Alkylation of polystyrene

Thioethers have also been prepared on cross-linked polystyrene by radical addition of thiols to support-bound alkenes and by reaction of support-bound carbon radicals (generated by addition of carbon radicals to resin-bound acrylates) with esters of l-hydroxy-l,2-dihydro-2-pyridinethione ( Barton esters Entry 6, Table 8.5). Additional methods include the reaction of metallated supports with symmetric disulfides (Entries 7-9, Table 8.5) and the alkylation of polystyrene-bound, a-lithiated thioani-sole [65],... 

Sulfoxides and sulfones can be prepared on cross-linked polystyrene by oxidation of thioethers. The most commonly used reagent for this purpose is MCPBA in DCM [8,12,32,57,80-82] or dioxane [50,83] (Table 8.6), but other oxidants such as H2O2 in acetic acid [34], oxone (Entry 7, Table 8.6), or oxaziridines [84] have also been used. PEG-bound thioethers have been converted into sulfones by oxidation with MCPBA in DCM [52,54] or with Os04/NMO [85], The oxidation of thioethers to sulfoxides requires careful control of the reaction conditions to prevent the formation of sulfones. Sulfones have also been prepared by S-alkylation of polystyrene-bound sulfi-nates (Entries 8 and 9, Table 8.6), by a-alkylation of sulfones (BuLi, THF, alkyl halide [86]), and by addition of sulfinyl radicals to resin-bound alkenes or alkynes (Entry 11, Table 8.6). 

Isothioureas can be prepared on insoluble supports by S-alkylation or S-arylation of thioureas (Entry 7, Table 14.6). Further methods for the preparation of isothioureas on insoluble supports include the N-alkylation of polystyrene-bound, A/,/V -di(alkoxy-carbonyl)isothioureas with aliphatic alcohols by Mitsunobu reaction (Entry 7, Table 14.6) and the addition of thiols to resin-bound carbodiimides [7]. Resin-bound dithio-carbamates, which can easily be prepared from Merrifield resin, carbon disulfide, and amines [76], react with phosgene to yield chlorothioformamidines, which can be converted into isothioureas by treatment with amines (Entry 8, Table 14.6). The conversion of support-bound a-amino acids into thioureas can be accompanied by the release of thiohydantoins into solution (see Section 15.9). The rate of this cyclization depends, however, on the type of linker used and on the nucleophilicity of the intermediate thiourea. 

Support-bound indoles can be modified in several ways. N-Alkylation of polystyrene-bound indoles has been achieved by treatment with reactive alkylating agents (Mel, BnBr, BrCH2C02R) in conjunction with NaH or KOrBu as a base in DMF at room temperature (Entries 1 and 2, Table 15.7). The aminomethylation of indole at C-3 proceeds smoothly on cross-linked polystyrene. The resulting (aminomethyl)in-doles are thermally unstable and undergo substitution reactions with various carbon nucleophiles (e.g. cyanide or nitroacetates) at higher temperatures (Entry 4, Table... 

Peptides can be chemically transformed on insoluble supports to yield other types of oligomer. These transformations include N-alkylation and reduction. N-Alkylation of polystyrene-bound peptides enables the preparation of peptide mimetics with improved enzymatic stability [270], Polyamines have been prepared by exhaustive reduction of peptides with borane [271] (see Section 10.1.6). N-Alkylated polyamines can be prepared on solid phase by reduction of the corresponding N-alkylated peptides [272]. 

Chloromethyl polystyrene was introduced by MerrifielcP into peptide synthesis. It was used, however, first as an intermediate for the synthesis of anion exchange resins. The synthesis of chloromethylated polystyrenes is best achieved by Friedel-Crafts alkylation of polystyrene with methoxymethylene chloride in the presence of a Lewis acid catalyst such as SnCl - s as shown in Scheme I.5.4.2. 

Friedel-Crafts alkylation of polystyrene with 3-nitro-4-hydroxybenzyl chloride... 

Benzene is alkylated with ethylene to produce ethylbenzene, which is then dehydrogenated to styrene, the most important chemical iatermediate derived from benzene. Styrene is a raw material for the production of polystyrene and styrene copolymers such as ABS and SAN. Ethylbenzene accounted for nearly 52% of benzene consumption ia 1988. 

The polymer-bound catalysts A-C. (Table 31) are prepared by reaction of the corresponding amino alcohols with partially chloromethylated 1 -2% cross-linked polystyrene. In the case of A, the enantioselectivity of the addition of dialkylzincs to aldehydes is higher than with the corresponding monomeric ephedrine derivatives (vide supra). Interesting insights into the mechanism of the alkylation of aldehydes by dialkylzinc reagents can be obtained from the experi-... 

An amide anion will prefer substitution if its basicity is sufficiently lowered by resonance, and can be useful where the neutral nitrogen is unreactive or otherwise unsuitable. Quaterniza-tion cannot be prevented in the alkylation of even free neutral imidazole, but an imidazolide anion will match with only one of the electrophilic sites terminating dimethylene spacer on polystyrene. 

Brown EG, Nuss JM. Alkylation of Rink s amide linker on polystyrene resin a reductive amination approach to modified amine-linkers for the solid phase synthesis of /Y-substiuited amide derivatives. Tetrahedron Lett 1997 38 8457-8460. 

The large demand for benzene is due to its use as a starting material in the production of polystyrene, acrylonitrile styrene butadiene rubber, nylons, polycarbonates and linear alkyl benzene detergent. All of these final chemical products that are suitable to form into consumer goods have multiple chemical transformations in various industrial processes to obtain them from benzene. Because the production of benzene does not involve a liquid adsorptive process on a zeolite, these processes are not described here but can be found in other sources. However, it is important to note that benzene is typically a large byproduct from an aromatics... 

Various transition metal catalysts, including those based on Rh, Pt, Pd, Co, and Ti, have been bound to polymer supports—mainly through the phosphenation reaction described by Eq. 9-65 for polystyrene but also including other polymers, such as silica and cellulose, and also through other reactions (e.g., alkylation of titanocene by chloromethylated polystyrene). Transition-metal polymer catalysts have been studied in hydrogenation, hydroformylation, and hydrosilation reactions [Chauvin et al., 1977 Mathur et al., 1980]. 

Alkylation of benzene and ethylene produces ethyl benzene, which is dehydrogenated to styrene for polystyrene. 

The ready alkylation of heterocyclic thiols lends this link to applications in solid-phase synthesis. Although much more work has been done in other heterocyclic systems, a prototype solid-phase synthesis has been described in which the pteridine is built from a 2- or 4-alkylthiopyrimidine attached to a cross-linked polystyrene support <20030BG1909, 2003TL1267> Oxidative cleavage was preferred using DMDO to avoid unwanted by-products... 

The percent ring substitution (% RS) of the polymer with active sites affects catalytic activity. Polystyrenes with < 25 % RS with lipophilic quarternary onium ions are swollen in triphase mixtures almost entirely by the organic phase. Water reduces the activity of anions by hydrogen bonding. In most triphase nucleophilic displacement reactions onium ion catalysts with <25% RS are highly active, and those with >40% RS, such as most commercial ion exchange resins, are much less active. However, low % RS is not critical for the reactions of hydroxide ion with active methylene compounds, as commericial ion exchange resins work well in alkylation of active nitriles. 

Not all nucleophilic displacement reactions require lightly substituted onium ion catalysts for activity. For alkylation of 2-naphthoxide ion with benzyl bromide (Eq. (6)) 40-100% RS, 2% CL polystyrene catalysts 15 and 16 work well54). A 51 % RS catalyst 11 gave good yields in reactions of anionic oxygen and sulfur nucleophiles with alkyl halides 91). 

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