Telomerization of ethylene and

Eberhardt and co-workers (12, 13) found that lithium alkyls are active toward the telomerization of ethylene and benzene when a tert-amine or chelating diamine, such as sparteine or N.N.JV. Af -tetramethylenethy-lenediamine (TMEDA), is used [Eqs. (1)—(3)]. 

Another byproduct of the reaction was a mixture of alkyl chlorides in which the alkyl groups had an even number of carbon atoms. These were obviously formed by telomerization of ethylene and hydrogen chloride 2). 

Fig. 36 Telomerization of ethylene and carbon tetrachloride and its relation to the Kharasch...

Asscher M, Levy E, Rosin H et al (1963) Telomerization of ethylene and carbon tetrachloride. Novel initiating system. Ind Eng Chem Prod Res Dev 2(2) 121-126... 

Freidlina RKh, Belyavskii AB (1961) Telomerization of ethylene and carbon tetrachloride or chloroform in the presence of the hexac arbonyls of chromium, molybdenum and tungsten. Izv Akad Nauk SSSR Otd Khim Nauk 1 177-178... 

Polyamide 11 is commercially produced by the polycondensation of 11-amino undecanoic acid, which is obtained from castor oil (see also Chapter 24). The monomer is also obtained by telomerization of ethylene and carbon... 

Carbon tetrachloride forms telomers with ethylene and certain other olefins (14—16). The mixture of Hquid products derived from ethylene telomerization may be represented CCl2(CH2CH2) Cl ia which nis 2l small number. Reaction of ethylene and carbon tetrachloride takes place under pressure and is induced by the presence of a peroxygen compound, eg, ben2oyl peroxide (17—19) or metal carbonyls (14,15). 

To circumvent the formation of ditelomers and to attempt recycling of the catalysts, the telomerization of polyols was studied in the presence of water using water soluble catalysts such as Pd/TPPTS (TPPTS = tris(m-sulfonato-phenyl) phosphine trisodium salt) [9, 12, 16, 17]. Behr et al. studied the telomerization of ethylene glycol under biphasic conditions. Under such reaction conditions, 80% of mono-telomer are formed and only traces of ditelomer and butadiene dimers are detected (Fig. 4). This is attributed to the solubility of the monomer in the catalyst phase. However, the catalyst is unstable and decomposes rapidly, leading to almost inactive catalyst after three runs. This is due to TPPTS oxidation during the work-up of the reaction and can be avoided by addition of 2.5 equiv. ligand in the solution prior to each run. 

Parvulescu et al. noted an interesting change in EG telomer product selectivity upon immobilization of an Pd/TPPTS catalyst on a basic support [58]. In an attempt to address the issues associated with recovery and reuse of the telomerization catalyst, the anionic TPPTS ligand was immobilized on various layered double hydroxides by ion exchange methods (Scheme 11). The use of these catalysts in the telomerization of methanol and ethylene glycol resulted in a remarkable shift in... 

If kp ktr and kr kp, there will be a large number of transfer reactions compared to propagation reactions, and only a low-molecular-weight polymer will be made. This process, called telomerization, is illustrated by the radical reaction of ethylene and CCI4 which yields waxy products of the general structure Cl(CH2CH2)nCCl3 with n < 12. The chain transfer and reinitiation reactions in this case are... 

Carbon dioxide has been object of detailed studies either as anion radical scavenger or as direct electrochemical substrate in organic syntheses. Among the dozens of examples of electroorganic syntheses of mono- and dicarboxylic acids even a telomerization of ethylene with C02 has been reported56,57. The reaction has the following stoichiometry ... 

Ethylenation of n-butyllithium, phenyllithium, and benzylic lithium compounds does not occur at low temperature and ordinary pressure (9). Under more rigorous conditions, telomerization of ethylene in aromatic hydrocarbons proceeds vigorously in the presence of an organolithium compound and an amine. Although n-butyllithium is introduced initially, rapid transmetalation occurs to the more acidic aromatic hydrocarbon (telogen) which subsequently adds to ethylene (taxogen) and initiates the carbanionic polymerization of ethylene. This polymerization proceeds to modest molecular weight, but it is terminated by transmetalation back to the aromatic hydrocarbon which initiates another chain to complete the catalytic cycle. 

The rate of telomerization of ethylene in toluene is, as expected, directly proportional to the RLi-TMEDA concentration at 0.04M to 0.10M (Table IV). Thus solubility of the catalyst is not a limiting factor at these concentration levels. With other amines, the influence of structure and concentration is analogous to that discussed in connection with transmetalation. 

Much of the early work with N-chelated organolithium compounds was concerned with polymeric reactions—in particular the telomerization of ethylene onto aromatic hydrocarbons such as benzene and toluene to produce long-chain alkylbenzenes (6,7, 8, 9). 

All the above reactions involve hydrogen—lithium interconversion (metalation). There are a limited amount of data available indicating that N-chelated organolithium intermediates also undergo nucleophilic addition to carbon-carbon double and triple bonds much more readily than does the organolithium reagent alone. Indeed, this enhanced reactivity toward addition reactions is a key factor in the telomerization of ethylene onto aromatic hydrocarbons (6, 7,8,9). 

An attempt to telomerize 1,1,1,5-tetrachloropentane (itself a 2 1 telomer of ethylene and tetrachloromethane) with ethylene, propylene, or vinylchloride in the presence of Fe(CO)5 and isopropanol gave only 1 1 adducts (normal Kharasch addition) [33] (Fig. 38). 

Fig. 37 Telomerization of ethylene, propylene, vinylchloride and vinylidenechloride with chloroform, 1,1,1,-trichloroethane and 1,1,1,3-tetrachloropropane [33-36, 61, 62]...

Zhiryukhina NP, Kamyshova AA, ETs C et al (1983) Synthesis of polychloroalkanes with several different chlorine-containing groups. Izv Akad Nauk SSSR Ser Khim 1 152-157 Freidlina RKh, Osipov BN (1971) Telomerization of ethylene with 1, 1, 1, 3-tetrachloropro-pane in the presence of iron pentacarbonyl and isopropyl alcohol. Izv Akad Nauk SSSR Ser Khim 12 2837-2839... 

Nylon 7 and nylon 9 are part of a process developed in Russia to form polyamides for use in fibers. The process starts with telomerization of ethylene. Afree-radical polymerization of ethylene is conducted in the presence of chlorine compounds that act as chain-transferring agents. The reaction is carried out at 120-200 C temperature and400-600 atmospheres pressure. The preferred chain-transferring agents for this reaction are CCI4 and COCh ... 

Although acetonitrile is one of the more stable nitriles, it undergoes typical nitrile reactions and is used to produce many types of nitrogen-containing compounds, eg, amides (15), amines (16,17) higher molecular weight mono- and dinitriles (18,19) halogenated nitriles (20) ketones (21) isocyanates (22) heterocycles, eg, pyridines (23), and imidazolines (24). It can be trimerized to. f-trimethyltriazine (25) and has been telomerized with ethylene (26) and copolymerized with a-epoxides (27). 

The conventional procedure involves 5 steps via telomerization of perfluoro-alkyl iodide with perfluoroethylene and ethylene followed by oxidation. The estimated scale of perfluorination of C8H17COOH or CH3S03H at a Ni anode in liquid HF in the US, Japan and UK amounts to about 100 tonnes per year cf. Table 8. 

The new recycling concept was apphed to several C - C bond-forming reactions, for example, to the telomerization of butadiene with ethylene glycol or carbon dioxide, to the isomerizing hydroformylation of frans-4-octene and to the hydroamino-methylation of 1-octene with morpholine. 

The telomerization of butadiene with ethylene glycol was chosen as an example for a reaction of a polar and a non-polar substrate to a semipolar product (Scheme 1). 

The catalyst system Pd(acac)2/TPPTS (TPPTS = trisulfonated triphenylphos-phine) was used in the experiments in which the telomerization of butadiene with ethylene glycol in TMS systems was investigated. However, the catalyst precipitates from many solvent mixtures as a yellow oil or solid, as soon as a homogenous phase is obtained. For this reason the solubihty of the catalyst was determined in various solvent systems. A solution of the catalyst in the mixture of ethylene glycol and water (si) and toluene (s2) was used in a weight ratio of 1 3. The various mediators s3 were added until a clear solution was formed or the catalyst precipitated. Only with DMF or DMSO can a clear solution be obtained. The addition of the catalyst to the polar phase causes an increase in the amount of s3 required to achieve a homogeneous system in the solvent system si toluene DMF the ratio increases from 1 5 4 to 1 5 4.4. 

Catalysis experiments were performed to investigate the telomerization of butadiene with ethylene glycol in selected TMS systems (e.g. si toluene DMF 1 5 4 or sl 2-octanol DMSO 1.35 3 5.2). With Pd/TPPTS as the catalyst a maximum yield of only 10% of the desired products could be achieved. With Pd/TPPMS the yield increased up to 43% in the TMS system si toluene isopropyl alcohol, but additional water had to be added to obtain a phase split after the reaction. The catalyst leaching is very high and 29% of the palladium used is lost to the product phase. 

Selective modification of polyols such as ethylene glycol, 1,3-propylene glycol, or glycerol with butadiene (1) has been studied [7-10]. The monosubstituted compounds are preferred due to their potential applications as surfactants, PVC plasticizers, or even in cosmetics. The telomerization of 1 with ethylene glycol yields a complex mixture including linear and branched mono- and ditelomers, as well as 1,3,7-octatriene and vinyl cyclohexene (Fig. 2) [11]. 

Recently, the Pd/TOMPP catalytic system was used in the telomerization of butadiene with a series of polyols and TON up to 10,000 was achieved with ethylene glycol or 1,3-propanediol [14],... 

Ethylene glycol (EG) may be obtained from cellulose by many ways, for instance, by the catalytic conversion over carbide catalysts [71], It is the simplest linear polyol available and often serves as a model for more complex substrates. Many reports are therefore available on the telomerization of EG. The possible telomer products are shown in Scheme 14, the linear mono-telomer typically being the desired compound. The mono-telomer can be used, after saturation of the double bonds, as a plasticizer alcohol in polyvinylchloride production, whereas application in cosmetics and surfactants has also been indicated [72]. Early examples include the work of Dzhemilev et al., who first reported on the telomerization of butadiene with EG in 1980, yielding a mixture of the mono- and di-telomers and butadiene dimers using a palladium catalyst activated by AlEt3 [73]. Kaneda also reported the use of EG in... 

---