Hydrogen chloride reaction with alcohols

Thionyl chloride reacts with alcohols to give alkyl chlorides The inorganic byprod nets m the reaction sulfur dioxide and hydrogen chloride are both gases at room tern perature and are easily removed making it an easy matter to isolate the alkyl chloride... 

Because tertiary alcohols are so readily converted to chlorides with hydrogen chloride, thionyl chloride is used mainly to prepare primary and secondary alkyl chlorides. Reactions with thionyl chloride are nonrrally carried out in the presence of potassium carbonate or the weak organic base pyridine. 

The reaction depended upon the marked difference in reactivity between the chlorine atoms and the fluorine atom in phosphorus oxydichlorofluoride. In general, the reaction with alcohols waa clear-cut, and most of the phosphorofluoridic esters were obtained in excellent yield and uncontaminated with the phosphoric triester. For example, when ethyl alcohol and phosphorus oxydichlorofluoride were allowed to react in the odd, diethyl phosphorofluoridate (VII, R = Et) was obtained in 93 per cent yield. No tertiary base was necessary to remove the hydrogen chloride produced in the reaction. The general process was patented during the war.1... 

To a mixture of 100 ml of liquid ammonia and about 80 mg of black iron oxide was added 0.78 g (0.02 atom) of potassium. When all of the potassium had reacted, 3.3 g of N,N-dimethyl-N -(2-pyridyl)ethylenediamine was added. After the addition of 75 ml of dry toluene the ammonia was removed on the steam bath. To the cooled and stirred mixture was added 4.26 g of p-chlorobenzyl chloride, and the reaction mixture was stirred on the steam bath for 11 hours. It was then filtered and concentrated to an oil. This concentrate was taken up in ether, and the ethereal solution was washed with water, dried over sodium sulfate, and concentrated. Distillation gave 2.96 g of yellow liquid. Treatment of this distillate with an equivalent quantity of hydrogen chloride in absolute alcohol and precipitation by the addition of anhydrous ether gave 2.33 g of the N,N-dimethyl-N -(4-chlorobenzyl)-N -(2-pyridyl)ethylenediamine hydrochloride. 

SAFETY PROFILE A highly corrosive irritant to the eyes, skin, and mucous membranes. Mildly toxic by inhalation, Explosive reaction with alcohols + hydrogen cyanide, potassium permanganate, sodium (with aqueous HCl), tetraselenium tetranitride. Ignition on contact with aluminum-titanium alloys (with HCl vapor), fluorine, hexa-lithium disilicide, metal acetylides or carbides (e.g., cesium acetylide, rubidium ace-tylide). Violent reaction with 1,1-difluoro-ethylene. Vigorous reaction with aluminum, chlorine + dinitroanilines (evolves gas). Potentially dangerous reaction with sulfuric acid releases HCl gas. Adsorption of the acid onto silicon dioxide is exothermic. See also HYDROGEN CHLORIDE (AEROSOL) and HYDROCHLORIC ACID. 

The synthesis of orthoesters from nitriles 12 is another example of acid-catalyzed etherification. In this reaction, a nitrile is treated with dry hydrogen chloride and an alcohol to form an iminoester hydrochloride. The dry iminoester hydrochloride is then allowed to react with an alcohol and an orthoester is produced. A possible mechanism for the reaction is the following ... 

As already mentioned under acetyl chloride, add-chlorides react with alcohols, phenols, primary and secondary amines, the chlorine atom uniting with the hydrogen of the hydroxyl-, amido-, or imido-group, with the elimination of hydrochloric add, while the residues combine to form an ester or a substituted amide. The value of the Schotten-Baumann reaction depends on the fact that this reaction is so essentially facilitated by the presence of sodium hydroxide or potassium hydroxide- that even in the presence of water the decomposition takes place, which in the absence of alkalies is not possible ... 

CHLORCYAN (506-77-4) CNCl C-N-CL Noncombustible gas. Violent polymerization can be caused by chlorine or moisture. Violent reaction with alcohols, alkenes, and alkynes (violent exothermic reaction) acids, acid salts, amines, strong alkalis, olefins, strong oxidizers. Contact with acid forms toxic hydrogen cyanide gas. Mixtures with benzene or cyanogen halides yield hydrogen chloride. In cmde form, this chemical trimerizes violently if catalyzed by traces of hydrogen chloride or ammonium chloride, forming cyanuric chloride. Alkaline conditions will convert this chemical to... 

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