Vinyl chloride iodide

Akzo Process. Akzo Zout Chemie has developed a route to vinyl chloride and soda ash from salt usiag an amine—solvent system catalyzed by a copper—iodide mixture (13). This procedure theoretically requires half the energy of the conventional Solvay processes. 

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). 

Ethyl tert-butvl ether. Ethylene dibromide, Ethyl ether, Ethvl sulfide. 2-Heptanone, Methanol, 2-Methyl-1,3-butadiene, 2-Methvl-2-butene. Methyl chloride, Methylene chloride, Methyl iodide. Methyl mercaptan, 2-Methylphenol, Methyl sulfide. Monuron. Nitromethane, 2-Nitropropane, A-Nitrosodimethylamine, 1-Octene, 2-Pentanone, Propylene oxide, Styrene, Thiram, Toluene, Vinyl chloride, o-Xylene, tn-Xylene Formaldehyde cyanohydrin, see Acetontrile,... 

The block copolymer of ethylene oxide and 3,3-dimethylthietane shows useful properties of complexing halogen and heavy metal salts (79MI51402). Thietanes can be polymerized with methylmagnesium iodide as well as with a variety of electrophiles such as methyl sulfate, trimethyloxonium tetrafluoroborate, triethylaluminum, boron trifluoride and phosphorus trifluoride (67IC1461, 67MI51400). Thietane (210) has been patented as a stabilizer for poly(vinyl chloride) (73USP3767615). 

The reaction can be carried out with aryl, heterocyclic and vinyl bromides and iodides and with some vinyl chlorides. It requires raised temperature but only normal CO pressure. If the primary or secondary amine is a strong enough base, it can be used in excess and the tertiary amine is not needed. The mechanism given in Scheme 42 was proposed for the reaction. It was not known whether the primary amine enters the reaction sequence at the point shown or at an earlier stage. 

Unlike other cross-coupling reactions, for which the scope has rapidly expanded in recent years, the range of electrophilic substrates that can be used successfully in the Sonogashira protocol is still rather limited. Vinylic substrates (iodides, bromides, chlorides, triflates, and more recently tosylates) typically yield the best results. For aromatic substrates, iodides and triflates are preferred over bromides, which in turn give far better yields than aryl chlorides. This latter aspect of the reaction is particularly frustrating when one considers the recent advances in the activation of aryl chloride substrates for reactivity in other cross-coupling protocols. ... 

The traditional scope for this reaction involved coupling alkenyl or aryl iodides or bromides with aryl, alkenyl, or alkynylzinc halides. However, recent modifications have allowed the scope to be extended to include additional electrophiles see Electrophile) such as aryl and vinyl chlorides, sulfonate esters, aryl ethers, and substrates with... 

Vinyl chlorides The anion can be alkylated by alkyl iodides (HMPT) or benzylic bromides in high yield. On pyrolysis at 160°, the products are converted into vinyl chlorides (cis- and trans-isomers). 

The reduction of vinyl halides most often is carried out via a metallation-protonation reaction. For instance, sodium in ethanol was employed by Barton et a/. for the reduction of a steroidal vinyl iodide (Scheme 44). A number of conditions for vinyl halide reduction to alkenes have been reported, representative examples of which include vinyl chloride and bromide reduction in acyclic systems with... 

The advantage of the small molar volume of VBr is shared by monomers like ethylene, vinyl chloride or vinyl iodide. But, the first two do not have a labile bond which could give radicals before main chain scission takes place (see Table 2). Vinyl iodide, on the other hand, has too labile a bond (C-I 221 kJ/mol, Egger and Cocks ), which probably would not even survive spinning operations. 

Organo Vinyl Tellurium (from Vinyl Tellurium Iodides) A solution of the vinyl tellurium iodide, prepared by addition of 0.25 g (1.0 mmol) iodine in benzene to the divinyl ditelluride (1.0 mmol) in 5 ml tetrahydrofuran at 0° under nitrogen, is added dropwise to a solution of the organo magnesium bromide in 10 m/ tetrahydrofuran at 0°. The mixture is stirred at 20° for 1 h, hydrolyzed with a saturated aqueous solution of ammonium chloride, extracted with diethyl ether, the extract dried with magnesium sulfate and evaporated. The product is chromatographed on silica gel with petroleum ether (30-60°)/ethyl acetate (9 1) as eluent. The following compounds were prepared in this manner (yields in parentheses are for the reactions with vinyl tellurium iodides) ... 

Similarity reaction of vinyl chloride with phenylacetylene in diethylamine using dichloro[bis(diphenylphosphino)ethane]palladium (II) and copper(I) iodide as a catalyst and a glass autoclave as a reaction vessel afforded 4-phenylbut-l-en-3-yne in 85% yield. 

Another reaction of considerable mechanistic interest reported by these workers 165) is the oxidative addition of methyl iodide, allyl chloride, or vinyl chloride to Pd(CO)(PPh3)3 to give the corresponding acyl... 

Problem 11.13 Hydrogen iodide adds to vinyl chloride more slowly than.to ethylene, and yields 1-chloro-l-iodoethane. (a) Draw the formula of the carbonium ion formed in the initial step of the addition to vinyl chloride, (b) Of addition to ethylene, (c) Judging from the relative rates of reaction, which w ould appear to be the more stable carbonium ion (d) Account for the difference in stability. 

ProMcai 25.1 Drawing all pertinent structures, account in detail for the fact that (a) nitration of chlorobenzene is slower than that of benzene, yet occurs predominantly ortho para (b) addition of hydrogen iodide to vinyl chloride is slower than to ethylene, yet yields predominantly 1-chloro-l-iodoethane. 

Vinyl chlorides react more sluggishly than bromides and iodides. Equations (w)-(x) show that chloride-lithium exchanges can work well, but with side reactions. The major alternative to Cl-Li exchange is metallation of the acidic a hydrogen (see 5.5.2.3.2), which occurs with vinyl fluorides if no other halogen is present. 

Vinyl halides. Vinyl halides, even the iodide, are not convertible to Grignard reagents by the usual procedure, but Normant found that vinyl chloride and vinyl bromide readily form vinylmagnesium halides in solution in tetrahydrofurane (THF) or in a diether of di- or triethylene glycol. See review. ... 

To get the diiodo telechelic structure, the authors used iodoform and methylene iodide as degenerative CTAs. SET involves the production of radical ions generating free radicals and anions or cations. Iodoform and methylene iodide can be activated both by degenerative transfer mediated by the growing PVC radicals and by SET. The reaction may be catalyzed by sodium dithionite (Na2S204). These catalyzed reactions allow the suppression of side reactions but also the scavenging of oxygen. The LRP of vinyl chloride resulted in diiodo PVC with Mn of 6000- 10 000 g mol 1 and with PDI of about 1.6. 

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