Sulfones, hydroxy

The surfactants described or characterized for waterflooding are summarized in Table 16-2. Conunercial alkene sulfonates are a mixture of alkene sulfonate, hydroxy alkane sulfonate, and olefin disulfonate [211]. 

Alpha Olefin Sulfonates. The direct reaction of alpha-olefins with a strong sulfonating agent yields a mixture of alkane sulfonates, hydroxy-lalkane sulfonates, and disulfonated products. These are known commercially as a-olefin sulfonates (AOS). AOS manufacture is generally more complex than ABS because the initial reaction product is a mixture of sultones as shown in Fig. 36.33. 

Figure 7.5 Telechelic Sulfonated Hydroxy Functional Monomer and Telechelic...

Telechelic compounds are oligomers or low-molecular-weight polymers carrying monofunctional terminal groups or reactive terminal groups, respectively, on both chain ends. Block sulfone copolymers have been synthesized from hydroxy-telechelic sulfonated PESs and fluorotelechelic PESs. As a monomer for the sulfonated hydroxy-telechelic compound, 3,3 -sulf-onyl bis-(6-hydroxybenzene sulfonic acid) disodium salt is used. This compound is synthesized from bis-(4-hydrox5 henyl)-sulfone by sulfona-tion with concentrated sulfuric acid and subsequent neutralization. 

Figure 7.8 Telechelic sulfonated hydroxy functional monomer and telechelic sulfonated fluoro functional monomer [34].

Heavy-duty (HD) additives keep solid combustion and oxidation products in suspension, thus avoiding deposits on metal surfaces, sludge formation and corrosive wear by neutralizing acidic decomposition products. Detergents, some of them RR-based, have sulfonate, hydroxy and/or carboxyl groups and usually contain metal ions or amine functions. More modem HD additives are based on methacrylates of fatty alcohols (Cn-ig), copolymerized with diethylaminoethyl methacrylate (9 1), vinylpyrollidone, N-vinylpyridine and hy-droxyethyl methacrylate. These ash-free dispersants may act also as VI improvers. Extreme-pressure (EP) additives ... 

When unsubstituted, C-5 reacts with electrophilic reagents. Thus phosphorus pentachloride chlorinates the ring (36, 235). A hydroxy group in the 2-position activates the ring towards this reaction. 4-Methylthiazole does not react with bromine in chloroform (201, 236), whereas under the same conditions the 2-hydroxy analog reacts (55. 237-239. 557). Activation of C-5 works also for sulfonation (201. 236), nitration (201. 236. 237), Friede 1-Crafts reactions (201, 236, 237, 240-242), and acylation (243). However, iodination fails (201. 236). and the Gatterman or Reimer-Tieman reactions yield only small amounts of 4-methyl-5-carboxy-A-4-thiazoline-2-one. Recent kinetic investigations show that 2-thiazolones are nitrated via a free base mechanism. A 2-oxo substituent increases the rate of nitration at the 5-position by a factor of 9 log... 

Direct sulfonation of thiazole, as well as of 2-substituted thiazoles, leads mostly to substitution m the 5-position (330-332). 4-Thiazole sulfonic acid has been prepared through direct sulfonation of 2.5-dibromothiazole with subsequent Rane% Ni reduction (330). Sulfonation of 2.5-dimethyl- and 2-piperidyl-5-methylthiazoles affords the corresponding 4-sulfonic acids as barium salts (247). The 2-hydroxy group facilitates the sulfonation (201. 236). When the 4- and 5-positions are occupied direct sulfonation can occur in the 2-position. 5-hydroxyethyl-4-methyl-2-thiazole sulfonic acid has been prepared in this manner (7). 

Chloro- and 2-acetamido-5-sulfide derivatives are readily oxidized to the corresponding sulfones, while curiously enough 2-hydroxy-5-arylsulfides are reported to be stable to oxidation (228, 55 )-... 

Similarly, 5-thiazole alkanoic acids and their salts are obtained from thioamides and /3-halo -y-keto acids (695). Thus thioarylamides condensed with 3-aroyl-3-bromopropionic acid (88) in isopropanolic solution in the presence of Na COs give first 4-hydroxy-2-aryl-A-2-thiazoline-5-acetic acid intermediates (89), which were dehydrated in toluene with catalytic amounts of p-toluene sulfonic acid to 2,4-diaryl-5-thiazole acetic acid (90) (Scheme 39) (657), with R = H or Me Ar = Ph, o-, m- or p-tolyl, o-, m-, or P-CIC6H4, 0-, m-, or p-MeOC(iH4, P-CF3C6H4, a-thienyl, a-naphthyl (657). 

Amino-3-hydroxy-7-nitro-l-naphthalene-sulfonic acid [6259-63-8]... 

Most xanthene dyes are classified as basic dyes by their method of appHcation acid dyes can be produced by introduction of sulfonic acid groups. The fluoresceins, which contain carboxy and hydroxy substituents, are also acid dyes for coloration of silk. Some of the fluoresceins in which the carboxy group has been esterified, are soluble in alcohol or other organic solvents and can be classified as solvent dyes. Mordant dyes can be produced by introducing o-dihydroxy or sahcyhc acid groups (2), which when metallised can have very good lightfastness. 

H-acid, l-hydroxy-3,6,8-ttisulfonic acid, which is one of the most important letter acids, is prepared as naphthalene is sulfonated with sulfuric acid to ttisulfonic acid. The product is then nitrated and neutralized with lime to produce the calcium salt of l-nitronaphthalene-3,6,8-ttisulfonic acid, which is then reduced to T-acid (Koch acid) with Fe and HCl modem processes use continuous catalytical hydrogenation with Ni catalyst. Hydrogenation has been performed in aqueous medium in the presence of Raney nickel or Raney Ni—Fe catalyst with a low catalyst consumption and better yield (51). Fusion of the T-acid with sodium hydroxide and neutralization with sulfuric acid yields H-acid. Azo dyes such as Direct Blue 15 [2429-74-5] (17) and Acid... 

Another example of manufacture in this series is the sulfonation of an aminonaphthalenesulfonic acid, followed by selected desulfonation, to make 6-amino-l,3-naphthalenedisulfonic acid (21). Thus, 2-amino-l-naphthalenesulfonic acid made by amination of 2-hydroxy-1-naphthalenesulfonic acid is added to 20 wt % oleum at ca 35°C. At this temperature, 65 wt % oleum is added and the charge is stirred for 2 h, is then slowly heated to 100°C and is maintained for 12 h to produce 6-amino-l,3,5-naphthalenetrisulfonic acid. The mass is diluted with water and maintained for 3 h at 105°C to remove the sulfo group adjacent to the amino group. After cooling to ca 20°C and filtration, 6-amino-l,3-naphthalenedisulfonic acid is obtained in 80% yield (55). 

Delignification Chemistty. The chemical mechanism of sulfite delignification is not fully understood. However, the chemistry of model compounds has been studied extensively, and attempts have been made to correlate the results with observations on the rates and conditions of delignification (61). The initial reaction is sulfonation of the aUphatic side chain, which occurs almost exclusively at the a-carbon by a nucleophilic substitution. The substitution displaces either a hydroxy or alkoxy group ... 

This mixture is known as Quinoline Yellow A [8003-22-3] (Cl 47000) and is most widely used with polyester fibers (109). Upon sulfonation, the water-soluble Quinoline Yellow S or Acid Yellow 3 [8004-92-0] (Cl 47005) is obtained. This dye is used with wool and its aluminum salt as a pigment. Foron Yellow SE-3GL (Cl Disperse Yellow 64) is the 3-hydroxy-4-bromo derivative. Several other quinoline dyes are commercially available and find apphcations as biological stains and analytical reagents (110). 

In other work, sulfone chemistry plays an integral part of the syntheses of both -carotene and vitamin A by workers at Kuraray. In this approach, the anion of C q P-cyclogeranyl sulfone (36) is condensed with the C q aldehyde (37). The resulting P-hydroxy sulfone (38) is treated with dihydropyran followed by a double elimination to yield vitamin A acetate. Alternatively, the P-hydroxy sulfone (38) can be converted to the 5-halo sulfone (39) and a similar double elimination scheme is employed (23,24) (Fig. 8). 

A.mina.tlon. Amination describes the introduction of amino groups into aromatic molecules by reaction of ammonia or an amine with suitably substituted halogeno, hydroxy, or sulfonated derivatives by nucleophilic displacement. Although reaction and operational conditions vary, the process always involves the heating of the appropriate precursor with excess aqueous ammonia or amine under pressure. 

In 1901, mercury cataly2ed a-sulfonation of anthraquinone was discovered, and this led to the development of the chemistry of a-substituted anthraquinone derivatives (a-amino, a-chloro, a-hydroxy, and a,a -dihydroxyanthraquinones). In the same year R. Bohn discovered indanthrone. Afterward flavanthrone, pyranthrone, and ben2anthrone, etc, were synthesi2ed, and anthraquinone vat dyes such as ben2oylaniinoanthraquinone, anthrimides, and anthrimidocarba2oles were also invented. These anthraquinone derivatives were widely used to dye cotton with excellent fastness, and formed the basis of the anthraquinone vat dye industry. 

Oxidation of thiophene with peracid under carefully controlled conditions gives a mixture of thiophene sulfoxide and 2-hydroxythiophene sulfoxide. These compounds are trapped by addition to benzoquinone to give ultimately naphthoquinone (225) and its 5-hydroxy derivative (226) (76ACS(B)353). The further oxidation of the sulfoxide yields the sulfone, which may function as a diene or dienophile in the Diels-Alder reaction (Scheme 88). An azulene synthesis involves the addition of 6-(A,A-dimethylamino)fulvene (227) to a thiophene sulfone (77TL639, 77JA4199). 

C3NS S N — — — Methyl 3-hydroxy-4-phenylisothiazole-5-sulfonate dehydromethionine... 

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