Relative reactivities of some dienes and acetylenes in copolymerization with sulfur dioxide

Ivin, K. J.; Walker, N. A.

doi:10.1002/pol.1971.150090823

Cited by 10 publications

(3 citation statements)

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“…This highly exothermic reaction results in a stable bisulfite (SO 3 H) adduct to the Schiff base formed by intermolecular interaction of carbonyl compounds with amino compounds [ Ingles , 1967]. Sulfur dioxide is also known to cause copolymerization of a number of open chain and cyclic monoalkenes, dienes, and acetylenes at room temperature [ Hazell and Ivin , 1962; Ivin and Walker , 1971]. Perhaps the most notable example for its atmospheric relevance are the sulfonated terpolymers of isoprene and piperylene: [SO 2 CH 2 CH = CHCH(CH 3 )] and [SO 2 CH 2 CH = C(CH 3 )CH 2 ] [ Ivin and Walker , 1971].…”

Section: Resultsmentioning

confidence: 99%

“…Sulfur dioxide is also known to cause copolymerization of a number of open chain and cyclic monoalkenes, dienes, and acetylenes at room temperature [ Hazell and Ivin , 1962; Ivin and Walker , 1971]. Perhaps the most notable example for its atmospheric relevance are the sulfonated terpolymers of isoprene and piperylene: [SO 2 CH 2 CH = CHCH(CH 3 )] and [SO 2 CH 2 CH = C(CH 3 )CH 2 ] [ Ivin and Walker , 1971]. More recently, sulfuric acid catalyzed aldol condensation of aldehydes and ketones has been recognized for the ability to form UV light‐absorbing dienes in atmospheric aerosols [ Noziere and Esteve , 2005].…”

Section: Resultsmentioning

confidence: 99%

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New revelations on the nature of organic matter in ice cores

et al. 2006

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[1] Analysis of organic species stored in ice cores provides a unique opportunity to obtain information about the environment of the past. Because of the trace nature of the organic components of interest, studying these species in molecular level detail within ice cores can be an analytical challenge. Using Fourier transform ion cyclotron resonance mass spectrometry with electrospray ionization, we have characterized, at an unprecedented molecular level, the organic material in an ice core collected from Franz Josef Land (Russia). Several thousand distinct molecular species are identified and provide clues to the principal sources of the organic matter. Humic-like substances have been identified in both modern and ancient ice, despite the remote marine setting of the ice field. Species containing sulfur heteroatoms are far more abundant in the modern ice, indicating that anthropogenic sulfur emissions are also present in the high-molecular weight organic compounds preserved in ice.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

New revelations on the nature of organic matter in ice cores

et al. 2006

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“…In the presence of malonic derivatives Trost and Li 22 realized carbon-carbon cross-coupling as illustrated in Scheme 6. Although sulfur dioxide has been used for a long time as food and beverage preservative, the organic chemistry of SO 2 has been limited to the Friedel-Crafts sulfinylation, 38,39 copolymerization of SO 2 with alkenes and alkynes, [40][41][42][43][44][45] the synthesis of sulfinates and sulfones from polar organometallic species, [46][47][48] the ring opening of epoxides and oxetanes 49 leading to polysulfites, 50,51 the isomerization of alkenes, [52][53][54][55] and the formation of sulfolenes by cheletropic additions with 1,3-dienes. [56][57][58][59][60][61] Other cycloadditions of SO 2 have been described for the reaction of ketenes and ketimines, [62][63][64][65][66][67][68] cyclic polyenes, 69 and quadricyclane.…”

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confidence: 99%

Umpolung with Sulfur Dioxide: Carbon-Carbon Cross-Coupling of Electron-Rich 1,3-Dienes and Alkenes; Application to the Enantioselective Synthesis of Long-Chain Polyketide Fragments

Turks¹,

Exner²,

Hamel³

et al. 2009

Synthesis

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At low temperature and in the presence of an acid catalyst, sulfur dioxide undergoes hetero-Diels-Alder additions with 1-oxy-1,3-dienes, giving unstable sultines, which are ionized into zwitterionic species and react as 1-oxyallylic cation intermediates (Umpolung with SO 2) with electron-rich alkenes such as allylsilanes or enoxysilanes. The b,g-unsaturated silyl sulfinates so-obtained can be desulfinylated in situ to generate polyketide fragments containing up to three contiguous stereogenic centers in one-pot operations. This reaction cascade can be applied in two-directional chain elongation approaches for the asymmetric synthesis of long chain polyketide fragments using 1-[(S)-or (R)-1-phenylethoxy]-1,3-dienes.

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Dehydrochlorination of poly(sulfonyl‐co‐2‐chloroethylene)

Cais

O’Donnell

1975

Makromol. Chem.

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Poly(sulfony1-co-2-chloroethylene)~ were shown to have an enhanced tendency to undergo dehydrochlorination compared with poly(viny1 chloride). Dehydrochlorination was observed under the following conditions: (a) during preparation of the copolymers by y-radiation initiated copolymerization of vinyl chloride and sulfur dioxide, (b) by y-irradiation of the polymer, (c) during ageing, (d) on heating and (e) in solution in basic solvents, such as DMSO. The dehydrochlorination was studied by microanalysis, by IR and UV spectroscopy and by 'H and 13C NMR. Hydrogen chloride was eliminated preferentially from chloroethylene units occurring between two sulfonyl units. The proportion chloroethylene units: sulfonyl units in poly(sulfony1-2-chloroethylene) decreased from ~2 : l at a copolymerization temperature of 0°C to ~1 : l at a temperature of -78 "C. The results show, that dehydrochlorination of copolymers prepared at low temperatures is a serious problem, especially with initiation by y-irradiation. ZUSAMMENFASSUNG:Poly(su1fonyl-co-2-chlorathylen) zeigt gegenuber Poly(viny1chlorid) eine erhohte Neigung zur Dehydrochlorierung. Diese Dehydrochlorierung wurdeunter folgenden Bedingungen beobachtet : (a) Wahrend der Herstellung der Copolymeren durch y-strahleninduzierte Copolymerisation von Vinylchlorid und Schwefeldioxid, (b) wahrend der y-Bestrahlung des Polymeren, (c) wahrend des Aufbewahrens, (d) beim Erhitzen und (e) in basischen Losungsmitteln wie z. B. DMSO. Die Dehydrochlorierung wurde mikroanalytisch, IRund UV-spektroskopisch sowie mit 'H und 13C NMR verfolgt. Chlorwasserstoff wird vorwiegend aus Chlorathylen-Bausteinen eliminiert, die isoliert zwischen Sulfonyl-Bausteinen stehen. Das Verhaltnis von Athylen-Bausteinen zu Sulfonyl-Bausteinen in den Copolymeren fallt von etwa 2: 1 fur die Copolymerisation bei 0°C auf etwa 1 : 1 bei -78°C. Die Ergebnisse zeigen, daB die Dehydrochlorierung von Copolymeren, die bei niedrigen Temperaturen dargestellt wurden, ein ernsthaftes Problem darstellt, besonders bei Initiierung mit y-Strahlen.

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Relative reactivities of some dienes and acetylenes in copolymerization with sulfur dioxide

Cited by 10 publications

References 5 publications

New revelations on the nature of organic matter in ice cores

New revelations on the nature of organic matter in ice cores

Umpolung with Sulfur Dioxide: Carbon-Carbon Cross-Coupling of Electron-Rich 1,3-Dienes and Alkenes; Application to the Enantioselective Synthesis of Long-Chain Polyketide Fragments

Dehydrochlorination of poly(sulfonyl‐co‐2‐chloroethylene)

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