Phosphorus-containing aldehydes

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... 

The first reported preparations of neutral phosphorus-containing aldehydes, where the phosphorus atom is linked to the aldehyde containing moiety through an oxygen atom is described by F. Ramirez et al (9) in 1969 and G. Sturtz and J. L. Kraus (8) in 1970. These preparations are illustrated in Eq. 5 and 4 of Table 1. 

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. 

A third type of derivative was the reaction product of a phosphorus-containing aldehyde with formaldehyde, analogous to the reaction of acetaldehyde with formaldehyde to form polymethanol derivatives. In the case of the phosphorus-containing aldehydes, this leads to a trifunctional additive. This reaction is i1 lustrated in Fig. 3. 

As an example, when phosphorus-containing aldehydes were added to paraformaldehyde in the presence of calcium oxide and water, an exothermic reaction occurs which leads to the formation of phosphorus-containing trimethanol propanes. Of the two examples shown in Fig. 3, Compound I is a crystalline solid. Since Compound II could not be crystallized, it is suspected of being contaminated with the ether III. 

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

Figure 3. Reactions of phosphorus-containing aldehydes with formaldehyde. (3)...

Block. H.D.. Phosphorus-containing aldehydes. Bayer A.-G., German Patent Appl. DE 2516341, 1976 Chem. Abstr. 86. 55580v. 1977. 

Dioxaphosphorinanes with R = 7-Pr (3) and Ph (4) have also been obtained from phosphorus-containing diols and aldehydes [79IZV2136, 79DOK(244)610]. Phosphorus-containing diols with P(III) are very labile and are capable of dissociation and disproportionation under the reaction conditions. This apparently explains the difference in the physical constants of diols obtained by different authors. 

The interaction of carboxyalkylphosphines with aldehydes belongs to the same type of reactions reported above. The phenyl-(a-hydroxyalkyl)-carboxyalkylphosphine products transform into phosphorus-containing lactones (10) and water [Eq. (8)] [72JPR66 73ZC(13)310]. 

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. 

The cyclization of the phosphorylated arylhydrazones, leading to compounds 168, presumably takes place through the initial formation of 3-phosphorylated indoles 69, which isomerize to compounds 168 in the course of the reaction. Such 3—>2 rearrangements are well-known [30, 180-182, 231]. The transposition of the phosphorus-containing substituent in indoles was first observed in [178, 179]. In the review [8] the data on the formation of 2-phosphorylindoles from the arylhydrazones of phosphorylpropionic aldehyde were considered proved, but the results on the cyclization of hydrazones of phosphorylacetaldehyde to the 2-isomers were placed under some doubt. 

Phosphorus-containing allyltitanium(IV) complexes, like (129), have been studied as well. - The synthetic importance of their addition products to aldehydes lies on their ready deoxygenation to afford (henes stereospecifically (equation 50). 

The asymmetric phosphorus-containing ligand DIOP, 2,2-0-isopropylidene-2,3-dihydroxy-l,4-bis(diphenylphosphino)butane, was incorporated into the chloromethylated polymers according to a literature procedure (20). The chloromethyl function was initially converted into the aldehyde, which was subsequently condensed with a tosylated diol, and the tosyl groups were ultimately converted into diphenylphosphine groups. 

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. ... 

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. ... 

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