Isomeric allylic chlorides

Mixtures of isomeric allylic chlorides are formed when 1,1-disubstituted allenes react with HC1.1,3-Disubstituted allenes yield products of both central and terminal carbon attacks. In contrast, selective transformations occur with HBr. The gas-phase, photocatalytic addition of HBr gives selectively vinylic bromides129 [Eq. (6.20)], while hydrobromination in solution phase yields allylic bromides130 [Eq. (6.21)] ... 

Both isomeric allylic chlorides (96) and (97) yield the vinyl phosphonate... 

Intramolecular addition of a 1,3-diene having a carbon nucleophile in the side chain is catalyzed by Pd(II), leading to an overall 1,4-oxidation of the diene (Scheme 10). Allylsilane can be used as a carbon nucleophile in the Pd(II)-catalyzed carboannulation. The reaction of the 1,3-diene (E)-29 with a catalytic amount of Li2PdCl4 in the presence of p-benzoquinone (1.5 equiv), which acts as an oxidant of Pd(0) generated in the reaction, and LiCl (2 equiv) in acetone-acetic add (2 1) gives a mixture of two isomeric allylic chlorides 30 (a/)3 = 3 1) in 68% yield (Scheme 11). The addition of the carbon and chloride across the diene proceeds completely in a stereoselective manner and only the l,4-5yn-addition products are obtained. 

Examples for necessary process improvements through catalyst research are the development of one-step processes for a number of bulk products like acetaldehyde and acetic acid (from ethane), phenol (from benzene), acrolein (from propane), or allyl alcohol (from acrolein). For example, allyl alcohol, a chemical which is used in the production of plasticizers, flame resistors and fungicides, can be manufactured via gas-phase acetoxylation of propene in the Hoechst [1] or Bayer process [2], isomerization of propene oxide (BASF-Wyandotte), or by technologies involving the alkaline hydrolysis of allyl chloride (Dow and Shell) thereby producing stoichiometric amounts of unavoidable by-products. However, if there is a catalyst... 

When aqueous NaOH is given as a base, isomerization of the product butenoic acids can be extensive depending on the nature and concentration of base. In dilute aqueous solutions alcohols do not react to form the respective esters, however, the reactions are strongly accelerated due to the increased solubility of the substrates in the catalyst-containing aqueous-alcoholic phase. For example, with 23-33 % (v/v) ethanol in water the [PdCl2(TPPTS)2]-catalyzed hydroxycarbonylation of allyl chloride proceeded with TOF-s of 1850-2400 h and with a vinylacetic/crotonic acid ratio of 21 [16]. Addition of [CuCb] increased the overall conversion rate (by a factor of 2 at [Cu]/[Pd] = 8) but at the same time the side reactions... 

Subsequently to rhodium coordination with the enyne to form X, oxidative addition with the allyl chloride affords a rhodium-7r-allyl complex. Then isomerization... 

A single chloro compound, trans-1 -phenyl-3-chloro-1 -butene (7), is formed in hydrochlorination of isomeric 1-phenyl-1,3-butadienes in AcOH135 (Scheme 6.2). The observation is interpreted by the formation of different isomeric allylic carbo-cations (6c and 6t). Rapid rotation of 6c to 6t before captured by the chloride ion ensures selective formation of 7. 

Allyl Chloride. The manufacture of allyl chloride, commercialized in 1945, was the first of several modem high-temperature chlorination technologies applied for hydrocarbons. Preheated dry propylene mixed with dry chlorine in a ratio of 4 1 is reacted at 500-510°C to produce allyl chloride.193-195 Chlorine reacts quantitatively in a few seconds. The main byproducts are isomeric monochloropropenes and dichloropropenes. Allyl chloride is used mainly in the manufacture of allyl alcohol and glycerol via epichlorohydrin. 

There are four processes for industrial production of allyl alcohol. One is alkaline hydrolysis of allyl chloride. A second process has two steps. The first step is oxidation of propylene to acrolein and the second step is reduction of acrolein to allyl alcohol by a hydrogen transfer reaction, using isopropyl alcohol. At present, neither of these two processes is being used industrially. Another process is isomerization of propylene oxide. Until 1984. all allyl alcohol manufacturers were using this process. Since 1985 Showa Denko K.K. has produced allyl alcohol industrially by a new process which they developed- This process, which was developed partly for the purpose of producing epichlorohydrin via allyl alcohol as the intermediate, has the potential to be the main process for production of allyl alcohol. The reaction scheme is as follows ... 

The addition of sodium phenylsulfinate nucleophiles to stereodefined acyclic allylic chlorides was reported to proceed with complete overall retention of configuration, indicating that this nucleophile adds with inversion of configuration, i.e. via attack at the allyl ligand (equation 193).21S A cyclohexenyl acetate substrate also showed predominant ligand addition, but some isomeric product was also produced (equation 194).216 This loss could be due to acetate epimerization of starting material, ir-allyl epimeriza-tion by PdL2, or by attack of the sulfur at the metal, followed by reductive elimination. 

Isoprenylation of Isopropenyl groups.1 Cyclic terpenes substituted by an isopropenyl group can be converted into sesquiterpenes with the bisabolane skeleton by addition of HOC1 under biphasic conditions to give an allylic chloride (10, 208-209) followed by a zinc-induced reaction with isovaleraldehyde to form an isomeric mixture of homoallylic alcohols. 

The direct allylation of aromatic compounds with allylic chlorides is achieved in the presence of a catalytic amount of indium metal. According to the authors, indium is considered to act as a Lewis acid (Equation (101)).399 Trialkylindiums react with acid chlorides to give ketones. When trialkylindiums are treated with air prior to the reaction with acid chlorides, esters are formed (Scheme 121).400 The reaction of cyclopentadienylindium(i) with aldehydes in aqueous media gives mixtures of the isomeric coupling products (Equation (102)).401... 

The isomerization of 3-chloropropene (allyl chloride) involves a transfer of the chlorine atom between two terminal carbon atoms, through an allylic TS state. The structures of the reactant, TS and the kinetic product are shown in Figure 4-20. Again, due to the reactant-product symmetry, only the part of the reaction path leading from the TS to a kinetic product will be discussed here. 

If we make the two ends of the allyl system more similar, say one end primary and one end secondary, things are more equal. We could consider the two isomeric butenyl chlorides. 

The palladium-catalyzed reaction of allyl chloride 11 with the benzyne precursor 104 to produces phenanthrene derivatives 131 is also known [83]. A plausible mechanism for this intermolecular benzyne-benzyne-alkene insertion reaction is shown in Scheme 38. Initially n-allyl palladium chloride la is formed from Pd(0) and 11. Benzyne 106, which is generated from the reaction of CsF and 104, inserted into la to afford the aryl palladium intermediate 132. A second benzyne insertion into 132 produce 133 and subsequent carbopalladation to the alkene afford the cyclized intermediate 134. f>- Iydride elimination from 134 followed by isomerization gave 9-methylphenanthrene 131. 

Bis(triphenylphosphine)palladium dichloride [(Ph3P)2PdCl2] can also be used as a catalyst for the phase-transfer carbonylation of halides. However, considerably more drastic conditions [95°C, 5 atm] are required when compared with Co2(CO)8 (44). The carbonylation of allyl chlorides can be catalyzed by nickel tetracarbonyl, giving isomeric mixtures of bu-tenoic acids. There is evidence for the intermediacy of polynuclear nickel-ates in this phase-transfer process (45). Acetylene insertion did not occur... 

The presence of a discrete organometallic species as well as the stereochemistry of the metalated diene were first checked by iodinolysis and bromolysis,but the corresponding iodo- and bromodienes were found to be unstable and rapidly isomerized to a mixture of E and Z isomers. Thus, in order to have a better picture of the stereochemical outcome of the process, the crude reaction mixture was treated with AT-chlorosuccinimide (Scheme 37), and the corresponding chlorodiene 103 was isolated in 60% yield with an isomeric ratio >98 2. As alternative solution, the stereochemistry of the reaction was also determined by addition of allyl chloride, in the presence of a catalytic amount of copper salt, to the dienyl zirconocene derivative [74]. Skipped triene 104 was... 

As usual, to further increase the scope of the reaction, transmetalation of dienyl zirconium complexes, such as 124-127Zr, into the corresponding dienyl organocopper derivatives was performed. Surprisingly, when 126Zr was trans-metalated to copper derivatives by addition of a catalytic amount of CuCl/2LiCl in the presence of allyl chloride for 1 h at +50 °C, a partial isomerization of the dienyl system was found (Scheme 49). 

Therefore, the isomerization reaction was also performed starting from the a-substituted enol ether 119 (Scheme 52). By using the tandem allylic C-H activation-elimination reactions, Z-120c is initially formed and by a transmetalation reaction into organocopper with a stoichiometric amount of CuCI/ 2LiCl, followed by heating at +50 °C for 1 h and reaction with allyl chloride, the resulting ( , )-diene 122 is obtained with an isomeric ratio of 90 10 but in a low 40% yield as described in Scheme 52. 

The preparation of cyclopropene has been achieved in the reaction of allyl chloride with sodium amide 1-Alkylcyclopropenes have analogously been synthesized from 2- and 3-alkylallyl chlorides but the products are liable to isomerize under the strongly basic conditions to alkylidenecyclopropanes and 1-alkenylcyclopropanes. The use of potassium amide gives the rearranged products in a higher extent than that with sodium amide (equation 24). Methylenecyclopropane has been prepared by the successive treatments... 

Castro and Kray have reduced the isomeric butenyl chlorides, using chromous sulfate (5). Again, allylic radicals were proposed as intermediates in the reaction. However, unlike the tin hydride reductions, 1-butene was obtained almost exclusively from each of the isomeric chlorides. The process has been described as occurring within a chromium complex. The preponderant formation of 1-butene from butenyl metal complexes has also been noted by others (12, 23, 46). 

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