Morpholine, 4-Ethyl

Beilstein Handbook Reference) AI3-24288 BRN 0102969 CCRIS 4818 EINECS 202-885-0 N-Ethylmorfolin Ethylmorpholine 4-Ethylmorpholine N-Ethylmorpholine HSDB 1644 Morpholine, 4-ethyl- NEM NSC 6110 Texacat NEM Toyoca -NEM. Catalyst for PU molded flexible, semirigid, and rigid applications. Amine-based catalyst for flexible slabstock PU foam. Liquid mp = -63° bp = 138.5° d = 0.9050 freely soluble in H2O, EtOH, Et20, soluble in Me2CO, CeHe LDso (rat orl) = 1780 mg/kg. Texaco Tosoh. 

Ethylmorpholine N-Ethylmorpholine. See Ethyl morpholine Ethyl morrhuate... 

C Cyclopropane, CO, ether, hydrogen sulfide, morpholine, ethyl ether, and ethylene or gases of equivalent hazard. ... 

H 2-iV-Morpholine ethyl Candida rugosa lipase from Meito Sangyo Co. (Lipase MY)/isooctane 42 37 40.7 92.6 63.6 50 109 ... 

In a similar manner the addition of ethyl azodicarboxylate to the morpholine enamine of cyclohexanone furnished the less substituted isomer (34) with the substituent in the axial orientation (2, 26). 

Although the enamine (30) underwent addition reaction with ethyl azido-dicarboxylate, it failed to add another mole of jS-nitrostyrene. In a similar manner the morpholine enamine of 2-methylcyclohexanone also failed to react with this olefin, i.e., jS-nitrostyrene, which is undoubtedly due to the 1,3-diaxial interaction between the methyl group and the incoming electrophile in the transition state. 

Another interesting example is found in the morpholine enamine of 2- -propylcyclohexanone (138), which consists of a 2 3 mixture of tri- and tetrasubstituted isomers. The radical ion from the tetrasubstituted isomer loses an ethyl radical, giving the base peak at m/e 180. 

The reaction of morpholine enamines of cyclic ketones with ethyl azodicarboxylate has also been demonstrated 56,136). The enamine (113) on reaction with ethyl azodicarboxylate can give the 2- or 2,6-bis(N,N di-carboxyhydrazino)cyclohexanones 199 and 200, respectively, on hydrolysis. 

At higher temperatures the mixture of 10 and methyl vinyl ketone yields the 1,4-carbocyclic compound as described previously. Methyl isopropenyl ketone (5), ethyl acetylacrylate (d), 2-cyclohexenone (21), and 1-acetyl-1-cyclohexene (22) also undergo this type of cyclization reaction with enamines at higher temperatures. This cycloalkylation reaction occurs with enamines made of strongly basic amines such as pyrrolidine, but the less reactive morpholine enamine combines with methyl vinyl ketone to give only a simple alkylated product (7). Chlorovinyl ketones yield pyrans when allowed to react with the enamines of either alicyclic ketones or aldehydes (23). 

E) Preparation of 2-( 1-Succinyloxyethyl)-3-Methyl-5-(2-Oxo-2,5-Dihydro-4-Furyl)Bemo[b] -Furan (409 CBj 8.65 grams of compound 3574 CB in 43 ml of pyridine are warmed for 30 minutes, on a water bath, with succinic anhydride. At the end of this, the pyridine is stripped off in vacuo. The mixture is treated with dilute sulfuric acid and with ether, the crystalline product filtered off, washed with water and with ether, and recrystallized from ethyl acetate (9.35 grams). MPq = 144°C (measured after drying at 90°C and 0.1 mm). Yield 77%. The product yields an equimolecular compound with morpholine. MPc= 136°C (from ethyl acetate). 

C) Preparation of Doxapram Hydrochloride [3,3-Diphenyl-1-Ethyl-4-(2-Morpholino-Ethylj-2-Pyrrolidinone Hydrochloride Monohydrate] A solution of 25 grams (0.076 mol) of 4-(2-chloroethyl)-3,3-diphenyl-1-ethyl-2-pyrrolidinone and 13.3 grams (0.153 mol) of morpholine in 500 ml of absolute ethanol was heated at 95°-120°C for 21 hours in a closed system and concentrated in vacuo. The residue was dissolved in 3(X) ml of two normal hydrochloric acid and extracted with 150 ml of ethyl acetate. A solid crystallized (13 g) during the extraction and was removed by filtration. MP 217°-219°C. The acid extracts were made basic with sodium hydroxide and extracted with ether, and the ether solution was concentrated in vacuo and the residue was suspended in six normal hydrochloric acid. Additional crystalline product formed and was recrystallized from two normal hydrochloric acid. Yield, 10 grams MP 217°-219°C. Total yield, 23 grams (70%). 

A mixture of 800 g of potassium o-bromo-benzoate, 1,500 ml of bis-(2-methoxyethyl)ether, 355 g of N-ethyl-morpholine, 375 g of 2,3-dimethylaniline, and 30 g of cupric acetate is heated gradually with stirring to 140°C over a period of 90 minutes. The hot reaction mixture is then acidified with 260 ml of concentrated hydrochloric acid and the acidified mixture divided into 2 equal portions. One liter of water is added to each portion and the mixtures allowed to cool. The N-(2,3-dimethylphenyl)anthranllic acid which separates upon cooling is collected by filtration and recrystallized from bis(2-methoxyethyl)ether MP 229° to 230°C (corr.). 

A solution of 1-benzyl-4-piperidone, ethyl cyanoacetate, powdery sulfur and morpholine in ethanol is heated moderately under reflux for about 20 minutes to dissolve the powdery sulfur. The mixture is heated under reflux for one further hour to complete the reaction. On standing at room temperature, the mixture yields a precipitate. The precipitate is collected by filtration, washed well with methanol and recrystallized from methanol to give 2-amino-6-benzyl-3-ethoxycarbonyl-4,5,6,7-tetrahydrothieno(2,3-c)-pyridine as almost colorless needles melting at 112° to 113°C. 

A solution of 5.0 g of a-ethyl-(3-(aminophenyl)propionic acid in 100 ml of water containing 5 ml of concentrated hydrochloric acid was added over a period of h hour to a stirred solution of 3.2 ml of Iodine monochioride in 25 ml of water and 25 ml of concentrated hydrochloric acid heated to 60°C. After addition was complete, the heating was continued for h hour longer at 60° to 70°C. A black oil separated which gradually solidified. The mixture was then cooled and sodium bisulfite was added to decolorize. Recrystallization of the product from methanol gave about 8 g of a-ethyl-(3-(2,4,6-triiodo-3-aminophenyl-pro-pionic acid, MP 147° to 150°C. The product could be further purified by precipitation of its morpholine salt from ether solution and regeneration of the free amino acid by treatment of a methanol solution of the morpholine salt with sulfur dioxide. The pure amino acid had the MP 155° to 156.5°C (corr). 

Besides aromatic tertiary amines, the aliphatic cyclic tertiary amines such as N-methyl(or ethyl) morpholine can also be used in coupling with BPO to enhance the Rp of MMA polymerization [20], Since the... 

The aziridine aldehyde 56 undergoes a facile Baylis-Hillman reaction with methyl or ethyl acrylate, acrylonitrile, methyl vinyl ketone, and vinyl sulfone [60]. The adducts 57 were obtained as mixtures of syn- and anfz-diastereomers. The synthetic utility of the Baylis-Hillman adducts was also investigated. With acetic anhydride in pyridine an SN2 -type substitution of the initially formed allylic acetate by an acetoxy group takes place to give product 58. Nucleophilic reactions of this product with, e. g., morpholine, thiol/Et3N, or sodium azide in DMSO resulted in an apparent displacement of the acetoxy group. Tentatively, this result may be explained by invoking the initial formation of an ionic intermediate 59, which is then followed by the reaction with the nucleophile as shown in Scheme 43. 

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