Additions acetyl chloride

Dissolve 10 g. of salicylic acid (o-hydroxybenzoic acid) in 7 ml. of dry pyridine contained in a too ml. conical flask. Then without delay (since this solution if allowed to stand tends to become a semi-solid mass) run in 7 5 ml. (8 3 g.) of acetyl chloride, adding about i ml. of the chloride at a time, and shaking the mixture continuously during the addition. The heat of the reaction causes the temperature of the mixture to rise rapidly ... 

Reduction of a nitro compound to a primary amine. In a 50 ml. round-bottomed or conical flask fitted with a reflux condenser, place 1 g. of the nitro compound and 2 g. of granulated tin. Measure out 10 ml. of concentrated hydrochloric acid and add it in three equal portions to the mixtiue shake thoroughly after each addition. When the vigorous reaction subsides, heat under reflux on a water bath until the nitro compound has completely reacted (20-30 minutes). Shake the reaction mixture from time to time if the nitro compound appears to be very insoluble, add 5 ml. of alcohol. Cool the reaction mixture, and add 20-40 per cent, sodium hydroxide solution imtil the precipitate of tin hydroxide dissolves. Extract the resulting amine from the cooled solution with ether, and remove the ether by distillation. Examine the residue with regard to its solubility in 5 per cent, hydrochloric acid and its reaction with acetyl chloride or benzene-sulphonyl chloride. 

A mixture of 0.30 mol of the tertiairy acetylenic alcohol, 0.35 mol of acetyl chloride (freshly distilled) and 0.35 mol of /V/V-diethylaniline was gradually heated with manual swirling. At 40-50°C an exothermic reaction started and the temperature rose in a few minutes to 120°C. It was kept at that level by occasional cooling. After the exothermic reaction had subsided, the mixture was heated for an additional 10 min at 125-130°C, during which the mixture was swirled by hand so that the salt that had been deposited on the glass wall was redissolved. After cooling to below 50°C a mixture of 5 ml of 36% HCl and 200 ml of ice-water was added and the obtained solution was extracted with small portions of diethyl ether. The ethereal solutions were washed with water and subsequently dried over magnesium sulfate. The solvent was removed by evaporation in a water-pump vacuum... 

Acetyl chloride frequently contains 1—2% by weight of acetic acid or hydrochloric acid. Phosphoms or sulfur-containing acids may also be present in the commercial material. A simple test for purity involves addition of a few drops of Crystal Violet solution in CHCl. Pure acetyl chloride will retain the color for as long as 10 min, but hydrochloric, sulfuric, or acetic acid will cause the solution to become first green, then yellow (34). 

Chloroacetyl chloride is manufactured by reaction of chloroacetic acid with chlorinating agents such as phosphoms oxychloride, phosphoms trichloride, sulfuryl chloride, or phosgene (42—44). Various catalysts have been used to promote the reaction. Chloroacetyl chloride is also produced by chlorination of acetyl chloride (45—47), the oxidation of 1,1-dichloroethene (48,49), and the addition of chlorine to ketene (50,51). Dichloroacetyl and trichloroacetyl chloride are produced by oxidation of trichloroethylene or tetrachloroethylene, respectively. 

The acid-catalyzed additions of bromide and chloride ion to thiiranes occurs readily, with halide preferentially but not exclusively attacking the most substituted carbon atom of the thiirane. The reaction of 1-substituted thiiranes with acetyl chloride shows a slight preference for halide attack at the less substituted carbon atom (80MI50601). For further discussion of electrophilic catalysis of halide ion attack see Section 5.06.3.3.2. The reaction of halogens with thiiranes involves electrophilic attack on sulfur (Section 5.06.3.3.6) followed by nucleophilic attack of halide ion on carbon. 

The acetyl chloride obtained is yellow in color, probably because of the presence of the sulfenyl chlorides mentioned above. The addition of cyclohexene will discharge the color (although a darker color develops later) and redistillation then yields a stable water-clear product. The yield of acetyl chloride varies from 60% to 85%, depending on the care with which liquids are transferred and the vapors are trapped. O he amount... 

As with other groups, halogens can substitute hydrogen in organic compounds containing additional functional moieties such as carboxylic acids to form acid chlorides, e.g. acetyl chloride CH3COCI. These are reactive acidic compounds liberating hydrochloric acid on contact with water. 

Organic Chlorides/Halides — Several organic compounds also are hydrolyzed (or react with water) to produce corrosive materials. Notable inclusions among these compounds are acetic anhydride ([CH3COJ2O), and acetyl chloride (CH3COCI), both of which produce acetic acid upon reaction with water. Both acetic anhydride and acetyl chloride are corrosive in addition, mixtures of the vapors of acetic anhydride and acetic acid are flammable in air, and acetyl chloride itself is flammable. 

Dehydrochlorination of bis(tnfluoromethylthio)acetyl chloride with calcium oxide gives bis(trifluoromethylthio)ketene [5] (equation 6) Elimination of hydrogen chloride or hydrogen bromide by means of tetrabutylammonium or potassium fluoride from vinylic chlorides or bromides leads to acetylenes or allenes [6 (equation 7) Addition of dicyclohexyl-18-crown-6 ether raises the yields of potassium fluoride-promoted elimination of hydrogen bromide from (Z)-P-bromo-p-ni-trostyrene in acetonitrile from 0 to 53-71 % In dimethyl formamide, yields increase from 28-35% to 58-68%... 

Into a stirred, cooled (10°-15°C) solution of 26.2 grams (0.1 mol) of 2-amino-5-chlorobenzo-phenone (3-oxime in 150 ml of dioxane were introduced in small portions 12.4 grams (0.11 mol) of chloracetyl chloride and an equivalent amount of 3 N sodium hydroxide. The chlor acetyl chloride and sodium hydroxide were introduced alternately at such a rate so as to keep the temperature below 15°C and the mixture neutral or slightly alkaline. The reaction was completed after 30 minutes. The mixture was slightly acidified with hydrochloric acid, diluted with water and extracted with ether. The ether extract was dried and concentrated in vacuo. Upon the addition of ether to the oily residue, the product, 2-chloroacetamido-5-chlorobenzophenone (3-oxime, crystallized in colorless prisms melting at 161°-162°C. 

The addition of acetic acid anhydride or acetyl chloride was found to accelerate the reaction. In certain instances other solvents are also used. Phosphates of higher molecular weight alcohols was formed by reaction with P4O10 or POCl3 in the presence of benzene [18-20]. Specific examples describe the reaction of P4O10 with diglycerides from vegetable oil in the presence of isopro-... 

Ab initio molecular orbital calculations are being used to study the reactions of anionic nucleophiles with carbonyl compounds in the gas phase. A rich variety of energy surfaces is found as shown here for reactions of hydroxide ion with methyl formate and formaldehyde, chloride ion with formyl and acetyl chloride, and fluoride ion with formyl fluoride. Extension of these investigations to determine the influence of solvation on the energy profiles is also underway the statistical mechanics approach is outlined and illustrated by results from Monte Carlo simulations for the addition of hydroxide ion to formaldehyde in water. 

E. Quench and purification. While the butyllithium addition is taking place, an acidic ethanol quench solution is prepared in a 3-L, two-necked, round-bottomed flask, equipped with a mechanical stirrer and a 250-mL, pressure-equalizing dropping funnel. The flask is charged with 1 L of absolute ethanol and the funnel with 250 mL of acetyl chloride. The ethanol is stirred rapidly and the flask is cooled with an ice bath as the acetyl chloride is added over a 30-40-min period and then the cooling bath is removed and stirring is continued for 20-30 min. After the main reaction mixture has been stirred for 30 min at room temperature, it is cooled with a dry ice-acetone bath. The acidic ethanol solution is cooled with an ice bath and the cold, main reaction mixture is quenched by addition (via a double-ended needle) into the rapidly stirred, cold, acidic ethanol solution over a 3 to 3.5 hr period (Note 16). 

A mixture of 250 g. of pure triphenylcarbinol (p. 98) and 80 cc. of dry benzene is placed in a 1-1. round-bottomed flask provided with a reflux condenser. The condenser is provided with a calcium chloride tube at the top (Note 1). The mixture is heated on a steam bath when it is hot, 50 cc. of acetyl chloride (Note 2) is added through the top of the condenser. Heating is continued while the mixture is shaken vigorously. In about five minutes all the solid triphenylcarbinol disappears and a clear solution results. In the course of ten minutes, an additional 100 cc. of acetyl... 

However, this oxime can be generated via another pathway involving 1,3-addition of acetyl chloride to nitronate (120) followed by elimination of acetyl nitrate. 

The addition of the acetyl chloride requires about fifteen minutes. After addition of about two-thirds of the acid chloride, the reaction mixture rapidly becomes semisolid. 

In a i-l. round-bottomed flask are placed 12 g. (0.5 gram atom) of magnesium powder, 37 g. (0.5 mole) of tert.-bvlyl alcohol, and 100 g. of anhydrous ether (Note 1). The flask is fitted with an addition tube, one arm of which bears a reflux condenser, and the other arm a dropping funnel. While the mixture is being shaken by hand, a solution of 55 g. (0.7 mole) of acetyl chloride (Note 2) in 50 g. of anhydrous ether is added dropwise (Note 3). A lively reaction gradually ensues with evolution of hydrogen, mixed with ether vapor and a little hydrogen chloride (Note 4). After all the acetyl chloride has been added, the reaction mixture is allowed to stand in a pan of cold water for one hour (Note 5). After another hour at room temperature the mixture is warmed in a water bath at 40-450 for one-half hour in order to complete the reaction. 

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