Poly- sulfonyl chloride

The following products are usually contained in the reaction mixture produced by sulfochlorination 1980 mono-, di-, and poly-sulfonyl chlorides chloro-mono-, -di-, and -poly-sulfonyl chlorides alkyl chloride and unchanged starting material of which the last two are unhydrolysable neutral oils. The individual products obtained on sulfochlorination of aliphatic hydrocarbons of low molecular weight can be separated by distillation, but it has also been found that the mono- can be separated from the poly-sulfonyl portions by treating the mixture with at least a five-fold amount of pentane and cooling to — 30°.206... 

Shai and Patchornik showed that poly(sulfonyl chloride) (prepared by chlorosulfonation of a macroporous resin) is an excellent reagent for the formation of 1-hydroxybenzotriazole (HOBt) esters of N-blocked amino acids, as in Scheme 41. 

Mw = 9300, Mw/Mn = 5.07). The poly (p-hydroxy styrene) was PHP-6817-24, obtained from Marusen Oil Co. (Mn = 3900, Mw = 10200, Mw/Mn = 2.62). Kodak micro positive developer 934 (934 developer) (predominantly tetramethyl ammonium hydroxide in water) was used at various dilutions with deionized water. M-cresyl naphthalene diazo-quinone sulfonate was prepsured by a pyridine catalyzed condensation of m-cresol with naphthalene diazoguinone sulfonyl chloride. 

Esterification Alumina. Boron trifluoride. Diazomethane. Dimethylformamide dimethyl acetal. Dimethylformamide dineopentyl acetal. Dimethyl sulfite. Diphenyidiazomethane. Ethyldicyclohexylamine. Ion-exchange resins. Isobutene. Methanesulfonic anhydride. 3 % Methanolic HCl (see Acetyl chloride). Methyl iodide. l-Methyl-3-p-tolyltriazine. Poly-phosphoric acid. Sulfosalicylic acid. Sulfuryl chloride. p-Toluenesulfonic acid. p-Tpluene-sulfonyl chloride. Triethylamine. Triethylorthoformate. Trifluoroacetic anhydride. Esterification of phosphoric acid Trichloroacetonitrile. 

The field of organic chemistry has seen the most extensive use of polymeric materials as aids in effecting chemical transformation and product isolation. Insoluble polymer supports have been used as handles to facilitate these functions. As chemical reagents can be bound to an insoluble polymer carrier and used in organic synthesis [117,118], polymer-bound reagents can also be used to assist in the purification step of solution-phase reactions [119,120]. The latter are known as scavenger resins. These are added to the reaction mixture upon completion of the reaction in order to quench and selectively bind to the unreacted reagents or by-products. The polymer-bound impurities are then removed firom the product by simple filtration to obtain pure compounds. For example, aminomethylated poly(styrene-co-divinyl benzene) can be used to remove acid chlorides, sulfonyl chlorides, isocyanates, thiocyanates, and proton. Similarly, 2-Chlorotrityl resins have been developed for the attachment of carboxylic acids, alcohols. 

The actual formation of hyperbranched material proceeds during the polymerization of 3,5-difluoro-4 -hydroxydiphenyl sulfone in the presence of 3,4,5-trifluorophenylsulfonyl benzene or tris(3,4,5-trifluorophenyl)phos-phine oxide as a core molecule. Cyclic oUgomers formed dining this polymerization contribute to a low-molecular-weight polymer ranging from 3400 to 8400 Dalton. A triazin-based AB2 monomer has also been described. This monomer is shown in Figure 7.8. A hyperbranched aromatic poly(ether sulfone) with sulfonyl chloride terminal groups has been prepared by the polycondensation of 4,4 -(m-phenylenedioxy)-bis-(benz-enesulfonyl chloride). The polymerization was carried out in nitrobenzene at 120°C for 3 h in the presence of a catalytic amount of FeCls. ... 

K. Matsumoto and M. Ueda. Synthesis of hyperbranched aromatic poly-(ether sulfone) with sulfonyl chloride terminal groups. Chem. Lett., 35 1196-1197,2006. 

NMP and admixed with the poly(amic acid). The photosensitive compound is added to this mixture. The compound generates an acid by irradiation with light. These compounds are also addressed as photo acid generators. A photosensitive compound is prepared by the condensation of 4,4c [ 1 - [4- [ 1 -(4-hydroxyphenyl)-1 -methylethyl]phenyl] ethyhdene] with l,2-naphthoquinone-2-diazido-5-sulfonyl chloride. Other types of photo acid generators are summarized in Table 15.10. 

The commercial synthesis of poly(phenylenes) starts with a mixture of 0-, m-, and p-terphenyl (subsequently referred to as Ar). The mixture is converted to chloroform-soluble prepolymers with m-benzene disulfonyl chloride. The arylation reaction consists of a thermal degradation reaction of the sulfonyl chloride in the presence of terphenyls. Presumably, this involves a free radical process, and not a Friedel-Crafts reaction ... 

Wudl and Heeger et al, [17] electrochemically synthesized the sodium salts and acid forms of poly(3-thiophene ethanesulfonate) and poly(3-thiophene butanesulfonate). The monomers 3-thiophene ethanesulfonate and 3-thiophene butanesulfonate were prepared by the route shown in Figure 4.1. However, attempts to electropolymerize these monomers or their sulfonic acid derivatives were not successful. Therefore, the monomers, 3-thiophene alkanesulfonate methyl esters, were polymerized first, followed by conversion of the ester to the sodium salt via the sulfonyl chloride derivative. The sodium salts of poly (3-thiophene ethanesulfonate) and poly( 3-thiophene butanesulfonate) are reportedly soluble in water in their neutral (insulating) and doped (conducting)... 

Various synthetic approaches have been demonstrated for the synthesis of PAEs since early days [35 0], PAEs were synthesized by Ullmann condensation between bisphenols and aryl fcis-halide monomers using Cu(I) salt/pyridine as catalyst [36], General Electric developed the first commercially successful PAE poly(2,6-dimethyl phenylene oxide) (PPO) [38], It was prepared by oxidative coupling of 2,6-dimethyI phenol. However, this process has its own restrictions, because it does not allow much structural variation or inclusion of any electron-withdrawing group into the polymer main chain. First attempts to synthesize polysulfones (PSF) were successfully done by Friedel-Crafts sulfonylation reaction of arylenedisulfonyl chlorides, for example, diphenyl ether-4,4 -disulfonyl chloride with diaryl ethers, for example, diphenyl ether, or by self-condensation of 4-phenoxy benzene sulfonyl chloride in the presence of FeCls [41], Whereas the former reaction involves side reactions (sulfonylation not only in the para- but also in the ort/io-position), the latter produces only the desired linear all-para products. 

In the chlorosulfonation 344 to 345 (Equation 109), the large steric size of the acetamido group effectively precludes o-sulfonation, so the p-sulfonyl chloride is essentially the sole product isolated. Studies of the chlorosulfonation of acetanilide 344 with excess chlorosulfonic acid (five equivalents) in the temperature range 0 to 100 °C indicated that the optimium temperature for the production of the monosulfonyl chloride 345 was 55-60 C. Some disulfonation occurred > 40 °C, poly sulfonation > 70 °C and even at 100 C (2 hours), die reaction gave no sulfone. ... 

Rubinstein, M. and Patchornik, A (1975) Poly(3,5-diethylstyrene. sulfonyl chloride. A new reagent for internucleotide bond synthesis. Tetrahedron 31, 1517-1519, Rubinstein, M. and Patchornik, A. (1975) A novel method for phosphodiester and internucleotide bond synthesis. Tetrahedron 31, 2107-2110. 

Organic polymers Polyethylene maleate Ethyl cellulose, fluoropolyol, phenoxy resin, poly(amidoxime), poly-1-butadiene, poly(epichloro-hydrin), polyethylene, poly-(ethylene m eate), poly(iso-prene), poly(methylmethacrylate), polystyrene, poly(vinyl chloride), poly(vinyl stearate), 1,1,1-tri-fluoroisopropyl methyl siloxane Cyclopentadiene [200 ppm-min] Benzene, 1-butanol, 2-buta-none, 1,2-dichloroethane, dichloropentane, methylacetamide, dimethyl-phosphite, dodecane, methane-sulfonyl fluoride, octane, a-pinene oxide, /-propyl-acetate, toluene, triamylphos-phite, tributylphosphate, water... 

An optically active polymer was obtained by Minoura and Sakota (74) from poly-vinyl-alcohol and a-(N-para-toluen-sulfonyl-ammino)-/8-methyl-butyryl-chloride. 

The reductive desulfonylation of a-sulfonyl esters with tin hydrides only succeeds with n-deficient heterocyclic sulfones (Eq. 104).175 These sulfones are inert under standard procedures using Al/Hg or Na/Hg, but undergo facile C-S cleavage with tin hydrides. Substitution of //-liu3Snl) for n-Bu3SnH gives access to a-deuterated esters.58 A catalytic version of the reaction is carried out with substoichiometric amounts of tributyltin chloride and an excess of poly(methyl-hydrosiloxane) (PMHS) in the presence of potassium fluoride. This method has been employed for the synthesis of 2-fluoroalkanoates (Eq. 105).58... 

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