Benzophenone chloride

NOTE.—If the dark red oil which separates at first in the reaction is decomposed at once by water, benzophenone chloride, (CeHs CCL, is obtained. This red oil, which is a molecular compound of benzophenone chloride and aluminium chloride, reacts on standing with more benzene and is converted into a substance of the composition (CeHs CCl.AlCL, which is a crystalline solid. Water decomposes this addition-product into its constituents. 

Tetraphenylethylene, (C6H5)2C = C(C6H5)2, is formed when a solution of benzophenone chloride is treated with zinc —... 

It is most conveniently prepared by boiling a mixture of benzophenone chloride and diphenylmethane —... 

Benzophenone Chloride, (C6H5)2CCl2, is so called because it can be formed by the replacement of the oxygen atom in benzophenone, (CH5)2CO, by chlorine. This is effected by heating the ketone with phosphorus pentachloride —... 

The reactions of benzophenone chloride are those which are characteristic of ketone chlorides. The presence of the phenyl groups brings about a reactivity which is greater than that shown by the analogous derivatives of aliphatic ketones. Benzophenone chloride reacts rapidly at room-temperature with zinc the halogen atoms are removed and tetraphenylethylene is formed —... 

When heated with water, benzophenone chloride is converted into benzophenone. The ketone chloride reacts with concentrated sulphuric acid in the cold and hydrochloric acid is formed. Benzophenone is precipitated when the solution is poured into water. Benzophenone chloride forms addition-products, which resemble to some extent double salts, with aluminium chloride, zinc chloride, and other chlorides. These compounds are decomposed by water into their constituents. 

Crystal Violet.—The preparation of this dye, which is the chloride of hexamethyl-pararosaniline, illustrates a method of preparing dyes of this class. The compound is manufactured by treating dimethylaniline with carbonyl chloride or tetra-methyl-diamino-benzophenone chloride —... 

TTie true ketones, in which the >CO group is in the side chain, the most common examples being acetophenone or methyl phenyl ketone, C HjCOCH, and benzophenone or diphenyl ketone, C HjCOC(Hj. These ketones are usually prepared by a modification of the Friedel-Crafts reaction, an aromatic hydrocarbon being treated with an acyl chloride (either aliphatic or aromatic) in the presence of aluminium chloride. Thus benzene reacts with acetyl chloride... 

Method 2. Into a 500 ml. round-bottomed flask place 120 ml. of dry A.R. benzene, and 35 g. (29 ml.) of redistilled benzoyl chloride. Weigh out 30 g. of finely-powdered, anhydrous aluminium chloride into a dry corked test-tube, and add the solid, with frequent shaking, during 10 minutes to the contents of the flask. Fit a reflux condenser to the flask, and heat on a water bath for 3 hours or until hydrogen chloride is no longer evolved. Pour the contents of the flask wliile still warm into a mixture of 200 g. of crushed ice and 100 ml. of concentrated hydrochloric acid. Separate the upper benzene layer (filter first, if necessary), wash it with 50 ml. of 5 per cent, sodium hydroxide solution, then with water, and dry with anhydrous magnesium sulphate. Isolate the benzophenone as in Method 1. The yield is 30 g. 

Beckmann rearrangement of benzophenone oxime to benz-anilide. Dissolve 2 g. of benzophenone oxime in 20 ml. of anhydrous ether in a small conical flask and add 3 g. of powdered phosphorus pentachloride (or 3 ml. of pure tbionyl chloride). Distil off the solvent and other volatile products on a water bath CAUTION ether), add 25 ml. of water, boil for several minutes and break up any lumps which may be formed. Decant the supernatant liquid, and recrystallise, in the same vessel, from boiling alcohol. The product is benzanilide, m.p. 163° confirm this by a mixed m.p. determination with an authentic specimen. 

Pd(II) salts promote the carbonylation of organomercury compounds. Reaction of phenylmercury chloride and PdCh under CO pressure affords benzophenone (429)[387]. Both esters and ketones are obtained by the carbonylation of furylmercury(Il) chloride in alcohol[388]. Although the yields are not satisfactory, esters are obtained by the carbonylation of aryl- and alkylmercuryfll) chlorides[389,390]. One-pot catalytic carbonylation of thiophene, furan, and pyrrole (430) takes place at the 2-position via mercuration and transmetallation by the use of PdCb, Hg(N03), and CuCl2[391]. 

Benzophenone is produced by the oxidation of diphenylmethane (350). This free from chlorine (FCC) route is favored for perfume uses. The Friedel-Crafts reaction of benzene and benzoyl chloride in the presence of aluminum chloride is also possible this reaction may proceed in the absence of catalyst at a temperature of 370°C and pressure of 1.4 MPa (351). 

In the ketone method, the central carbon atom is derived from phosgene (qv). A diarylketone is prepared from phosgene and a tertiary arylamine and then condenses with another mole of a tertiary arylamine (same or different) in the presence of phosphoms oxychloride or zinc chloride. The dye is produced directly without an oxidation step. Thus, ethyl violet [2390-59-2] Cl Basic Violet 4 (15), is prepared from 4,4 -bis(diethylamino)benzophenone with diethylaruline in the presence of phosphoms oxychloride. This reaction is very useful for the preparation of unsymmetrical dyes. Condensation of 4,4 -bis(dimethylamino)benzophenone [90-94-8] (Michler s ketone) with AJ-phenjl-l-naphthylamine gives the Victoria Blue B [2580-56-5] Cl Basic Blue 26, which is used for coloring paper and producing ballpoint pen pastes and inks. 

Benzoyl chloride is an important benzoylating agent. In this use the benzoyl radical is introduced into alcohols, phenols, amines, and other compounds through the Friedel-Crafts reaction and the Schotten-Baumaim reaction. Other significant uses are in the production of benzoyl peroxide [94-56-0], benzophenone [119-61-9], and in derivatives employed in the fields of dyes, resins, perfumes, pharmaceuticals, and as polymerization catalysts. 

The reaction of propiophenone with thionyl chloride in pyridine provides 3,4-diben-zoylthiophene (79H(l2)46i). The boron trifluoride catalyzed reaction of benzophenone with f-butyl isocyanide gives an indole derivative (Scheme 84b) (67TL3881). Another... 

Diphenylmethane has been prepared with aluminum chloride as a catalyst from methylene chloride and benzene, from chloroform and benzene as a by-product in the preparation of triphenylmethane, and from benzyl chloride and benzene. It has been prepared by the reduction of benzophenone with hydriodic acid and phosphorus, or with sodium and alcohol. It has also been made by heating a solution of benzyl chloride in benzene with zinc dust, or with zinc chloride. The above method is only a slight modification of the original method of Hirst and Cohen. ... 

In a 3-I. three-necked flask, fitted with a mechanical stirrer, a reflux condenser, and a separatory funnel, are placed 24.3 g. (i gram atom) of magnesium turnings, 500 cc. of absolute ether, a crystal of iodine, and a 5- to lo-cc. portion of 126.5 g- cc., I mole) of freshly distilled benzyl chloride (b.p. 177-179°). In a few minutes the reaction starts (Note 1) and is controlled if necessary by cooling with a wet towel. The stirrer is started and the balance of the benzyl chloride is run in as fast as the refluxing will permit. The addition requires from one to two hours, and when completed the mixture is refluxed ofi the steam bath with stirring for three hours. With the stirrer stUl running, 182 g. (r mole) of benzophenone (Org. Syn. Coll. Vol. i, 89) dissolved in 500 cc. of absolute ether is added at such a rate that the mixture refluxes rapidly. This requires about twenty minutes and then the reaction mixture is allowed to stand for two hours (Note 2). 

If a substituted aromatic hydrocarbon is used, the ketone gioLip then enteis the paia-position, or, if this is occupied, the oitho-position. Substituted aromatic acid chlorides may. also be used, and if the acid is dibasic and has two caiboxyl chloiide gioups, two molecules of the aromatic hydiocaibon may be. attached. If phosgene is used with two molecules of benzene, benzophenone is obtained. 

An ingenious synthesis of 1-arylisoindolcs has been developed by Vebor and Lwowski, based upon the reaction of an o-phthalimido-methylbenzophenone (41, R = aryl) with hydrazine (Table IV). The benzophenone is prepared by a Friedel-Crafts reaction with o-phthalimidomethylbenzoyl chloride (40). The mechanism of isoindole formation can be represented sehematically by a sequence involving attack by hydrazine at the imide to give the ring-opened hj drazide (42), followed by cyclization to phthalazine-l,4-dione (44) with displacement of the o-aminomethylbenzophenone (43). Intramolecular condensation of the latter can lead, via the isoindolenine... 

The actual mechanism by which a particular reaction proceeds strongly depends on the nature of the organomagnesium reagent. For instance benzophenone reacts with methylmagnesium bromide by a polar mechanism, while the reaction with t-butylmagnesium chloride proceeds for steric reasons by a SET-mechanism. 

The oxygen atom in these molecules can in many cases be dispensed with as well substitution of sulfur for nitrogen affords a molecule whose salient biologic properties are those of a sedative and tranquilizer. Friedel-Crafts acylation of the n-butyl ether of thiophenol with benzoyl chloride gives the corresponding benzophenone. Reduction of the ketone (15) followed by... 

It has been shown that glyeine amides of aminobenzophenones are readily converted to the corresponding benzodiazepines in vivo. Peptides which terminate in such a moiety should thus serve as a benzodiazepine prodrug after hydrolysis by peptidases. One of the glycine residues in lorzafone (194)is presumably removed metabolicaUy in this manner to give a benzodiazepine precursor which spontaneously cyclizes. Acylation of benzophenone 190 with the trityl protected dipeptide 191, as its acid chloride 192, affords the amide 193. Removal of the trityl protecting group with acid yields lorzafone (194) [50]. 

An analogous sequence leads to the anthelmintic agent, etibendazole (50). Reaction of the benzophenone 47, which can be obtained by acylation of o-nitroaniline with g-fluorobenzoyl chloride, with ethylene glycol leads to acetal 48. Sequential reduction of the nitro group and cyclization of the resulting diamine (49) with N,N-dicarbomethoxy-S-methylthiourea gives the benzimidazole etibendazole (50) fl6]. 

Chloro-1 -methyl-6-phenyl4H-s-triazolo-[4,3-a] [1,4] -benzodiazepine A stirred suspension of 5-chloro-2-[3-(bromomethyl)-5-methyl4H-1,2,4-triazol4-yl] -benzophenone (391 mg, 0.001 mol) in tetrahydrofuran (15 ml) was cooled in an ice-bat hand treated with a saturated solution of ammonia in methanol (12.5 ml). The resulting solution was allowed to warm to ambient temperature and stand for 24 hours. It was then concentrated in vacuo. The residue was suspended in water, treated with a little sodium bicarbonate and extracted with methylene chloride. The extract was washed with brine, dried with anhydrous potassium carbonate and concentrated. The residue was crystallized from methylene chloride-ethyl acetate to give... 

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