Dichloro Methyl Phosphine

METHYL KETONES AUyltrimethyl-silane, Bis(acetonitrilo)chloronitro-palladium (11). Dicarb ony lbis( triphenyl-phosphine)nickel. Dichloro-dicyano-benzoquinone. Hydrogen peroxide-Palladium acetate. Meldrum s acid. Palladium r-butyl peroxide trilluoro-acctate. Palladium tl) chloride. 

CF3H, Methane, trifluoro-cadmium complex, 24 55 mercury complex, 24 52 CF3NOS, Imidosulfurous difluoride, (fluorocarbonyl)-, 24 10 CH2, Methylene ruthenium complex, 25 182 CH2CI4P2, Phosphine, methylenebis-(dichloro)-, 25 121 CH3, Methyl cobalt complexes, 23 170 mercury complexes, 24 143-145 platinum complex, 25 104, lOS CNO, Cyanato silicon complex, 24 99 CN2OS2, l,3k, 2,4-Dithiadiazol-5-one, 25 53 CO, Carbon monoxide chromium complexes, 21 1, 2 23 87 cobalt complex, 25 177 cobalt, iron, osmium, and ruthenium complexes, 21 58-65 cobalt-osmium complexes 25 195-197 cobalt-ruthenium cluster complexes, 25 164... 

QSP3C2H4, Phosphine, chIorobis[(dichloro-phosphino)methyl]-, 25 121 CI Co4N,2O32C 2H40 4H2O, Cobalt(III), tetra-(jL-hydroxo( i4-oxalato)-tetrakis-[triammine-, hexaperchlorate, tetrahy-drate, 23 114... 

P3CISC2H4, Phosphine, chlorobis[ dichloro-phosphino)methyl]-, 25 121 P3CI3N3OC2H3, Poly[2,2,4,4,6-pentachloro-6-(ethenyloxy)-l,3,5,2k 4k 6k -triaza-triphosphorine], 25 77... 

Notable examples of general synthetic procedures in Volume 47 include the synthesis of aromatic aldehydes (from dichloro-methyl methyl ether), aliphatic aldehydes (from alkyl halides and trimethylamine oxide and by oxidation of alcohols using dimethyl sulfoxide, dicyclohexylcarbodiimide, and pyridinum trifluoro-acetate the latter method is particularly useful since the conditions are so mild), carbethoxycycloalkanones (from sodium hydride, diethyl carbonate, and the cycloalkanone), m-dialkylbenzenes (from the />-isomer by isomerization with hydrogen fluoride and boron trifluoride), and the deamination of amines (by conversion to the nitrosoamide and thermolysis to the ester). Other general methods are represented by the synthesis of 1 J-difluoroolefins (from sodium chlorodifluoroacetate, triphenyl phosphine, and an aldehyde or ketone), the nitration of aromatic rings (with ni-tronium tetrafluoroborate), the reductive methylation of aromatic nitro compounds (with formaldehyde and hydrogen), the synthesis of dialkyl ketones (from carboxylic acids and iron powder), and the preparation of 1-substituted cyclopropanols (from the condensation of a 1,3-dichloro-2-propanol derivative and ethyl-... 

Phosphine, (2-bromophenyl)dichloro-, 2,991 Phosphine, (w-chloroalkyl)dichloro-, 2, 991 Phosphine, chlorodimethyl-, 2, 991 Phosphine, chloro(dimethylamino)-, 2, 991 Phosphine, chlorodiphenyl-, 2, 990 Phosphine, cyclohexyl(o-anisyl)methyl-rhodium complexes asymmetric hydrogenation, 6, 251 Phosphine, [(dialkylphosphino)alkyl]diphenyl-, 2, 994 Phosphine, dichloromethyl-, 2, 991 Phosphine, dichlorophenyl-, 2, 990 Phosphine, diethylphenyl-, 2, 992 Phosphine, dimethyl-, 2,992 Phosphine, dimethylphenyl-, 2,992 Phosphine, diphenyl-, 2, 992 Phosphine, ethyldiphenyl-, 2, 992 Phosphine, ethylenebis(diethyl-, 2, 993 Phosphine, ethylenebis(diphenyl-, 2,993 Phosphine, ethylenebis(phenyl-, 2,992 Phosphine, ethylidynetris[methylene(diphenyl-, 2,994 Phosphine, [(ethylphenylphosphino)hexyl]diphenyl-, 2, 994... 

The reaction of (31 X = K) with chlorotrimethylstannane yields the stannylphosphine (31 X = SnMe3), which on subsequent treatment with dichloro(methyl)phosphine, is converted into the... 

Biphilic Reactions.—A most thorough investigation into the cycloaddition of buta-1,3-diene with dichloro(methyl)phosphine (30) has revealed some of the factors which influence the composition of the final products.32 Thus the A3-phospholen 1-oxide (31) is the product of the cycloaddition at room temperature, but at 90 °C the isomeric A2-phospholen 1-oxide (32) predominates after work-up. The yields of (31) and (32) are improved by a new work-up involving methanolysis rather than hydrolysis of the intermediate salts.32... 

Synthetic studies of various cyclic phosphine oxides continue to be published. Thus a methanolic work-up leads to an 88% yield of 1-methylphospholen 1-oxides (6) from dichloro(methyl)phosphine, and detailed S1P n.m.r. and mass spectra have been described.10 The oxides (7) and (8) have been prepared11 as shown. Structural... 

The most important complex of this type is [Rh(NO)Cl2(PPh3)2], which was first prepared in 1962. The tri(cyclohexyl)phosphine and triphenylarsine analogs were also prepared at this date. The dichloro complexes were precipitated when excess neutral ligand was allowed to react with [Rh(NO)2Cl],. The preparative routes available for [Rh(NO)Cl2(PPh3)2] are summarized in Scheme 43. Again AT-methyl-lV-nitrosotoluene-p-sulfonamide is the most convenient source of the nitrosyl ligand.202,1323... 

For the synthesis of 18 trichlorophosphine is alkylated to dichloro[bis(tri-methylsilyl)methyl]phosphine by means of the appropriate Grignard reagent. The subsequent elimination of HC1 can be achieved with, for example, diazabicyclo-octane (DABCO), however, the use of triethylamine is advantageous for the work-up.37,38... 

The solution is stirred overnight and allowed to warm up to room temperature. Remove all volatile components by evaporation under reduced pressure on the vacuum line using an efficient cooling trap. It is necessary to remove all traces of phosphorus(lll) chloride from the dichloro [bis(trimethylsilyl)methyl]phosphine before the next step. 

The cyclic phosphinate (96) has been isolated from the reaction of dichloro(methyl)phosphine with the ethoxycarbonylimine derived from hexafluoroacetone. Treatment of trichloro(organo)phosphonium-hexafluorophosphate salts with dichloro(diethylamino)phosphine results in the halophosphonium salts (97). Some reactions of dichloro(-)menthylphosphine have been reported.As usual, nucleophilic displacement reactions of halogenophosphines have received attention as routes to new systems of interest as ligands.Of particular interest in this connection is a report of the synthesis of the phosphorus-functionalised calixarenes (98). Only one chlorine atom of dichloro(phenyl)-phosphine is replaced on treatment with an excess of dicyclohexylamine, enabling the stepwise synthesis of the chiral aminophosphines (99), described as air-stable solids. 

Remarkable diastereoselectivity has been achieved in the synthesis of dinucleoside methylphosphonates from the reactions of dichloro-(methyl)phosphine with suitably protected nucleosides at low temperatures.Various phosphapolyboranes have been obtained from the reactions of dichloro(methyl)phosphine with polyborane... 

Preparation.— The importance of simple chlorophosphines to organophosphorus chemistry is reflected in the development of new routes to (1) and (2). For those requiring fairly large quantities of chlorodimethylphosphine (1), a one-pot preparation from red phosphorus is now available, The procedure involves a furnace, packed with red phosphorus, copper powder, glass wool, and active carbon, into which chloromethane is passed. Dichloro(methyl)phosphine (3) is also formed, and conditions can be adjusted to give (3) as the predominant product. 

Preparation.—short review has appeared of the chemistry of dichloro-(methyl)phosphine (17) and chlorodimethylphosphine (18), and the established, but not wholly satisfactory, preparations have been discussed. In a more recent paper, several minor, but significant, improvements are suggested in two of the better known routes to (17) and (18). ... 

The 2-pentenenitrile, 2-methyl-3-butenenitrile, and methylglutaronitrile in Figure 1.1 are by-products of this reaction sequence. duPont is still studying the phosphines used as ligands for the nickel in an effort to find one bulky enough to favor terminal addition only.214 Reduction of the various nitriles leads to the amines in Figure 1.1, including the cyclic ones. The 2,3-dichloro-l,3-buta-diene is probably a by-product in the synthesis of 2-chloro-1,3-butadiene used to make Neoprene rubber. duPont also polymerizes acrylonitrile to prepare poly (acrylonitrile) fiber (Orion). Acetonitrile is obtained as a by-product of the ammoxidation of propylene to produce acrylonitrile (reaction 1.20). 

Since the double-bond isomerization was at first unrecognized and later recognized only in the hydrolysis products, the position of the double bond in most of the compounds described in the literature must be regarded as uncertain. The only proved facts seem to be that with isoprene dichloro(phenyl)-phosphine gives the 2-phospholene derivative, that dichloro(methyl)phosphine and dibromo(phenyl)phosphine give the 3-phospholene, whereas also with 2,3-dimethylbutadiene dichloro(phenyl)phosphine gives the non-isomerized product of type (1).38,39... 

Bicyclo[2.2.1]heptadiene behaves analogously to the conjugated dienes, affording with dichloro(methyl)phosphine at room temperature the tetracyclic compound (4).49... 

A rational process involving a copper catalyst in a flow tube at 360° has been worked out for the preparation of dibromo(methyl)phosphine and (bromo)dimethylphosphine and the corresponding chloro compounds ethyl halides give only poor yields by this technique, and butyl bromide does not react at all.177,178 Dichloro(trichloromethyl)phosphine has also been obtained on y-irradiation of white phosphorus in carbon tetrachloride, yields being up to 41% at 130°.179... 

Addition of trichlorosilane or dichloro(methyl)silane to olefins can also be effected in the presence of tertiary amines such as pyridine, N,N,N, N -tetra-methylethylenediamine, and tributylamine or in the presence of tertiary phosphines such as triphenylphosphine.365 Amides such as dimethylformamide, V,W-diethylbenzamide, and V,7V-dibutylacetamide exert a similar catalytic effect.366 The mechanism of these base-catalyzed hydrosilations is probably also ionic. 

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