Phosphorus pentachloride aluminum chloride

Rearrangement with Aluminum Chloride-Phosphorus Pentachloride... 194... 

Dypnone has been prepared by the action of sodium ethoxide, aluminum bromide, phosphorus pentachloride, aluminum triphenyl, zinc diethyl, calcium hydroxide, anhydrous hydrogen chloride, aluminum chloride, and aluminum Zer/.-butoxide on acetophenone. It has been prepared by the action of aniline hydrochloride on acetophenone anil followed by treatment with hydrochloric acid. The preparation of aluminum ZcrZ.-butoxide has been described (p. 8). The procedure described is a modification of that by Adkins and Cox. ... 

In contrast to the low yield when hydrogen chloride is employed, an 88% yield of 2,4,6-triphenyl- 1,3,5-triazine (7) is obtained when chlorosulfonic acid is used as catalyst in a molecular ratio of 3 1 (CiSOjH/PhCN) at 0-5 C C and a reaction time of 12 to 24 hours.174 Trifluo-romethanesulfonic acid as a catalyst and solvent trimerizes benzonitrile at 91 °C in a yield of 66%.175 Lewis acids alone, such as aluminum, zinc, iron or titanium chlorides, phosphorus pentachloride, and boron trifluoride, have a considerably lower catalytic activity than the corresponding mixtures of Lewis acid with various promotors, such as mineral acids, organic acids and water. These differences are attributed to a change in the structure of the active complexes with the aryl cyanides. 

Octa-O-acetylcellobiose can, likewise, be rearranged by the action of corresponding excesses of aluminum trichloride and phosphorus pentachloride, and thereby gives the heptaacetate of 4-0-j3-d-glucopyranosyl-a-D-altropyranosyl chloride in 40-45% yield. Again, inversion at C-2 and C-3 of the reducing residue is observed. The formation of D-mannose and D-altrose derivatives is observed when penta-O-acetyl-D-glucopyranose is treated with aluminum trichloride-phosphorus pentachloride. ... 

The method is essentially that discovered by Boeseken and Prins - and studied further by Prinsd Pentachloroethane can be used in place of tetrachlorethylene, as it is converted into the unsaturated compound in the presence of aluminum chloride. irwiyw.-Heptachloropropane has been obtained also by the action of phosphorus pentachloride on pentachloroacetone, and by treating dichloroacetyl chloride with aluminum chloride. ... 

Conversion of the phenoxypropanoic acid into the acid chloride enhances the ease of cyclization and the use of phosphorus pentachloride and aluminum chloride provides an example of this technique (51JA4205). The formation of 3-aminochroman-4-one has been achieved in this way starting from 2-amino-3-phenoxypropanoic acid (76TL271). Cyclization of the phenoxyethanoic acid shown in Scheme 234 occurs on reaction with sodium methoxide to give the chroman-3-one (63JCS5322). 

The 8-oxo-7-phenylacetylamino-5-thia-l-aza-bicyclo[4.2.0]oct-l-ene-2-carboxylic acid benzhydryl ester is reacted with phosphorus pentachloride/pyridine reagent in methylene dichloride, and the reaction mixture is thereafter cooled to -35°C and treated with methanol to produce hydrochloride of 7-amino-8-oxo-5-thia-l-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid benzhydryl ester. This hydrochloride is reacted with 4-(3-aminothiophen-2-yl)-5-oxohex-3-enoic acid 3-methylbut-2-enyl ester. Then 7-[2-(2-benzoylamino-thiazol-5-yl)(3-tert-butyl-4,4-dimethylpent-2-enoxycarbonyl)-pent-2-enoylamino]-8-oxo-5-thia-l-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid synthesized is reacted with aluminum chloride in anisole and diluted hydrochloric acid and then with dimethylmalonate to give 5-thia-l-azabicyclo(4.2.0)oct-2-ene-2-carboxylic acid, 7-(((2Z)-2-(2-amino-4-thiazolyl)-4-carboxy-l-oxo-2-butenyl)amino)-8-oxo-, (6R,7R)- (Ceftibuten). 

With Thionyl Chloride. Although thionyl chloride has been more widely used in the preparation of acid chlorides for cyclization with both stannic and aluminum chloride, it is perhaps less generally advantageous than phosphorus pentachloride. If it is desired to obtain the acid chloride essentially free of by-products, thionyl chloride presents some advantage in that these by-products of the reaction are gaseous and therefore may be eliminated readily. Since, moreover, the reagent has a... 

In all of these processes, it is not clear whether the aluminum chloride, the phosphorus pentachloride, or both are the primary chlorinating agents. While phosphorus pentachloride alone in chloroform has been reported9 to produce tetraacetyl-a-D-fructosyl chloride from /3-D-fructose pentaacetate, its action on /3-D-glucose pentaacetate in the absence of... 

The structure XXII for rhynehophylline has been confirmed, and the relative stereochemistry at C-15 and C-20 has been elucidated, by a total synthesis (80) of (+) JV-methylrhynchophyllane (XXVI) (Marion s N-methylisorhynchophyllane), which had been prepared earlier by methyl-ation of (iso)rhynchophyllane with sodium methoxide and methyl iodide (28). The lactone (XXVII) of threo-3,4-diethyl-5-hydroxyvaleric acid was converted by reaction with phosphorus pentachloride into the corresponding S-chloroacid chloride (XXVIII), which on treatment with methylaniline gave the anilide XXIX. Reduction of XXIX with lithium aluminum hydride gave the aldehyde XXX, which slowly reacted with... 

Chlorobenz[d]isothiazole-l, 1-dioxide ( pseudosaccharin chloride ) (6)3,24.25, lee, 25i, 26i, 262 displays the reactivity of a cyclic imidoyl chloride263 resembling very much carboxylic acid halides. In previous sections preparation of 3, 4, 5, 13, 68, 86, 89 from 6 has been mentioned. Derivatives of 6 substituted in the phenyl ring have been described.250 Interestingly, Meadow observed231 that crude 6 and material that contained phosphorus pentachloride reacted with thiols more readily than the pure compound. In the reaction of 6 with aromatic sulfonamides, aluminum chloride had been added for activation.252... 

Acetaldehyde reacts with phosphorus pentachloride to produce 1,1-dicbloroethane [75-34-3] and with hypochlorite and hypoiodite to yield chloroform [67-66-3] and iodoform [75-47-8], respectively. Phosgene [75-44-3] is produced by the reaction of carbon tetrachloride with acetaldehyde in the presence of anhydrous aluminum chloride (75). Chloroform reacts with acetaldehyde in the presence of potassium hydroxide and sodium amide to form l,l,l-trichloro-2-propanol [7789-89-1] (76). 

An oxidant. Combusdble when exposed to heat and flame. Moderate explosion hazard when exposed to heat or flame. Explosive reacdon with solid or concentrated alkali + heat (e.g., sodium hydroxide or potassium hydroxide), aluminum chloride + phenol (at 120°C), aniline + glycerol + sulfuric acid, nitric + sulfuric acid + heat. Forms explosive mixmres with aluminum chloride, oxidants (e.g., fluorodinitromethane, uranium perchlorate, tetranitromethane, sodium chlorate, nitric acid, nitric acid + water, peroxodisulfuric acid, dinitrogen tetraoxide), phosphorus pentachloride, potassium, sulfuric acid. Reacts violendy with aniline + glycerin, N2O, AgC104. To fight fire, use water, foam, CO2, dry chemical. Incompadble with potassium hydroxide. When heated to decomposidon it emits toxic flames of NOx. See also NITRO COMPOUNDS OF AROMATIC HYDROCARBONS. 

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