Phosphorus trichloride, reaction + metal

Another general method for converting alcohols to halides involves reactions with halides of certain non-metallic elements. Thionyl chloride, phosphorus trichloride, and phosphorus tribromide are the most common examples of this group of reagents. These reagents are suitable for alcohols that are neither acid-sensitive nor prone to structural rearrangements. The reaction of alcohols with thionyl chloride initially results in the formation of a chlorosulfite ester. There are two mechanisms by which the chlorosulfite... 

At the time of our investigation the only known coordination compounds of chlorophosphines (aside from phosphorus trichloride complexes) were the nickel-(0) compounds, tetrakis(methyldichlorophosphine)nickel-(0) (20) and tetrakis-phenyldichlorophosphine) nickel- (0) (17). Tetrakis (methyldichlorophosphine) -nickel-(0) is noteworthy in that it represents a still rare example of the direct reaction of a ligand with an elemental transition metal to give a complex, while tetrakis (phenyldichlorophosphine) nickel- (0), like tetrakis (trichlorophosphine) -nickel-(0), was obtained readily via the carbonyl. AD chlorophosphine-nickel-(O) complexes, including the phosphorus trichloride complex, Ni(PCl3)4, are compounds relatively stable in the atmosphere, but show poor stability in almost any organic solvent, even under strictly anaerobic conditions. 

Platinum(II)15 and palladium(II)16 complexes of phosphorus trichloride undergo solvolysis in water and alcohols to form complexes with orthophosphorous acid or orthophosphite ligands (equation 6). Similar reactions occur between the palladium(II) phenyldichlorophosphine complex (8) and the diols ethyleneglycol and catechol, but new chelate rings are not formed (Scheme 2). Solvolysis also occurs with attack of diphenylphosphinic acid or a similar diphenylchlorophosphine complex (9) (equation 7). The palladium complexes (8) and (9) are unstable to excess methanol, water or base and undergo reduction. Similarly, the phosphorus trichloride gold(I) complex (10) is reduced by water, but forms stable products on reaction with alcohols (equation 8).15 During the above reactions, the phosphorus—metal bond remains intact and the overall process is one of substitution at phosphorus. 

The redistribution reaction in lead compounds is straightforward and there are no appreciable side reactions. It is normally carried out commercially in the liquid phase at substantially room temperature. However, a catalyst is required to effect the reaction with lead compounds. A number of catalysts have been patented, but the exact procedure as practiced commercially has never been revealed. Among the effective catalysts are activated alumina and other activated metal oxides, triethyllead chloride, triethyllead iodide, phosphorus trichloride, arsenic trichloride, bismuth trichloride, iron(III)chloride, zirconium(IV)-chloride, tin(IV)chloride, zinc chloride, zinc fluoride, mercury(II)chloride, boron trifluoride, aluminum chloride, aluminum bromide, dimethyl-aluminum chloride, and platinum(IV)chloride 43,70-72,79,80,97,117, 131,31s) A separate catalyst compound is not required for the exchange between R.jPb and R3PbX compounds however, this type of uncatalyzed exchange is rather slow. Again, the products are practically a random mixture. 

Many binary compounds of non-metals with non-metals are known, but such compounds usually can exist only out of contact with water. For example, phosphorus trichloride is completely hydrolyzed by water. Write the equation for this reaction, and treating it as a metathesis, conclude which element in the phosphorus trichloride is to be regarded as the positive constituent. 

Although no explanation was given for the spontaneous, unexpected oxidation steps 79- 78a and 78a- 34, it is reasonable to assume that the initially present tri-valent phosphorus compounds (phosphorus trichloride and 5-chloro-5H-dibenzo-phosphole 85, respectively), and/or the alkyl halide stemming from the halogen metal exchange reaction used for preparing 2,2 -dilithiobiphenyl, may play an active role here. 

Phosphorus trichloride reacts with organic compounds including Grignard reagents and metal alkyls to give numerous alkyl derivatives. Typical reactions can be illustrated by the following equations ... 

Chlorophosphepines 86 were synthesized in low yield (20-25%) from binaphthyls 84 in two steps, via initial metallation with BuLi and a subsequent reaction of 85 with phosphorus trichloride <2002TL4849>. 

Titanacyclopropenes 31 reacts smoothly with dichlorophosphines or phosphorus trichloride with extrusion of the titanium fragment and formation of the phosphirenes 32 or 33, respectively. The transition metal complexes themselves are generated in situ from either a dichlorotitanium complex (Equation 26) or tetraisopropoxytitanium (Equation 27) by reactions with alkynes <19980M2677>. Analogous chemistry can be carried out with zircona-cyclopropenes <1998CC1177>. 

Cycloaddition of diazomethane to phospholes is a key step in the synthesis of the homophospholes (189). A simple route to phospholyl anions is offered by the reaction of the zircona-cyclopentadienide (190) with phosphorus trichloride, giving the intermediate chlorophosphole (191) which, on treatment with lithium metal, gives the related phospholyl derivative (192). ... 

A) Reactions of Hydroxyl Group. Recall the reaction of ethanol with metallic sodium, phosphorus trichloride and acetyl chloride. 

The Darzens synthesis of glycidic esters by condensation of carbonyl compounds with a-haloesters is an important and useful method" that has been extended in phosphorus chemistry. Unquestionably, the most general and perhaps most widely employed method for the synthesis of dialkyl 1,2-epoxyalkylphosphonates involves the reaction of dialkyl chloromethylphosphonates with carbonyl compounds. These synthetically useful phosphonates are readily obtained by standard alcoholysis of chloromethylphosphonic dichloride under anhydrous conditions. The latter is obtained in up to 67% yield from phosphorus trichloride and paraformaldehyde at 250°C. Several variations on the preparation of dialkyl 1,2-epoxyalkylphosphonates from dialkyl chloromethylphosphonates and different carbonyl partners have been reported. The conditions for generating the a-metallated dialkyl chloromethylphosphonates were found to be critical because of their notorious instability. 

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