of the formula R-NH-CH2-CHR1-NR2R3 (VIII) to give the hydrochloride of an amide of formula (IX), and reacting (IX) with an amine HNR5R6 (X) to give (I). Of the cpds. (I), N-(1-ethyl-2-pyrrolidinylmethyl)-2-methoxy-5-sulphamoyl-benzamide is a known cpd. with psychotropic, spasmolytic and antiemetic activity. Simple and cheap process which proceeds through intermediates which can readily be purified so that (I) of high quality is obtd.

Preparation and characterisation of some niobium and tantalum penta-alkoxide co-ordination complexes

Abstract: The first isolated niobium pentamethoxide complexes Nb(OMe)5,L (I; L = pyridine, γ-picoline, morpholine, hydrazine, trimethylamine oxide, and hexamethylphosphoramide) are reported, together with Ta(OMe)5,N2H4. N.m.r. and i.r. spectra are discussed in terms of formation of octahedral six-co-ordinate niobium complexes. In these complexes hydrazine behaves as a unidentate ligand.

Triazines and related products. Part XII. Reactions of 3,4-dihydro-4-imino-1,2,3-benzotriazines and 1,2,3-benzotriazin-4(3H)-ones in secondary amines

Abstract: 3-Substituted 3,4-dihydro-4-imino-1,2,3-benzotriazines (1a–g) undergo ring opening in piperidine, morpholine, and pyrrolidine to afford the o-cyanophenyltriazenes (2a–g), respectively. Attack by the bases at the exocyclic imino-substituent is implicated in these isomerisations since the 3-benzyltriazine (1h) and the 3-substituted 4-arylimino-3,4-dihydro-1,2,3-benzotriazines (4a–e) are all unreactive. Similarly, reaction of the bases at the exocyclic imino-group of the N-hydroxy-tautomer of 4-aminobenzotriazine 3-oxide (6) leads to o-azidobenzonitrile (8).The fused 1,2,3-benzotriazines (11) and (13) react with secondary amines to afford 3,3-dialkyl- or polymethylenetriazenes, but the reactivity of 3-substituted 1,2,3-benzotriazin-4(3H)-ones (19) towards piperidine and its analogues is dependent on the nature of the 3-substituent.