Phosphonium chloride derivatives

Highly moisture-sensitive phosphonium chloride derivatives are produced from the reactions of phosgene with (MejN) jP(S)NHj or (EtjN)P(S)(NH2) j. Equations (10.51) and (10.52) [778]. [(Et2N)P(Cl)(NH j) j]Cl was noted to react further with phosgene, as illustrated... 

Biocides. Two phosphine derivatives are ia commercial use as biocides. These are tetrakis(hydroxymethyl)phosphonium sulfate [55566-30-8] and tributyl(tetradecyl)phosphonium chloride [8741-28-8]. These compounds are sold by Albright and Wilson Ltd. and EMC, respectively. The preparation... 

Since the buckminsterfullerenes and C70 were discovered in 1990, there has been extreme interest in these compounds and their derivatives. The first fulleride radical anion, Cgo, was prepared by bulk electrolysis using tetraphenyl-phosphonium chloride supporting electrolyte in dichlorobenzene [76]. Since there are no protons, the spectrum exhibits only one line. Furthermore, because the spin density is so uniformly distributed in the molecule, HFS from naturally... 

Reaction of 8-fluoro-5H-pyrido[l, 2,3-de] [1,4]benzoxazine-3,7(2H,6H)-dione and triphenyl(methoxymethyl)phosphonium chloride in the presence of KOf-Bu gave 7-[(methyloxy)methylidene]-3-oxo derivative, which was reacted with Me3SiCl in the presence Nal in MeCN at ambient temperature for 18 h to yield 7-carbaldehyde derivative (08WOP2008/ 116815). 

Treatment of 1-nitro- and 5-nitroquinoline derivatives 279 with allyltriphenyl-phosphonium chloride in the presence of DBU and Ti(OPr% results in annulation of the pyrrole entity to the starting molecule (03SL1465). In the first step, the reaction probably produces 1-hydroxypyrroles 280 which are converted without isolation into pyrroles 281 and 282 after adding triethylamine and ethyl bromoacetate (Scheme 81). 

Other most successful durable treatment is based on tetrakis (hydroxymethyl) phosphonium derivatives. Very well-known brand marketed as Proban CC (Rhodia, previously Albright Wilson) involves padding of tetrakis (hydroxymethyl) phosphonium chloride (THPC) urea solution onto the cotton fabric, curing with ammonia in a specially designed reactor to generate a highly cross-linked three-dimensional polymer network. The fabric is then treated with hydrogen peroxide, which converts P3+ to the P5+ state. The reactions are shown in Scheme 24.2. Other similar commercial product is Thor s Aflammit P. In literature many combinations of tetrakis (hydroxymethyl) phosphonium derivatives with other salts have been reported,50 but the most successful so far has been the THPC-urea-NH3 system discussed earlier. 

Reaction of tris(2-pyridyl)phosphane (8) with chlorine in methylene dichloride or acetonitrile gave chlorotris(2-pyridyl)phosphonium chloride or its covalent isomer tris(2-pyridyl)phosphonium dichloride (20). Treatment of the dichloride derivative with dilute HCl afforded the coupling product, 2,2 -bipyridine (16), whereas tris(2-pyridyl)phosphine oxide (9) was isolated from the reaction with sodium hydroxide. 

The structure HPO(OH)2 represents phosphorous acid as a derivative of a very strong acid, phosphonium ion. This ion is so strong an acid that it needs a high pressure of HCl to prevent phosphonium chloride, PH4CI, from decomposing into PH3 and HCl at room temperatures. Although the acidic strength of phosphonium ion... 

The synthon (117) is derived from the optically active C22-allenic apocarotenal 118 which is prepared via a Wittig condensation of the (3S)-Ci5-allenic aldehyde 103 with the Cy-phosphonium chloride 119. Reduction of the aldehyde group in 118 (a mixture of 11Z and 11 ) with NaBH4, followed by acetylation, yields the acetate 120, which is converted into the sulphone 117 by heating under reflux with sodium sulphinate in propan-2-ol and water. Condensation between the (all- )-allenic sulphone 117 and the formyl ester (5R,6S)-116 under the conditions of the sulphone method furnishes a mixture (ca. 1 1) of the optically active peridinin (108) and its (11 )-isomer and these are cleanly separated by preparative HPLC in the dark Scheme 27) [70,72]. 

A general synthesis of -(2-oxoalkyl) 0,f7-dialkyl phosphoroselenoates (89) involves the interaction of enol silyl ethers and the pseudo phosphonium salts derived from OTTO-irialkyl phosphoroselenoates and sulphuryl chloride. ... 

One of the earliest reports on use of a phosphonium salt as an IL in such a process was that of Kaufmann and co-workers (9). In this work, the use of tri-butyl(hexadecyl)phosphonium bromide as a recyclable medium for the palladium-mediated Heck coupling of aryl halides with acrylate esters was reported (9). While these reactions proceeded without the use of an additive ligand, elevated temperatures (100 °C) were required and the process was most efficient only with more activated aryl halides [Eq. (1)]. More recently, the use of trihexyl(tetradecyl)-phosphonium chloride (Cyphos IL 101) has been reported as a useful medium for the Suzuki cross-coupling of aryl halides with boronic acid derivatives [Eq. (2)] [10]. In this process, a soluble palladium precursor such as Pd2(dba)3-CHCl3 was dissolved in the phosphonium salt, forming a dark orange solution. This solution was stable in the absence of oxygen for an extended period of time and could be... 

Triphenylphosphine and its derivatives have been used to convert a variety of compounds into nitriles (see also pp. 246 and 254). Phosphine-alkylenes react with nitrosyl chloride to give a hydroxyimino phosphonium chloride (54) which decomposes on prolonged boiling in chloroform or THE to a nitrile in moderately good yield [126],... 

A -alkyl derivatives of tubercidin and of 9-(6-deoxy-6-nitro-j8-D-glucopyrano-syl)adenine have been reported. Guanosine reacted with tetrakis(hydroxy-methyl)phosphonium chloride to give the JV -substituted phosphine (499). The preparation and properties of osmium-ligand complexes of nucleosides are mentioned in Chapter 18. ... 

Some compounds are named as derivatives of the simple phosphoms hydrides (phosphines). For example, dimethylphosphine [676-59-5], (CH2)3PH triphenylphosphine oxide [791-28-6], (CgH3)3P=0 1,2-dimethyldiphosphine [53684-00-7], CH PHPHCH diethyliodophosphine [20472-47-3], (C2H3)2PI phosphonium iodide [12125-09-6], PH" P tetramethylphosphonium chloride [1941 -19-1], (CH3) P" C1 and phenylphosphonium bromide [55671-96-0], CgH PHjBr-. 

Previous syntheses of terminal alkynes from aldehydes employed Wittig methodology with phosphonium ylides and phosphonates. 6 7 The DuPont procedure circumvents the use of phosphorus compounds by using lithiated dichloromethane as the source of the terminal carbon. The intermediate lithioalkyne 4 can be quenched with water to provide the terminal alkyne or with various electrophiles, as in the present case, to yield propargylic alcohols, alkynylsilanes, or internal alkynes. Enantioenriched terminal alkynylcarbinols can also be prepared from allylic alcohols by Sharpless epoxidation and subsequent basic elimination of the derived chloro- or bromomethyl epoxide (eq 5). A related method entails Sharpless asymmetric dihydroxylation of an allylic chloride and base treatment of the acetonide derivative.8 In these approaches the product and starting material contain the same number of carbons. 

The first synthesis of derivatives (77) of pentatetraene-carboxylic acid has been reported using a Wittig reaction of 1-H-allene-l,3-dicarboxylate monoester chlorides (76) in the presence of triethylamine.60 In one case an intermediate was obtained and was converted to (77) by further treatment with base. The reaction of carbon suboxide with phosphonium ylides has also... 

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