Ethers hydrogenation

Into a 500 ml. three-necked flask, provided with a mechanical stirrer, a gas inlet tube and a reflux condenser, place 57 g. of anhydrous stannous chloride (Section 11,50,11) and 200 ml. of anhydrous ether. Pass in dry hydrogen chloride gas (Section 11,48,1) until the mixture is saturated and separates into two layers the lower viscous layer consists of stannous chloride dissolved in ethereal hydrogen chloride. Set the stirrer in motion and add 19 5 g. of n-amyl cyanide (Sections III,112 and III,113) through the separatory funnel. Separation of the crystalline aldimine hydrochloride commences after a few minutes continue the stirring for 15 minutes. Filter oflF the crystalline solid, suspend it in about 50 ml. of water and heat under reflux until it is completely hydrolysed. Allow to cool and extract with ether dry the ethereal extract with anhydrous magnesium or calcium sulphate and remove the ether slowly (Fig. II, 13, 4, but with the distilling flask replaced by a Claisen flask with fractionating side arm). Finally, distil the residue and collect the n-hexaldehyde at 127-129°. The yield is 19 g. 

Alkyl aryl ether Hydrogen halide A phenol Alkyl halide... 

Explosive reactions can occur between oxygen and a wide range of chemicals including organic compounds (such as acetone, acetylene, secondary alcohols, hydrocarbons), alkali and alkaline earth metals, ammonia, biological specimens previously anaesthetized with ether, hydrogen and foam rubber. 

Violent reaetions have oeeuiTed between ozone and many ehemieals, a small seleetion being aeetylene, alkenes, dialkyl zines, benzene/mbber solution, bromine, earbon monoxide and etliylene, diethyl ether, hydrogen bromide, and nitrogen oxide. 

A mixture of 3 -hydroxypregna-5,l6-dien-20-one acetate (10 g), 70 ml of ethanol and 2 ml of methoxylamine is refluxed for 12 hr (Note methoxyl-amine hydrochloride leads to oxime formation). After cooling, another 1.75 ml of methoxylamine is added and the reaction is refluxed for another 12 hr. The solvent is removed in vacuo and the residue is dissolved in ether. Hydrogen chloride gas is passed into the ether solution and the white crystalline salt (113) is filtered off and washed with ether (85% yield crude mp 228-229°). 

The determination of position of protonation by reaction with diazomethane was performed as follows The enamine was treated at —70° with ethereal hydrogen chloride and the suspension of precipitated salt was treated with diazomethane and allowed to warm slowly to —40°, at which temperature nitrogen was liberated. The reaction with lithium aluminum hydride (LAH) was carried out similarly except that an ether solution of LAH was added in place of diazomethane. The results from reaction of diazomethane and LAH 16) are summarized in Table 1. 

To a stirred solution of 5.7 g (0.02 m) of 4-benzyloxy-2-ureidoacetophenone in 100 ml of chloroform is added 3.2 g (0.02 m) of bromine. The mixture is stirred at room temperature for about 45 minutes and the solution is concentrated in vacuo at 25°-30°C. The amorphous residue (hydrobromide selt of 4-benzyloxy-a-bromo-3-ureidoacetophenone) is dissolved in 80 ml of acetonitrile and 98 g (0.06 m) of N-benzyl-N-t-butylamine is added. The mixture is stirred and refluxed for 1.5 hours, then it is cooled toOt in an ice bath. Crystalline N-benzyl-N-t-butylamine hydrobromide is filtered. The filtrate is acidified with ethereal hydrogen chloride. The semicrystalline product is filtered after diluting the mixture with a large excess of ether. Trituration of the product with 60 ml of cold ethanol gives 4-banzyloxy-Of-( N-benzyl-N-t-butylamino)-3-ureidoacetophenone hydrochloride, MP 200°-221°C (decomposition). 

Bromo-2 -(3"-dimethylaminopropyl)-amino4 potassium carbonate (5 g) and copper powder (0.4 g). It is then heated under reflux for 4B hours, cooled, and the insoluble matter filtered off. After washing with dimethylformamide (20 cc), the filtrate is taken up in distilled water (200 cc). The base formed is extracted with ether (3 times with 50 cc), the ethereal solution is dried over sodium sulfate, the ether driven off on a water-bath and the residue distilled. In this way there is obtained 3[Pg.321]

There was obtained a mixture of N-(2 -diethylamino-2 -methylethyl)phenthiazine and N-(2 -diethylamino-1 -methylethyDphenthiazine in the form of a viscous yellow oil, BP 202° to 205°C/2 mm. This oil was treated in ethereal solution with ethereal hydrogen chloride and gave a white solid which was fractionally crystallized from ethylene dichloride. The less soluble fraction, N-(2 -diethylamino-2 -methylethyl)phenthiazine hydrochloride formed colorless rhombs, MP 223° to 225°C. The more soluble N-(2 -diethylamino-1 -methylethyl)-phenthiazine hydrochloride was obtained as colorless prismatic needles, MP 166° to 168°C. 

A mixture of 50 grams of the above prepared piperazine, 30.1 grams of sodium carbonate and 200 ml of benzene is heated to reflux and treated with 39.5 grams of 3-bromopropanol over 1.5 hours. The resulting mixture is refluxed for 2 hours, then filtered, extracted with dilute hydrochloric acid, basified, extracted with benzene, and the extracts are concentrated and distilled to give 1-benzyloxyethyl-4-(3-hydroxypropyl)-piperazine, BP 1BB°to 190°C (0.15 mm). The free base is converted to the dihydrochloride salt by treatment of an alcoholic solution with ethereal hydrogen chloride to separate the salt. 

On the addition of ethereal hydrogen chloride to a solution of the base in isopropanol and recrystallization from anhydrous ethanol of the salt formed, there is obtained 3-dimethyl-sulfamovl-10-(2-dimethvlaminopropyl)phenthiazine hydrochloride (2.1 grams), MP 214°C with decomposition. After dissolving the product in anhydrous ethanol and adding meth-anesulfonic acid there is obtained fonazine mesylate. 

The hydrochloride salt was precipitated as an oil from an ethereal solution of the base with ethereal hydrogen chloride. It was crystallized from butanone MP 170° to 171.5°C. 

Chloro-2,2,2-trifluoroethyl dichloromethyl ether Hydrogen fluoride... 

The combined filtrate and washes were concentrated to 1.6 liters and the concentrate containing the dl-2-(N-methylamino)isocamphane washed once with about 350 cc water, and then dried over anhydrous sodium sulfate. The dried ether concentrate was then cooled in an ice bath and with stirring a cold saturated ethereal-hydrogen chloride solution was added slowly until acid to Congo red required, about 440 ml anhydrous ether saturated (at 0°C) with HCI gas. After precipitation was complete, the white crystalline dl-2-(N-methylamino)isocamphane hydrochloride was filtered, and washed with anhydrous ether... 

Dihydro-17a-ethynyl-18-homo-oestradiol 3-methyl ether Hydrogen chloride... 

The hydrochloride salt of this amine was prepared by dissolving the amine in ether and adding ethereal hydrogen chloride to the ether solution. The solid hydrochloride salt which precipitated was racrystallized from an ethanol-ether mixture and was found to melt at 154°-155°C. 

To a solution of 16.4 g (0.05B mol) of the free base in 75 ml of dry acetonitrile is added dropwise while cooling (ice bath) and stirring 14.5 ml (0.053 mol) of 3.6N ethereal hydrogen chloride. An equal volume of anhydrous ether is addedand the product altered, dried and recrystallized from monochlorobenzene. The product melts at about 177°C to 17B°C with sintering at about 176°C. The yield is about 11.0 g (60%). 

The extract is dried over potassium carbonate and evaporated and the residue is distilled in vacuo. 3-(10-phenthiazinyl)-2-methyl-1-dimethylaminopropane (12.6 grams) is collected, distilling between 150° and 175°C under a pressure of about 0.3 mm Hg. By dissolving this base in acetone and adding ethereal hydrogen chloride, a hydrochloride is obtained,... 

If the total reaction time is less than approximately 1.75 hours, starting material remains. Therefore, if the ethereal hydrogen chloride is added in less than 1.5 hours, the subsequent stirring must be lengthened accordingly. 

Alkyl Hydrogen Sulfonic Acid (ROS03H) and Ether Hydrogen Sulfuric Acid R(0CH2-CH2)n0S03H Neutralization... 

When the filter cake contains hydrogen chloride, it is very hygroscopic. It should therefore be covered immediately with dry ether after the ethereal hydrogen chloride solution has been aspirated. 

Chloro-2-ethynyladamantane (33) was the major product when 31 was reacted with concentrated hydrochloric acid. If 1,4-dioxane was used as the solvent, 82% of 2-(formylmethylene)adamantane (32) was obtained together with only 3% of the chloro product 33 (equation 11). It is remarkable that no reaction takes place even under reflux conditions with ethereal hydrogen chloride29. 

Add a 1 M excess of nitroethylene dropwise to liquid 5-benzyloxyindole (or other indole) on a steam bath over two hours. Cool, filter and recrystallize from methylene chloride-petroleum ether. Hydrogenate at two atmospheres over 10% palladium-carbon... 

By very careful hydrogenation (with stannous chloride in ethereal hydrogen chloride) phenyl azide has been converted into the exceedingly sensitive phenyltriazene (Dimroth), which, as has been shown, can be reconverted into the former by dehydrogenation. As in the case of the aliphatic diazo-compounds, an open chain structural formula has lately also been assigned to hydrazoic acid and its esters, so that the changes just mentioned may be formulated as follows ... 

The protected propargylamines 224 (R = H, CH2C02Me or CH2CH2C02Me) react with aqueous formaldehyde under copper bromide catalysis to yield the allene derivatives 225. Deprotection with ethereal hydrogen chloride affords the free amines218. 

Another example of a transannular cyclization that occurs in the solid state is provided by the epoxy alcohol 31. This compound is stable when dissolved in organic solvents and in 0.25N sulfuric acid. However, the crystals transform rapidly to 32. Although the process is accompanied by partial melting, it appears to be a true solid-state one. Interestingly, the reaction is slowed down appreciably when the dry crystals are covered with ether. Hydrogen bromide is eliminated in the reaction and it may be that an acid-catalyzed process is also occurring in the presence of solvent this process may be slowed down by the dissolution of the decomposition products in the solvent (77). 

Hydrogen bonding Because there is no 0—H bond in an ether, hydrogen bonding does not occur between ether molecules. Ethers can accept hydrogen bonding from water molecules. 

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