Sulfur-Containing Functional Groups

Nonsulfur Vulcanizing Agents. Many high performance specialty elastomers do not contain diene moieties in their molecular structure and therefore cannot be sulfur-cured. These elastomers require cross-linking agents capable of reacting with the specific functional group(s) contained by the specific elastomer. Some common nonsulfur curatives include peroxides, difunctional resins, and metal oxides. 

Recognize the common functional groups that contain sulfur or phosphorus. 

Functional groups can contain many elements, but the most common are oxygen and nitrogen. Sulfur and the halogens are less commonly encountered. Some functional groups are part of the molecular backbone. These include the multiple bonds between backbone carbon atoms of compounds such as ethene (ethylene), ethyne (acetylene), and benzene. 

FUNCTIONAL GROUPS THAT CONTAIN NITROGEN l.k FUNCTIONAL GROUPS THAT CONTAIN SULFUR... 

Sulfation and Sulfonation. a-Olefin reactions involving the introduction of sulfur-containing functional groups have commercial importance. As with many derivatives of olefins, several of these products have appHcations in the area of surfactants (qv) and detergents. Typical sulfur reagents utilized in these processes include sulfuric acid, oleum, chlorosulfonic acid, sulfur trioxide, and sodium bisulfite. 

One class of aromatic polyethers consists of polymers with only aromatic rings and ether linkages ia the backbone poly(phenylene oxide)s are examples and are the principal emphasis of this article. A second type contains a wide variety of other functional groups ia the backbone, ia addition to the aromatic units and ether linkages. Many of these polymers are covered ia other articles, based on the other fiinctionahty (see Polymers containing sulfur, POLYSULFONES). 

Peracids. Peracids are compounds containing the functional group —OOH derived from an organic or inorganic acid functionaHty. Typical stmctures include CH2C(0)OOH derived from acetic acid and H0S(0)200H (peroxymonosulfuric acid) derived from sulfuric acid. Peracids have... 

As seen in Figure 1, the organo sulfur compounds are methylated at the boiling point (90°C) of dimethyl carbonate, whereas methylation (or alkylation with other alkyl groups) of other functional groups requites higher temperatures. This has resulted in the selective methylation of sulfhydryl groups of compounds that contain other substituents that can be alkylated. The other substituents can then be alkylated at elevated temperatures (63). 

The use of an acidic solution of p-anisaldehyde in ethanol to detect aldehyde functionalities on polystyrene polymer supports has been reported (beads are treated with a freshly made solution of p-anisaldehyde (2.55 mL), ethanol (88 mL), sulfuric acid (9 mL), acetic acid (1 mL) and heated at 110°C for 4 min). The colour of the beads depends on the percentage of CHO content such that at 0% of CHO groups, the beads are colourless, -50% CHO content, the beads appear red and at 98% CHO the beads appear burgundy [Vdzquez and Albericio Tetrahedron Lett 42 6691 200]]. A different approach utilises 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole (Purpald) as the visualizing agent for CHO groups. Resins containing aldehyde functionalities turn dark brown to purple after a 5 min reaction followed by a 10 minute air oxidation [Coumoyer et al. J Comb Chem 4 120 2002]. 

Sulfides are sulfur analogs of ethers they contain the C—S—C functional group. They are named as alkylthio derivatives of alkanes in substitutive lUPAC nomenclature. The functional class lUPAC nmnes of sulfides are derived in the same manner as those of ethers, but the concluding word is sulfide. 

Groups. Supplement S The Chemistry of Sulfur-Containing Functional Groups (S. Patai and Z. Rappoport, eds.), p. 659. Wiley, New York, 1993. 

Thiols (R—S—H) and sulfides (R—S—R ) are sulfur analogs of alcohols and ethers, respectively. Both functional groups are found in various biomolecules, although not as commonly as their oxygen-containing relatives. 

Another difference between diese catalysts is found in dieir functional group tolerance. Catalysts such as 12 are more robust to most functionalities (except sulfur and phosphorus), moisture, oxygen, and impurities, enabling them to easily polymerize dienes containing functional groups such as esters, alcohols, and ketones.9 On die other hand, catalyst 14 is more tolerant of sulfur-based functionalities.7 The researcher must choose die appropriate catalyst by considering the chemical interactions between monomer and catalyst as well as the reaction conditions needed. 

One of the longest known synthetically prepared surfactants are the fatty alcohol sulfates, which were prepared on technical scale before 1940. Along with their ethoxylated counterparts, the fatty alcohol ether sulfates, which appeared on the stage shortly after, their use in toiletries is very popular but they can also be found in products for textile industry and auxiliaries in emulsion polymerization. With the exception of soaps, the mentioned anionic surfactants all have a sulfur-containing functional group. Denying the differences between these, their skin irritancy potential is remarkably high. 

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