Arylation Aluminum chloride

The preference for O acylation of phenols arises because these reactions are kmetically controlled O acylation is faster than C acylation The C acyl isomers are more stable how ever and it is known that aluminum chloride is a very effective catalyst for the conversion of aryl esters to aryl ketones This isomerization is called the Fries rearrangement... 

Ai lepiesents an aiyl group. Diaiyl products are obtained after long reaction times. Other Friedel-Crafts catalysts, eg, ZnCl2, FeCl2, FIF, and BF, can also be used. In most cases, stoichiometric amounts of the catalyst ate requited. Flowever, strong complexation of the phosphine by the catalyst necessitates separation by vacuum distillation, hydrolysis, or addition of reagents such as POCl to form more stable aluminum chloride complexes. Whereas yields up to 70—80% are possible for some aryl derivatives, yields of aliphatic derivatives are generally much less (19). 

The course of reduction of unsaturated and aromatic ketones is more complicated. Diaryl ketones, alkylaryl ketones and some aryl alcohols are smoothly reduced to the corresponding hydrocarbons. The recommended way of performing these reductions is to add an equimolar mixture of aluminum chloride and the ketone in ether to an equimolar mixture of aluminum chloride and LiAlH4 in ether. 

Thakar and Subba Rao showed that reductions with diborane give the same result regardless of whether diborane is generated externally or produced internally by the action of NaBH4 and boron trifluoride or aluminum chloride. They found that alicyclic or dialkyl ketones are not reduced beyond the alcohol stage even under drastic conditions however, diaryl ketones are hydrogenolyzed under normal conditions, while aryl ketones or a,i5-unsatu-rated ketones are hydrogenolyzed, in part, under drastic conditions. 

On reaction with acyl chlorides and acid anhydrides, phenols may undergo either acylation of the hydroxyl group (O-acylation) or acylation of the ring (C-acylation). The product of C-acylation is more stable and predominates under conditions of thennodynamic control when aluminum chloride is present (see entry 6 in Table 24.4, Section 24.8). O-acylation is faster than C-acylation, and aryl esters are fomned under conditions of kinetic control. 

Fries rearrangement (Section 24.9) Aluminum chloride-promoted rearrangement of an aryl ester to a ring-acylated derivative of phenol. 

An analogous reaction is the Houben-Hoesch reaction,(sometimes called the Hoesch reaction) using nitriles 7 to give aryl ketones 8. This reaction also is catalyzed by Lewis acids often zinc chloride or aluminum chloride is used. The Houben-Hoesch reaction is limited to phenols—e.g. resorcinol 6—phenolic ethers and certain electron-rich aromatic heterocycles ... 

In the case of alkylation using allylsilancs in the presence of aluminum chloride as a catalyst, allylsilanes containing one or more chlorine substituents on the silicon react with aromatic compounds at room temperature or below 0 C to give alkylated products. 2-aryl-1 -silylpropanes.- while allyltrimethylsilane did not give the alkylated product but instead dimerized to give the allylsilylation product.. S-itrimethylsilyli-d-itrimethylsilylrnethyl)- 1-pentene (Eq. (1 )). In the alkylation reaction, the reactivity of allylsilanes increased as the number of chlorine... 

Nametkin and co-workers hrst reported the alkylation of benzene derivatives with allylchlorosilanes in the presence of aluminum chloride as catalyst. " 2-(Aryl)propylsilanes were obtained from the alkylation of substituted benzenes (Ph—X X = H, CL Br) with allylsilanes such as allyldichlorosilane and allyltrichlo-rosilane.The yields ranged from 34 to 66% depending upon the substituents on the benzene ring, but information concerning reaction rates and product isomer distribution was not reported. 

Monoalkylation products, 3-aryl-1,1 -dichloro-1 -silabutanes, were obtained from the alkylation of aromatic compounds with I in the presence of aluminum chloride catalyst in good isolated yields (60-80%) along with small amounts of higher alkylation products. Dialkylation products were obtained in yields ranging from 2 to 8% when a 5-fold excess of the aromatic compounds with respect to 1 was used. The amount of dialkylated products can be further reduced by using a greater excess of the aromatic compounds. 

One further example of this principle of bridging the aryl groups of a triarylmethane phthalide was reported in 1986.108 Thus, treatment of phthalide 27 with aluminum chloride results in the formation of the spirobenzanthracene 28 as shown in Scheme 11. These color formers also exhibit absorption in the near infrared spectral region, but no further reports of such compounds have since been published. 

For the preparation of aryl esters from phosphorus oxychloride, a Lewis acid is generally added as a catalyst. Commonly, aluminum chloride with an excess of phosphorus oxychloride added to the phenol provides excellent yields (Equation 4.2).4... 

Reaction of 2-amino-5-aryl-thiadiazole (88 R = Ar) with aryl nitriles in the presence of aluminum chloride produced the aryl amidine (89) which was oxidized with lead tetraacetate to yield the 2,6-diaryl-[ 1,2,4]-triazolo[5,1 -( ]-1,3,4-thiadiazoles (90) <91 UC(B)435>. 

Treatment of veratrole (191) with excess of 2,5-dichloro- (192) or 2,6-dichloro-1,4-benzoquinone in 70% sulfuric acid yields dibenzofurans and other products. Thus 2,5-dichloro-1,4-benzoquinone (192, Scheme 49) affords the dibenzofuran 193, the diarylquinone 194 and the triphenylene 195. The quinol formed by acid-catalyzed addition of veratrole (191) to the quinone 192 is presumably oxidized to the arylquinone 196, which can form the dibenzofuran 193 or undergo further arylation. The quinone 196 is also available by arylation of 2,5-dichloro-1,4-benzoquinone (192) with 3,4-di-methoxybenzenediazonium chloride in buffered solution. On treatment with 70% sulfuric acid, the arylquinone 196 affords the dibenzofuran 193 (88%). The cyclization can also be effected photochemically. The aryl-quinones available by treatment of 2,5- and 2,6-dichloro-1,4-benzoquinones with buffered solutions of diazotized 4-methoxy-3-methyl- and 3-methoxy-4-methylaniline have been cyclized to 2-dibenzofuranols by the agency of aluminum chloride in hot benzene. ... 

Unsaturated 5(4H)-oxazolones undergo a Friedel-Crafts reaction with aromatic hydrocarbons in the presence of a Lewis acid. In particular, a 2-aryl-4-benzylidene-5(4H)-oxazolone 598 reacts with o- or p-xylene in the presence of aluminum chloride via ring opening and subsequent dearylation to yield 599 as indicated in Scheme 7.191. ... 

Frjedel-Crafts Reaction. Any organic reaction brought about by the catalytic action of anhydrous aluminum chloride or related, so-called Lewis acid type catalysts. Discovered in 1877 by C. Friedel and J.M. Crafts, who later uncovered most of the types of reaction such as substitution, isomerization, elimination, cracking, olefin polymerization, addition, etc. Commonly used to displace an aromatic hydrogen atom with an alkyl, aryl or acyl chain... 

The Friedel-Crafts alkylation of aromatic compounds by oxetanes in the presence of aluminum chloride is mechanistically similar to the solvolyses above, since the first step is electrophilic attack on the ring oxygen by aluminum chloride, followed by a nucleophilic attack on an a-carbon atom by the aromatic compound present. The reaction of 2-methyloxetane and 2-phenyloxetane with benzene, toluene and mesitylene gave 3-aryl-3 -methyl-1-propanols and 3-aryl-3-phenyl-l-propanols as the main products and in good yields (equation 27). Minor amounts of 3-chloro-l-butanol and 4-chloro-2-butanol are formed as by-products from 2-methyloxetane, and of 3-phenyl-l-propanol from 2-phenyloxetane (73ACS3944). 

Cyclization (Scheme 8) was accomplished using either phosphoryl chloride or aluminum chloride. A range of substituents were introduced into the benzene ring (alkyl, aryl, or CN) or the 3- or 4-position (alkyl or aryl) and selenium successfully replaced sulfur in these reactions. 

Fluorides with fluorine-phosphorus bonds also react with Lewis acids tert-Butylpentafluorocyclotriphosphazenes are arylated in the presence of aluminum chloride [26] (equation 18)... 

FRIEDEL-CRAFTS REACTION. Aluminum chloride anhydrous, introduced by Friedcl and Crafts, is used as reagent, generally in CS solution to avoid rise in temperature, for the preparation of (I) aryl-alkyl hydrocarbons, (2) di- and triphenylmethane and derivatives, and (3) aryl-alkyl and diaryl ketones, Other chlorides, such as those of zinc, irun(lll), and liniiV), are often effective in certain cases. 

In 1949, Werner187 announced the synthesis of several 3-alkyl- and 2,3-dialkylbenzo[6]thiophenes by the cyclodehydration of (arylthio)-acetones with phosphorus pentoxide or zinc chloride [Eq. (5)]. The reaction has since been widely used to synthesize alkyl- and aryl-substituted benzo[6]thiophenes (Table IV). Cyclodehydration proceeds most conveniently with PPA,297 298 but concentrated sulfuric acid,299,300 hydrofluoric acid, 299 aluminum chloride in benzene301 or chlorobenzene,302 zinc chloride and hydrochloric acid,303 a melt of aluminum and sodium chlorides,304 and phosphorus pentoxide in boiling o-dichlorobenzene 305 have been less widely used. 

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