Showing papers on "Morpholine published in 1993"

Transfer of the nitroso group in water/AOT/isooctane microemulsions: intrinsic and apparent reactivity

Abstract: The kinetics of the transfer of the nitroso group from N-methyl-N-nitroso-p-toluenesulfonamide to each of seven secondary amines (piperazine, N-methylbenzylamine, piperidine, dimethylamine, morpholine, pyrrolidine, and diisopropylamine) was studied using a wide variety of water/AOT/isooctane microemulsions as reaction media The diverse kinetic behavior of the various amines can be explained quantitatively on the basis of a single model taking into account the distribution of the amine among the aqueous and isooctane phases and their mutual interface; the reaction itself always takes place at the interface. The relative reactivities of the amines are discussed in comparison with the order observed in water. © 1993 American Chemical Society.

A Versatile Synthetic Method of 1-Alkylazulenes and Azulene by the iReactions of 3-Methoxycarbonyl-2H-cyclohepta(b)furan-2-one with in situ Generated Enamines.

Abstract: Methyl 3-alkylazulene-1-carboxylates were synthesized in high yields by the reaction of 3-methoxycarbonyl-2H-cyclohepta[b]furan-2-one with in situ generated morpholine enamines of aldehydes. Treatment of the esters with 100% phosphoric acid gave 1-alkylazulenes in excellent yields. Azulene was also synthesized in a good yield via methyl azulene-1-carboxylate with a modification of this method.

The process for transport of agents across the skin and compositions and articles useful therein

Abstract: New and improved method for the transdermal administration of agents is provided utilizing iontophoresis in conjunction with a water-insoluble, stratum corneum-lipid modifier. The lipid modifier may be used prior to iontophoresis or simultaneously therewith. The lipid modifier may be selected from a wide variety of moieties of the general formula R-X where R is a C5 to C28 alkyl or unsaturated alkyl and X is a member of the following:1,3-dioxane; 1,3-dioxolane; lactam; morpholine; -COOH; -OH;-COOR'; -C-N(R')2; cyclo ethylene and propylene carbonates;-CONH2; -(CH2-CH2O)n H; acetals, and hemiacetals; and wherein R' is lower alkyl (e.g., C1 to C3) and n is as integer of from 1 to 20. Optionally there may be present a polar, water-soluble chemical compound from the group of alcohols, glycols, lactams, dioxolanes, esters, ureas, morpholine and the like. Compositions and articles useful in the processes of the present invention are also provided.

Quantitative evidence for the mechanism of RNA cleavage by enzyme mimics. Cleavage and isomerization of UpU by morpholine buffers

Abstract: The cleavage of 3',5''-UpU to form the 2',3'-cyclic phosphate and uridine and the simultaneous isomerization of the substrate to 2',5''-UpU have been studied in morpholine buffer. The total rate of cleavage with morpholine buffer at 90/10 base to acid ratio and constant ionic strength shows an increase with increasing buffer concentration up to 1 M, but the isomerization rate shows a decrease, followed by a constant rate below that of the uncatalyzed process. A similar increase in rate of cleavage-but decrease in rate of isomerization-is also seen with a 95/5 morpholine/morpholinium buffer and with data that can fit the theoretical equations using those parameters that are common for the 90/10 buffer

Dissociation constants of some alkanolamines

Abstract: The dissociation constants of piperidine (PD), 1-piperidineethanol (1–PE), N-methylmorpholine (MML), 4-(2-hydroxyethyl)morpholine (4-EML), and tropine (TP) have been determined at 15.0, 25.0, 35.0,...

Palladium(II)-catalyzed synthesis of optically active tetrahydro- 1,4-oxazine derivatives

Abstract: Three different types of morpholine derivatives 1-3 could be obtained from allylic amine substrates 4 in high yield and excellent diastereoselectivity by slight variation of the Pd(II)-Cu(II) reagents system

Reactions of 5-(arylimino)-4-chloro-5H-1,2,3-dithiazoles with primary and secondary alkylamines: novel synthesis of (arylimino)cyanomethyl alkylamino disulfides and their mechanisms of formation

Abstract: Reactions of 5-(arylimino)-4-chloro-5H-1,2,3-dithiazoles with alkylamines such as isopropylamine, piperidine, pyrrolidine, and diethyamline in methylene chloride at room temperature gave (arylimino)-cyanomethyl alkylamino disulfides (14-83%) along with N'-aryl-N-alkylcyanoformamidines (0-88%). The yields of the latter increase and those of the former decrease with the concentration of the amine. In addition, some of the latter compounds were independently synthesized by treatment of the former with cyclic amines such as piperidine, pyrrolidine, and morpholine in methylene chloride at room temperature (22-97%). The results indicate that the former compounds are involved as intermediates in the formation of the latter in these reactions. However, when [(p-nitrophenyl)imino]cyanomethyl (pentane-1,5-diyl)amino disulfide was treated with sterically bulky amines such as tert-butyl- and diethylamines at reflux and room temperature, respectively, cyanoformamidines having a piperidine moiety rather than tert-butyl- and diethylamino groups were obtained as the only isolable products. Two pathways which involve initially either direct nucleophilic attack of alkylamines on the imino carbon or on the sulfur α to the amino group of (arylimino)cyanomethyl alkylamino disulfides are proposed to rationalize the results

Aggregation studies of lithium dialkylamides. The role of aggregates in the carbonylation reaction

Abstract: 13 C NMR spectroscopy and isotopic exchange in carbonylation intermediates have been successfully employed to characterize aggregation of lithium dialkylamides in THF solution. It is shown that lithium (3-oxapentamethylene)amide forms a 1:1 mixed aggregate with morpholine. The aggregate remains even in diluted THF solution. Lithium pentamethyleneamide also forms aggregates with piperidine while the less acidic amines do not form mixed aggregates with the corresponding lithium dialkylamide either in the solid state or in THF solution

Microemulsion cleansers and their uses

Abstract: This invention relates to microemulsion cleaners comprising (a) an organic solvent (b) a surfactant blend comprising an anionic and nonionic surfactant (c) a glycol ether (d) morpholine, and (e) water. These cleaners can be used for removing baked-on oil and carbon deposits.

Autoclavable containers comprising poly(aryl ether sulfones) having environmental stress-crack resistance

Abstract: An autoclavable container comprising a poly(aryl ether) resin capable of withstanding at least 1000 cycles of steam sterilization at a stress level of 500 psi without stress-crack failure, said steam sterilization cycle conducted for 30 min. at 270° F. and 27 psi using aqueous morpholine at a concentration of 50 ppm.

Quaternary ammonium carboxylate inner salt compositions as controlled activity catalysts for making polyurethane foam.

Abstract: Prepn. comprises reacting a polyisocyanate and a polyol in the presence of a blowing agent, cell stabiliser and a catalyst compsn., with a quat., ammonium carboxylate inner salt of formula R2-R1-N(+)-R3-R'4-CO2(-) (I), where R1, R2 and R3 are 1-12C alkyl, 5-8C cycloalkyl, 6-10C aryl or an alkyl, cycloalkyl or aryl contg. a heteroatom, alternately R1 and R2 or R1, R2 and R3 form a ring system with N atom, and R4 is divalent R1. Pref. R1, R2 and R3 can be methyl, ethyl, propyl, butyl, lauryl, N,N-dimethylaminoethyl, N,N-dimethylaminopropyl, cyclopentyl, cyclohexyl, phenyl or p-tolyl; R1 and R2 can form piperidine, morpholine or imidazole with a N atom; or R1, R2 and R3 can form triethylenediamine, 3-quinuclidinol or 1,8-diazabicyclo(5,4,0)undec-7-ene with an N atom; and R4 is methylene, ethylene, propylene or phenylene.

The effect of ortho substituents on the mechanism of aromatic nucleophilic substitution reactions in dipolar aprotic solvents

Abstract: The reactions of 2,6-dinitrophenyl phenyl ether and of 6-methyl-2,4-dinitrophenyl phenyl ether with piperidine, morpholine, butylamine and benzylamine are base catalysed in both dimethyl sulfoxide and acetonitrile. The reaction of 2-phenoxy-3,5-dinitropyridine with aniline is base catalysed in acetonitrile, but not in dimethyl sulfoxide, and its reactions with piperidine, morpholine, butylamine and benzylamine in acetonitrile are also base catalysed. The results are discussed in terms of the prevailing theories of aromatic nucleophilic substitution reactions. Increase in activation of the substrate increases the k2/k–1 and k3/k–1 ratios. For ortho substituents, steric/steroelectronic effects in the transition state reduce both k–1, the rate constant for the decomposition of the zwitterionic intermediate to reactants, and k2 and k3, the rate constants for its decomposition to products. When the substrate has two ortho groups the different behaviour of primary and secondary amines found with substrates containing only one ortho-nitro group is not observed.

Simultaneous UV-spectrophotometric determination of CS2 and COS using the piperidine, pyrrolidine, ethylenediamine or morpholine reagent

Abstract: The success of a spectrophotometric method for the determination of dithiocarbamate or tetramethylthiuram disulphide (thiram) fungicide residues based on the quantification of the evolved CS2 after an acid hydrolysis of the fungicide depends on the sensitivity and selectivity of the CS2 absorbing reagent. In the present study piperidine, pyrrolidine, ethylenediamine and morpholine and their corresponding optimum reaction conditions with CS2 and COS were spectrophotometrically investigated for their suitability as CS2 and COS absorbing reagents. The CS2-amine and COS-amine adducts, formed after the absorption of the CS2 and COS gases in an alcoholic amine, exhibit different UV-absorption spectra which facilitated the quantification of both CS2 and COS. The sensitivity of the amines to CS2 and COS and the stability of the CS2-amine and COS-amine adducts were found to be dependent on the reaction time between the CS2 and COS with the amine, the concentration and the temperature of the alcoholic amine reagent. Under optimized conditions, ethylenediamine, pyrrolidine and morpholine proved to be equally sensitive to both CS2 and COS just as the previously reported piperidine. Furthermore, the sensitivity of piperidine to COS was improved. The sensitivity optimized amine reagents, dissolved in methanol instead of ethanol and with detection limits for both CS2 and COS down to 0.3 μg/ml, should provide new and cheaper means in the residue analysis of dithiocarbamate and tetramethylthiuram disulphide (thiram) fungicides based on the evolved CS2 and COS after an acid hydrolysis.

Synthesis of α-Amino Isocyanides and α-Alkylthio Isocyanides

Abstract: α-Morpholinobenzyl isocyanide and three 1-(aryl[or alkyl]thio)alkyl isocyanides are synthesized in good yields by the dehydration of N-(α-morpholinobenzyl)formamide and N-[1-(alkylthio)alkyl]formamides, themselves prepared from 1-(1-formylaminoalkyl)benzotriazoles with morpholine or with thiols

Improved iontophoretic administration of drugs

Abstract: New and improved method for the transdermal administration of agents is provided utilizing iontophoresis in conjunction with a water-insoluble, stratum corneum-lipid modifier. The lipid modifier may be prior to iontophoresis or simultaneously therewith. The lipid modifier may be selected from a wide variety of moieties of the general formula R-X where R is a C₅ to C₂₈ alkyl or unsaturated alkyl and X is a member of the following: 1,3-dioxane; 1,3-dioxolane; lactam; morpholine; -COOH; -OH; -COOR'; -C-N(R')₂; cyclo ethylene and propylene carbonates; -CONH₂; -(CH₂-CH₂O) n H; acetals, and hemiacetals; and wherein R' is lower alkyl (e.g., C₁ to C₃) and n is an integer of from 1 to 20. Optionally there may be present a polar, water-soluble chemical compound from the group of alcohols, glycols, lactams, dioxolanes, esters, ureas, morpholine and the like. Compositions and articles useful in the processes of the present invention are also provided.

v-Triazolines. Part 34. Thermal behaviour of 1-(2-aminophenyl)-4,5-dihydro-5-morpholino-1,2,3-triazoles: new synthesis of 2-alkylquinoxalines

Abstract: 4,5-Dihydro-5-morpholino-1-(2-nitrophenyl)-1,2,3-triazoles 4 are prepared by reaction of an aldehyde with morpholine and the appropriate aryl azide. On reduction 1-(2-aminophenyl)-4,5-dihydro-5-morpholino-1,2,3-triazoles 5 are formed. Thermal rearrangement of compounds 5 affords unstable 2-alkyl -3-amino -1,2,3,4-tetrahydroquinoxalines 7, which undergo deamination to 2-alkyl-1,2-dihydroquinoxalines 8. Oxidation of these affords 2-alkylquinoxalines 10. The mechanism of the thermal rearrangement of triazoles 5 is investigated and discussed.

Reactions of 5-methylphenanthridinium iodide with nucleophiles and reaction products conversion.

Abstract: Reactions of 5-methylphenanthridinium iodide with nucleophiles and reaction products conversion.Reactions of 5-methylphenanthridinium iodide (I) with oxygen, nitrogen, and carbon nucleophiles, respectively. were studied. 5-Methylphenanthridinium iodide (I) yielded in the basic aqueous medium 5-methyl-6-phenanthridone (II) and 5.6-dihydro-5-methylphenanthridine (III). By NMR spectroscopy in the D2O-CD3CN solution 5,6-dihydro-6-deuteroxy-5-methylphenanthridine (IVb) (pseudobase) was observed as an immediate unstable product. 5-Methylphenanthridinium iodide (I) gave the corresponding adducts with methoxide and ethoxide anions, morpholine, piperidine, pyrrolidine, cyanide anion and acetone. Their structure was determined by IR. H-1 and C-13 NMR spectroscopy. Reactions of 5,6-dihydro-5-methyl-6-morpholinophenanthridine (VII) were followed by NMR spectroscopy. Morpholino adduct VII gave in the CD3CN-D2O solution pseudobase IVb and its products of disproportionation: oxophenanthridine II and dihydrophenanthridine III. Treatment of 5,6-dihydro-5-methyl-6-morpholinophenanthridine (VII) with H2O/D2O in (CH3)2CO/(CD3)2CO led to CH3COCH2-/CD3COCD2- adduct XIa/XIb formation, respectively.

Synthesis and antiinflammatory activity of 3-substituted-4-amino-5-mercapto-4(h)-1,2,4-triazole.

Abstract: "Various 3-substituted-4-amino-5-mercapto-4(H)- 1,2,4-triazoles were synthesised by treating morpholine/piperidine acetic/propionic/(alpha-methyl) propionic acid hydrazides successively with alcoholic potassium hydroxide-carbondisulfide and hydrazine hydrate.All the compounds were screened for their antiinflammatory activity against carrageenan induced rat paw edema and cotton pellet granuloma pouch at mg/100 grams B.W. Three compounds [B,C,D] were found to have significant activity. The detailed antiinflammatory activity and acute toxicity were studied, the former in comparison with phenyl butazone."

Cyclopenta-1,2,3-dithiazoles and related compounds

Abstract: Treatment of 3-phenylinden-1 -one oxime 6 with disulfur dichloride gives the indenodithiazole 2 directly in 58%; in the presence of Hunig's base the yield rises to 90%. Indenone oxime 9 and indanone oxime 11 with disulfur dichloride both give the chlorinated indenodithiazole 10, in up to 80% with Hunig's base. Similarly, cyclopentanone oxime gives the deeply violet trichlorocyclopentadithiazole 13(ca. 25%) at 4 °C in tetrahydrofuran with Hunig's base or in dimethylformamide without added base. A mechanism (see Scheme 1) is proposed for this extensive transformation in which a simple saturated oxime is converted into a highly functionalised heteroaromatic compound by the formation of 7 new bonds; this mechanism is based on the activation to chlorodeprotonation of all the cyclopentane positions, in turn, by the dithiazole ring. Analogously, cycloheptanone oxime 17 gives the red pentachlorocycloheptadithiazole 21, by the formation of 10 new bonds, and now di-, tri-, and tetrachloro intermediates, 18–20, can also be isolated; tetrahydrobenzocycloheptenone oxime 22 gives the analogous dichloro 23 and trichloro 24 compounds, and the acyclic oxime 25 gives the monocyclic dithiazole 27, all in modest yield. The chlorine in compound 10 is displaced by morpholine and pyrrolidine, but similar displacements in the trichloro compound 13 are unsuccessful since its heterocyclic ring is destroyed by nucleophiles. The pentachloro compound 21 is more stable than 13 towards nucleophiles, but less stable towards m-chloroperbenzoic acid, and these observations are explained in terms of the dipolar structures 13a and 21a.