Antimony alkyls

Due to the thermal instabilities of SbH3, MeSbH2, and Me2SbH, trimethylantimony (Me3Sb) is the conventional precursor used to grow antimony-containing materials.154,155 In order to reduce the pyrolysis temperature a number of other antimony alkyl compounds have also been investigated and are listed in Table 9. 

Other catalysts which may be used in the Friedel - Crafts alkylation reaction include ferric chloride, antimony pentachloride, zirconium tetrachloride, boron trifluoride, zinc chloride and hydrogen fluoride but these are generally not so effective in academic laboratories. The alkylating agents include alkyl halides, alcohols and olefines. 

My work on long-lived (persistent) carbocations dates back to the late 1950s at Dow and resulted in the first direct observation of alkyl cations. Subsequently, a wide spectrum of carbocations as long-lived species was studied using antimony pentafluoride as an extremely strong Lewis acid and later using other highly acidic (superacidic) systems. 

In eontrast, dialkylhalonium salts sueh as dimethylbromonium and dimethyliodonium fluoroantimonate, whieh we prepared from excess alkyl halides with antimony pentafluoride or fluoroantimonie acid and isolated as stable salts (the less-stable chloronium salts were obtained only in solution), are very effective alkylating agents for heteroatom eompounds (Nu = R2O, R2S, R3N, R3P, ete.) and for C-alkylation (arenes, alkenes). 

Particular drawbacks of using alkylsiHcon and alkyltin haHdes with AlCl for the cationic polymerization of terpenes are low yields and the fact that they require rigorously dried feeds (<50 ppm H2O) to be effective. Increased water content results in lower yields and lower softening points (85). Catalyst systems comprised of AlCl with antimony haHdes in the presence or absence of a lower alkyl, alkenyl, or aralkyl haHde are particularly effective in systems containing up to 300 ppm H2O (89,90). Use of 2—12 wt % of a system composed of 2—3 parts AlCl, 0.7—0.9 parts SbCl, and 0—0.2 parts of an organic... 

There are two main subclasses ofhydroperoxid.es organic (alkyl) hydroperoxides, ie, ROOH, and organomineral hydroperoxides, ie, Q(OOH), where Q is sihcon (43), germanium, tin, or antimony. The alkyl group in ROOH can be primary, secondary, or tertiary. Except for ethylbenzene hydroperoxide, only alkyl hydroperoxides are commercially important. 

Many organic peroxides of metals have been hydrolyzed to alkyl hydroperoxides. The alkylperoxy derivatives of aluminum, antimony, arsenic, boron, cadmium, germanium, lead, magnesium, phosphoms, silicon, tin, and zinc yield alkyl hydroperoxides upon hydrolysis (10,33,60,61). 

This reaction gives fair-to-good yields of monoorganotin tribromides and trichlorides when quaternary ammonium or phosphonium catalysts are used (149). Better yields are obtained with organic bromides and staimous bromide than with the chlorides. This reaction is also catalyzed by tri alkyl antimony compounds at 100—160°C, bromides are more reactive than chlorides in this preparation (150,151). a,C0-Dihaloalkanes also react in good yield giving CO-haloalkyltin trihaHdes when catalyzed by organoantimony compounds (152). 

Halostibines, Dihalostibines, and Related Compounds. Alkyl dichi oro- and alkyldibromostibines are readily prepared by the alkylation of the corresponding antimony trihaUde with an organolead reagent (67,104) ... 

The alkylation can also be accompHshed using tetraalkyltin compounds. Alkyldiiodostibines are formed in about 20% yield via the interaction of alkylmagnesium iodides and antimony trichloride (67). Dialkylchlorostibines are obtained in good yields by the cleavage of tetraalkyldistibines using sulfuryl chloride (91) ... 

C H Sb, however, both possess trigonal-bipyramidal geometry. In addition to compounds of the type R Sb, mixed compounds of the type R R Sb or R3R 25b, where R and R may be alkyl, alkenyl, alkynyl, or aryl groups, are known. Thus triethyl dimethyl antimony [67576-92-5], CgH2 Sb, has been prepared (197) ... 

Alkyl silyl ethers are cleaved by a variety of reagents Whether the silicon-oxygen or the carbon-oxygen bond is cleaved depends on the nature of the reagent used Treatment of alkoxysilanes with electrophilic reagents like antimony tri-fluonde, 40% hydrofluonc acid, or a boron tnfluonde-ether complex results in the cleavage of the silicon-oxygen bond to form mono-, di-, and tnfluorosiloxanes or silanes [19, 20, 21) (equations 18-20)... 

A one-pot synthesis of alkyl perfluoroalkyl ketones has been developed. Phosphoranes, generated in situ, are acylated with a perfluoroacyl anhydnde, and the resultmg phosphonium salts are hydrolyzed with alkali [4S (equation 48) Hydrolysis of a carbon-sulfur bond in 2-chloro-2,4,4-trifluoro-1,3-dithietane-S-trioxide, which can be obtained from 2,2,4,4-tetrachloro-l,3-dithietane by fluor-mation with antimony trifluoride followed by selective oxidations, opens the nng to produce 2-chloro-1,1,2-trifluorodimethyl sulfone [49] (equation 49)... 

The main product of the alkylation of pentafluorobenzene with 1,1,2-trichloro-tnfluoroethane in the presence of antimony pentafluoride is (i chlorononafluo roethyl benzene [159] (equation 1J6)... 

Polyfluoropropenes alkylate fluormated ethylenes in the presence of antimony pentafluoride This condensation proceeds by initial formation of an allyl cation [175] (equation 150)... 

The reactions of some fluorinated ethers may result in the elimination of alkyl fluorides In the case of 2-methoxyperfluoro-2-butene, treatment with antimony pentafluoride gives perfluoro-3-buten-2-one and methylfluoride [107] By reacting 2-chloro-l,l,2-trifluorodiethyl ether with boron trifluoride etherate or with aluminum chloride, chlorofluoroacetyl fluoride can be obtained with the elimination of ethyl fluonde [108] (equations 76 and 77)... 

Fluonnation and skeletal transformation of fluorinated cycloalkanes occurs in the reaction with antimony pentafluoride at high temperature [777] In the case of perfluorinated benzocyclobutanes, an unexpected alicyclic ring cleavage has been observed Perfluorinated alkyl benzocyclobutanes, when treated with antimony pentafluoride, ean be converted to perfluorinated styrenes and then transformed to perfluorinated indans [77S, 779]... 

A mixture of monolauryl phosphate sodium salt and triethylamine in H20 was treated with glycidol at 80°C for 8 h to give 98% lauryl 2,3-dihydro-xypropyl phosphate sodium salt [304]. Dyeing aids for polyester fibers exist of triethanolamine salts of ethoxylated phenol-styrene adduct phosphate esters [294], Fatty ethanolamide phosphate surfactant are obtained from the reaction of fatty alcohols and fatty ethanolamides with phosphorus pentoxide and neutralization of the product [295]. A double bond in the alkyl group of phosphoric acid esters alter the properties of the molecule. Diethylethanolamine salt of oleyl phosphate is effectively used as a dispersant for antimony oxide in a mixture of xylene-type solvent and water. The composition is useful as an additive for preventing functional deterioration of fluid catalytic cracking catalysts for heavy petroleum fractions. When it was allowed to stand at room temperature for 1 month it shows almost no precipitation [241]. 

Studies of metal alkyls and aryls deal largely with arsenic, germanium and antimony, although some work has also been done on tellurium, mercury, thallium, bismuth and lead. The major contributions can be neatly divided into four periods early studies by Maddock, Sutin and H 1155).56).57) studies by the Polish >- >- and the Strasbourg >- 2).79) groups, work by Riedel and and most recently a series... 

Antimony pentachloride is a reactive Lewis acid that can be used for Friedel-Crafts reactions and some other Lewis-acid-catalyzed reactions. The HF-SbF5 system is known as magic acid, and carbocations are stabilized in this medium.353 By using the HF-SbF5 system, alkylation of acetophenone (a relatively unreactive aromatic compound) has been achieved (Scheme 87). 

The colorless tris(0-ethyl dithiocarbonato)arsenic(III) and yellow antimony(III) complexes have been prepared from the corresponding metal trichlorides using this procedure. Tris-(alkyl trithiocarbonato)-, tris(0,0 -dialkyldithiophosphato)-, and other tris(0-alkyl dithiocarbonato)indium(III) complexes can undoubtedly be prepared from the potassium or sodium derivatives of the ligands using this procedure. 

Alkyl migration has not been found in protonated furan derivatives. Neither 2,5-dimethylfuran nor 2,3,5-trimethylfuran undergo any change other than protonation in fluorosulfonic acid containing antimony pentafluoride. On the other hand, migrations will occur during cyclization until the product corresponds to a protonated furan (Scheme 29).19... 

Unlike the reaction of alkyl aryl ketoximes with tetrasulfur tetranitride <1996CHEC-II(4)355>, the treatment of alkyl methyl ketoximes 189 with tetrasulfur tetranitride antimony pentachloride complex in either benzene or toluene at 50-80°C gave low yields (3-37%) of 3-alkyl-4-methyl-l,2,5-thiadiazoles 190 (Equation 39) <1999H(50)147>. Compounds 190 were volatile and the low yields are in part attributed to their loss as the solvent was removed in vacuo. Suprisingly, only single regioisomers were obtained. 3-Heptanone oxime 191 did, however, give a mixture of two isomers 192 and 193 (Equation 40). 

The reason for such a behaviour of arsenic acid is that arsenic is a member of the group 5A elements in the periodic table. Phosphorus and antimony are also group 5 elements and are known to be chemically similar to arsenic. On this basis [8,9], the antimonic acids were found to be poor cassiterite collectors. The alkyl phosphonic acids were not selective collectors. The ethylphenylene phosphonic acid was found to produce similar or better results compared to /7-tolyl arsonic acid. The structural formula for phosphonic acid (Figure 21.5) is similar to that of /7-tolyl arsonic acid but arsenic was replaced with phosphoms. The styrene phosphonic acid radicals are C6H5-CH-CH and p-ethylphenylene CH3-CH2-C6H4. 

The pyrolysis was studied in a toluene carrier flow system over the temperature range 475-603 °C. Most runs were carried out at 16-17 torr with a contact time of 1-2 sec. He ratio % decomposition (gas anaiysis)/% decomposition (antimony recovered from reaction zone) varied from 0.91 at 475 °C to 0.75 at 603 °C. Apparent first-order rate coefficients based on both metal and gas analysis increased with decreasing alkyl concentration (log k/log[Sb(CH3)3] = 0.28 at all temperatures). Corrected for this effect, fc24t0rr/ 6torr = 1-3, indicating a small uni-molecular pressure effect. 

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