Ketone from benzenes

Problem 18.6 What acid chloride would be needed to prepare each of the following ketones from benzene using a Friedel-Crafts acylation ... 

The following ketone, isolated from the roots of several members of the iris family, has an odor like that of violets and is used as a fragrance in perfumes. Describe the synthesis of this ketone from benzene. (See Examples 9.7,9.9)... 

The ketones are readily prepared, for example, acetophenone from benzene, acetyl chloride (or acetic anhydride) and aluminium chloride by the Friedel and Crafts reaction ethyl benzyl ketones by passing a mixture of phenylacetic acid and propionic acid over thoria at 450° and n-propyl- p-phenylethylketone by circulating a mixture of hydrocinnamic acid and n-butyric acid over thoria (for further details, see under Aromatic Ketones, Sections IV,136, IV,137 and IV,141). 

Michler s ketone [4,4 -bis(dimethylamino)benzophenone] [90-94-8] M 268.4, m 179", pK 9.84. Dissolved in dilute HCl, filtered and ppted by adding ammonia (to remove water-insoluble impurities such as benzophenone). Then crystd from EtOH or pet ether. [Suppan J Ghent Soc, Faraday TransI 71 539 1975.] It was also purified by dissolving in benzene, then washed with water until the aqueous phase was colourless. The benzene was evaporated off and the residue recrystd three times from benzene and EtOH [Hoshino and Kogure J Phys Ghent 72 417 1988],... 

Ergometrine crystallises, with solvent, from benzene in needles or from methyl ethyl ketone in prisms both forms have m.p. 162-3° (dec.). From ethyl acetate it crystallises at — 4° in thin, solvent-free plates, m.p. 160-1° (dec.), and at atmospheric temperature on concentration in vacuo in diamond-shaped plates, B.0-5EtAc, m.p. 130-2° (dec.), from which the combined solvent is not removed at 100° in vacuo. By crystallisation from acetone, Grant and Smith obtained a second form in long needles, m.p. 212° (dec.), which appears to be the more stable, since the form, m.p. 162-3°, tends to pass into it on keeping. Ergometrine has [o]d — 44° (CHCI3) - - 42-2° or + 62-6° (c = 1-7, EtOH) or... 

Tamoxifen is a drug used in the treatment of breast cancer. How would you prepare tamoxifen from benzene, the following ketone, and any other reagents needed ... 

The synthesis of cycloheptatrienyl ketones 233 from benzene and a-diazoketones 232 proceeds in essentially quantitative yield the products were not isolated but directly transformed into benzyl ketones 234 through the action of trifluoroacetic acid 229 ... 

Four poly(ether ketone)s obtained from 2,2-bis[4-(4-fluorobenzoyl)-phenyl]-1,1,1,3,3,3-hexafluoropropane (9) or 2,2-bis[4-(4-fluorobenzoyl)-phenyl]propane (10) with Bisphenol AF (1) or Bisphenol A (4) are all soluble in chloroform, benzene, THF, and aprotic polar solvents such as DMF, DMAc, and NMP.15 Poly(ether ketone) from 9 and 1, which has the highest fluorine content, dissolves easily in ethyl acetate. 

Table IV, which presents data (84T1667 88JOC2942) on the ring-chain equilibria of 2-hydroxymethyIarene carbaldehydes and ketones, shows that the change from benzene 34 to the 2,3-disubstituted naphthalene 35 deriva-...

A ketone can also be formed with a Friedel-Crafts acylation. The process requires an acid chloride and an aromatic compound. An aldehyde can t be formed by this procedure because the appropriate acid chloride, formyl chloride (HCOCl), is unstable and decomposes to carbon monoxide and hydrogen chloride. Figure 10-12 illustrates the preparation of acetophenone from benzene and acetyl chloride. 

An organic/fluorous biphasic approach (CsFnBr/benzene) to the synthesis of methyl ketones from terminal alkenes with TBHP in the presence of catalytic amounts of the palladium catalyst 215 was presented by Betzemeier and Knochel in 1998 (Scheme 139) °. 

Problem 15.14 Synthesize (a) p-methoxybenzaldehyde from benzene (b) cyclohexylethanal by hydrobora-tion and oxidation (c) phenylacetaldehyde, using 1,3-dithiane (d) phenyl n-propyl ketone from a dithiane (e) cyclohexyl phenyl ketone from PhCOOH and RLi (/) 2-heptanone, using a cuprate ... 

Problem 15.18 Prepare the following compounds from benzene, toluene, and alcohols of four or fewer C s (a) 2-methylpropanal (isobutyraldehyde), (b) p-chlorobenzaldehyde, (c) p-nitrobenzophenone (p-NOjCftH4COC,.H,), (d) benzyl methyl ketone, (e) p-methylbenzaldehyde. ... 

The block-polymers containing a middle block of polystyrene and two blocks of polyethylene oxide have some unusual properties. They are soluble in methyl ethyl ketone and cannot be precipitated from this solvent by methanol. Addition of water produces a slight cloudiness but still no precipitation although the block polymer is not soluble in pure water. The polymer is also soluble in benzene, but addition of water to this solution causes its precipitation. On the other hand, neither homopolystyrene nor homo-polyethylene oxide or their mixtures are precipitated from benzene solution by addition of water. This strange behaviour is explained by Richards and Szwarc (45) in terms of hydrogen bonding which depends on the chemical potential of water in the aqueous layer and therefore also in the benzene solution. 

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