Photochemical and radical initiator-induced reaction of allylic indium compounds

Intramolecular cyclization of allylic radicals generated from allylindium compounds both by photolysis or by the reaction of radical initiators was examined. The photolysis of allylic indium compounds, prepared from 8-bromo- or 8-iodooct-1,6-dienes and powdered indium metal, led to the formation of the 5-exo-trig products. Benzoyl peroxide as a radical initiator was also effective for the cyclization. In contrast, the radical initiators with oxidizing nature, such as tert-butyl hypochlorite, induced iodocyclization producing iodomethylcyclopentane via an oxidation of the iodide on the indium atom.     

Structural Effects in the Addition–Fragmentation Reaction of Allylic Onium Salts

Allylic onium salts with different hetero‐atoms and various substituent groups at the allylic double bond have been shown to be very efficient initiators for cationic polymerization. When attacked by a radical, they become radical cations, which are highly unstable species, and undergo fragmentation into smaller radical cations called onium radical cations. The reaction mechanism involves radical formation, addition and fragmentation. In our previous work, radical initiators generated in the same way and under the same conditions are studied experimentally for their ability to affect the polymerization efficiency. Here, the factors affecting the polymerization efficiency are discussed theoretically using semi‐empirical quantum mechanical techniques. The type of radical species, substituent group at the allylic side, the heteroatom at the onium side and the onium group itself are analyzed separately. For this purpose, the geometries of different onium radical cations to be fragmented are optimized and the strength of the C–heteroatom bond to be broken and the size of the radical cations after fragmentation are considered.     

Generation of allylic indium by hydroindation of 1,3-dienes and one-pot reaction with carbonyl compounds

A hydroindation of 1,3-dienes by dichloroindium hydride (HInCl2) generates allylic indiums that react with carbonyl or imine moieties in a one-pot treatment. The former reaction proceeds in a radical manner, and the latter is ionic allylation. Moreover, both reactions require no additives such as radical initiators, Lewis acids, or transition metal catalysts.     

Functionalized cyclopentanes via radical cyclizations using thiocarbonate derivatives as initiators and terminators

A radical-based cyclization is described that employs xanthates or cyclic thionocarbonates as initiators and allylic dithiocarbonates or allylic thiocarbamates as terminators.     

A Strategy for Controlling the Polymerizations of Thiyl Radical Propagation by RAFT Agents

The ability to extend the polymerizations of thiyl radical propagation to be regulated by existing controlled methods would be highly desirable, yet remained very challenging to achieve because the thiyl radicals still cannot be reversibly controlled by these methods. In this article, we reported a novel strategy that could enable the radical ring-opening polymerization of macrocyclic allylic sulfides, wherein propagating specie is thiyl radical, to be controlled by reversible addition–fragmentation chain transfer (RAFT) agents. The key to the success of this strategy is the propagating thiyl radical can undergo desulfurization with isocyanide and generate a stabilized alkyl radical for reversible control. Systematic optimization of the reaction conditions allowed good control over the polymerization, leading to the formation of polymers with well-defined architectures, exemplified by the radical block copolymerization of macrocyclic allylic sulfides and vinyl monomers and the incorporation of sequence-defined segments into the polymer backbone. This work represents a significant step toward directly enabling the polymerizations of heteroatom-centered radical propagation to be regulated by existing reversible-deactivation radical polymerization techniques.     

Photochemistry of carbonyl photoinitiators. Photopolymerisation,flash photolysis and spectroscopic study

The photochemistry of eight aromatic carbonyl based photopolymerisation initiators is examined and compared using u.v. absorption, phosphorescence, micro-second flash photolysis, steady-state photolysis and photopolymerisation rates for n-butyl methacrylate. In the latter case, conversion rates are significantly greater in the presence of a tertiary amine (diethylmethylamine). In both the presence and absence of the amine, the photofragmenting type initiators are more efficient than the hydrogen abstracting benzophenone. Benzil exhibits the most notable conversion rates from being the least efficient in the absence of the amine to the most efficient in its presence. There is no definite correlation between ε_max and phosphorescence quantum yields with photopolymerisation rates, although it is significant that overall the phosphorescence quantum yields are enhanced to varying extents by the tertiary amine. End-of-pulse transient absorption spectra between 300 and 380 nm (λ_{max at} ∼ 340 nm) for the photo-fragmenting initiators in 2-propanol are tentatively assigned to the benzoyl radical, whereas benzophenone gives the typical ketyl radical formed via hydrogen atom abstraction at ∼ 500 nm. In the former case, transient formation is reduced by up to 50% in the presence of the tertiary amine except for benzoin and Irgacure 184. In the case of benzophenone, ketyl radical formation is enhanced significantly. All transients are strongly quenched by oxygen indicating that the triplet state is directly involved in free radical formation. Transient formation from benzil appeared to be the least affected by oxygen and this effect may well account for its high efficiency during polymerisation. Addition of the hydrogen donors benzhydrol and a secondary amine (diethylamine) enhances ketyl radical formation in the case of benzophenone in 2-propanol, confirming the mechanism of hydrogen atom abstraction. In the cases of benzil and benzoin, transient formation is not affected indicating that photofragmentation is the primary step in free radical formation. A steady-state photolysis study in ethyl acetate in the absence and presence of the hydrogen atom donors appears to support this conclusion. The application of these results in terms of current mechanisms is discussed.     

Syntheses with Radicals—C?C Bond Formation via Organotin and Organomercury Compounds [New Synthetic Methods (52)]

C? C bond formation is one of the most important synthetic steps in the construction of organic molecules. In the last few years it has been increasingly achieved by radical addition to alkenes. In such reactions the adduct radicals have to be trapped by an donor subsequent to the C? C bond formation in order to prevent polymerization. This task can be accomplished with organotin and organomercury hydrides, the use of which has led to new synthetic methods. The occurrence of radical chain reactions in which reactions take place between radicals and nonradicals is decisive for the success of the synthesis. In these cases small amounts of radical initiators suffice and numerous functional groups may be used in the C? C bond-forming reactions. The yields and selectivities of these radical reactions are often very high.     

Polymerization of diethylene glycol bis(allyl carbonate) by means of di-sec-butyl peroxydicarbonate

The initial stages of the free radical polymerization of diethylene glycol bis(allyl carbonate) at temperatures of 35–65°C have been studied. The polymer is unsaturated and cyclization to give a 16-membered ring occurs only to a small extent. The kinetic order with respect to the initiator, di-sec-butyl peroxydicarbonate, has an average value of 0.79; the order increases slightly with peroxydicarbonate concentration over the range 0.018–0.22M. The molecular weight of the polymer isolated after 3% polymerization is close to 19,000. It shows no significant dependence on initiator concentration or on temperature. The dominant feature of the bulk polymerization, as in free radical polymerization of the other allyl and diallyl monomers, is degradative chain transfer in which the growing polymer radical abstracts a hydrogen atom from a monomer unit to give a relatively unreactive allylic radical. The dependence of rate on initiator concentration is rationalized if some of these allylic radicals are able to reinitiate polymerization. The transfer constant to monomer is 0.014 at 50°C, assuming that the main termination step involves mutual termination of allylic radicals. Carbon tetrachloride is an active transfer agent with a transfer constant of 0.20 ± 0.04 at 50°C. Toluene, which is less active, has a transfer constant of 0.0064 at 50°C and also retards the polymerization. Some kinetic studies have been made with other initiators, including di-2-methyl-pentanoyl peroxide which initiates polymerization at temperatures as low as 13°C.     

油溶和水溶性羰基引发剂的光化学

本文回顾了在羰基引发剂的作用下烯烃单体光引发聚合的最新机理。报道了有关多种当前通用的新型羰基引发剂的光物理和光化学的近期工作,其中包括 UV 吸收,发光光谱和闪光光解的研究。还报道了油溶性引发剂对丙烯酸丁酯的光聚合效应。证明油溶性引发剂实质上是经过三重态来起作用,其中包含一个从溶剂中攫取氢的引发步骤。对于硫杂蒽酮衍生物来说,它们从叔胺接受电子的能力及其光聚合效应之间有一定的关系。从闪光光解获得的证据说明在这种情况下存在着自由基阴离子,但是基于二苯酮和苯基酮的引发剂则没有。预料后者直接从胺攫氢是通过三重态羰基或是引发剂的自由基。有证据表明联苯甲酰主要是通过光裂解来起作用。水溶性硫杂蒽酮引发剂的作用主要是经过单重态,其中包含引发时攫氢一步。在这种情况下,自由基的形成不受氧的影响。     

Experimental evidence for cobalt(III)-carbene radicals: key intermediates in cobalt(II)-based metalloradical cyclopropanation

New and conclusive evidence has been obtained for the existence of cobalt(III)-carbene radicals that have been previously proposed as the key intermediates in the underlying mechanism of metalloradical cyclopropanation by cobalt(II) complexes of porphyrins. In the absence of olefin substrates, reaction of [Co(TPP)] with ethyl styryldiazoacetate was found to generate the corresponding cobalt(III)-vinylcarbene radical that subsequently dimerizes via its γ-radical allylic resonance form to afford a dinuclear cobalt(III) porphyrin complex. X-ray structural analysis reveals a highly compact dimeric structure wherein the two metalloporphyrin units are arranged in a face-to-face fashion through a tetrasubstituted 1,5-hexadiene C(6)-bridge between the two Co(III) centers. The γ-radical allylic resonance form of the cobalt(III)-vinylcarbene radical intermediate could be effectively trapped by TEMPO via C-O bond formation to give a mononuclear cobalt(III) complex instead of the dimeric product. The allylic radical nature and related reactivity profile of the cobalt(III)-carbene radical, including its inability to abstract hydrogen atoms from toluene solvent, were established by DFT calculations.     

Free radical ring‐opening polymerization of cyclic allylic sulfides: Liquid monomers with low polymerization volume shrinkage

The free radical polymerization of four methylated cyclic allylic sulfides was examined with reference to their polymerization volume shrinkage and the effect of ring size on reactivity. The compounds examined were 2‐methyl‐5‐methylene‐1,3‐dithiane ( 5 ) (solid), 2‐methyl‐6‐methylene‐1,4‐dithiepane ( 6 ) (liquid), 6‐methyl‐3‐methylene‐1,5‐dithiacyclooctane ( 7 ) (liquid), and 6,8‐dimethyl‐3‐methylene‐1,5‐dithiacyclooctane ( 8 ) (liquid). The monomers were stable materials not requiring any special handling or storage conditions. They were polymerized in bulk using thermal azobisisobutyronitrile (AIBN, VAZO88) and photochemical initiators (Ciba DAROCUR 1173) and in benzene solutions (AIBN, 70 °C). The six‐membered ring monomer 5 was unreactive whereas seven‐membered ring monomer 6 polymerized to high conversion in bulk. In addition, 6 did not polymerize in benzene solution at 70 °C at [ 6 ] = 1.25M. Eight‐membered ring monomers 7 and 8 polymerized in bulk to complete conversion with thermal and photochemical initiators to give lightly crosslinked materials. Near complete conversion to soluble polymers could be obtained in solution polymerizations in benzene. Soluble polymers were also obtained in photochemical initiated bulk polymerizations by lowering initiator concentrations or length of irradiation. The methyl substituent had no effect on which allylic carbon–sulfur bond fragmented in the ring‐opening step. The polymerization volume shrinkages of monomers 7 and 8 were 1.5 and 2.4% respectively and together with monomer 4 (1.5–2.0% shrinkage) are the best available liquid free radical ring‐opening monomers that can be polymerized in bulk at room temperature. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 202–215, 2001     

Regiochemistry in radical cyclization of allenes

The cyclization of allenic radicals was systematically studied for the first time by computational methods. It was found that the theoretical results at the ONIOM(QCISD(T)/6-311+G(2df,2p):UB3LYP/6-311+G(2df,2p)) level were in good agreement with all the available experimental data. For the cyclization of penta-3,4-dien-1-yl radicals the major product was penta-1,2-diene from direct reduction whereas a small amount of vinylcyclopropane may also be produced. For the cyclization of hexa-4,5-dien-1-yl radicals the major product is 1-methyl-cyclopentene. Furthermore, for the cyclization of hepta-5,6-dien-1-yl radicals both vinylcyclopentane and 1-methyl-cyclohexene are produced. Marcus theory analysis indicated that the formation of an olefinic radical product always had a lower intrinsic energy barrier than the formation of an allylic radical product. On the other hand, the formation of an olefinic radical product was always much less favorable than the formation of an allylic radical product in the thermodynamic term. For the cyclization of substituted hexa-4,5-dien-1-yl radicals, substitution at the allene moiety does not affect the regioselectivity where the allylic radical product is always favored. For the cyclization of hepta-5,6-dien-1-yl radicals, substitution at the allene moiety dramatically affects the regioselectivity, where some radical-stabilizing groups such as -CN and -COMe may even completely reserve the regioselectivity.     

STUDIES ON THE POLYMERIZATION OF 2,2,6,6-TETRAMETHYL PIPERIDINYL METHACRYLATE

The radical homo-and co-polymerization of 2,2,6,6-tetramethyl piperidinyl methacrylate (TM-PM) with various initiators have been studied. It was found that, with azo-type initiators, the poly-merization proceeded readily, while with acyl peroxide initiators, the polymerization was inhibitedeffectively because of the formation of the stable TMPM-oxyl radical, identified by ESR. Thisobservation was further confirmed by the absence of inhibition effect on the addition of 2,2,6,6-tetramethyl 4-piperidinol to the polymerization system, whereas remarkable inhibition was observed onthe addition of the stable 2,2,6,6-tetramethyl 4-piperidinol N-oxyl radical. The reaction mecha-nism was discussed. We also found that when TMPM reacted with BPO in petroleum ether, N-benzoyloxy 2,2,6,6-tetramethyl 4-piperidinyl methacrylate was formed, and this novel compound has been characterizedwith IR, ESR, NMR and Mass Spectroscopy.     

Molecular Radical Chain Initiators for Ambient‐ to Low‐Temperature Applications

An overview of methods for the initiation of radical chain reactions by specific initiator compounds, which generate radicals, is given. These can be utilized to initiate any kind of radical chain reaction by transforming substrates into the desired radical intermediates. Azo initiators, peroxides, nitroxides, trialkylboranes, dialkyl zinc compounds, and type I photoinitiators are discussed, as well as methods of redox‐ and sonochemical initiation. Methods of direct radical formation from the substrates, such as photoredox catalysis or high‐energy irradiation, are not included. The focus of this review lies on rather “low” temperatures in the range of 50 °C down to ?78 °C, which can be useful to achieve more selective reactions. Illustrative applications of such radical chain initiators in a variety of reactions are discussed, including stereoselective ones and polymerizations.     

固体酸／碱和引发剂促进渣油轻质化的初步研究

在塔河常渣悬浮床加氢转化体系中，外加固体酸、固体碱和自由基引发剂的方法用于促进渣油轻质化。结果发现，固体酸USY、HY和固体碱CaO、MgO不同程度地改变了渣油加氢裂化反应的生焦率和裂化转化率，其中对于生焦率的促进效果明显。自由基引发剂偶氮二异丁腈和过氧化特二丁基显著改变了塔河常渣裂化产物分布，有效地促进了渣油热裂化反应。渣油加氢裂化产物中气体收率和生焦率略有增加，裂化产物收率明显上升，尾油收率明显下降。随着自由基引发剂质量分数的增加，上述变化趋势更加明显。低温下自由基引发剂的改善效果明显优于在较高温度下的的改善效果。就以上两种引发剂相比，过氧化特二丁基的作用明显优于偶氮异丁腈。     

The Impact of Resonance Stabilization on the Intramolecular Hydrogen‐Atom Shift Reactions of Hydrocarbon Radicals

A series of intramolecular H‐atom shift reactions of both alkenyl and allylic radicals were investigated by using CBS‐QB3 electronic structure calculations. In the first set of reactions, an alkyl radical site was converted into an allylic radical site. In the second set, an allylic radical was converted into another allylic radical. The results are discussed in the context of a Benson‐type model to examine the impact of the transition‐state partial resonance stabilization on both the activation energies and the pre‐exponential factors. In most cases, the differences in the activation energies relative to those for the analogous alkyl radicals are primarily due to the barriers of the bimolecular reaction component of the activation energy. For the first set of reactions, there is additional entropy loss relative to the alkyl radical analogues. This additional loss of entropy may be smaller than some previous estimates. The pre‐exponential factors for the second set of reactions are generally similar to those of the analogous alkyl radical reactions (once the double bond in the transition state is accounted for).     

Fundamental studies of grafting reactions in free radical copolymerization. III. Grafting of styrene,acrylate, and methacrylate monomers onto cis-polybutadiene using benzoyl peroxide initiator in solution polymerization

Benzoyl peroxide (BPO), due to its higher radical reactivity as compared to AIBN, is known to promote grafting onto cis-polybutadiene. Switching from AIBN to BPO initiator made a dramatic difference in the extent of grafting for styrene and methacrylate monomers, but only a modest difference for acrylate monomer. For styrene and methacrylate monomers, graft site formation is due to BPO initiator radical attack onto the backbone via allylic hydrogen abstraction. Significant levels of grafting are achieved and depend upon the relative concentrations of monomer and backbone polymer but not upon the level of initiator. For acrylic monomer, graft site formation was found to be due to polymer radical attack at the double bond in the backbone. Abstraction of allylic hydrogen also occurs but results in retardation of the overall reaction rate. Graft level was dependent upon initiator and back-bone polymer concentrations but not upon monomer concentration. The effective role of the initiator is only to produce polymer radicals; the BPO has no direct role in the formation of effective graft sites. © 1995 John Wiley & Sons, Inc.     

Thiyl radical-mediated cleavage of allylic C-N bonds: scope, limitations, and theoretical support to the mechanism

Thiols mediate the radical isomerization of allylic amines into enamines. The reaction results in the cleavage of the allylic C-N bond, after treatment with aqueous HCl. The mechanism involves the abstraction of an allylic hydrogen alpha to nitrogen by thiyl radical, followed by a return hydrogen transfer from the thiol to the carbon gamma to nitrogen in the intermediate allylic radical. The scope and limitations of the reaction with respect to the nature of the thiol, to the structure of the allylic chain, and to the nature of the substituents at nitrogen were investigated. The experimental results were interpreted on the ground of DFT calculations of the C-Halpha BDE in the starting allylic amines, and of the C-Hgamma BDE in the resulting enamines. The efficiency of the initial hydrogen transfer is the first requirement for the reaction to proceed. A balance must be found between the S-H BDE and the two above-mentioned C-H BDEs. The incidence of stereoelectronic factors was analyzed through NBO calculations performed on the optimized geometries of the starting allylic amines. Additional calculations of the transition structures and subsequent tracing of the reaction profiles were performed for the abstraction of Halpha from both the allyl and the prenyl derivatives by p-TolS(*). The latter allowed us to estimate the rate constant for the abstraction of hydrogen by thiyl radical from an N-prenylamine and an N-allylamine.     

4-甲基丙烯酸2,2,6,6-四甲基哌啶醇酯自由基聚合的研究

本文研完了不同引发体系对带受阻胺基团的单体4-甲基丙烯酸2,2,6,6-四甲基哌啶醇酯(TMPM)自由基聚合的影响。分析比较了偶氮型引发剂和过氧化物引发聚合的结果,并讨论了以过氧化苯甲酰(BPO)引发TMPM聚合的阻聚机理。发现TMPM与BPO反应生成一个新的化合物——4-甲基丙烯酸-N-苯甲酰氧基2,2,6,6-四甲基哌啶醇酯。用IR、ESR、NMR及质谱等方法,对此化合物的结构进行了测定与表征。     

Coagulum formation and elimination in emulsion copolymerization of tribromostyrene with styrene

Coagulum formation in emulsion polymerization of tribromostyrene and also in its copolymerization with styrene has been shown to be due to thermal polymerization. The latter takes place in the monomer reservoirs, even in the absence of radical generating initiators, converting them into sticky particles which then form the undesired coagulum. The coagulum formation phenomenon can thus be remedied by reducing the thermal initiation level through a semi-batch emulsion polymerization method, by lowering the polymerization temperature, and reduction of the collision frequency of monomer/polymer particles.