Acetyl chloride, reaction with sodium

Acetyl chloride, reaction with sodium formate, 50, 1 with propylene, aluminum chloride, and quinoline to give trans-3-pentene-2-one,... 

In fact, these reactions likely involve 13-dioxocarbenium ions, which can also be prepared from pyranosyl chloride and reduced to acetals thus endo- and exo-1,2-0-ethylidene-a-D-allapyranoses have been prepared from penta-O-acetyl-p-D-allopyranosyl chloride (reaction with sodium borohydride) [88]. These types of 1,2-acetoxonium ions ate also known to react with dialkylcadmium to give 1,3-diacetals [89]. 

Reduction with excess lithium aluminum hydride gave the diol 449 and the enamine alcohol 450. Reaction of the latter with acetyl chloride and aqueous sodium hydroxide solution gave the 1-acetyl derivative, which was reduced catalytically under pressure to deoxylimapodine (446) in almost quantitative yield. When this compound was heated with mercuric acetate in 5% acetic acid at 65-70°, -acetylaspidoalbidine (445) was isolated in 64% yield (Scheme 20). The product was identical with an authentic sample (212). 

Addition of 2,4-dimethylbenzenesulfenyl chloride to the glycal derived from tetra-O-acetyl-neuraminic acid methyl ester, followed by reaction with sodium methylthiolate, furnished the 2-methylthio-3-thiosialic acid derivative 14. Its use as a glycosyl donor is referred to in Chapter 4, and the azido phenylselenation of a furanoid glycal is covered in Chapter 9. 

Nitrophenyl-a-L-fuco/galacto/rhamno/manno-pyranosides can be made by the reaction of the acetate protected sugar with p-nitrophenol and zinc chloride at 120 °C under vacuum [7]. p-Nitrophenyl-p-D-gluco/galactopyranoside can be generated from the reaction of the acetylated hexopyranosyl bromides with sodium p-nitrophenoxide in DMF [8], followed by deprotection, and /7-nitrophenyl-(3-D-mannopyranoside can be synthesised from mannose via 2,3 4,6-di-0-cyclohex-ylidene-a-D-mannopyranose [9]. 

Some chlorides of organic acids, e.g. benzoyl chloride, were prepared by Cahours by the action of phosphorus pentachloride on the acids, but not acetyl chloride, as he specifically says. Bechamp later used phosphorus trichloride. Gerhardt first prepared pure acetyl chloride by distilling anhydrous sodium acetate with phosphorus oxychloride, and by the action of acetyl chloride on anhydrous sodium acetate he discovered acetic anhydride. By similar methods the anhydrides of other monobasic organic acids were obtained, including mixed anhydrides. Gerhardt formulated the reaction ... 

The diethyl ester of citric acid (6.50) was similarly converted to the half-ester (6.51) with Arthobacter sp (ATCC 19140).59 Acetylation of the alcohol and conversion to the acid chloride was followed by reaction with sodium azide to give acyl OH A O,Py OH... 

Reflux 1 g. of the sulphonamide with 2-5 ml. of acetyl chloride for 30 minutes if solution is not complete within 5 minutes, add up to 2-5 ml. of glacial acetic acid. Remove the excess of acetyl chloride by distillation on a water bath, and pour the cold reaction mixture into water. Collect the product, wash with water and dissolve it in warm sodium bicarbonate solution. Acidify the Altered solution with glacial acetic acid Alter oflF the precipitated sulphonacetamide and recrystaUise it from aqueous alcohol. 

Acetyl chloride test. In a small, dry test-tube treat 0 -5 ml. of the compound with 0-3-0-4 ml. of redistUled acetyl chloride and note whether reaction occurs. Add 3 ml. of water and neutralise the aqueous layer with solid sodium bicarbonate. Look for a product different from the original alcohol. 

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. 

The important chemical properties of acetyl chloride, CH COCl, were described ia the 1850s (10). Acetyl chloride was prepared by distilling a mixture of anhydrous sodium acetate [127-09-3J, C2H202Na, and phosphorous oxychloride [10025-87-3] POCl, and used it to interact with acetic acid yielding acetic anhydride. Acetyl chloride s violent reaction with water has been used to model Hquid-phase reactions. 

Acetylsalicylic acid [50-78-2] (i9-acetyoxyben2oic acid) was first synthesized in 1853 by reaction of acetyl chloride with sodium saUcylate. As a dmg, acetylsahcyhc acid was introduced in Germany in 1899 and into the United States in 1900. The first U.S. patent (35) for the manufacture of acetylsaUcyhc acid expired in 1917. Aspirin is a registered trademark of Bayer in many nations, but in the United States and the United Kingdom, aspirin is accepted as the generic name for acetylsahcyhc acid (36). 

Various processes involve acetic acid or hydrocarbons as solvents for either acetylation or washing. Normal operation involves the recovery or recycle of acetic acid, any solvent, and the mother Hquor. Other methods of preparing aspirin, which are not of commercial significance, involve acetyl chloride and saHcyHc acid, saHcyHc acid and acetic anhydride with sulfuric acid as the catalyst, reaction of saHcyHc acid and ketene, and the reaction of sodium saHcylate with acetyl chloride or acetic anhydride. 

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