Phosphorus-containing ketones

The first completely esterified phosphorus-containing ketone is described by R. G. Harvey (7) who used a synthesis route first described by G. Kamai and V. A. Kukhtln (6) for the preparation of... 

The phosphorus containing ketone PhC(0)P(0)(OMe)a does not react with sodium thiolate, but will react with the thiol in the presence of... 

Figure 2). -Diketones 35 and j5-ketoesters 36-38 are commonly used as CH-acidic ketones 24. Cyanoketones 39 and 40, nitroketones 41, as weU as ketones substituted with beteroaromatic 42, sulfur-containing 43, and phosphorus-containing groups 44 and 45 are also favored (Figure 2). Syntheses... 

The phosphonic group can be introduced in position 4 of a pyran ring (66) by utilization of phosphorus-containing UN 67 in a reaction with methylene-active ketones 35 or 36 on continuous heating in ethanol (00PS(165)17) (Scheme 15). 

Analogues of (751) react with derivatives of phosphorus-containing acids to form 1-phosphoryl-imidazoles (90CHE599). The same compound also silylates ketones to give enol silyl ethers and/or siloxyalkylimidazoles (Scheme 107) (87JC271). 

Peptidomimetics in which one amide bond is replaced by a phosphinic acid (R-P(0H)(=0)-R phosphinic peptides ) are of interest as potential protease inhibitors [17-19]. These compounds have been prepared either from orthogonally protected phosphorus-containing monomers [17,18,20], or by forming the phosphorus-containing fragments on solid phase, as sketched in Figure 11.4 [19,21], Phosphinic acids have been prepared on solid phase mainly by reaction of carbon electrophiles with monoalkylphosphinates. As carbon electrophiles, acrylates, aldehydes, reactive alkyl halides, or a, 3-unsaturated ketones can be used. 

Treatment of dienyl aryl ketones with P4S10 affords phosphorus-containing heterocycles which generate dienyl aryl thioketones upon heating262 (equation 28). 

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. ... 

One of these approaches, conducted by R. L Muntz and E. N. Walsh (3), was to prepare derivatives of phosphorus-containing aldehydes and ketones. Although phosphorus-containing aldehydes and ketones are themselves functional additives, they also offer a number of routes to introduce additional functionality into phosphorus-containing additives. These phosphorus-containing... 

Examples of phosphorus-containing aldehydes and ketones prepared during our study are shown in Table 2. These were prepared using the methods described either by R. G. Harvey (7) or G. Sturtz and J. L. Kraus (8). The preparations are described in detail in reference (3). As can be seen, some of these compounds were Isolated as acetals or ketals. 

A second type of derivative of phosphorus-containing aldehydes and ketones was prepared from a Mannich-type condensation of a phosphorus-containing carbonyl compound, such as 3-(diethyl phosphono)butanal with diethyl phosphonate and diethanol amine, to form a phosphorus-rich diol, l-((diethyl)phosphono]-l-CN,N-di(hyroxyethyl)amino]-3-C(diethyl)phosphono] butane as shown In Eq. 2 of Fig. 2. Examples of the preparation of such diols are shown as Ex 3 and 4 of Table 3. 

Compounds Prepared from Phosphorus - Containing Aldehydes and Ketones... 

The Wittig reaction involves the interaction of an aldehyde or ketone with a phosphorus-containing carbanionic species, in which the phosphorus is bonded directly to the carbanionic site. At the time of discovery of the reaction, that specification described the triphenylphosphonium alkylides 343 later developments employed the anions from tert-phosphine oxides, the use of which has been described elsewhere in this series and also from a wide variety of phosphonic and phosphinic esters. This latter application will be considered more fully in Chapter 6. An early application of the reaction to the synthesis of alkenephosphonic acids, and which involved an ylide, employed the stable compound 344, generated from 345 by the action of a strong base. Reactions between 344 and aliphatic or aromatic aldehydes at 100 °C in toluene or dmso gave the diphenyl esters of (alk-1-enyl)phosphonic acids or (2-arylethenyl)phosphonic acids. ... 

The chemistry of the reactions of phosphorus-containing carbanions with carbonyl compounds may be revisited (Section III.B.3) those between diethyl (aryllithiomethyl)phosphonates and ketones have been used to prepare diethyl (l-aryl-2-hydroxy-2,2-disubsti-tuted-ethyl)phosphonates, formed with high jj -stereoselectivity . Modro et al. have extended their studies on the interaction of aldehydes with diethyl prop-2-enylphosphonate carbanion when the reaction products are warmed, dissociation of the kinetically... 

Phosphonate monomers of type 1 were made from the reaction of allyl glycidyl ether with hydroxy-functionalized phosphonic acid. To obtain azo-phosphonated products (type 2), multicomponent reactions (amine-, aldehyde/ketone-, or phosphorus-containing compounds) such as the Kabachnick-Fields," Mannich," or Moedritzer ° reactions, were used. These reactions generated in a selective way the a-aminoallq lphosphonate products. 

This reaction can be used to convert a ketone into an alkene by forming a new C—C bond at the location of the carbonyl moiety. The phosphorus-containing reagent that accompHshes this transformation is called a phosphorane, and it belongs to a larger class of compounds called ylides. An ylide is a compound with two oppositely charged atoms adjacent to each... 

Poly(vinyl aldehyde)s, Poly(vinyl ketone)s, and Phosphorus-Containing Vinyl Polymers... 

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