Acetyl chloride, hydrolysis

Later studies on acetyl chloride hydrolysis were those of Hudson and Moss90, using a stopped-flow apparatus at 27°C and working with dioxan-water mixtures (19.6-75.6 v/v), and Cairns and Prousnitz102 with acetone/water (15.35% v/v) at low temperatures. The value of the Grunwald-Winstein103... 

A fixed-bed reactor for this hydrolysis that uses feed-forward control has been described (11) the reaction, which is first order ia both reactants, has also been studied kiaeticaHy (12—14). Hydrogen peroxide interacts with acetyl chloride to yield both peroxyacetic acid [79-21-0] and acetyl peroxide... 

Hydrolysis. 1,1,1-Trichloroethane heated with water at 75—160°C under pressure and in the presence of sulfuric acid or a metal chloride catalyst decomposes to acetyl chloride, acetic acid, or acetic anhydride (54). However, hydrolysis under normal use conditions proceeds slowly. The hydrolysis is 100—1000 times faster with trichloroethane dissolved in the water phase than vice versa. Refluxing 1,1,1-trichloroethane with ferric and gallium chloride... 

These can be prepared as for the benzoates using either acetic anhydride with 3N NaOH or acetyl chloride in pyridine. They are hydrolysed as described for the benzoates. This hydrolysis can also be carried out with aqueous 10% NaOH solution, completion of hydrolysis being indicated by the complete dissolution of the acetate in the aqueous alkaline solution. On steam distillation, acetic acid also distils off but in these cases the phenols (see above) are invariably solids which can be filtered off and recrystallised. 

Acid anhydrides aie more stable and less reactive than acyl chlorides. Acetyl chloride, for example, undergoes hydrolysis about 100,000 times more rapidly than acetic anhydride at 25°C. 

More recently the acylation of aldehyde enamines has been reinvestigated (75) and shown to proceed normally when the enamine is added to the acid chloride. The morpholine enamine of isobutyraldehyde (98), on being added to an ether solution of acetyl chloride, afforded the iminium salt (99), from which the ketoaldehyde (100) was obtained in 66% yield by hydrolysis (75). 

HHTs derived from AMPA diethyl ester 56 also reacted with acetyl chloride to generate glyphosate nitriles 58 following cyanide displacement with the resulting iV-acetyl-Af-chloro-methyl-AMPA diethyl ester 57. Subsequent acidic hydrolysis of 58 gave GLYH3 (58). 

Acetyl chloride gives rise to hydrolysis reactions that are particularly violent. When a reactor was washed with water, this gave rise to a violent detonation that destroyed the equipment. It was caused by water being in contact with acetyl chloride residues that were in the pipes leading to the reactor. 

Acetylacetone has been prepared by the reaction of acetyl chloride with aluminum chloride followed by hydrolysis,3 and by the condensation of acetone with ethyl acetate under the influence of sodium,4 sodamide,5 and sodium ethoxide,5-6-7 and by the reaction of acetone and acetic anhydride in the presence of boron trifluoride.8... 

Even the mildest pulping process, hydrotropic extraction, i.e. repeated extraction with concentrated aqueous solutions of organo-philic electrolytes such as sodium xylenesulfonate or cymenesulfonate, has failed because of an outlet for the extracted lignin, wliich is precipitated by mere dilution of the solution. Other methods based on hydrolysis of the wood with acids, e.g. HCl, HNO3, AICI3, acetic acid, acetyl chloride, SOg, or phenol, are merely of laboratory interest. 

Acyclic C-nucleoside analogs of type 4.3 (1203 and 1205) were made from the lithiated 2,4-dimethoxy-5,6-dimethylpyrimidine (1204) (94MI10). Treatment with acetyl chloride caused the hydrolysis of the OMe groups. 

Use of a large, lipophilic nitrogenous component results in a 1idocaine like, local anesthetic type cardiac anti-arrhythmic drug, lorcainide (20). Synthesis begins with the Schiff s base (1 ) derived by reaction of p-chloro-aniline and borohydride followed by acylation with phenyl acetyl chloride produces amide 1 . Selective hydrolysis with HBr followed by alkylation with isopropyl bromide completes the synthesis of lorcainide (20). ... 

A very popular alternative to aspirin and acetaminophen is ibuprofen, which has tradenames such as Motrin and Advil . It can be synthesized from isobutylbenzene by a Friedel-Crafts acylation with acetyl chloride, followed by formation of a cyanohydrin. Treatment with H2/Pd reduces the benzylic hydroxyl to a hydrogen and hydrolysis of the nitrile gives the carboxylic acid. There are at least six published syntheses of ibuprofen. This illustrates the difficulty of knowing which technology a particular company is using. At the other extreme is the proprietary nature of some syntheses, where they have not yet been published. 

Ibuprofen Ibuprofen, 2-(4-iTo-butylphenyl)propionic acid (3.2.23), can be synthesized by various methods [88-98]. The simplest way to synthesize ibuprofen is by the acylation of Mo-butylbenzol by acetyl chloride. The resulting iTo-butylbenzophenone (3.2.21) is reacted with sodium cyanide, giving oxynitrile (3.2.22), which upon reaction with hydroiodic acid in the presence of phosphorus is converted into 2-(4-iTo-butylphenyl)pro-pionic acid (3.2.23), which subsequently undergoes phases of dehydration, reduction, and hydrolysis. 

The prototype for this class of compounds is ibufenac (42-3), developed by a group at Boots in the UK. This drug was to be quickly superseded by its a-methylated congener, ibuprofen, from the same laboratory [43]. The mechanistically very complex Wilgerodt reaction constitutes the key to the preparation of ibufenac. Thus, reaction of the acetylation product (42-1) from isobutyl benzene and acetyl chloride with sulfur and morpholine leads to the transposition of the oxidized function to the terminal carbon and formation of thiomorpholide (42-2). Hydrolysis of the thioamide... 

---