The Chemistry of the Zinc Oxide Cure of Halobutyl

1984 ◽  
Vol 57 (4) ◽  
pp. 813-825 ◽  
Author(s):  
I. Kuntz ◽  
R. L. Zapp ◽  
R. J. Pancirov
Keyword(s):  
Zinc Oxide ◽  
Zinc Chloride ◽  
Reaction Pathway ◽  
Diels Alder ◽  
Crosslinking Reaction ◽  
Conjugated Diene ◽  
Carbon Carbon Bonds ◽  
Carbon Bonds ◽  
Chloride Catalyst ◽  
Major Reaction

Abstract The studies described in this papier lead to certain conclusions. The crosslinking reaction of halobutyl with zinc oxide does not give rise to ether crosslinks. All the evidence indicates that the chemistry involves the formation of carbon-carbon bonds by an alkylation type chemistry. The dehydrohalogenation of the halobutyl to form a zinc chloride catalyst is a key feature of the crosslinking chemistry. But conjugated diene butyl and Diels-Alder reactions are not the major reaction pathway for the zinc oxide crosslinking reaction. These conclusions have significance for the zinc oxide cure of CR which has an active allylic halide structure formed by 1,2-monomer enchainment.

Zinc Oxide Crosslinking Reaction of Polychloroprene Rubber

1989 ◽  
Vol 62 (1) ◽  
pp. 1-12 ◽  
Author(s):  
Yoshiaki Miyata ◽  
Masao Atsumi
Keyword(s):  
Molecular Weight ◽  
Zinc Oxide ◽  
Main Chain ◽  
Reaction Pathway ◽  
Main Reaction ◽  
Low Molecular Weight ◽  
Crosslinking Reaction ◽  
Chain Component ◽  
Carbonium Ion ◽  
Intermolecular Reaction

Abstract There was some ambiguity on the reality of the formation of ether crosslinks in the ZnO crosslinking of CR. This report clearly indicates the absence of the ether crosslinks. The main reaction pathway of the ZnO crosslinking of CR is the addition of the carbonium ion formed from the isomerized 1,2 unit to the double bond in the neighboring 1,4 unit, catalyzed by ZnCl2. The isomerized 1,2 unit is formed by the rearrangement of allylic chlorine in the 1,2 unit. The crosslinking reaction takes place between one curing site and one main chain component, not between two curing sites. The intramolecular cyclization predominantly occurs as compared with the intermolecular reaction (crosslinking) in Scheme 2. Therefore, the efficiency of the ZnO crosslinking of CR is quite small as expected from the concentration of the curing sites (1,2 units). Model polymer of low molecular weight and NMR spectroscopy have led to a better understanding of the chemistry of this process.

The synthesis and reactivity of α-oxosulfines

1989 ◽  
Vol 67 (3) ◽  
pp. 369-381 ◽  
Author(s):  
Ian W. J. Still ◽  
Donald V. Frazer ◽  
Donna K. T. Hutchinson ◽  
Jeffery F. Sawyer
Keyword(s):  
Crystal Structures ◽  
Reaction Pathway ◽  
Reactive Intermediates ◽  
Crystallographic Analysis ◽  
Diels Alder ◽  
Electrophilic Addition ◽  
X Ray ◽  
Major Reaction ◽  
Sulfenic Acids

Thiochroman-4-one and cyclohexanone have been converted into the corresponding α-oxosulfines and the behaviour of these reactive intermediates with a range of alkenes and alkynes has been examined. In contrast to some earlier work, the major reaction pathway does not involve formation of the initially expected Diels–Alder adducts but instead a series of adducts involving electrophilic addition to the alkene or alkyne, with concomitant deoxygenation and incorporation of chlorine. The structures of these adducts have been determined by the usual spectroscopic means and, in two representative cases, by X-ray crystallographic analysis. The crystal structures, which include unusual features such as relatively short S … O nonbonding contacts, are discussed in detail. Keywords: (α-oxo)sulfines, sulfenic acids, X-ray analysis, electrophilic addition.

scholarly journals Broad scope gold(i)-catalysed polyenyne cyclisations for the formation of up to four carbon–carbon bonds

2017 ◽  
Vol 15 (10) ◽  
pp. 2163-2167 ◽  
Author(s):  
Zhouting Rong ◽  
Antonio M. Echavarren
Keyword(s):  
Single Step ◽  
Simultaneous Formation ◽  
Broad Scope ◽  
Carbon Carbon Bonds ◽  
Carbon Bonds ◽  
First Time ◽  
High Stereoselectivity

The polycyclisation of polyeneynes catalyzed by gold(i) has been extended for the first time to the simultaneous formation of up to four carbon–carbon bonds, leading to steroid-like molecules with high stereoselectivity in a single step with low catalyst loadings.

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