Butyl Sulfone

A mixture of 14.8 g. (0.20 mole) of n-butyl alcohol and 41.9 g. (0.22 mole) of p-toluenesulfonyl chloride is stirred and cooled to 0° 

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Potassium or lithium derivatives of ethyl acetate, dimethyl acetamide, acetonitrile, acetophenone, pinacolone and (trimethylsilyl)acetylene are known to undergo conjugate addition to 3-(t-butyldimethylsiloxy)-1 -cyclohexenyl t-butyl sulfone 328. The resulting a-sulfonyl carbanions 329 can be trapped stereospecifically by electrophiles such as water and methyl iodide417. When the nucleophile was an sp3-hybridized primary anion (Nu = CH2Y), the resulting product was mainly 330, while in the reaction with (trimethylsilyl)acetylide anion the main product was 331. 

Other alkyl sulfones studied are di-isopropyl, methyl isopropyl and di-t-butyl sulfones. 

Di-f-butyl sulfone is different from the other dialkyl sulfones in that RH is mainly alkene and not alkane [G(isobutene) = 3.2 and G(isobutane) = 1.2]. The preference for isobutene over isobutane means that the formation of the alkene cannot be due to disproportionation of two t-butyl radicals but is due to a hydrogen atom expulsion as suggested by Bowmer and O Donnell70... 

More recently, a number of reports dealing with 1,3-sulfonyl shifts which proceed by other mechanisms have been published. For example, Baechler and coworkers suggested that the higher activation enthalpy observed for the isomerization of the deuterium labeled methallyl sulfone 72 in nitrobenzene at 150°C as compared to the corresponding sulfide, together with the positive entropy of activation may be taken as evidence for a homolytic dissociation mechanism (equation 44). A similar mechanism has also been suggested by Little and coworkers for the gas-phase thermal rearrangement of deuterium labelled allyl sec-butyl sulfone, which precedes its pyrolysis to alkene and sulfur dioxide. 

Acrylamide copolymers designed to reduce undesired amide group hydrolysis, increase thermal stability, and improve solubility in saline media have been synthesized and studied for EOR applications. These polymers still tend to be shear sensitive. Acrylamide comonomers that have been used include 2-acrylamido-2-methylpropane sulfonate, abbreviated AMPS, (1,321-324), 2-sulfo-ethylmethacrylate (325,326), diacetone acrylamide (324, 326), and vinylpyrrolidinone (327,328). Acrylamide terpolymers include those with sodium acrylate and acrylamido-N-dodecyl-N-butyl sulfonate (329), with AMPS and N,N-dimethylacrylamide (330), with AMPS and N-vinylpyrrolidinone (331), and with sodium acrylate and sodium methacrylate (332). While most copolymers tested have been random copolymers, block copolymers of acrylamide and AMPS also have utility in this application (333). 

The noncovalent binding of a series of oxo-squaraine dyes 9a-e to BSA was evaluated by measurement of absorption, emission, and circular dichroism [63]. The magnitude of the association constants (Ks) for the dye-BSA complexes depended on the nature of the side chains and ranged from 34 x 103 to 1 x 107 M-1. Depending on the side chains, the Ks increase in the order [R1 = R2 = butyl-phthalimide] < R1 = R2 = cetyl] <[RJ = R2 = ethyl] <<[R = butyl-phthalimide, R2 = butyl-sulfonate] <<[RJ = R2 = butyl-sulfonate]. These dyes seem to interact mainly with a hydrophobic cavity on BSA. However, the association constants Ks increase substantially when the side chains are selected from butyl sulfonate. 

DI-t-BUTYL PEROXIDE DI-n-BUTYL SULFONE DIETHYLENE GLYCOL DIETHYL ETHER... 

One of the first detailed studies on these systems was that of Beaman (26), who showed that methacrylonitrile polymerizes by an anionic chain mechanism when treated with various bases, including Na in liquid ammonia at —75° C. He noted also that low molecular weight polymers are obtained from reaction of acrylonitrile with butylmagnesium bromide. Foster (56) extended the liquid ammonia method to copolymerization studies in which acrylonitrile was combined with styrene, with methyl methacrylate and with vinyl butyl sulfone. Satisfactory data were obtained only with the sulfone, in which case there was some tendency for alternation. 

Butyl sulfides, dl32, dl33 Butyl sulfite, dl34 Butyl sulfone, dl35 Butyrolactam, p275... 

Scheme 2.22 Independent pathways in the solvolysis of 3-aryl-2-butyl sulfonates (60) established by the absence of crossover product.

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