Reaction Of Morpholine Research Articles

Kinetic and equilibrium studies of ?-adduct formation and nucleophilic substitution in the reactions of morpholine with 1,3,5-trinitrobenzene and some phenyl aryl ethers in dimethyl sulphoxide

Reactions of morpholine in dimethyl sulphoxide at unsubstituted ring positions of 1,3,5-trinitrobenzene, and phenyl 2,4,6-trinitrophenyl ether, yield anionic σ-adducts via zwitterionic intermediates. Reactions at the 1-position of phenyl 2,4,6-trinitrophenyl ether, phenyl 2,4-dinitronaphthyl ether, and phenyl 2,4-dinitrophenyl ether result in substitution of the phenoxy groups. In both these reaction types proton-transfer is rate-limiting. Comparison of kinetic and equilibrium data with those for corresponding reactions of piperidine shows that rate constants for proton transfer are similar for the two amines, but equilibrium constants for zwitterion formation have lower values for morpholine, the less basic amine. Implications for base catalysis are discussed.

Mechanism of bimolecular substitution reactions of hydroximoyl halides with amines in actonitrile solution

AbstractThe reaction in acetonitrile solution of (Z)‐O‐methylbenzohydroximol chlorides [ArC (Cl)NOCH3] with morpholine, pyrrolidine and azetidine gives the corresponding (Z)‐amidoximes [ArC(NR1R2)NOCH3] in acetonitrile. The rates of these reactions were measured under pseudo‐first‐order conditions (excess amine). The reactions were found to follow overall second‐order kinetics (first order in amine). The Hammett ρ‐value (with σ) for the reaction with pyrrolidine is +0·92. The reaction of the p‐nitro compound with pyrrolidine gives a significant element effect [k(p‐nitrobenzohydroximoyl bromide)/k(p)‐nitrobenzohydroximoyl chloride = 10]. A Brϕonsted β‐value of 0·38 was estimated from the reactions of morpholine and piperidine with the p‐nitrohydroximoyl chloride. The slower reaction of (E)‐O‐methyl‐p‐nitrobenzohydroximoyl chloride with azetidine gives primarily the (E)‐amidoxime (E:Z ≈ 98:2) This reaction also follows second‐order kinetics. The kinetic observations made in this study are compared with the corresponding results obtained in earlier work in benzene solution. It is suggested that in acetonitrile solution the reactions proceed by an addition–elimination mechanism with rate‐determining loss of chloride ion (AN + DN#). It is further suggested that acetonitrile is assisting in the breakdown of the tetrahedral intermediates formed in these reactions.

CYCLIC S-N COMPOUNDS AND PHOSPHORUS REAGENTS: III1

Abstract Reactions of Ph3PN-S3N3 (I) with ammonia and various amines (primary, secondary and tertiary) have been studied in CH3CN-C6H6 mixture (5:1) at 50°C. In the case of ammonia, t-butylamine, morpholine, pyrrolidine and triethylamine, the eight membered heterocycle 1,5-(Ph3PN)2S4N4 (II) was isolated in better yields compared to earlier methods. Bis(morpholino) sulfide was also isolated from reactions of morpholine. However pyrrole, pyridine, diphenylamine and urea gave no reaction with (I).

Zur Reaktion von N‐(N′,N′‐Dialkyl(aryl)amino‐thiocarbonyl)benzimidoylchloriden mit Kaliumthiocyanat

Reactions of N‐(N′,N′‐Dialkyl(aryl)amino‐thiocarbonyl)benzimidoylchlorides with Potassium ThiocyanateThe treatment of the title compound N‐(amino‐thiocarbonyl)‐benzimidoylchloride 1 with potassium thiocyanate leads in dependence on the solvents (methanol, acetic acid, acetone) either to the 1,3,5‐thiadiazine‐2‐thione 2a–d or to the ring opened isothiocyanate 4a, b. In the case of methanol the N‐(amino‐thiocarbonyl)benzimidates were formed as by‐products.The structure of the products is confirmed by analytical data and by chemical transformations. 2a reacts with methyl iodide to form the 2‐methylthio‐6‐morpholino‐4‐phenyl‐1,3,5‐thiadiaziniumiodide 3a. From 4a and water the N‐(morpholino‐thiocarbonyl)benzamide 5a arises. The reaction of morpholine with 4a yields the benzamidine 6a.

Catalysis by amine salts of some aromatic nucleophilic substitution reactions

The reaction of 1-chloro-2,4-dinitrobenzene with aniline in acetonitrile is catalysed by R4NY where Y is Cl, Br, I, or toluene-p-sulphonate, but not by 1,4-diazabicyclo [2.2.2.] octane (DABCO). When the nucleophile is changed to n-butylamine or morpholine, addition of tetraethylammonium chloride has only a small effect; the reactions of all three nucleophiles are not catalysed by tetraethylammonium perchlorate. The reaction of 1-fluoro-2,4-dinitrobenzene with aniline is strongly catalysed by tetraethylammonium chloride, to a lesser extent by the bromide and toluene-p-sulphonate and also by trimethylamine hydrochloride, but not by tetraethylammonium perchlorate. The reactions of morpholine with 1-fluoro-2,4-dinitrobenzene and piperidine with 2,4-dinitrophenyl phenyl ether are not catalysed by amine salts. The results are consistent with the formation and stabilisation of the intermediate formed in aromatic nucleophilic substitution reactions by the anions of the salts, when the nucleophile is aniline.

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

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.

Reaction of 2,4-dinitrophenyl phenyl ether with morpholine in dimethyl sulphoxide, acetonitrile, tetrahydrofuran, and ethyl acetate and of 1-chloro-2,4-dinitrobenzene with morpholine in ethyl acetate

The reaction of morpholine with 2,4-dinitrophenyl phenyl ether is base-catalysed in all the solvents investigated. The values of k3/k2 provide information about the mechanism of the uncatalysed decomposition of the intermediate formed in nucleophilic aromatic substitution in solvents of high dielectric constant.The reaction of morpholine with 1-chloro-2,4-dinitrobenzene in ethyl acetate is not base-catalysed. Comments are made on the mechanism of base-catalysed nucleophilic aromatic substitution in solvents of low dielectric constant and basicity.

X-Ray crystal structure of the novel bis-quaternary dispiro system obtained from the reaction of morpholine with hexakis(bromomethyl)benzene

In contrast to the six-fold substitution of hexakis(bromomethyl)benzene (Ia) by aniline to give the hexa-amine (Ib), reaction of (Ia) with morpholine occurs with dispiro-annelation yielding (II); the structure of this novel product was deduced spectroscopically and its detailed molecular geometry was determined by X-ray crystallography.

ChemInform Abstract: COMPARATIVE REACTIVITY OF COMPOUNDS OF THE TYPE R‐CO‐CHO AND R‐CO‐CHX2. REACTION OF MORPHOLINE, PIPERIDINE, AND N‐METHYL ETHANOLAMINE WITH GLYOXYLIC ACID DERIVATIVES

Chemischer InformationsdienstVolume 7, Issue 21 Preparative Organic Chemistry ChemInform Abstract: COMPARATIVE REACTIVITY OF COMPOUNDS OF THE TYPE R-CO-CHO AND R-CO-CHX2. REACTION OF MORPHOLINE, PIPERIDINE, AND N-METHYL ETHANOLAMINE WITH GLYOXYLIC ACID DERIVATIVES ARLETTE LE ROUZIC-BELLEVRE, ARLETTE LE ROUZIC-BELLEVRESearch for more papers by this author ARLETTE LE ROUZIC-BELLEVRE, ARLETTE LE ROUZIC-BELLEVRESearch for more papers by this author First published: May 25, 1976 https://doi.org/10.1002/chin.197621078Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume7, Issue21May 25, 1976 RelatedInformation

The kinetics of the reactions of piperidine, n-butylamine, morpholine, and benzylamine with 1-fluoro- and 1-chloro-2,4-dinitrobenzenes in acetonitrile

The kinetics of the reactions designated in the title have been studied as a function of amine concentration. The only system to show base catalysis is the reaction of morpholine with 1-fluoro-2,4-dinitrobenzene. The results are analysed in terms of the effects of nucleophile basicity and the change from primary to secondary amine on the mechanism of nucleophilic aromatic substitution.

Reactions of allene with amines and active methylene compounds; adduct formation in the presence of nickel complexes

Reactions of morpholine, pyrrolidine, di-n-propylamine, aniline, and n-butylamine with allene in the presence of a nickel salt and di-isopropoxyphenylphosphine have been studied. Mixtures of 1 : 1, two 1 : 2, and two 1 : 3 amine-allene adducts were formed, and with the exception of n-butylamine, the 1 : 3 adducts constituted >50% of the product amines. An essentially analogous reaction occurred with the active methylene compounds, diethyl malonate, ethyl acetoacetate, benzyl cyanide, and benzyl methyl ketone with the preferential formation of 1 : 3 adducts; the inclusion of either sodium phenoxide or sodium borohydride to the catalyst system was found necessary for reaction. The mechanism has been interpreted in terms of a 1 : 1 and 2 : 1 allene-nickel intermediate and a 3 : 1 allene–bisallyl-nickel intermediate. The specificity of reaction has been suggested to be a consequence of the σ, π character of the bis-π-allylnickel complex with preferential reaction of the nucleophilic active hydrogen compound at a π-allylnickel bond.

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

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.

Reactions of thiolsulphonates with amines

The equilibrium constants for the reaction of morpholine with methyl or t-butyl toluene-p-thiolsulphonates have been measured in acetonitrile–water (7 : 1,v/v) at 25 °C. Contrary to previous data they are 2·5 × 10–3 and 3·4 for the methyl and t-butyl substrates respectively. In the same solvent medium have been measured the reaction rates and the activation parameters of the nucleophilic displacement reaction of morpholine with the same substrates. The overall mechanism is discussed.

Reactions in frozen aqueous solutions : The kinetics of the reaction of morpholine with Dihydrothiophen-2(3H)-one and with methyl formate

The reactions of morpholine with dihydrothiophen-2(3H)-one and with methyl formate have been studied in frozen solution at -10�C. The rates for these reactions are the same as those found when reaction is carried out at the same temperature in simple solutions with concentrations equal to those present in the equilibrium liquid phase of the partly frozen solution. These observations show that the change in rate is a pure concentration effect. There is no need to assume any change in order or mechanism of reaction in the frozen solution as was claimed by Bruice and Butler.

Vinylamines—VIII : The reaction of cyclohexanone enamines with 1- and 2-nitropropene

Enamines containing a trisubstituted double bond were obtained by reaction of morpholine, piperidine and pyrrolidine enamines of cyclohexanone with 1-nitropropene. Different results were obtained in the reaction of the same enamines with 2-nitropropene. A cycloaddition reaction occurred between 1-N-morpholino-cyclohexene and 2-nitropropene in ether at 0°, leading to an oxazine derivative. The structures of the products were determined by spectral and chemical evidence. In acetonitrile at 0° or in ether at room temperature the same enamine reacted with 2-nitropropene to give an enaminic mixture, where the less substituted alkylated isomer appeared to be the minor component. Analogous behaviour was shown by piperidine and pyrrolidene enamines. The mechanism and the stereochemistry of these reactions have been discussed. The formation of diadducts of a different nature from morpholine and pyrrolidine enamines with excess 2-nitropropene is also reported.

Dialkylaminomethyl Sulfides: An Improved Synthesis.

DURING another study, several dialkylaminomethyl alkyl (aryl) sulfides were required. A survey of the literature revealed two significant references on their preparation (1,2). According to these 'reports, the dialkylaminomethyl sulfides are formed in erratic yields. For example, from the reactions of morpholine and formaldehyde with thiophenol and rn-thiocresol, the corresponding morpholinomethyl aryl sulfides were obtained in yields of 33 and 79%, respectively (1 ) . Grillot prepared the dialkylaminomethyl aryl sulfides by combining the reactants a t 20°C. and then holding at 8OoC. for 2 to 3 hours. McLeod and Robinson used somewhat milder conditions to prepare the dialkylaminomethyl alkyl sulfides in yields of 50 to 60% ( 2 ) . Their reactions were at room temperature employing a saturated potassium carbonate solution. The inconsistent yields prompted an investigation of this seemingly simple The method of McLeod implies that the reaction will occur under moderate conditions; however, the use of K?CO1 seemed superfluous. If a basic medium is required, the amine should furnish the necessary basicity even after reaction with formaldehyde. Working on this premise, a series of aminosulfides was prepared. The reaction was carried out by adding the secondary amine to a formaldehyde solution maintained at 25 to 30°C., then the thiol was added while maintaining the same temperature. Excellent yields (85 to 95%) of dialkylaminomethyl sulfides were obtained from both aliphatic and aromatic mercaptans. The reaction can be represented by the equation: