Preparation sulfonation

This sulfonate, prepared from B0CNHCH2CH2C(CH3)2CH20H and the sulfonyl chloride (Pyr, 100% yield) is cleaved by initial BOC cleavage to release the free amine after pH adjustment to 7-8. Intramolecular displacement occurs to release the sulfonate and a pyrrolidine. ... 

The formation of complexes involved two steps. In the first step, the ionene bromide was converted to ionene hydroxide by replacing the Br ions with OH ions. In the second step, the equivalent quantities of acid and ionene were mixed together. Polymerizations were carried out mostly in water-isopropanol solution. AIBN or 4,4-azobis-4-cyanovaleric acid was used as initiator. Polymerization of p-styrene sulfonic acid onto various ionenes was studied as a function of the charge density of the template. It was shown that a linear dependence of rate on charge density prevailed. From the results obtained, the authors concluded that the monomeric counterions possess mobility along the linear template. PolyCvinyl sulfonate) prepared on the template displays a different stereo-structure from polyCvinyl sulfonate) prepared in solution. 

Supplementing the keryl benzene sulfonates prepared according to Reaction I, above, are those products derived from olefins according to the equations ... 

In the Horner-Emmons reaction (Scheme 3), the sulfonylphosphonate carbanion 5 is formed in the presence of NaH and then reacts with an aldehyde to produce the intermediate 6 that undergoes in situ elimination to yield the vinyl sulfones and phosphonate anion. The sulfonyl group can stabilize the anion in the sulfonylphosphonate 5. The vinyl sulfones that are produced by this method using aldehydes as starting materials are exclusively the E (trans) isomers. The E-isomers of the vinyl sulfones are shown in the NMR spectra based on the coupling constants of the vinylic protons. Although strongly basic conditions are used in the Horner-Emmons reaction and a-amino aldehydes are easily racemized, the amino acid vinyl sulfones prepared by this method still show substantial optical activity. However, the enantiomeric purity of these compounds has not been determined. 5 ... 

Resin-bound 7-keto sulfones, prepared in a straightforward, three-step process comprising alkylation of a resin-bound sulfinate salt, alkylation of a sulfone-supported anion with an epoxide, and Jones oxidation of the 7-hydroxy sulfone, provided a source of structurally diverse three-carbon fragments <2004JC0928>. Reaction with a phenylenediamine to give the 1,5-benzodiazepine presumably occurs via initial imine formation followed by expulsion of the resin-bound sulfone, which acts as a traceless linker (Scheme 73). Yields for this process are a modest 10-38%. 

Hydrogen peroxide attacks the sulfur atom in preference to the double bond in allyl phenyl sulfide and allyl benzyl sulfide to give allyl phenyl sulfoxide (64%) and allyl benzyl sulfone (85%), respectively. Olefinic sulfones may also be obtained by dehydrohalogenation of /3-haloalkyl sulfones prepared by this method. Oxidation of sulfides has been utilized in the preparation of sulfones containing other common functional groups such as the amide, tro, amino, and ester groups. 

Nitrileoxidomethyl)penam sulfone, prepared in a few steps from commercially available (- -)-6-aminopenicilla-nic acid by treatment of oxime 617 with NCS and followed by dehydrochlorination with bis(tributyltin)oxide, underwent smooth 1,3-dipolar cycloaddition reactions with various alkynes, and alkenes, to give cycloadducts 618 in moderate to good yields. Some acid derivatives 618 (R = H) showed potent /3-lactamase inhibitory activity (Scheme 148) <20000L3087>. 

Anionic desilylation of a-silylated tra j-4,5-epoxythiacyclononane 1,1-dioxide (6) obtained from quenching the lithio sulfone prepared at — 90 °C with butyllithium by trimethylsilyl triflate followed by epoxidation with 3-chloroperoxybenzoic acid, resulted in formation of transannular cyclization products whose distribution is dependent on the stereochemistry of the starting material. 

The neopentyl sulfonate, prepared from the sulfonyl chloride (Pyr, 95% yield), is cleaved nucleophilically under rather severe conditions (Me4NCl, DMF, 160°C, 16 h, 100% yield). These may also be cleaved by acidolysis (CH3CN, H2O, 0.1% TFA, 4-5 days), with LiBr, butanone, reflux, 48 h, or liquid HF, ra-cresol, 100% yield. ... 

The present procedure, similar to that of Fujita for the preparation of alkynyl(phenyl)iodonlum tetrafluoroborates, RC5CIPh BF4, is simpler, much more general and in most cases gives significantly better yields. Table I gives yields of alkynyl(phenyl)iodonium sulfonates prepared by this procedure. 

MatedLaJLs. Kraft lignin samples were obtained from WESTVACO Corp., Charleston, South Carolina they were commercial preparations traded under the name INDULIN-AT. Lignin sulfonate preparations were procured from GEORGIA PACIFIC Corp., Bellingham, Washington their commercial name is LIGNOSITE (spray-dried from fermented calcium spent sulfite liquor). 

Materials. The studies reported here have been made with monoiso-meric sodium dodecyl sulfate, sodium dodecyl sulfonate and sodium decyl sulfonate prepared by Professor E. J. Eisenbraun of Oklahoma State University. The sodium dodecyl benzene sulfonate was a commercial sample purchased from Research Organic/Research Inorganic Chemical Corp. All materials used for background solutions were prepared from reagent grade materials, and the water was distilled from permanganate. Solutions were prepared on a mass basis with corrections for buoyancy. 

A large number of sulfones prepared by this method are tabulated in Suter s The Organic Chemistry of Sulfur. 152e... 

Treatment of 155 with iodine in chloroform (iododemercuration) yielded the iodo-sulfoxide 156 as the sole product (approx. 40%), whereas, under analogous reaction conditions the S(7)-epimeric organomercuri compound 158 gave approx. 40% of the same iodide 156. However, the S(7)-epimeric iodide 159 was also formed to a smaller extent (approx. 8%). Both sulfoxides 156 and 159 were converted to the same sulfone 162 by oxidation with hydrogen peroxide which by iododemercuration of 161 could also be obtained as an approx. 1 1-mixture with the C(10) -epimer 163. The latter compound was identical with the sulfone prepared via the sulfoxide... 

Poly(diallylammonium halide-sulfone) prepared from methyl dodecyldialkyl ammonium halide and SO2 to give an alternating copolymer for bactericidal... 

Figure 16.2 Dependence of the time of saturation of 50% functional groups with (C4H9)4N ions on the resin water uptake for the sulfonates prepared by crosslinking (1-3) linear polystyrene with (1) 1,4-bis(chloromethyl diphenyl), (2) p-xylylene dichloride, and (3) monochlorodimethyl ether (4) styrene-1 % DVB copolymer crosslinked with 1,4-chloromethyl diphenyl (5) sulfonates based on conventional styrene-DVB copolymers numbers denote the degree of crosslinking. (After [371].)...

M. Schuster, C.C. de Araujo, V. Atanasov, H.T. Andersen, K.-D. Kreuer, J. Maier, Highly sulfonatedpoly(phenylene sulfone) Preparation and stability issues. Macromolecules 2009, 42(8), 3129-3137. 

Schuster M, de Araujo CC, Atanasov V, Andersen HT, Kreuer KD, Maier J. Highly sulfonated polyCphenylene sulfone) preparation and stability issues. Macromolecules 2009 42(8) 3129-37. 

A process to manufacture synthetic sulfonates was developed by Suntech Inc.. According to this process, caustic is used to neutralize the product, which minimizes the water usage during the process. Various companies such as Exxon and Shell have employed synthetic sulfonates for improving oil recovery. Several more expensive synthetic sulfonates also have been used as additives in the EOR processes. In such cases, a portion of the petroleum sulfonate prepared by sulfonation of gas/oil or crude oil is replaced with the synthetic sulfonates. It has been observed that the surfactant formulations containing mixed petroleum sulfonate and synthetic sulfonate have resulted in improved oil recovery. 

Vinyl and aryl sulfonates Preparations and applications in total synthesis 12COS806. 

Siegmund G., Klemm D., Cellulose Cellulose sulfonates preparation, properties, subsequent reactions, Polym. News, 27, 2002, 84-90. 

Scheme 8.7 Four-conponent coupling for sulfone preparation in formal synthesis of apoptolidin.

The synthetic sequence involving formation of a thioether, oxidation to the corresponding sulfone and the RBR need not be performed consecutively, although it almost invariably is when applied to the synthesis of complex targets. An example in which divorcing the sulfone preparation from the RBR was actually beneficial to the synthetic strategy is seen in the total synthesis of the resorcylic acid macrolactone (RAL) aigialomycin D by Harvey and coworkers. ... 

N. Gao, S. Zhang, Phenolphthalein-based cardo poly(arylene ether sulfone) preparation and application to separation membranes, J. Appl. Polym. Sci. 128 (1) (2013) 1-12. 

The sulfones prepared can be metallated with KHMDS at low temperature and, unlike the related benzothiazolyl and 1-phenyl-li/-tetrazolyl systems, show excellent stability with little tendency to self-condense. Selectivities observed in olefinations are good to excellent in favor of the Z-isomers (eq 3). 

Reaction of ee-Alkylated Sulfones. Racemic and optically active a-chloro- keto />-tolyl sulfones, prepared by oxidation of the corresponding sulfoxides, undergo Favorskii rearrangement... 

Bromo methallyl sulfone, prepared from methallyl phenyl sulfone, has proven to be a good substrate for stereoselective synthesis of trisubstituted methylenecyclopentanes with a variety of different Michael receptors. For example, the trans trans-trisubstituted methylenecyclopentane was efficiently prepared in 93% yield by a cascade Michael addition/cyclization beginning with ethyl ( )-crotonate (eq 22). The phosphonate sulfone reagent, readily available from methallyl phenyl sulfone, was used for the selective synthesis of 1,3-dienes. The synthesis included... 

---