Showing papers on "Morpholine published in 1987"

Ruthenium-catalyzed synthesis of vinyl carbamates from carbon dioxide, acetylene, and secondary amines

Abstract: Les amines secondaires etudiees sont pyrrolidine, piperidine, morpholine et diethylamine; obtention egalement de petites quantites de N,N-dialkyl O-[methylene-1 allyl] carbamates

Phosphorus–nitrogen compounds. Part 50. Further studies on the formation of bicyclic cyclotetraphosphazatetraene derivatives

Abstract: The reactions of hexachloro-2,6-bis(ethylamino)cyclotetraphosphazatetraene, N4P4Cl6(NHEt)2, with pyrrolidine, piperidine, morpholine, diethylamine, or cyclopropylamine give bicyclic N4P4(NRR′)5(NHEt)(NEt), as well as monocyclic derivatives N4P4(NRR′)6(NHEt)2(NRR′= pyrrolidino, piperidino, morpholino, diethylamino, or cyclopropylamino). The reactions of N4P4Cl8 with cyclopropylamine give the bicyclic, N4P4(NHC3H5)6(NC3H5), and monocyclic, N4P4(NHC3H5)8, products, the former being the first structure of its kind with an α-branched alkyl group at the bridgehead to be isolated. Salient features of the 1H and 31P n.m.r. spectra of these bicyclic phosphazenes are discussed and related to their structures. Likely reaction mechanisms are considered.

N-nitrosation and N-nitration of morpholine by nitrogen dioxide in aqueous solution : effects of vanillin and related phenols

Abstract: La presence de vanilline augmente la proportion de nitrosomorpholine formee a partir de morpholine et de NO2, sans doute en raison de la presence d'un groupement hydroxyle dans la molecule. Etude de l'action de toute une serie de phenols sur la nitrosation ou la nitration, en fonction du pH et en relation avec la formation de nitrosamines dans les produits alimentaires

N-nitrosoamine and N-nitroamine formation: factors influencing the aqueous reactions of nitrogen dioxide with morpholine

Abstract: The formation of nitrosamine and nitroamine from low levels of nitrogen dioxide (1-99 ppm) and morpholine in aqueous solution was examined. We have shown for the first time that significant quantities of N-nitromorpholine form at physiological pH; the rate of N-nitration was more than double that of N-nitrosation at 37/sup 0/C, pH 7.4. The effects of temperature, pH, reactant concentration, and various anions on both nitration and nitrosation reactions are presented. In addition to pH effects, a deuterium effect was observed for the nitration reaction, suggesting that hydrogen abstraction is a rate-limiting step in product formation. Possible reaction mechanisms are described, and the implications for carcinogen formation in vivo due to low-level NO/sub 2/ exposure are discussed. 16 references, 7 figures, 4 tables.

Nitroso transfer from α-nitrosamino aldehydes: implications for carcinogenesis

Abstract: Six alkylnitrosamino ethanols (R-N(NO)-CH2CH2OH; R = Me, nBu, sBu, iBu, tBu, HOCH2CH2-), including the potent carcinogen N-nitrosodiethanolamine, have been shown to undergo efficient liver alcohol dehydrogenase catalyzed oxidation to their corresponding alpha-nitrosamino aldehydes. Five structurally representative nitrosamino-ethanals (R-N(NO)CH2CHO, R = 4-ClC6H4-, CH3-, nBu-, tBu-, HOCH2CH2-) have been synthesized. Each of these compounds demonstrates the unusual property of facile transnitrosation to a secondary amine. Transnitrosation to dimethylamine, pyrrolidine, morpholine and N-methylaniline has been shown. This reaction occurs rapidly at room temperature in organic solvents but is somewhat slower in aqueous buffer due to extensive equilibrium formation of gem diols by hydration of the aldehyde group. In aqueous media the transnitrosation rate increases with increasing pH from 7 to 9 and does not occur at pH 4. Transnitrosation to primary amines results in deamination (benzylamine----benzyl alcohol). The transnitrosation reaction is accompanied by the formation of imines of glyoxal (R - N = CH - CH = N - R) which appear as primary amines and glyoxal in aqueous solution. Other products have also been characterized as well. These chemical and biochemical data, taken together with results in other laboratories, provide strong support for our hypothesis that certain beta-oxidized nitrosamines can be activated to proximate or ultimate carcinogens by biochemical oxidation to produce highly reactive nitrosamines.

Cyclic ether formation with N-(phenylthio)morpholine

Abstract: Cyclic ethers with 5- to 7-membered rings are formed by sulphenoetherification of unsaturated alcohols with N-(phenylthio)morpholine and trifluoromethanesulphonic acid.

Nonacidic nitration of secondary amines

Abstract: Nitration de dimethyl- et diethyl-amines, piperidine, pyrrolidine, morpholine a l'aide de nitrate de [methyl-1 trifluoromethyl-1] ethyle ou de dinitrate de bis-chloromethyl-2,2 propanediol-1,3. Obtention de nitramines et de quelques nitrosamines

Preparation of morpholine

Abstract: Morpholine and other cyclic imines are obtained by reacting diethylene glycol and other appropriate diols with ammonia under hydrogenating conditions in the gas phase in the presence of a catalyst which contains copper, a smaller amount of nickel and alumina.

Method for chemically cleaning slightly soluble scale

Abstract: PURPOSE: To perfectly dissolve and remove slightly soluble scale formed and stuck on the surface of an iron-based metal by applying a mixed soln. prepd. by adding an amine type alkali agent and hydrazine hydrate to polyaminocarboxylic acid and adjusted to a prescribed basicity. CONSTITUTION: An amine type alkali agent is added to an aq. soln. of polyaminocarboxylic acid (e.g., EDTA) having 10W30wt.% concn. to adjust the pH to 6.5W9.0. The polyaminocarboxylic acid is converted into salt and a chelating agent which easily forms chelate with a scale forming metal is produced. Hydrazine hydrate is then added to the chelating agent to adjust the pH to 7.0W9.5 and a corrosion inhibitor such as an org. amine type inhibitor is further added. By applying the resulting mixed soln., slightly soluble scale formed and stuck on the surface of an iron-based metal is perfectly dissolved and removed at 120W160°C. One or more among an aq. ammonia soln., gaseous ammonia, morpholine, cyclohexylamine, mono-, di- and triethanolamine are used as the amine type alkali agent. COPYRIGHT: (C)1989,JPO&Japio

Morpholine containing amino acid derivatives

Abstract: Amino acid derivatives represented by formula ##STR1## wherein His represents an L-histidyl group, X represents a straight or branched alkoxy group having 1 to 7 carbon atoms, a straight or branched alkylamino group having 1 to 7 carbon atoms, a cycloalkyloxy group having 3 to 7 carbon atoms, a morpholino group, said alkoxy group having one or more halogen atoms as substituents; or a pharmaceutically acceptable salt, are useful in the treatment of hypertension.

Optimum conditions for the Willgerodt-Kindler reaction. III: Amine variation

Abstract: Etude de la synthese d'amides de l'acide benzenethioacetique a partir de soufre, d'amines et d'acetophenone

Method for chemically cleaning hardly soluble scale

Abstract: PURPOSE:To dissolve and remove hardly soluble steam oxidized scale by adding one or more kinds of compds. such as ammonia and morpholine, hydrazine hydrate and a corrosion inhibitor to polyaminocarboxylic acid, adjusting the pH and using the resulting mixed liq. CONSTITUTION:One or more among an aq. ammonia soln., gaseous ammonia, morpholine, cyclohexylamine, monoethanolamine, diethanolamine and triethanolamine are added to polyaminocarboxylic acid and the pH is adjusted to 3.5-5.5 to prepare a cleaning liq. Hydrazine hydrate is added to the cleaning liq., the pH is adjusted to 4-6 and a corrosion inhibitor is further added to prepare a mixed liq. Scale formed on the surface of an iron-based metal is dissolved and removed with the mixed liq.

Substituted thiazoles and oxazoles and 2-hydroxy-morpholines

Abstract: Substituted thiazoles, oxazoles and 2-hydroxy morpholine compounds useful in the treatment of diabetes mellitus and obesity are described.

Chemical structure of networks resulting from curing of diglycidylamine-type resins with aromatic amines: 1. Detection and characterization of cyclisation reactions on model compounds

Abstract: A model compound (I), representative of the structure resulting from the first step of curing in diglycidylamine-aromatic amine systems, was prepared from diglycidylamine and N-ethylaniline. After thermal treatment, the fraction resulting from intramolecular processes, that is to say possessing the same molecular weight as the initial compound (I), was isolated by preparative GPC. This fraction was shown by GPC, HPLC and 13C NMR spectroscopy, to contain morpholine, as well as corresponding 7-membered cyclic ethers which were identified by comparison with the products of a process said to actually give morpholine derivatives. Another non ether-forming cyclisation reaction was also detected, resulting in the formation of a 3-hydroxy-1,2,3,4 tetrahydroquinoline derivative, by attack on an aromatic nucleus by the epoxy directly bonded to it. Apparently, this reaction has not been previously described.

REACTIONS OF N-(p-CHLOROSULFONYLPHENYL)MALEIMIDE

Abstract: N-Phenylmaltimide reacted with chlorosulfonic acid to give an excellent yield of the sulfonyl chloride (1), which with dimethylamine or aniline (2 equivs.) afforded the corresponding sulfonamides (2,3). However, use of more dimethylamine (4 equivs.) caused opening of the imido ring and addition to the double bond to yield the dimethylamide (12). Similar reaction with diethylamine in methanol resulted in nucleophilic ring-opening by the solvent leading to the methyl ester (13). Analogous reactions with morpholine, pyrrolidine and piperidine (3 equivs.) proceeded with addition and substitution to give 7–9. N-(p-chlorosulfonylphenyl)-3,4-dichloromaleimide (15) reacted with amines with substitution of both the 3- and sulfonyl chlorine atoms to give the sulfonamides (16–21). 3-Chloro-4-phenoxy-N-phenylmaleimide reacted with chlorosulfonic acid to give the bis-sultonyl chloride (22); condensation with dimethylamine caused displacement of the 4-(p-chlorosulfonyl-phenoxy) group to give 16. The various re...

Fused azolium salts. 10. Selective ring openings of isomeric fused thiazolium salts with nucleophiles

Abstract: Etude de la scission de thiazolo [3,2-b] et -[2,3-a] isoquinoleiniums et de thiazolo [3,2-a] quinoleiniums

Method of manufacturing polyphenylene ethers

Abstract: The invention relates to the method of manufacturing polyphenylene ethers by an oxidative coupling reaction of monomeric phenols in a solvent mixture comprised of an aromatic hydrocarbon with 6-8 carbon atoms and an aliphatic alcohol with 1-4 carbon atoms in a volumetric ratio of the hydrocarbon to the alcohol of 92.5:7.5 to 50:50, in the presence of a catalyst comprised of cupric chloride, a secondary diamine, and morpholine.

Novel aminoalkylthio derivatives of triazolopyridine or triazoloquinoline, the processes for their preparation, and drugs, useful especially as analgesics, in which they are present

Abstract: The present invention relates to novel compounds corresponding to the formula: ##STR1## in which: n represents an integer between 1 and 8 and optimally 2 or 3; (CH 2 ) n --N can also form a ring or a heterocycle, for example having 5 to 7 atoms and preferably 6 atoms; R 1 and R 2 can represent hydrogen or a lower alkyl having 1 to 5 carbon atoms or can form, together with the nitrogen, a ring such as pyrrolidine, piperidine, morpholine, thiomorpholine, phenyltetrahydropyridine, piperazine or piperazine N-substituted by an alkyl, a phenyl or a heterocycle; in the case of the phenyltetrahydropyridines and the phenylpiperazines or heteroarylpiperazines, the phenyl or the heterocycle may or may not be substituted by halogens or methoxy, thiomethyl, hydroxyl, nitro, amino, cyano, lower alkyl, trifluoromethyl or trichloromethyl groups; and R 3 , R 4 and R 5 can represent hydrogen, a lower alkyl, a hydroxyalkyl or hydroxybenzyl group, a halogen, a trifluoromethyl, a methoxy, a thiomethyl or a nitro or two of them can form a ring, in particular a phenyl in the case of the triazoloquinolines or the triazoloisoquinolines; and the non-toxic acid addition salts. These products are useful as drugs and possess analgesic properties, acting especially on the central nervous system as minor tranquilizers.

Polycarbonyl heterocyclics. [V]. Synthesis of pyrrolo[3,4-c]pyridine and Furo[3,4-c]-pyridine derivatives by the Ring Transformation of Thiazolidine-4-on Derivatives

Abstract: 2-(Aroyl, methylidene)-3-aryl-5-dicyanomethylene thiazolidine-4-on derivatives 2 under morpholine treatment formed complex 3 The acid hydrolysis of 3 leads to pyrrolo [3,4-c]-pyridine derivatives 4 On treatment of 3 with aqueous sodium hydroxide and subsequent acidification [3,4-c]pyridine derivatives 5 are formed

Synthesis and reactions of 2,3-dihydrothiazolo[3,2-a]pyrimidine derivatives

Abstract: The reaction of 2-amino-2-thiazoline (1) with acetylene carboxylates (2) afforded 5-substituted 2, 3-dihydro-7H-thiazolo [3, 2-a] pyrimidin-7-ones (3). 7-Bromomethyl-2, 3-dihydro-5H-thiazolo [3, 2-a] pyrimidin-5-one (10) was obtained by the reaction of 1 with γ-bromoacetoacetyl bromide. Treatment of 10 with N-bromosuccinimide provided the 6-bromo compound (12). The 7-bromomethyl compounds (10 and 12) were converted to 7-morpholinomethyl derivatives by treatment with morpholine. When 3a (unsubstituted-), 3b (5-ethoxycarbonyl-), and 3c (5-hydroxymethyl-) were treated with 5% hydrochloric acid, covalent hydration occurred across the 5, 6-carbon-carbon bond, giving 5-hydroxy-2, 3, 5, 6-tetrahydro-7H-thiazolo [3, 2-a] pyrimidin-7-one derivatives (16a, 16b, and 16c). On the other hand, in the case of 11 (7-methyl-) and 17 (5-phenyl-), the dihydrothiazole ring was cleaved to give 3 (and 1) - (2-mercaptoethyl) -6-methyl (and phenyl) -2, 4 (1H, 3H) -pyrimidinedione (19 and 18).

Amine salts of azo compounds

Abstract: The compounds of the formula … … where a and b are each independently of the other halogen, -CH3, -C2H5, -OCH3, -OC2H5 or the group of the formula -NHCOC1-C4-alkyl, c and d are each independently of the other -H, halogen, -CH3, -C2H5, -OCH3, -OC2H5 or the group of the formula -NHCOC1-C4-alkyl and R is -CH3, phenyl, -COOCH3, -COOC2H5, -NHCOC1-C4-alkyl or -CONHC1-C4-alkyl, and R , R , R and R are each independently of the others -H, unsubstituted or chlorine- or HO-substituted C1-C4-alkyl, C7-C9-aralkyl, C5-C8-cycloalkyl, unsubstituted or halogen-, methyl- or methoxy-mono- to -trisubstituted phenyl, a heterocyclic radical of the benzimidazole, benzoxazole, benzothiazole or pyridine series, or R and R together are combined with the nitrogen atom to form a pyrrolidine, imidazolidine, piperidine, piperazine or morpholine radical or R /R and R together are combined with the nitrogen atom to form a pyrrole, pyridine, picoline, pyrazine, quinoline or isoquinoline radical are highly suitable for colouring macromolecular organic material.

Structure–reactivity relationships and the rate–determining step in the reactions of methyl salicylate with primary amines

Abstract: The aqueous cleavage of methyl salicylate has been studied in the buffer solutions of various primary mono- and di-amines as well as secondary amines at 30°C Both ionized (MS−) and nonionized (MSH) methyl salicylate are reactive toward primary mono- and di-amines The second-order rate constants for the reactions of MS− with primary mono- and di-amines of pKa > 94 exhibit Bronsted plot of slope (βnuc) of 082 This high value of βnuc is attributed to an intramolecular proton transfer in a thermodynamically unfavorable direction in the rate-determining step in a stepwise process for the formation of monoanionic tetrahedral intermediate However, a concerted process for the formation of a monoanionic tetrahedral intermediate in the reactions of MS− with amine nucleophiles wherein expulsion of leaving group is a rate-determining step is not completely ruled out The α-effect nitrogen nucleophiles hydroxylamine and hydrazine reveal, respectively, ca 104- and 103-fold higher reactivity compared to other amine nucleophiles of comparable basicity The value of βnuc of 103 obtained for the reactions of primary monoamines with MSH is ascribed to the expulsion of leaving group as the rate-determining step The significantly lower value of βnuc of 060 obtained in the reactions of MSH with both monoprotonated and unprotonated diamines is explained in terms of possible occurrence of intramolecular general acid-base catalysis Intramolecular general base catalysis is responsible for the enhanced nucleophilic reactivity of primary amines toward MS− Dimethylamine, piperidine, morpholine, and piperazine have no detectable nucleophilic reactivity toward MS−