Phosphorus Compounds Ring Ketones

Intermediates such as 224 resulting from the nudeophilic addition of C,H-acidic compounds to allenyl ketones such as 222 do not only yield simple addition products such as 225 by proton transfer (Scheme 7.34) [259]. If the C,H-acidic compound contains at least one carbonyl group, a ring dosure is also possible to give pyran derivatives such as 226. The reaction of a similar allenyl ketone with dimethyl mal-onate, methyl acetoacetate or methyl cyanoacetate leads to a-pyrones by an analogous route however, the yields are low (20-32%) [260], The formation of oxaphos-pholenes 229 from ketones 227 and trivalent phosphorus compounds 228 can similarly be explained by nucleophilic attack at the central carbon atom of the allene followed by a second attack of the oxygen atom of the ketone at the phosphorus atom [261, 262], Treatment of the allenic ester 230 with copper(I) chloride and tributyltin hydride in N-methylpyrrolidone (NMP) affords the cephalosporin derivative 232 [263], The authors postulated a Michael addition of copper(I) hydride to the electron-... 

Phosphorus-containing Ring Systems. - A range of new chiral oxazaphospholidine oxides 266 and 267 have been synthesised and used as catalysts in asymmetric reductions of ketones with diborane. Mannich-type cyclisation reactions of 5-amino-3-benzylthio-4-cyano(ethoxycarbonyl)pyrazoles with dichlorophenylphosphine and aromatic aldehydes in the presence of cation exchange resin have been used to prepare a number of 6-oxo-6-phospha-4,5,6-trihydroimidazolo[l,2-b]pyrazoles, e.g. 268. Some of these compounds have herbicidal activity and this report is typical of a number of similar ones in the Chinese literature. A number of metallocycles, e.g. 269, have been reported as products from reactions of transient zirconocene-benzyne intermediates with phosphaimines followed by sulfuration or selenation. ... 

Annulation of a ring-ketone and a fluorine atom (attached to different rings) is achieved by heating the compound (28-6) in either DMF containing potassium carbonate or pyridine-phosphorus pentasulphide. 

A thioamide of isonicotinic acid has also shown tuberculostatic activity in the clinic. The additional substitution on the pyridine ring precludes its preparation from simple starting materials. Reaction of ethyl methyl ketone with ethyl oxalate leads to the ester-diketone, 12 (shown as its enol). Condensation of this with cyanoacetamide gives the substituted pyridone, 13, which contains both the ethyl and carboxyl groups in the desired position. The nitrile group is then excised by means of decarboxylative hydrolysis. Treatment of the pyridone (14) with phosphorus oxychloride converts that compound (after exposure to ethanol to take the acid chloride to the ester) to the chloro-pyridine, 15. The halogen is then removed by catalytic reduction (16). The ester at the 4 position is converted to the desired functionality by successive conversion to the amide (17), dehydration to the nitrile (18), and finally addition of hydrogen sulfide. There is thus obtained ethionamide (19)... 

Electrochemical reduction of a,a -dibromoketones affords the unstable cyclo-propanone, which is in equlibrium with the dipolar intermediate 22. The cyclopro-panone hemiacetal is isolated in yields of 40 - 85 % from reaction in acetonitrile and methanol at -20 °C [99], The dipolar form can be trapped in a cycloaddition process with furan [100], Reaction with acetic acid leads to the a-acetoxy-ketone.[101]. Unstable three membered heterocyclic rings are intermediate in the reduction of sulphur and phosphorus linked dibromo compounds 23. In these reactions, the heteroatom is extruded leaving ci - and trans-stilbenes as the isolated products [102,103],... 

Amino-l,3,4-oxadiazoles (205) on treatment with cr-halogeno-ketones gave intermediate quaternary salts 206 that did not cyclize directly to imidazo[2,l-6]oxadiazoles (208) with base. Hydrolysis of 206 with aqueous potassium carbonate caused ring-opening at C-2 with subsequent closure to the imidazolone 207. These latter compounds could be cyclized to 208 with phosphorus oxychloride.204c 21 246... 

The ring synthesis of many heteroaromatic compounds frequently involves cyclization of a suitable precursor with loss of either water or a simple alcohol such as methanol or ethanol. This may be brought about by treatment with polyphosphoric acid (PPA), which is prepared by dissolving phosphorus pentoxide in concentrated phosphoric acid. In the example of Protocol 14 this approach is used to prepare 3-phenylbenzofuran 55 from phenoxymethyl phenyl ketone 54. The temperature must be carefully controlled, however, since as shown in Scheme 14, an acid-catalysed rearrangment by way of 56 gives the isomeric 2-phenylbenzofuran 57 at higher temperature. This useful feature allows the convenient preparation of either 55 or 57 uncontaminated by the other isomer. 

Compounds derived from Aldehydes and Ketones Reaction between PCI3 and Unsaturated Ketones, Mechanism of Reaction of PClj with Benzaldehyde, 1 4 Addition of Phenyldichlorophosphme, Interaction of Phosphorus Halides with Distyryl Ketone and Phenyl Cinnamylidene Methyl Ketone, Action of PCI3 on turated Aldehydes and Ketones, Interaction of Di-phenylohlorophosphine with Benzaldehyde and Benzal etophenone, Addition of Alkoxy- and Aryloxy-chlorophosphines to Carbonyl Compounds— Phosphorus Derivatives of Dimethylaniline— Derivatives of Dibenzyl-methane and Hydroxymethylene Camphor— Heterocydio Rings containing... 

When W-acetyltetrahydrojervine (LXIV) is reacted with phosphorus pentachloride a desoxychloro derivative (LXXXIV) is formed which on ring scission with sulfuric acid in acetic anhydride-acetic acid gives rise to the 0,iV-diacetyl compound LXXXV. This on partial hydrolysis with alkali affords an W-acetyl compound (LXXXVI) which on reacetylation yields an isomeric diacetyl derivative (LXXXVII) in analogy with similar reactions of tetrahydrojervine. The AT-acetyl derivative (LXXXVI) on chromic acid oxidation formed a ketone (LXXXVIII) with a reactive carbonyl (66). 

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