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Catalyst stannic chloride

Recently Russian workers claimed that the presence of cocatalysts was not a necessary requirement for cationic polymerization of styrene and isoprene with stannic chloride catalyst provided the temperature and/or the dielectric constant of the medium was high enough (53—55). Similar ideas have also been expressed by Japanese investigators (56). [Pg.514]

This situation is somewhat reminiscent to that encountered in enzyme chemistry where the active biocatalyst is a combination of an apo-enzyme and a coenzyme, the components alone being complete inactive. Substrate specificity, which is so characteristic for enzymatic processes is also high in carbonium ion chemistry. For example styrene is polymerized by titanium tetrachloride—water, but not by titanium tetrachloride— alkyl chlorides 37) however, with stannic chloride catalyst alkyl chlorides are effective cocatalysts 88). In the same vein Plesch (93) showed that water is a better cocatalyst than acetic or chloroacetic acid in conjunction with titanium tetrachloride in isobutene polymerization, but Russel (94) found just the opposite with stannic chloride. [Pg.518]

Chlorinization of hen7ene with stannic chloride catalyst Ferric-chloride-catalyzed hydrochlorination of I-hexadecene Hydrochlorination of octyl and dodecyl alcohols NH, in H2S04... [Pg.34]

The above condensation takes place in dichloroethane, with stannic chloride catalyst at 50 The maximum reaction rate varies with both the initial concentration of l,4-dimethyl-2,5-dichloro-methylbenzene, shown above, and the initial concentration of SnCU. Crosslinked polystyrene particles or beads also form by Friedel-Craft suspension crosslinking of polystyrene with l,4-dichloromethyl-2,5 dimethylbenzene The polymer is dissolved in nitrobenzene and a two-phase reaction occurs in 70% by weight of an aqueous suspension of ZnCh. Poly(vinyl alcohol) can be used as the suspending agent. [Pg.429]

Stannic chloride is a very effective catalyst for this Friedel-Craft reaction [186]. lodomethylation can also be carried out in the same manner with similar results [179]. When the reactions are carried out on cross-linked styrene copolymers with chlorodimethyl ether and stannic chloride catalyst, they are accompanied by strong morphological changes [187]. If these reactions are carried out with low levels of chloromethylating agents or catalysts, they occur more or less homogeneously. Larger levels... [Pg.598]

The stannic chloride catalyst effective in the model compound studies was ineffective with the polymers. The catalyst was complexed and deactivated by the tetrabutyl titanate catalyst used in the resin preparation. [Pg.582]

Lewis-acid catalysis of Diels-Alder reactions is now commonplace but the use of iron(O) to catalyse the addition of butadiene to an ynamine is worthy of note [e.g. (132) -> (133)]. Also somewhat unusual is the asymmetric induction observed when chiral dichloroaluminium alkoxides such as (134) are used as catalysts. Finally a cautionary note in one case the presence of the stannic chloride catalyst brings about the rearrangement of the initial adduct (135) into (136). °°... [Pg.262]

Alkyltin Intermedia.tes, For the most part, organotin stabilizers are produced commercially from the respective alkyl tin chloride intermediates. There are several processes used to manufacture these intermediates. The desired ratio of monoalkyl tin trichloride to dialkyltin dichloride is generally achieved by a redistribution reaction involving a second-step reaction with stannic chloride (tin(IV) chloride). By far, the most easily synthesized alkyltin chloride intermediates are the methyltin chlorides because methyl chloride reacts directiy with tin metal in the presence of a catalyst to form dimethyl tin dichloride cleanly in high yields (21). Coaddition of stannic chloride to the reactor leads directiy to almost any desired mixture of mono- and dimethyl tin chloride intermediates ... [Pg.547]

A telomerization reaction of isoprene can be carried out by treatment with 2-chloro-3-pentene, prepared by the addition of dry HCl to 1,3-pentadiene (67). An equimolar amount of isoprene in dichi oromethane reacts with the 2-chloro-3-pentene at 10°C with stannic chloride as catalyst. l-Chloro-3,5-dimethyl-2,6-octadiene is obtained in 80% yield by 1,4-addition. [Pg.465]

Carbonyl Compounds. Cychc ketals and acetals (dioxolanes) are produced from reaction of propylene oxide with ketones and aldehydes, respectively. Suitable catalysts iaclude stannic chloride, quaternary ammonium salts, glycol sulphites, and molybdenum acetyl acetonate or naphthenate (89—91). Lactones come from Ph4Sbl-cataly2ed reaction with ketenes (92). [Pg.135]

Stannic chloride is also used widely as a catalyst in Eriedel-Crafts acylation, alkylation and cycHzation reactions, esterifications, halogenations, and curing and other polymerization reactions. Minor uses are as a stabilizer for colors in soap (19), as a mordant in the dyeing of silks, in the manufacture of blueprint and other sensitized paper, and as an antistatic agent for synthetic fibers (see Dyes, application and evaluation Antistatic agents). [Pg.65]

The reaction of higher alkyl chlorides with tin metal at 235°C is not practical because of the thermal decomposition which occurs before the products can be removed from the reaction zone. The reaction temperature necessary for the formation of dimethyl tin dichloride can be lowered considerably by the use of certain catalysts. Quaternary ammonium and phosphonium iodides allow the reaction to proceed in good yield at 150—160°C (109). An improvement in the process involves the use of amine—stannic chloride complexes or mixtures of stannic chloride and a quaternary ammonium or phosphonium compound (110). Use of these catalysts is claimed to yield dimethyl tin dichloride containing less than 0.1 wt % trimethyl tin chloride. Catalyzed direct reactions under pressure are used commercially to manufacture dimethyl tin dichloride. [Pg.72]

Hydrogen haHde addition to vinyl chloride in general yields the 1,1-adduct (50—52). The reactions of HCl and hydrogen iodide [10034-85-2], HI, with vinyl chloride proceed by an ionic mechanism, while the addition of hydrogen bromide [10035-10-6], HBr, involves a chain reaction in which a bromine atom [10097-32-2] is the chain carrier (52). In the absence of a transition-metal catalyst or antioxidants, HBr forms the 1,2-adduct with vinyl chloride (52). HF reacts with vinyl chloride in the presence of stannic chloride [7646-78-8], SnCl, to form 1,1-difluoroethane [75-37-6] (53). [Pg.414]

A typical cationic polymeriza tion is conducted with highly purified monomer free of moisture and residual alcohol, both of which act as inhibitors, in a suitably dry unreactive solvent such as toluene with a Eriedel-Crafts catalyst, eg, boron triduoride, aluminum trichloride, and stannic chloride. Usually low temperatures (—40 to —70°C) are favored in order to prevent chain-transfer or sidereactions. [Pg.514]

The epoxidation is generally conducted in two steps (/) the polyol is added to epichlorohydrin in the presence of a Lewis acid catalyst (stannic chloride, boron triduoride) to produce the chlorohydrin intermediate, and (2) the intermediate is dehydrohalogenated with sodium hydroxide to yield the aliphatic glycidyl ether. A prominent side-reaction is the conversion of aliphatic hydroxyl groups (formed by the initial reaction) into chloromethyl groups by epichlorohydrin. The aliphatic glycidyl ether resins are used as flexibilizers for aromatic resins and as reactive diluents to reduce viscosities in resin systems. [Pg.366]

The reaction was carried out in excess of the acid chloride with cooling and gave yields of 55-80%. Of the catalysts tested, stannic chloride gave the best results. ... [Pg.312]

Acctothicnone has been prepared by treating thiophene with acetyl chloride in the presence of aluminum chloride1 or stannic chloride,2 and by treating 2-chloromercurithiophene with acetyl chloride.3 The present method is essentially that of Stadnikoff and Goldfarb.2 Stannic chloride is superior to aluminum chloride as a catalyst for this reaction as the latter induces polymerization of the thiophene. [Pg.2]

Catalysis by stannic chloride in the chlorination of alkylbenzenes in the absence of solvent has been shown to be first-order in catalyst so that the kinetic equation... [Pg.110]

Since there is inherent in reactions which give low selectivities, the possibility that non-competitive conditions are responsible, Olah and Overchuck359 have measured directly the rates of benzylation, isopropylation, and fer/.-butylation of benzene and toluene with aluminium and stannic chlorides in nitromethane at 25 °C. Apparent second-order rate coefficients were obtained (assuming that the concentration of catalyst remains constant), but it must be admitted that the kinetic plots showed considerable departure from second-order behaviour. The observed rate coefficients and kreh values determined by the competition method are given in Table 88, which seems to clearly indicate that the competitive ex-... [Pg.152]

For the reaction of stannic chloride with toluene (this aromatic being used here because of the lower effectiveness of the catalyst), different kinetics were obtained the rate expression being... [Pg.170]

Satchell476 also measured the first-order rate coefficients for dedeuteration of [4-3H]-anisole by acetic acid or acetic acid-hydrochloric acid media containing zinc and stannic chlorides (Table 128). The rates here paralleled the indicator ratio of 4-nitrodiphenylamine and 4-chloro-2-nitroaniline, so that the implication is that a linear relationship exists between log k and the unknown H0 values. The results also show the rate-enhancing effect of these Friedel-Crafts catalysts, presumably through additional polarisation of the catalysing acid, for in the absence of them, exchange between acetic acid and anisole would be very slow. Other studies relating to the effect of these catalysts are reported below (p. 238). [Pg.207]

Shatenshtein et a/.S19 have also measured the effect of boron trifluoride as a catalyst for hydrogen exchange in acetic acid and have compared it with stannic chloride (Table 157). The logarithm of the rate coefficient was linearly related to... [Pg.241]

Two pieces of direct evidence support the manifestly plausible view that these polymerizations are propagated through the action of car-bonium ion centers. Eley and Richards have shown that triphenyl-methyl chloride is a catalyst for the polymerization of vinyl ethers in m-cresol, in which the catalyst ionizes to yield the triphenylcarbonium ion (C6H5)3C+. Secondly, A. G. Evans and Hamann showed that l,l -diphenylethylene develops an absorption band at 4340 A in the presence of boron trifluoride (and adventitious moisture) or of stannic chloride and hydrogen chloride. This band is characteristic of both the triphenylcarbonium ion and the diphenylmethylcarbonium ion. While similar observations on polymerizable monomers are precluded by intervention of polymerization before a sufficient concentration may be reached, similar ions should certainly be expected to form under the same conditions in styrene, and in certain other monomers also. In analogy with free radical polymerizations, the essential chain-propagating step may therefore be assumed to consist in the addition of monomer to a carbonium ion... [Pg.219]

Homogeneous catalysts are also often used in cationic and anionic polymerization processes. Lewis acid catalysts, such as boron trifluoride and stannic chloride, accept protons from co-... [Pg.86]

The zinc chloride-mediated tandem Mukaiyama aldol-lactonization reaction of aldehydes 21 and thiopyridylketene acetals 22 gave mainly the trans isomer 23. However, if the catalyst is stannic chloride and the reaction is carried out at -78 °C, then the cyclization is highly diastereoselective and yields the cis-isomer 24 <990L1197>. [Pg.73]


See other pages where Catalyst stannic chloride is mentioned: [Pg.214]    [Pg.106]    [Pg.388]    [Pg.426]    [Pg.4941]    [Pg.214]    [Pg.106]    [Pg.388]    [Pg.426]    [Pg.4941]    [Pg.423]    [Pg.78]    [Pg.209]    [Pg.37]    [Pg.284]    [Pg.285]    [Pg.293]    [Pg.151]    [Pg.151]    [Pg.170]    [Pg.184]    [Pg.238]    [Pg.241]    [Pg.45]    [Pg.226]    [Pg.338]    [Pg.18]   
See also in sourсe #XX -- [ Pg.23 , Pg.50 , Pg.75 ]




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