Chlorostyrenes

Write a structural formula for each of the following compounds (a) o Ethylanisole (b) m Chlorostyrene (c) p Nitroaniline... 

Some polymers from styrene derivatives seem to meet specific market demands and to have the potential to become commercially significant materials. For example, monomeric chlorostyrene is useful in glass-reinforced polyester recipes because it polymerizes several times as fast as styrene (61). Poly(sodium styrenesulfonate) [9003-59-2] a versatile water-soluble polymer, is used in water-poUution control and as a general flocculant (see Water, INDUSTRIAL WATER TREATMENT FLOCCULATING AGENTs) (63,64). Poly(vinylhenzyl ammonium chloride) [70304-37-9] h.a.s been useful as an electroconductive resin (see Electrically conductive polya rs) (65). 

Table 11. Loss of Isopentane from Foaming-in-Place Chlorostyrene Beads in Open Storage, wt %...

Chloropropionitrile, 41 o-Chlorostyrene, 41 Chlorosulphonic acid, 41 Chlorothalonil, 41 o-Chlorotoluene, 41 Chloroxuron, 41... 

During the early 1960s, various vinyl monomers (e.g. styrene, /-butyl styrene, chlorostyrene, vinyl chloride, vinyl acetate, acrylonitrile, acrylates, especially methyl methacrylate) were used to treat wood, and po-... 

Phenylsuccinic acid has been prepared by the action of potassium cyanide and alcohol upon a-chlorostyrene 1 by the reaction... 

Enantioconvergent hydrolysis of para-chlorostyrene oxide (Figure 6.67) using a one-pot sequential bienzymatic strategy provided the corresponding (R)-diol in high yield (96% ee, yield = 93%) [186]. The second enzyme was added after about 50% conversion because the first one was sensitive to inhibition by the (R)-diol. 

Figure 6.68 Enantioconvergent hydrolysis of m-chlorostyrene oxide using a single biocatalyst.

The enantioconvergent biohydrolysis of m-chlorostyrene oxide (Figure 6.68) in the presence of a recombinant S. tuberosum EH afforded the corresponding (JJ)-diol in a nearly quantitative yield [187]. The (S)-epoxide was attacked at the benzylic (more substituted) carbon whereas the (R)-epoxide was attacked at the terminal (less substituted) carbon. 

Although the above system does not work for the IH of, e.g., 2-isopropenylaniline, a somewhat unexpected extension has been pointed out [159]. Reaction of anilines with 2-chlorostyrene in the presence of t-BuOK (1.5 equiv.) affords N-arylindolines in a one-pot reaction (53-58% yield) (Eq. 4.35) [159]. 

The reaction mechanism is believed to involve a domino hydroamination-in-tramolecular arynic condensation. Indeed, the same results are obtained from either 2- and 3-chlorostyrenes [159]. 

In the last example, where p-chlorostyrene-12% DVB resin was sequentially polysulfonated and chlorinated and base treated to give resin E, characterized by high exchange capacity, stability and low bleed. We hypothesize that blocking the para position to sulfonation in the polymer leads to enhanced stability. 

This procedure has been used in the preparation of other nitrostyrenes in the following yields o-nitrostyrene (40%),2 / -nitrostyrene (41%),2 and 3-nitro-4-hydroxystyrene (60%).2 A better procedure for more volatile styrenes involves simultaneous decarboxylation and codistillation with quinoline from the reaction flask. This method has been used to prepare the following styrenes o-chlorostyrene (50%),3 4 m-chlorostyrene (65%),4 -chlorostyrene (51%),4 m-bromostyrene (47%),4 o-methoxystyrene (40%),4 -methoxystyrene (76%),4 m-cyano-styrene (51%),3 and j -formylstyrene (52%).9... 

Figure 5 is an ORTEP computer plot of the first 50 backbone carbons in a typical chain. Only the fluorine atoms of the sidechains are shown. The various hard sphere exclusions conspire dramatically to keep the fluorines well separated and the chain highly extended even without introducing any external perturbations. The characteristic ratio from the computer calculations is about 11.6 from data for poly(p-chlorostyrene), CR = I l.l, poly(p-bromostyrene), CR = 12.3, and poly(styrene), CR = 10.3 (all in toluene at 30°C), we expect the experimental value for the fluoro-polymer to be in the range of 10 to 12. 

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