Phosphinous chloride, dimethyl

According to the latter approach, reducing sugars 128 were reacted with triethylammonium dimethyl boranophosphate in the presence of bis(2-oxo-3-oxazolidinyl)phosphinic chloride as condensing reagent, 3-nitro- 1,2,4-triazole as nucleophilic catalyst and A,A-diisopropyl-A-ethyl-amine to provide boranophosphate triester derivatives 129 as anomeric... 

IrCI02P4C jH32, Iridium(l-t-), (carbon-diox-ide)bis[ 1,2-ethanediyIbis(dimethyl-phosphine)]-, chloride, 21 100... 

A comparison of the dimethyl derivatives of phosphinic chloride (MeaPOCl) and phosphochloridate [(MeO)2POCl] indicated that the latter was less reactive toward oxygen nucleophiles than dimethylphosphinic chloride, which suggests that phosphinic chloride derivatives should react with carboxylate anions to form mixed anhydrides more rapidly than phosphoro-chloridates [119]. Fast formation of mixed anhydrides is an important consideration in coupling reactions. A further advantage of the use of phosphinic carboxylic mixed anhydrides is the elimination of the potential substitution... 

The treatment of 1,1-dimethyl-3-oxobutanol (diacetone alcohol) with PCI3 in the presence of Et3N leads, even at low temperature, to the formation of much 4-methylpent-3-en-2-one (mesityl oxide) together with moderate amounts of the phosphonic diester 264 when this material is stored, or when it is heated in vacuo, elimination of mesityl oxide occurs and the acid 265 (R = H) results". The outcome of this reaction is somewhat different in the absence of the triethylamine, when the final product is the cyclic phosphinic chloride 266. 

A high yield of methylphosphonous dichloride can be obtained by heating phosphorus trichloride with methyl iodide and aluminium trichloride. A complex is first formed (Kinnear-Perrin reaction), and this can then be reduced with aluminium (6.151). In an extension of this reaction, dimethyl-phosphinous chloride can be obtained from the monomethyl compound by treatment with methyl and aluminium chlorides in a similar way (6.152). 

I1CIO2P4C13H32, Iridium(l+), (carbondioxide)-bis[ 1,2-ethanediylbis(dimethyl-phosphine)]-, chloride, 21 100 IrC104P3CiiH27, Iridium, chloro[(formyl-KC-oxy)formato-KO-(2 - )]tris-(trimethylphosphine)-, 21 102 IrCIP3C 7H4i, Iridium, chloio(ti -cyclo-octene)tris( trimethyl-phosphine)-, 21 102... 

The red and orange forms of RhCl[P(C6H5)3]3 have apparently identical chemical properties the difference is presumably due to different crystalline forms, and possibly bonding in the solid. The complex is soluble in chloroform and methylene chloride (dichloromethane) to about 20 g./l. at 25°. The solubility in benzene or toluene is about 2 g./l. at 25° but is very much lower in acetic acid, acetone, and other ketones, methanol, and lower aliphatic alcohols. In paraffins and cyclohexane, the complex is virtually insoluble. Donor solvents such as pyridine, dimethyl sulfoxide, or acetonitrile dissolve the complex with reaction, initially to give complexes of the type RhCl[P(C6H6)3]2L, but further reaction with displacement of phosphine may occur. 

Asymmetric telomerization of isoprene and methanol by using chiral phosphines, such as menthyldiphenylphosphine, gave an optical yield of 17.6%. The telomerization of methanol and isoprene using w-allylpalla-dium chloride and PBu3 in the presence of sodium methoxide in a mixed solvent of methanol and isopropyl alcohol at room temperature for 2 days produced l-methoxy-2,6-dimethyl-2,7-octadiene (89) (80%) and 1-meth-oxy-2,7-dimethyl-2,7-octadiene (91) (15%) (91). After 2 days, the reaction mixture was heated at 80°C for 8 hours, and 2,6-dimethyl-l,3,7-octatriene (88) (75%) and 2,7-dimethyl-1,3,7-octatriene (85) (14%) were obtained. Also, NiCl2(Bu3P)2 was used as a cocatalyst for the formation of 88. 

Dimethyl(trimethylsilyl)phosphine (63) reacts with aluminium chlorides with cleavage of the silicon-phosphorus bond,58 as shown for aluminium trichloride. The same phosphine (63) reacts with the cobalt derivative (64) as shown.59... 

Chloroform, Chloropicrin, 1,1-Dichloroethylene, Endrin, Hexachlorocyclopentadiene, Methyl chloride. Methylene chloride, Tetrachloroethylene, 1,1,1 -Trichloroethane, Trichloroethylene Phosphine, see Pentachlorobenzene, Phorate Phosphoric acid, see Dichlorvos, Ethephon. Glvphosate. Malathion, Mevinphos, Parathion, Sulfotepp, Tributyl phosphate, Trichlorfon Phosphoric acid, dimethyl ester, see Mevinphos, Oxvdemeton-methvl Phosphorothioic acid, see Parathion Photoaldrin, see Aldrin Photoaldrin chlorohydrin, see Dieldrin Photodieldrin, see Aldrin, Dieldrin Photoheptachlor, see Heptachlor Photoketoaldrin, see Aldrin Phthalaldehyde, see Naphthalene Phthalaldehydes, see Tolnene Phthalic acid, see Anthracene, Benzo[a]anthracene, Benzyl bntyl phthalate, Dichlone. Diethyl phthalate, Dimethyl phthalate, Naphthalene, Naptalam. I ene... 

DIENES Bcn/.yldtlotobis(Iriphenyl-phosphine)palladium(ll). Copper(I) bromide-Dimethyl sulfide. Palladium(Il) chloride. Tetrakis(triphenyEphosphine)-palladium. Titanium IVichloride-Lithium aluminum hydride. 

Alkyl ethers of benzoin Benzil dimethyl ketal 2-Hydroxy-2-methylphenol-l-propanone 2,2-Diethoxyacetophenone 2-Benzyl-2-At, V-dimethylamino- l-(4-morpholinophenyl) butanone Halogenated acetophenone derivatives Sulfonyl chlorides of aromatic compounds Acylphosphine oxides and bis-acyl phosphine oxides Benzimidazoles... 

Dimethyl-1-(trimethylsiloxy)propylidene(trimethylsilyl)phosphine 8 is prepared by the reaction of pivaloyl chloride with tris(trimethylsilyl)phosphine (see Protocol 3). 

SAFETY PROFILE Poison by inhalation and ingestion. A corrosive eye, skin, and mucous membrane irritant. Potentially explosive reaction with water evolves hydrogen chloride and phosphine, which then ignites. Explosive reaction with 2,6-dimethylpyridine N-oxide, dimethyl sulfoxide, ferrocene-1,1 -dicarboxylic acid, pyridine N-oxide (above 60°C), sodium -L heat. Violent reaction or ignition with BI3, carbon disulfide, 2,5-dimethyl pyrrole + dimethyl formamide, organic matter, zinc powder. Reacts with water or steam to produce heat and toxic and corrosive fumes. Incompatible with carbon disulfide, N,N-dimethyl-formamide, 2,5-dimethylpyrrole, 2,6-dimethylpyridine N-oxide, dimethylsulfoxide, ferrocene-1,1-dicarboxylic acid, water, zinc. When heated to decomposition it emits highly toxic fumes of Cl" and POx. 

Selenolates prepared from diphenyl or dimethyl diselenide by reduction with NaBH4 smoothly transform various benzylic alcohols 24 into the corresponding selenides 25 in the presence of aluminum chloride (Scheme 30 a) [41]. AICI3 is considered to activate the alcohol substrate by coordinating to the oxygen. Similar transformations are possible by the reaction of alcohols with phenyl selenocyanate in the presence of tributyl phosphine [52]. When the selenolate is reacted with aromatic aldehydes or ketones 26 in the presence of AICI3, the corresponding benzylic selenides 27 are obtained in moderate yields (Scheme 30b) [41]. 

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