Amines ethyl acetate

Uses. Nearly half the ethyl alcohol produced in petrochemical plants (not the stuff fermented for human consumption) is used as a chemical intermediate in the manufacture of ethyl acrylate, ethyl amines, ethyl acetate (when you pop the cap on nail polish remover, you smell ethyl acetate), ethylene chloride, glycol ethers, acetaldehyde, and acetic acid. However, you will see in the chapters on acetaldehyde and acetic acid, there are now more competitive routes than those based on ethyl alcohol. 

Allow a mixture of 0-5 g. of the tertiary amine and 0-5 ml. of colourless methyl iodide to stand for 5 minutes. If reaction has not occurred, warm under reflux for 5 minutes on a water bath and then cool in ice water. The mixture will generally set solid if it does not, scratch the sides of the tube with a glass rod. RecrystaUise the solid product from absolute alcohol, ethyl acetate, acetone, glacial acetic acid or alcohol-ether. 

Dissolve 2-3 g. of methyl p-toluenesnlphonate in 10 ml. of dry benzene, add 1 g. of the amine, and boU the mixture for 20-30 minutes. Cool, and filter the precipitated quaternary salt. Recrystallise by dissolving the solid in the minimum volume of boiling ethyl alcohol and then adding ethyl acetate until crystallisation commences. Filter the cold mixture, dry rapidly on a porous plate, and determine the m.p. immediately. 

PMMA is not affected by most inorganic solutions, mineral oils, animal oils, low concentrations of alcohols paraffins, olefins, amines, alkyl monohahdes and ahphatic hydrocarbons and higher esters, ie, >10 carbon atoms. However, PMMA is attacked by lower esters, eg, ethyl acetate, isopropyl acetate aromatic hydrocarbons, eg, benzene, toluene, xylene phenols, eg, cresol, carboHc acid aryl hahdes, eg, chlorobenzene, bromobenzene ahphatic acids, eg, butyric acid, acetic acid alkyl polyhaHdes, eg, ethylene dichloride, methylene chloride high concentrations of alcohols, eg, methanol, ethanol 2-propanol and high concentrations of alkahes and oxidizing agents. 

Addition compounds form with those organics that contain a donor atom, eg, ketonic oxygen, nitrogen, and sulfur. Thus, adducts form with amides, amines, and A/-heterocycles, as well as acid chlorides and ethers. Addition compounds also form with a number of inorganic compounds, eg, POCl (6,120). In many cases, the addition compounds are dimeric, eg, with ethyl acetate, in titanium tetrachloride-rich systems. By using ammonia, a series of amidodichlorides, Ti(NH2) Cl4, is formed (133). 

Solubility. One of PVP s more outstanding attributes is its solubility in both water and a variety of organic solvents. PVP is soluble in alcohols, acids, ethyl lactate, chlorinated hydrocarbons, amines, glycols, lactams, and nitroparaffins. SolubiUty means a minimum of 10 wt % PVP dissolves at room temperature (moisture content of PVP can influence solubiUty). PVP is insoluble in hydrocarbons, ethers, ethyl acetate, j -butyl-4-acetate, 2-butanone, acetone, cyclohexanone, and chlorobenzene. Both solvent polarity and H-bonding strongly influence solubiUty (77). 

Although in the dry state carbon tetrachloride may be stored indefinitely in contact with some metal surfaces, its decomposition upon contact with water or on heating in air makes it desirable, if not always necessary, to add a smaH quantity of stabHizer to the commercial product. A number of compounds have been claimed to be effective stabHizers for carbon tetrachloride, eg, alkyl cyanamides such as diethyl cyanamide (39), 0.34—1% diphenylamine (40), ethyl acetate to protect copper (41), up to 1% ethyl cyanide (42), fatty acid derivatives to protect aluminum (43), hexamethylenetetramine (44), resins and amines (45), thiocarbamide (46), and a ureide, ie, guanidine (47). 

Grouping Acetone Ethane Ethyl-acetate Acetylene Ethyl amine Ethylene Acetaldehyde Ethyl glycol Crude oil Ethyl-ether Carbon disulphide Ethyl Nitrite... 

The hydrochloride is prepared in the usual manner by dissolving the amine in anhydrous ether and adding to it the requisite amount of dry gaseous hydrochloric acid,dissolved in absolute alcohol. There is obtained a white crystalline powder melting at 150°C, very soluble in water and alcohol,very slightly soluble in ether and ethyl acetate. 

The benzene was distilled from the extract and the residue of d-N-methyl-N-benzyl-)3-phenyl-isopropylamine was distilled at reduced pressure. The thus obtained free base, distilling at 127°C at a pressure of 0.2 mm of mercury and having an np of 1.5515, was dissolved in ethyl acetate and a molar equivalent of ethanolic hydrogen chloride was added thereto. Anhydrous ether was added to the mixture and d-N-methyl-N-benzyl-)3-phenylisopropyl-amine hydrochloride precipitated from the reaction mixture as an oil which was crystallized from ethyl acetate to give crystals melting at 129° to 130°C. 

Of this product, 4.5 g in 30 cc of dry isopropyl alcohol are refluxed for 16 hours with 2.5 g of (3-chloroethyl dimethyl amine. The solution is cooled and filtered clear from the solid by-product. The solvent is removed under reduced pressure on the steam bath and the residue is washed with anhydrous ether. It is dissolved in ethyl acetate from which it crystallizes. It is the hydrochloride of (3-(dimethylamino)ethyl ester of 2-phenyl-2-( 1-hy-droxycyclopentyl) ethanoic acid, melting at 134° to 136°C. 

In order to obtain a pure product the amine is dissolved in about 700 cc. of boiling ethyl acetate under a reflux condenser. When the amine has dissolved the solution is rapidly cooled and stirred, whereupon the amine separates in almost white crystals. Further crops of crystals may be obtained on concentrating the solution and cooling. The last portions may be colored, hut one... 

Normally ethyl acetate is used for the acylation of primary amines, in many cases, as acyl donor and solvent. Other acylating agents such as alkyl methoxy acetates are... 

Although catalytic hydrogenation is the method most often used, double bonds can be reduced by other reagents, as well. Among these are sodium in ethanol, sodium and rerr-butyl alcohol in HMPA, lithium and aliphatic amines (see also 15-14), " zinc and acids, sodium hypophosphate and Pd-C, (EtO)3SiH—Pd(OAc)2, trifluoroacetic acid and triethylsilane (EtsSiH), and hydroxylamine and ethyl acetate.However, metallic hydrides, such as lithium aluminum hydride and sodium borohydride, do not in general reduce carbon-carbon double bonds, although this can be done in special cases where the double bond is polar, as in 1,1-diarylethenes and in enamines. " °... 

The strategy for the asymmetric reductive acylation of ketones was extended to ketoximes (Scheme 9). The asymmetric reactions of ketoximes were performed with CALB and Pd/C in the presence of hydrogen, diisopropylethylamine, and ethyl acetate in toluene at 60° C for 5 days (Table 20) In comparison to the direct DKR of amines, the yields of chiral amides increased significantly. Diisopropylethylamine was responsible for the increase in yields. However, the major factor would be the slow generation of amines, which maintains the amine concentration low enough to suppress side reactions including the reductive aminafion. Disappointingly, this process is limited to benzylic amines. Additionally, low turnover frequencies also need to be overcome. 

Titanium(IV) iodide is extremely hygroscopic. It dissolves in water with decomposition, and it fumes in air owing to hydrolysis. It forms 2 1 adducts with ammonia,7 pyridine,33 and ethyl acetate.34 With excess ammonia it undergoes ammo-nolysis to give ammonobasic titanium(IV) iodides.7 Analogous aminolysis reactions occur when titanium(IV) iodide is treated with an excess of primary or secondary amine.36 Titanium(IV) iodide is sparingly soluble in petroleum ether, moderately soluble in benzene, and even more soluble in chlorinated hydrocarbons and carbon disulfide. At elevated temperatures it... 

The resultant ethylmalonate-protected-amine compound is concentrated in vacuo and then purified using silica gel chromatography with a hexane/ethyl acetate (1 1) eluent. 

Remove the solvent in vacuo and purify the resultant mixture using silica gel chromatography. The initial eluent is toluene, which will remove the unreacted Cgo, and then followed by a 10 1 mixture of toluene/ethyl acetate to elute the desired Cgo-protected-amine derivative. 

With these solid supports in hand, we turned our attention to a new route to the synthesis of our target molecule 23 (Scheme 8). The tricky reductive amination should be replaced by an N-alkylation. To that end, bromoacetic acid is attached to 24c using DIC and Hiinig s base followed by the nucleophilic substitution with the corresponding benzy-lamine in DMSO/toluene (1 1), which can be easily monitored by the Beilstein test, followed by sulfonamide formation in DCM using N-methylmorpholine as base. For the final cleavage, 2% TFA in DCM is used and the resulting solution is filtered in a saturated NaHCC>3 solution to neutralise the acid before evaporation of the solvent. The crude product was then crystallised from ethyl acetate/heptane to yield the desired product in 27% yield overall and 99A% HPLC purity (see Table 4). 

Paper chromatography has been used to separate and detect pseudoephedrine hydrochloride from other pharmacologically active amines. Whatman No. 1 paper developed in n-butanol water 95% acetic acid (4 5 1), n-butanol toluene water 95% acetic acid (10 10 5 5), ethyl acetate water 95% acetic acid (3 3 1), or chloroform water 95% acetic acid (10 5 4) gave Rf values of 0.73, 0.35, 0.57, and 0.52 for pseudoephedrine hydrochloride respectively. Visualization of pseudoephedrine hydrochloride was done by spraying the chromatogram with 0.5% bromcresol green in methanol or 0.2% nin-hydrin in acetic acid butanol 5 95.30... 

A 4 g 3-indoleacetic acid (I) in ether. I reat with PCi5 as described elsewhere here to get 2.7 g of the chloride (II). Dissolve 2.7 g (II) in 40 ml ethyl acetate and add 2 ml piperidine (or equimolar amount other amine), 3.5 ml N-ethyl-piperidine in 40 ml ethyl acetate. Let stand three hours at room temperature and filter. Wash filtrate with IN HCI, 10% Na carbonate and evaporate in vacuum to get 1 g of the amide (III) (test for activity). Add 1 g (111) in 25 ml ether to 1.4 g lithium aluminum hydride in 50 ml ether stir four hours at room temperature and reflux one-half hour. Cool and carefully add water until no more bubbling. Add 3 ml 20% NaOH and dry. evaporate in vacuum to get 1 g piperidine analog of DMT... 

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