Phosphorous substitution

Finally, the synthetic importance of phosphorous-substituted lithium halocarb-enoids has been demonstrated by making extensive use of the reactions of diethyl a-monohalo- and a,a-dihalolithioalkylphosphonates with electrophiles. 

Phosphorous substituted carbodiimides are less stable than most of the other carbodiimides. For example, the carbodiimides Ph2P(0)N=C=NR cannot be distilled without decomposition. However, carbodiimides (Et0)2P(0)N=C=NR can be purified by vacuum distillation. 

Phosphorous substituted carbodiimides 4 are synthesized by dehydrosulfurization of the corresponding thioureas 3 with HgO. ... 

The reaction of phosphorous substituted carbonimidoyl dichlorides 10 with arylamines in the presence of triethylamine affords the corresponding carbodiimides 11. The reaction proceeds via the intermediate chloroformamidines. The dehydrochlorination of the intermediate chloroformamidine occurs in diethyl ether at room temperature. 

The silver salt of cyanamide reacts with BrFaP or Ph2P(X)Cl to give bis-phosphorous substituted carbodiimides. For example, a 52 % yield of bis(difluorophosphinyl)carbodiimide 12 is obtained from the silver salt of cyanamide and bromodifluorophosphine. ... 

The reaction of bis(trimethylsilyl)carbodiimide with P(S)P3 at 140-150 °C gives 35 % of the mono phosphorous substituted carbodiimide 20. ... 

The remaining chapters are carbodiimides with unsaturated substituents, halogenated carbodiimides, acyl-, thioacyl- and imidoylcarbodiimides, silicon substituted carbodiimides, nitrogen substituted carbodiimides, phosphorous substituted carbodiimides, sulfur substituted carbodiimides, metal substituted carbodiimides, cyclic carbodiimides, polymeric carbodiimides and application of carbodiimides. 

Phosphorous-substituted zeolites were also claimed to be produced via direct synthesis with various structures (13). However these were of the ternary type i.e. Both silicon, aluminium and an additional T atom were simultaneously present in the zeolite lattice. 

Carretero and coworkers have further extended the scope of N-sulfonyl imine heterodienophiles in enantioselective copper-catalyzed aza-Diels-Alder reactions (Scheme 17.65) [94]. In contrast to previous work that had been limited to the highly reactive N-tosyl imine of ethyl glyoxylate, chiral Cu(I) complexes of phosphino sulfenyl ferrocenes catalyze cycloaddition of Danishefsky s diene (286) to N-tosyl imines (292) of both aromatic and aliphatic aldehydes. Phosphorous substitution proved to play a critical role in both reactivity and enantioselectivity of the reaction with complex [151 CuBr]2 bearing 1-naphthyl substituents on the phosphorous... 

Figure 9.10 Lewis dot stmcture of doped Si. The phosphorous substitutional impurity forms n-Si while boron forms p-Si.

The 7 glutamyl phosphate formed m this step is a mixed anhydride of glutamic acid and phosphoric acid It is activated toward nucleophilic acyl substitution and gives glutamine when attacked by ammonia... 

Reactions. Heating an aqueous solution of malonic acid above 70°C results in its decomposition to acetic acid and carbon dioxide. Malonic acid is a useful tool for synthesizing a-unsaturated carboxyUc acids because of its abiUty to undergo decarboxylation and condensation with aldehydes or ketones at the methylene group. Cinnamic acids are formed from the reaction of malonic acid and benzaldehyde derivatives (1). If aUphatic aldehydes are used acryhc acids result (2). Similarly this facile decarboxylation combined with the condensation with an activated double bond yields a-substituted acetic acid derivatives. For example, 4-thiazohdine acetic acids (2) are readily prepared from 2,5-dihydro-l,3-thiazoles (3). A further feature of malonic acid is that it does not form an anhydride when heated with phosphorous pentoxide [1314-56-3] but rather carbon suboxide [504-64-3] [0=C=C=0], a toxic gas that reacts with water to reform malonic acid. 

Phosphoric acid, aside from its acidic behavior, is relatively unreactive at room temperature. It is sometimes substituted for sulfuric acid because of its lack of oxidising properties (see SuLFURic ACID AND SULFURTRIOXIDe). The reduction of phosphoric acid by strong reducing agents, eg, H2 or C, does not occur to any measurable degree below 350—400°C. At higher temperatures, the acid reacts with most metals and their oxides. Phosphoric acid is stronger than acetic, oxaUc, siUcic, and boric acids, but weaker than sulfuric, nitric, hydrochloric, and chromic acids. 

Hydroxyapatite, Ca2Q(PO (OH)2, may be regarded as the parent member of a whole series of stmcturaHy related calcium phosphates that can be represented by the formula M2q(ZO X2, where M is a metal or H O" Z is P, As, Si, Ga, S, or Cr and X is OH, F, Cl, Br, 1/2 CO, etc. The apatite compounds all exhibit the same type of hexagonal crystal stmcture. Included are a series of naturally occurring minerals, synthetic salts, and precipitated hydroxyapatites. Highly substituted apatites such as FrancoHte, Ca2Q(PO (C02) (F,0H)2, are the principal component of phosphate rock used for the production of both wet-process and furnace-process phosphoric acid. 

Anodic Oxidation. The abiUty of tantalum to support a stable, insulating anodic oxide film accounts for the majority of tantalum powder usage (see Thin films). The film is produced or formed by making the metal, usually as a sintered porous pellet, the anode in an electrochemical cell. The electrolyte is most often a dilute aqueous solution of phosphoric acid, although high voltage appHcations often require substitution of some of the water with more aprotic solvents like ethylene glycol or Carbowax (49). The electrolyte temperature is between 60 and 90°C. 

Of the many methods which have been published so far for the substitution of existing crowns, probably the most straightforward are Friedel-Crafts alkylation or acylation reactions. Cygan, Biernat and Chadzynski have reported the successful di-t-butylation of dibenzo-24-crown-8 using t-butanol as alkylating agent s . The crown was heated at 100° for 4 h in the presence of excess t-butanol and 85% phosphoric acid. The product was obtained as a crystalline (mp 52—74°) solid in 93% yield. The alkylated crowns are presumably a mixture of isomers substituted once in each ring as illustrated in Eq. (3.14). 

Note Phosphoric acid [8] and hydrochloric acid [6, 9] have both been suggested in the literature as substitutes for phthalic acid. The addition of sodium dithionite [9] is also occasionally mentioned and sometimes no additives are employed [10]. The alternative reagents offer no advantages over the phthalic acid containing reagent since they usually cause more background coloration. The limits of detection are about 0.1 —0.5 pg per chromatogram zone [5]. 

A considerable number of examples will be found in the text in which halo-genated and other substituted olefins are produced. Their modes of fonnation do not usually differ in principle from the corresponding unsubstituted case. However, some special methods have been used, for example, the direct preparation of halo olefins from ketones with phosphorous hahdes, or via hydrazones. 

It has generally been assumed that phosphorous oxychloride-pyridine dehydrations, the elimination of sulfonates, and other base catalyzed eliminations (see below) proceed by an E2 mechanism (see e.g. ref. 214, 215, 216). Concerted base catalyzed eliminations in acyclic systems follow the Saytzelf orientation rule i.e., proceed toward the most substituted carbon), as do eliminations (see ref 214). However, the best geometrical arrangement of the four centers involved in 2 eliminations is anti-coplanar and in the cyclohexane system only the tran -diaxial situation provides this. 

Halogen-substituted olefins may be obtained from hydrazones by the action ofN-halocompounds. 327, /. 328.372 (Chloro compounds of this type may also be made by the direct action of phosphorous pentachloride on the ketone, e.g. ref. 329, 330.)... 

In 1909, Robinson demonstrated the utility of acylamidoketones as intermediates to aryl-and benzyl-substituted 1,3-oxazoles through cyclization with sulfuric acid. Extension of sulfuric acid cyclization conditions to alkyl-substituted oxazoles can give low yields, for example 10-15% for 2,5-dimethyl-l,3-oxazole. Wiegand and Rathbum found that polyphosphoric acid can provide alkyl-substituted oxazoles 4 in yields equal to or greater than those obtained with sulfuric acid. Significantly better yields are seen in the preparation of aryl- and heteroaryl-substituted oxazoles. For example, reaction of ketoamides 5 with 98% phosphoric acid in acetic anhydride gives oxazoles 6 in 90-95% yield. ... 

Substituents in the 6-position (cf. 267) show appreciable reactivity. 6-Bromo-as-triazine-3,5(2j, 4j )-dione (316) undergoes 6-substitution with secondary amines or hydrazine, with mercaptide anions or thiourea (78°, 16 hr), with molten ammonium acetate (170°, 24 hr, 53% yield), and with chloride ion during phosphorous oxychloride treatment to form 3,5,6-trichloro-as-triazine. The latter was characterized as the chloro analog of 316 by treatment with methanol (20°, heat evolution) and hydrolysis (neutral or acid) to the dioxo compound. The mercapto substituent in 6-mercapto-as-triazine-3,5(2iI,4if)-dione is displaced by secondary... 

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