Showing papers on "Morpholine published in 1979"

The chemistry of nitroso-compounds. Part 11. Nitrosation of amines by the two-phase interaction of amines in solution with gaseous oxides of nitrogen

Abstract: The formation of secondary N-nitrosoamines when MeCN solutions of amines are brought into contact with gaseous NO, N2O3, and N2O4 at 25 °C is reported. With NO, N-nitrosoamine formation from piperidine, morpholine, and diphenylamine occurs very slowly (t½ca. 8 days). Reaction rates are largely independent of the amine, suggesting that oxidation of NO by adventitious oxygen is the slow step. Very much faster reactions are observed, however, with N2O3 and N2O4. With a ca. 10-fold excess of N2O3 or N2O4, quantitative yields of both N-nitrosopiperidine and N-nitrosodiphenylamine are found in less than 3 min. With a 27-fold excess of piperidine and N2O4 only, ca. 8%N-nitropiperidine and 92%N-nitrosopiperidine are obtained. Rapid reactions also ensue when solutions of either primary aromatic or secondary amines dissolved in 0.1M-aqueous NaOH are brought into contact with gaseous N2O3 and N2O4. With a ca. 2–400-fold excess of these nitrogen oxides, 12–65% of the amine is converted either to N-nitrosoamine or diazonium ion in less than 3 min. Competitive hydrolysis of the nitrogen oxide by the solvent is not HO–-catalysed and the amine : H2O reactivities are in ca. 1 000 : 1. The extent of N-nitrosation varies insignificantly over a wide range of basicities (pKa, 11.12 to –1.0), but no reaction occurs with either 2,4-dinitroaniline or N-butyl-acetamide. With N2O4, smaller amounts of N-nitroamines form concurrently and increase with decreasing amine basicity. The results are discussed in relation to amine nitrosation by N2O3 and N2O4 in aqueous acidic solutions. It is suggested that the lower selectivity for the dissolved gaseous reagents may relate to the presence of more reactive N2O3 and N2O4 isomers. The results also show that carcinogenic N-nitrosoamines form under a much wider range of experimental conditions than previously known, some of which are relevant to atmospheric pollution.

Substituted morpholine derivatives and compositions

Abstract: Substituted morpholine derivatives, such as, for instance, the compound 2-[α-(2-methoxy-phenoxy)-benzyl]-morpholine are disclosed. The claimed compounds are active on the central nervous system, and may be used as antidepressant agents.

The transnitrosation of secondary amines S-nitrosocysteine in relation to N-nitrosamine formation in cured meats.

Abstract: The reactions at 37°C of S-nitrosocysteine hydrochloride with three secondary amines, N-methylaniline, morpholine and pyrrolidine, have been studied at pH 2.65, 5.5 and 9.75. The reactions result in the formation of the N-nitroso derivatives of the three amines at all three pH values studied. The rates of N-nitrosation and final yields of products in these reactions were compared with those in reactions in which the N-nitrosation of the secondary amines was effected by nitrite. The comparative rates varied considerably according to the amine being studied and the reaction pH. The relevance of these findings to nitrosamine formation in cured meat and in vivo are discussed. Reaction of S-nitrosocysteine hydrochloride with all three amines at pH 9.75 and with N-methylaniline at pH 5.5 resulted in some N-nitrosamine formation in the headspace above the reaction mixture. The stability of S-nitrosocysteine hydrochloride was studied as a function of pH. The compound was fairly stable at pH 2.65, but decomposed rapidly at pH 5.5 and 9.75. The decomposition reaction at pH 5.5 followed three-halves order kinetics, but that at pH 9.75 did not conform to simple kinetics.

[10] Modification of the 3′ terminus of tRNA by periodate oxidation and subsequent reaction with hydrazides

Abstract: Publisher Summary The long known selective periodate oxidation of the 3'-terminal cis-diol of tRNAs results in the formation of a reactive dialdehyde exhibiting a readiness to react with nucleophilic amino components, for example, amines, semicarbazides, thiosemicarbazides, hydrazines, and hydrazides. The main potential problem in the 3'-terminal labeling of ribonucleic acids via periodates oxidation is the lability of the dialdehyde toward basic compounds. Therefore, β-elimination of the terminal adenosine dialdehyde is catalyzed, for example, by hydroxyl ions, amines, hydrazines, or semicarbazides. Isonicotinic acid hydrazide was used for the radioactive labeling and chain-length determinations of tRNA. Spectroscopic structure determinations provided evidence for the formation of the morpholine structure. These products are stable over a pH range of 2-10. Analysis of the modified tRNA species is performed by splitting 4-5 A 260 units with T2 RNase and separating the digestion mixture by thin-layer electrophoresis. The detection of the different substances is possible by fluorescent quenching in ultraviolet light and detection of the radioactive labeled spots with a scanner for thin-layer plates.

2-Dibromomethylbenzoyl: an acyl protecting group removable under exceptionally mild conditions

Abstract: 2-Dibromomethylbenzoate esters may be converted, at room temperature, into the corresponding alcohols in high yields by treatment first with silver perchlorate in the presence of 2,4,6-collidine in wet acetone or tetrahydrofuran and then with morpholine.

Addition of nitrogen-, oxygen-, and sulphur-containing nucleophiles to aryl ethynyl ketones

Abstract: Addition of some nitrogen-, oxygen-, and sulphur-containing nucleophiles to the aryl ethynyl ketones (1)–(4) has been examined. Addition of o-phenylenediamine and o-aminophenol yielded the corresponding cis-β-aminovinyl ketones (5)–(7) and (10)–(12). Addition of secondary amines (morpholine and piperidine) yielded the trans-β-aminovinyl ketones (13)–(20). Catechol reacted with aryl ethynyl ketones to furnish 1,3-benzodioxole derivatives (21)–(23), salicylic acid and 2-hydroxy-3-naphthoic acid to give the oxalactones (24)–(30). However, 2-hydroxy-1-naphthoic acid yielded a mixture of the oxalactones (31)–(33) and 3-naphthoxy-1-arylprop-2-enones (35) and (36). Similarly thiosalicylic acid gave the corresponding thialactones (40) and (41) as addition products. Salicylaldehyde reacted with ethynyl phenyl ketone to give 3-benzoylchrom-3-en-2-ol (38).

The cobalt catalyzed reductions using carbon monoxide and water. the n-alkylation of morpholine by carbonyl compounds

Abstract: The cobalt carbonyl complex modified by α, ω-bis(diphenylphosphino) alkane (PCnP, n=2 or 3) was an effective catalyst for the N-alkylation of morpholine by carbonyl compounds, in which carbon monox...

1-Aryl-4-aryl:sulphonyl-3-amino-propoxy-1H-pyrazole derivs. - hypolipaemics and hypocholesterolaemics of low toxicity and non-ulcerogenic

Abstract: 1-Aryl-4-arylsulphonyl-3-aminopropoxy -1H-pyrazole derivs. of formula (I) and their salts are new: (where R1 is H, halogen, 1-3C alkyl or alkoxy or CF3- gp. in meta or para position; R2, R3, R4 are H, halogen, 1-3C alkyl or alkoxy or CF3-; R5, R6 are each H or lower alkyl or together, and with the N atom to which they are attached, form a 5- or 6-membered heterocycle (piperidine or pyrrolidine) opt. contg. another heteroatom such as O (morpholine). (I) have hypolipaemic and hypocholesterolaemic properties. Suitable daily doses are 0.3-0.15 g, split up into two or three doses per 24 hrs. Even in amounts far greater than this (20-30 mg/kg) (I), eg. 4-gamma-(p-chlorophenylsulphonyl)-3-dimethylaminopropoxy-1-phenyl- -1H-pyrazole (I') affects neither the CNS nor the cardiac/circulatory and respiratory system, and is non-ulcerogenic. (I) are of low toxicity e.g. LD50 for mice is 125 mg/kg i.p. and 670 mg/kg p.o.

The chemistry of nitroso-compounds. Part 15. Formation of N-nitrosamines in solution from gaseous nitric oxide in the presence of iodine

Abstract: Quantitative results are reported for the N-nitrosation of piperidine, morpholine, and N-methylpiperazine by NO (saturated) and iodine under anaerobic conditions in solvent EtOH, EtOH–water, and MeCN at 25 °C. The reactions are very much faster than those with NO in the absence of iodine, with maximum yields of N-nitrosamine being obtained in ca. 5–30 min depending on the solvent. The rates, however, are largely independent of the initial concentrations of either amine or iodine, and are similar for all three amines despite their different basicities. With excess of amine, 2 moles of N-nitrosamine are obtained per mole of iodine. Otherwise, the limiting yields of N-nitrosamine depend on both the concentration and basicity of the amine, with ca. 50, 66, and 100% reacting for piperidine, morpholine, and N-methylpiperazine, respectively. Addition of NaOH to the reaction solution, however, increases the yield to 100% throughout. Both added NaN3 and thiourea inhibit the formation of N-nitrosamines. The mechanism of these reactions is considered to involve rate-limiting formation of NOI (principally from NO and I2) followed by rapid reaction with the amine base. The amine cation is unreactive; NaN3 and thiourea inhibit reaction by competing for the NOI reagent. The results are also discussed in relation to human exposure to carcinogenic N-nitrosamines.

Morpholine derivatives and use as polyurethane catalyst

Abstract: Covers a method of producing a polyurethane by utilizing specific morpholine compounds as a catalyst in reacting an organic polyisocyanate with an organic polyester polyol or polyether polyol in the presence of said catalyst. Said amines fall within the following structural formula: ##STR1## where R is lower alkyl and x=0-4.

Bis(N-acetyl-DL-leucinate)copper(II) complexes and their amine adducts.

Abstract: A compound of the type Cu(AcLeu)2 and its amine adducts of the type Cu(AcLeu)2Bn (AcLeu=N-acetyl-DL-leucinato ion; n=2 and B=pyridine, 3- and 4-methylpyridine, N-methylpiperazine, morpholine, and piperidine; n=1 and B=1,10-phenanthroline, 2,2′-bipyridyl, piperazine, and pyridazine) were prepared and investigated by means of electronic, infrared and EPR spectroscopy and magnetic moment measurements. The results suggest a tetragonal configuration for the Cu(AcLeu)2 complex and the amine adducts with CuO4 and CuO2N2 chromophores, respectively. For the green Cu(AcLeu)2·pid complex a binuclear configuration similar to that observed for the bis(acetato)copper(II) monohydrate complex is suggested. The amino acid in all the complexes is found to coordinate toward the carboxylato group. In the assignment of the way in which the carboxylato group coordinates, in addition to the difference between their antisymmetric and symmetric stretching frequencies, we also pay special attention to the position of the symmetric...

Sampling and analysis of some corrosion inhibiting amines in steam condensates 1

Abstract: The analysis of corrosion inhibitors, such as morpholine (MOR), cyclohexylamine (CHA), diethylaminoethanol (DEAE) and octadecylamine (ODA) in steam condensates sampled in four hospitals and one food processing plant, is described. An aqueous injection‐gas chromatographic procedure was developed for the analysis of DEAE; mixtures of CHA and MOR were determined by a similar method. ODA was quantitated by a colorimetric method. Levels of amines were consistently low (4.2 mg/L) in steam sampled in systems in which the addition of amines to the boiler feed water was continuously metered. In a closed‐loop, low pressure system in which the amine formulation was added in a single dose to the boiler in an irregular manner, concentrations of amines in steam condensates were high (10,200 to 13,900 mg/L).

Some heterocyclic phosphorochloridates and the formation of other heterocyclic organophosphorus compounds

Abstract: Pyrrolidine, morpholine, and β-hydroxyethylmorpholine have been phosphorylated with phosphorus oxychloride, phenylphosphorodichloridate, p-chlorophenylphosphorodichloridate and thiophosphoryl chloride. The resultant phosphorodichloridates have been condensed with a wied range of nucleophilic reagents, e.g. amines, hydrazines, phenols and isobutanol. Piperazine with phosphorus oxychloride (2 mols) gave the N(1) N(4)-diphosphorotetrachloridate, which was characterized as the tetracyclohexylamidate. β-Hydroxyethylpiperazine was similarly phosphorylated to the N,O-diphosphorotetrachloridate which was characterized as the tetraphenylhydrazidate. Condensation of pyrrolidine (2 mols) with phosphorus oxychloride (1 mol) afforded N,N′-dipyrrolidinophosphorochloridate which was reacted with phenylhydrazide and sodium azide. The phosphoroazide with triphenylphosphine afforded the corresponding triphenylphosphinimine. N-Phenyl N′-pyrrolidinophosphorochloridate with aqueous pyridine gave the corresponding pyr...

Heterocycles in organic synthesis. Part 7. Synthesis of furfuryl derivatives via 2,4,6-trisubstituted pyridinium salts

Abstract: Nucleophilic displacement of the amino-group of furfurylamine by initial conversion into a 2,4,6-trisubstituted pyridinium perchlorate provides a convenient preparation of a wide variety of novel furfuryl derivatives. 2,4,6-Triphenylpyridinium derivatives are more reactive than their 2,4,6-trimethyl analogues. 2-(2,4,6-Triphenylpyridiniomethyl)furan is smoothly brominated in the 5-position, and the brominated product undergoes nucleophilic replacement of the pyridinio group with morpholine.

Bis Adducts of Imidazole, Morpholine and their Derivatives with Bis(acetylacetonato)nickel(II)

Abstract: Nitrogen donor ligands such as imidazole, morpholine and their derivatives (L) react with bis(acetylacetonate)nickel(II), Ni(AA)2, to form new solid 1 ∶2 adducts of the type Ni(AA)2L2, where nickel(II) is hexacoordinate. The adducts were characterised by elemental analysis, electronic and i.r. spectra, and magnetic susceptibility measurements. The ν(Ni-O) of the Ni(AA)2 is shifted to lower frequencies upon adduct formation, showing direct coordination of the donor molecules with the metal ion. Imidazole is bonded to nickel(II) through the “pyridine nitrogen” and morpholine through the “N” atom. The new Ni(AA)2L2 adducts are paramagnetic and have a pseudooctahedral structure with the two L' s in the extraplanartrans-position.

Enamine chemistry. Part 26. Preparation of substituted adamantane-2,4-diones and bicyclo[2.2.2]octan-2-ones

Abstract: Reaction of αβ-unsaturated acid chlorides with the morpholine or pyrrolidine enamines derived from 4-benzoyl-4-methylcyclohexanone gives the corresponding 6-hydroxy-7-methyl-6-phenyladamantane-2, 4-dione in moderate to good yield Enamines from 4-acetyl-4-phenyl (or 4-ethoxycarbonyl) cyclohexanone could not be isolated owing to their preferential cyclisation into 1 -phenyl (or 1 -ethoxycarbonyl) 4-substituted aminobicyclo[222]octan-2-ones

A Novel Approach to cis-Jasmone and Dihydrojasmone from 2-(2-Benzothiazolylthio)-2-(3-oxobutyl)oct-5-en(or -an)oic Acid by Electrolytic Procedure

Abstract: cis-Jasmone (7a) and dihydrojasmone (7b) have been synthesized by facile five-step processes starting from methyl acetoacetate involving electrolysis procedure. Methyl 2-(2-benzothiazolylthio)oct-5-en(or -an)oate, prepared from methyl 2-acetyloct-5-en(or -an)oate (1) by the reaction with the N-(2-benzothiazolylthio)morpholine, were allowed to react with methyl vinyl ketone, leading to the Michael adducts 4. After hydrolysis of 4, the corresponding acids 5 were electrolyzed to afford the desired 1,4-diketone 6 in 45–48% overall yields (based on 1), whose base-catalyzed cyclization gave 7 smoothly.

2,4-Di:amino-phenoxy-alkylamine cpds. - are oxidn. hair dye coupler components, prepd. from 2,4-di:nitrophenol with chloro-alkylamine

Abstract: New (2,4-diaminophenoxy)-alkylamines have formula (I), (where R is -(CH2)n-NR1R2 or -CHMeCH2-NR1R2, in which n is integer 1-5; each R1 and R2 is 1-4 C-alkyl, or R1 and R2, together with the N atom, for a morpholine, piperidine or pyrrolidine ring). (I), and their salts with organic or inorganic acids, are used as coupler components in oxidn. hair dyes. (I) form strong, fast brown to black and blue shades; are soluble in water, resist storage, are non-toxic and cause no skin-irritation.

Alkylated 2:phenyl morpholine derivs. - having antidepressant and cardiovascular activity, prepd. by cyclising hydroxyalkyl phenyl ethanol(s)

Abstract: 2-Phenyl morpholine derivs. of formula (I) and their acid addn. salts are new (where R1,R2 and R3 are each H or 1-4C alkyl, at least one of these being other than H). (I) are antidepressants and cardiovascular agents. (I) may be prepd. using a cpd. of formula (II) as starting material.

Gas phase morpholine prodn. - from di:ethylene glycol and ammonia over mixed metal hydrogenation catalyst

Abstract: Prodn. of morpholine (I) comprises gas-phase reaction of diethylene glycol and NH3 in presence of H2 at elevated temp. and 1-30 atmos. over a Ni-Cu-Cr-Ti catalyst. Pref the catalyst comprises (by wt.) 25-55% NiO; 15-40% CuO, 0.7-7% Cr2O3 and 20-40% TiO2. (I) is an intermediate for vulcanisation accelerators, optical brighteners, surfactants, pharmaceuticals and dyes, and is also a solvent and corrosion inhibitor. Its derivs. are used in mfr. of polyurethane foams. Yields are improved (75-78 wt. %) and catalyst life extended (e.g. 2000 hrs. which is 3 times that of conventional catalysts).

Catalytic conversion of butadiene into octadienes by nickel(0) complexes, morpholine, and formaldehyde

Abstract: N-Hydroxymethylmorpholine, the product of the reaction of morpholine with formaldehyde, is an efficient H-donor molecule in the hydrodimerisation of butadiene catalysed by nickel(0) complex–phosphine systems; N-formylmorpholine is obtained as a byproduct.

Synthesis of 2-Cinnamoyl-1,3-indandione Derivatives and their Reactions with Hydrazine, Hydroxylamine Hydrochloride, Thiourea, Secondary Amines and Diethyl Oxalate

Abstract: A series of 2-cinnamoyl-1,3-indandiones (2a-e) were obtained by condensing 1 with aldehydes. Treatment of 2 a with hydrazine or hydroxylamine hydrochloride gave 2-(5-phenyl-2-pyrazolinyl or -isoxazolinyl)-1,3-indandione (3 and 5) respectively, and when treated with thiourea gave 2-(6-phenyl-2-thioxo-4-pyrimidinyl)-1,3-indandione (6).The formation of 2-(β-piperidino-, -morpholino- and -arylmercaptohydrocinnamoyl)- 1,3-indandiones (7a-b and 8a-b) from 2 a was investigated. Compound 7b when treated with hydrazine gave 9. The 2-(α, β-dimorpholinohydrocinnamoyl) derivative (11) was obtained by the action of morpholine on the dibromo derivative (10). The Michael condensation of 2a with ethyl acetoacetate or acetyl acetone was investigated. Treatment of 1 with benzaldehyde in (3:1) molar ratio gave 14, which reacted with diethyl oxalate to give 15. Cyclization of 15 with polyphosphoric acid lead to the formation of 16.

Process for the simultaneous production of 2-(2-aminoalkoxy)alkanol and morpholine

Abstract: A process for simultaneously producing a 2-(2-aminoalkoxy)alkanol compound and a morpholine compound is disclosed wherein an oxydialkanol is contacted with ammonia in the presence of a catalytically effective amount of a hydrogenation/dehydrogenation catalyst at a temperature of from about 190° C. to about 230° C. and at a pressure ranging from about 700 psig to about 2200 psig, said oxydialkanol having the formula: ##STR1## wherein each R is, independently, a hydrogen or a lower alkyl radical; and recovering said 2-(2-aminoalkoxy)alkanol compound and said morpholine compound from the resulting reaction mixture.