Showing papers on "Morpholine published in 1983"

Reaction of quinoxaline derivatives with nucleophilic reagents.

Abstract: 2-Chloro-3-methylquinoxaline reacts with aromatic amines in basic medium forming 2-arylamino-3-methylquinoxalines, also it reacts with mercaptoacetic acid. The 3-methyl-2(1H)-quinoxalinone condenses with aromatic aldehydes forming the corresponding 3-(substituted styryl)-2(1H)-quinoxalinones which add bromine in acetic acid to yield the corresponding dibromo derivatives which react with morpholine, sodium methoxide, and piperidine to give the corresponding compounds. 3-Methyl-2(1H)-quinoxalinone undergoes side-chain bromination to yield 3-bromomethyl-2(1H)-quinoxalinone, which reacts with aromatic amines, sodium salt of saccharine, potassium phthalimide··· 3-Methyl-2(1H)-quinoxalinone with P2S5 gave 3-methyl-2(1H)-quinoxalinethione which reacts with 2-aminoethanol, dimethyl sulfate, and halo acids.

Electrolyte for zinc-bromine storage batteries

Abstract: A negative electrolyte for electrolyte circulation-type storage batteries has a composition basically comprising zinc bromide as an active material and this active material is mixed with specified amounts of quaternary ammonium bromides of heterocyclic compounds such as morpholine, pyridine and pyrrolidine or ammonia as a bromine complexing agent and a dendrite inhibitor with or without specified amounts of Sn 2+ and Pb 2+ .

Conformational effects on the activity of drugs. 10. Synthesis, conformation, and pharmacological properties of 1-(2,5-dimethoxyphenyl)-2-aminoethanols and their morpholine analogues

Abstract: In order to obtain a better understanding of the effects that structural parameters have on the changes of adrenergic activity when 1-aryl-2-aminoethanol derivatives are converted into their corresponding 2-arylmorpholine cyclic analogues, we synthesized 1-(2,5-dimethoxyphenyl)-2-aminoethanol derivatives 5-7 and their morpholine analogues 8-10. The preferred conformation of amino alcohols and their cyclic analogues have been determined through an H NMR and IR study. Compounds 5 and 6 showed both alpha-stimulating and alpha-blocking activity on rat vas deferens, the effect depending on the concentration employed; on the same isolated tissue, N-isopropyl derivative 7 and the morpholine analogues 8-10 exhibited only alpha-blocking activity. As for the beta-adrenergic activity, only the open-chain compound 7 possessed a moderate blocking effect on isolated guinea pig atria. The results of this work seem to indicate that the changes of pharmacological activity involved in the transformation of the adrenergic drugs into their morpholine analogues are influenced more by characteristic features of the aromatic moiety than by the ethanolamine or propanolamine structure of the drugs.

The nitrosating agent in mice exposed to nitrogen dioxide: improved extraction method and localization in the skin.

Abstract: We reported previously that mice exposed to atmospheric NO2 contained a nitrosating agent (NSA) that reacted with morpholine in aqueous methanol homogenates of the mice to give N-nitrosomorpholine. We have now found that N-nitrosomorpholine was also produced by reacting morpholine with ether extracts of aqueous homogenates prepared from NO2-exposed mice. After exposure to NO2 for 4 hr, mice contained NSA (5.0 nmol/g tissue, corrected to 50 ppm NO2 and assuming that 1 mol NSA yields 1 mol N-nitrosomorpholine). This is 3.6 times the concentration observed by our previous method. Some NSA (0.6 nmol/g tissue) was also detected in untreated mice. The NSA in ether extracts was nonvolatile and stable on storage at -15° or for short periods in the presence of water at pH 1 to 10, but it was decomposed by a pH 1 solution of nitrite scavengers. It reacted to similar extents with three different secondary amines. Eighty-eight % of the NSA occurred in the skin, one-third of which was in the hair. The high skin concentration occurred when the bodies but not the heads of mice were exposed to NO2, indicating that the major exposure route was the skin. The NSA might consist of α-nitro or other activated nitrite esters derived from unsaturated lipids.

Polymers from 1,2-Disubstituted Ethylenic Monomers. V. Radical Polymerization of Dimethyl Maleate in the Presence or Absence of Isomerization Catalyst

Abstract: Although dimethyl maleate (DMM) did not give any homopolymer with a radical initiator, it was polymerized in the presence of some amines via a monomer-isomerization radical polymerization mechanism, i.e., DMM isomerized to dimethyl fumarate (DMF) which then homopolymerized. For this polymerization, some primary or secondary aliphatic amines served as isomerization catalysts, and morpholine showed the most efficient activity. The activation energies for the monomer-isomerization radical polymerization of DMM with di-tert-butyl peroxide in the presence of morpholine and for the isomerization from DMM to DMF with morpholine were 95.9 and 23.0 kJ/mol, respectively. Morpholine was also observed to act as a retarder in radical polymerization of DMF. Moreover, the relationships between rates or copolymer compositions and the feed monomer compositions in the copolymerization of DMM with styrene in the presence of morpholine were found to become close to those of DMF with styrene, although both relationsh...

Kinetic studies on the formation ofN-nitroso compounds VII. Nitrosation of morpholine in acetate buffer

Abstract: The kinetics of the nitrosation of morpholine in acetate buffer have been studied. It was found that in the experimental conditions used the effective nitrosating agent is dinitrogen trioxide, whose formation is promoted by the acetate ion in accordance with the scheme: No reaction between nitrosyl acetate and the a mine was observed, probably owing to the low concentration of the former. The proposed mechanism explains the experimental facts that no catalysis by the buffer is observed in conditions in which the rate controlling step is the reaction of N2O3 with the amine, and that the catalytic effect has only been observed when the formation of the nitrosating agent is also rate controlling. Values have been calculated for several equilibrium and kinetic constants involved in the mechanism proposed.

Catalysis of condensation reactions

Abstract: Certain hydrogen phosphate and pyrophosphate compositions are employed as catalysts for organic condensation reactions. Particularly high conversions and selectivities are obtained by the use of synergistic mixtures of in cyclization reactions such as in the conversion of hydroxyethylpiperazine to triethylenediamine and morpholine to dimethylaminoethylmorpholine.

Heterocyclic systems. Part 14. Condensation reactions of 2-(4-oxo-4H-1-benzopyran-3-yl)-1,3-dioxolane

Abstract: Nitrogen nucleophiles under 1,4-addition with the title acetal (4; R = H, Me, and Cl) to give an intermediate that ultimately produces in most cases the same product as is obtained from the corresponding aldehyde (3) under similar conditions. Thus, compound (4) condenses with piperidine and morpholine to give the enamino ketone (14; R1R2=–[CH2]5–, –[CH2]2O[CH2]2–), with aniline to give the chromanone (15; Z = H, Me, and OMe), and with o-phenylenediamine to give the dihydrodiazepine (16), the latter being dehydrogenated to the unsaturated compound (17) by boiling in acetic acid. On being refluxed with hydrazine (5) in pyridine, the acetal (4; R = H) affords smoothly the benzoylpyrazole (20; R′= H, Ph), whereas (4; R = Me or Cl) even with equimolar proportions of hydrazine in refluxing ethanol gives predominantly, if not exclusively, the pyrazole (25; R′= H, Ph). Guanidine and urea with (4) give the fused aminopyrimidine (33) and the hydroxy analogue, respectively.

Synthesis of morpholinium [13C] formate and its application in the synthesis of [8‐13C] purine base

Abstract: Morpholinium [13C]formate is obtained by neutralizing an aqueous solution of equivalent amounts of sodium [13C]formate and hydrochloric acid with morpholine. Morpholinium [13C]formate is isolated in crystalline form and characterized. Treatment of 6-hydroxy-2,4,5-triaminopyrimidine sulfate with morpholinium [13C]formate at 200° affords [8-13C]guanine in 80% yield. There is no necessity to synthesize and isolate [13C]-N-formylmorpholine and the intermediate N5-[13C]formyl pyrimidine derivative. Mass spectrometric analysis shows that the molar isotopic concentration of 13C label in guanine is identical to that of the morpholinium [13C]formate and there is no isotopic scrambling. The same procedure when used with 4,5,6-triaminopyrimidine sulfate affords adenine in 85% yield.

The Nitroprusside Ion as a Nitrosating Reagent. Kinetic Studies on the Nitrosation of Morpholine

Abstract: This article reports a kinetic study of the nitrosation of morpholine (MOR) by the nitroprusside ion, [Fe(CN)5NO]2−, to form N-nitrosomorpholine, a substance of proven carcinogenicity. The reaction is of order one with respect to the nitroprusside ion and order two with respect to morpholine. The influence of the pH and the ionic strength of the medium on the rate of reaction has been studied in detail. A reaction mechanism is proposed whose first step is a fast reaction between the amine and the coordinated nitrosyl group to form a complex which reaches equilibrium with the reagents and then reacts with another molecule of amine to produce the corresponding nitrosamine and the complex [Fe(CN)5MOR]3−. The acidity constant of morpholine has been determined kinetically.

Relationship of spontaneous chemical transformation of arylsulfonylhydrazones of 2-pyridinecarboxaldehyde 1-oxide to anticancer activity.

Abstract: The arylsulfonylhydrazones of 2-pyridinecarboxaldehyde 1-oxide represent a relatively new class of antineoplastic agents with the potential for clinical usefulness. The requirement for spontaneous chemical transformation of these agents to exert anticancer activity was evaluated using as the prototype the most potent member of this class synthesized to date, the 3,4-dimethoxybenzene sulfonylhydrazone of 2-pyridinecarboxaldehyde 1-oxide (3,4-DSP). 3,4-DSP was chemically unstable, decomposing with a half-life of 19 min in 0.01 m potassium phosphate buffer (pH 7.4) at 37°. The major chemical decomposition product was identified as 2-pyridylcarbinol 1-oxide by comparison with the authentic compound. This carbinol is hypothesized to be formed via the intramolecular abstraction of hydrogen from the arylsulfonylhydrazone, a process that leads to the release of 3,4-dimethoxybenzenesulfinic acid and the formation of 1-oxidopyridin-2-yldiazomethane, which subsequently reacts with water. The diazomethane intermediate is a potent alkylating agent which, if generated in cells, would have the potential to alkylate nucleophilic groups of biologically important macromolecules. The proposed reactive species was trapped using both 4-(4-nitrobenzyl)pyridine (NBP) and morpholine, and the latter product was characterized by mass spectroscopy. The importance of the chemical formation of an alkylating species to cytotoxicity was demonstrated by studies in which solutions of 3,4-DSP were “aged” prior to addition to L1210 leukemia cells in culture and prior to incubation with NBP. The “aging” of 3,4-DSP for 20 min resulted in a 4-fold decrease in cytotoxicity, and aging for 1 to 3 hr led to complete loss of cytotoxicity. Correspondingly, a 20-min aging period decreased alkylation of NBP by 51%, and 3-hr aging resulted in essentially no alkylation of the nucleophile. Further support for the above proposed chemical activation pathway was provided by correlations between in vitro cytotoxicity, in vivo antineoplastic activity, chemical stability, and the degree of alkylation of NBP by a wide variety of arylsulfonylhydrazones. The lack of the 1-oxide, envisioned to be required for intramolecular hydrogen abstraction, the steric prevention of the abstraction, or the replacement of the proton of the nitrogen of the side-chain by a methyl group resulted in a marked increase in chemical stability and a corresponding loss of the ability to alkylate NBP and to inhibit the replication of L1210 leukemia cells in culture.

Use of morpholine neutralized phosphate and thiophosphate esters as ethylene furnace anti-coking antifoulants

Abstract: OF THE DISCLOSURE An improved method of reducing fouling and corrosion in ethylene cracking furnaces using petroleum feedstocks, comprising treating the petroleum feedstock with at least 10 ppm of a compound chosen from the group consisting of phosphite esters, phosphate esters, thiophosphite esters, thiophosphate esters and mixtures thereof, said esters being characterized by the formulae:

Nitroimidazoles. part xi. some halonitro- and dinitroimidazoles

Abstract: Methylation of 2-chloro-4-nitroimidazole (6), obtained from imidazole in four steps, either with dimethyl sulphate or with diazomethane affords a mixture of 2-chloro-l-methyl-5-nitroimidazole (10) and the 4-nitro-isomer (7). The corresponding dinitro compounds 11 and 8 are formed in the methylation of 2,4-dinitroimidazole (5), 8 being converted to 7 by the action of POCl3. Reaction of 10 with the sodium salt of N-methanesulphonyl-2-imidazolidinone provides the potent amoebicide, 1-methylsulphonyl-3-(1-methyl-5-nitroimidazol-2-yl)-2-imidazolidinone (2). The isomer 14 is synthesised from 7 in low yield. Ethylation of 5 leads to preponderant N-alkylation, providing a mixture of l-ethyldinitroimidazoles (9) and (12), but a small amount of N,C-diethyl derivative 15 is also obtained. The formation of 15 from 5 is rationalised. The diiodination product of imidazole is shown to be 4,5-diiodoimidazole (19), nitric acid transforming it to 4-iodo-5-nitroimidazole (20). Methylation of 20 affords a mixture of isomeric 1 -methyliodonitro derivatives (21) and (22). The structures of 21 and 22 are established by 13C NMR data as well as by conversion into morpholine derivatives 26 and 24 respectively which also arise from 1-methylchloronitroimidazoles (25) and (23). A mechanism is proposed for the reported conversion of 5 into 4-chloro-5-nitroimidazole (32) in boiling 2-chloroethanol.

Kinetic study of the reaction of 2,4,6-triphenylpyrylium ion with amines. Base-catalyzed ring-opening reaction of 2H-pyran intermediates

Abstract: Cinetique des reactions de l'ion triphenyl-2,4,6 pyrylium avec butylamine, cyclohexylamine, pyrrolidine piperidine et morpholine conduisant aux amides vinyliques a cycle ouvert correspondants. Influence de la nature, primaire ou secondaire, des amines utilisees sur l'etape determinant la vitesse

Catalyst system and process for the production of polyurethanes

Abstract: A catalyst and process are provided for producing polyurethanes by contacting an organic polyol and an organic isocyanate with a catalyst comprising an N-substituted alkoxyalkyl piperazine and preferably additionally comprising an N-alkoxyalkyl morpholine wherein the alkylene moieties of the morpholine and piperazine are independently selected from the group consisting of C1 to about C5 alkylene moieties, and wherein the alkoxy moieties are independently selected from the group consisting of C1 to about C3 alkoxy moieties.

Synthesis of imidazo(1,5-a)pyrimidines.

Abstract: Les composes du titre substitues en 2 ou 4 sont obtenus par cyclisation par POCl 3 d'acylamino-1' alkyl-2 dihydro-3,4 methyl-6 pyrimidones-4 suivie de reactions nucleophiles des chloro-2- et chloro-4 imidazo [1,5-a] pyrimidines formees

Synthesis of 1-aryl-3-methyltriazenes by base-promoted decomposition of 1-aryl-3-hydroxymethyl-3-methyltriazenes

Abstract: En presence d'amines (methylamine, morpholine, pyridine) on etudie la decomposition des aryl-1 hydroxymethyl-3 methyl-3 triazenes

Process for the preparation of cis-2,6-dimethyl morpholine

Abstract: 1. A process for the preparation of 2,6-dimethylmorpholine containing a high proportion of the cis-isomer by cyclization of diisopropanolamine with sulfuric acid, working up the reaction mixture with sodium hydroxide solution, and distilling and drying the crude product obtained, wherein diisopropanolamine containing from 0 to 20 percent of water, and excess 90 to 120 percent strength sulfuric acid are simultaneously metered in such a manner into the reaction space, while stirring but without cooling, that the temperature of the reaction medium increases to 85 to 170 degrees C, and the reaction mixture is then heated at 150 to 190 degrees C for 1 to 25 hours while water is distilled off.

Studies on Sulfenamides. VIII. Anodic Oxidation of 2-Nitrobenzenesulfenamides Derived from Secondary Cyclic Amines

Abstract: Methyl 2-nitrobenzenesulfenate (5) was formed by controlled potential electrolysis (CPE) of N-(2-nitrophenylthio) amines (morpholine (1), piperidine (2), pyrrolidine (3), thiomorpholine (tetrahydro-4H-1, 4-thiazine) (4)) in methanol at a glassy carbon anode. A yellow powder obtained by the electrolysis of 1 reacted with triethylamine to give 2, 4-bis (o-nitrophenylthio)-5, 6-dihydro-1, 4-oxazine (7). CPE of 1-4 in acetonitrile gave 2, 2'-dinitrodiphenyldisulfide (6). These results suggest that the initial step of anodic oxidation of 1-4 in acetonitrile is an EC process (an electron transfer process followed by a chemical reaction), while that in methanol is an ECE process (an electron transfer process followed by a chemical reaction and then an electron transfer process). Enamine is considered to be one of the intermediates in the anodic oxidation of 1-4 in methanol.