Benzenes allylic alcohols

Isoamyl acetate Heptane Dioxane Benzene Allyl alcohol... 

Aside of benzene the chemist has a choice in which allyl she can use. Allyl alcohol, allyl bromide or allyl chloride can be used with equal success but allyl alcohol is a nice bonus because it is easier... 

Allyl alcohol, TsOH, benzene, — H20. These conditions were used to pre-... 

The checkers found this distillation to require about 15 hours. The distillate is the ternary azeotrope. It consists of 8.5% water, 9.2% allyl alcohol, and 82.2% benzene, and boils at 68.2°. The aqueous layer contains some allyl alcohol, though this loss is insignificant, since only about 15 ml. of the aqueous layer is obtained from each mole of lactic acid used. 

Allyl alcohol [107-18-6] M 58.1, b 98°, d4 0,857, no 1.4134. Can be dried with K2CO3 or CaSOa, or by azeotropic distn with benzene followed by distn under nitrogen. It is difficult to obtain peroxide free. Also reflux with magnesium and fractionally distd [Hands and Norman Ind Chem 21 307 1945],... 

Using the above procedures, allyl a-azido alkyl ethers of type 281 were prepared by employing an unsaturated alcohol such as allyl alcohol [76] (Scheme 32). The reaction of an aldehyde with allyl alcohol and HN3 in a ratio of 1 3 9 carried out in the presence of TiCl4 as catalyst provided azido ethers 281, 283, and 285 in 70-90% yield. The ratio of reagents is critical to ensure a high yield of azido ether and to prevent formation of acetal and diazide side products [75]. Thermolysis of azido alkenes 281, 283, and 285 in benzene (the solvent of choice) for 6-20 h led to 2,5-dihydrooxazoles 282,284, and 286, respectively, in 66-90% yield. 

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... 

It has also been shown that dimethylsilyl enolates can be activated by diisopropylamine and water and exhibit a high reactivity toward iV-tosyl imines to give Mannich-type reaction products in the absence of a Fewis acid or a Bronsted acid.51 For example, the reaction of [(1-cyclohexen-l-yl)oxy]dimethylsilane with 4-methyl-A -(phenylmethylene)benzene sulfonamide gave re/-4-methyl-N- (f )-[(15)-(2-oxocyclohexyl)phenyl-methyl] benzenesulfonamide (anti-isomer) in 91% yield stereoselectively (99 1 anti syn) (Eq. 11.30). On the other hand, Fi and co-workers reported a ruthenium-catalyzed tandem olefin migration/aldol and Mannich-type reactions by reacting allyl alcohol and imine in protic solvents.52... 

In 1959, Kharasch et al.43 reported an allylic oxyacylation of olefins. In the presence of f-butyl perbenzoate and a catalytic amount of copper salt in refluxing benzene, olefin was oxidized to allyl benzoate, which could then be converted to an allyl alcohol upon hydrolysis. It is desirable to introduce asymmetric induction into this allylic oxyacylation because allylic oxyacylation holds great potential for nonracemic allyl alcohol synthesis. Furthermore, this reaction can be regarded as a good supplement to other asymmetric olefinic reactions such as epoxidation and dihydroxylation. 

Additional results of the enhancement in phenol conversion (to dihydroxy benzenes) and oxidation of allyl alcohol (to glycidol and allylic oxidation products) catalyzed by TS-1 in various solvents are illustrated in Fig. 46. In solvents with high dielectric constants, the heterolytic cleavage of the 0-0 bond... 

In situ EPR experiments in the presence of different substrates (allyl alcohol, benzene, phenol, or toluene) reveal that type A species is involved in epoxidation reactions. Species B is more active than A in ring hydroxylation reactions. A comparison of the toluene results with those of phenol/benzene suggests that while species B is involved in ring hydroxylations, the A-type species are possibly involved in... 

Acetyl chloride, see 1.1.1-Trichloroethane Acetyl-CoA, see Cyclohexane Acetylene, see Benzene. Ethylenimine, Hexachloroethane, TCDD Acrolein, see Acrylonitrile, Allyl alcohol, Atrazine. Acrylamide, see Acrylonitrile Acrylic acid, see Acrylamide, Ethyl acrylate. Methyl acrylate... 

Acrylonitrile, Alachlor. Allyl chloride, Allyl alcohol. Benzene, Butane, Chloroethane, Cyclohexene, Chloroprene, Cvclonentene. Dazomet. 1,1-Dichloroethylene, s/m-Dichloromethyl ether, Dimethylamine, A,lV-Dimethylaniline, 2,3-Dimethylbutane, 1,4-Dioxane, Epichlorohydrin,... 

The first reactions concerned (Simons and Archer, 27) alkylation of benzene with propylene to form isopropylbenzene, with isobutene to form f-butylbenzene and di-f-butylbenzene, and trimethylethylene to form amylbenzene. Later on (Simons and Archer, 28) studied these and other reactions in more detail and showed that high yields could be obtained and that the product was not contaminated with tars or other obnoxious impurities. It was shown that the products obtained with trimethylethylene were mono- and di-f-amylbenzene, that phenyl-pentane resulted from the use of pentene-2, and that cyclohexene produced cyclohexylbenzene. Cinnamic acid reacted with benzene (Simons and Archer, 29) to form /3-phenylpropionic acid and allyl benzene reacted with benzene to form 1,2-diphenylpropane. It is interesting to note that although allyl alcohol reacted with benzene to form 1,2-diphenylpropane, the intermediate in the reaction, allylbenzene, was isolated and identified. This shows that in this case the hydroxyl reacted at a more rapid rate than the double bond. Both di- and triisobutylene reacted with phenol (Simons and Archer, 30) at 0°, when using hydrogen fluoride containing only relatively small quantities of water, to form f-butyl-benzene, but diisobutylene with 70% hydrogen fluoride produced p-f-octylphenol. Cyclohexene reacted with toluene to form cyclohexyl-toluene and octene-1 rapidly reacted with toluene to form 2-octyltoluene (Simons and Basler, 31). 

Butyl alcohol and benzene gave both mono- and di-i-butylbenzene (Simons et al., 37). Allyl alcohol reacted with benzene to produce both allylbenzene and 1,2-diphenylpropane. (Simons and Archer, 38.) The activity of the hydroxyl group is indicated in the fact that 2-phenyl-propanol was not separated. Benzyl alcohol reacted with benzene to form diphenylmethane (Simons and Archer, 39) despite the fact that this reaction is reported (Calcott et al., 34) to form 1,2,3,4,5,6-hexa-phenylcyclohexane by the polymerization of the alcohol. Isopropyl alcohol with benzene gave isopropylbenzene, 1,4-diisopropylbenzene,... 

Danishefsky dienes [98] cycloadd to Cjq in refluxing toluene or benzene [5, 38, 99-101]. The diene 103 adds in 60% yield to Cjq to give the desilylated ketone 104 [5,101]. Acid-catalyzed methanol elimination then furnishes the enone 105 in 82% yield (Scheme 4.17). As already described, this enone can be reduced by DIBAL-H to the corresponding alcohol for further functionalization. The same a,(3-un-saturated alcohol can also be obtained in better yield by Diels-Alder reaction of Cg0 with butadiene, followed by oxidation with singlet oxygen to the allylic hydroperoxide and PPhj reduction to the desired alcohol [101]. This sequence yields the allylic alcohol in 53%, starting from Cjq without the need of isolating intermediates. 

Rather different are two N-alkylations effected with mercuric acetate 9-(3-oxobut-l-yl)carbazole (29 R = CH2CH2COCH3) was formed from car-bazole and but-l-en-3-yne in ethanolic solution containing a trace of concentrated sulfuric acid/° and a low yield of 9-allylcarbazole was produced on reaction with allyl alcohol in benzene... 

The copper-catalyzed photobicyclization of acyclic 1,6-dienes to bicyclo[3.2,0]heptanes using the bis[copper(l) lrifluoromethanesulfonate]benzene complex has found general and synthetic utility in the conversion of diallyl and homoallyl vinyl ethers to 3- or 2-oxabicyclo[3.2.0]heptanes,5 6 of /V-allyl-A -2-methyl-2-propenecarbamates to iV-carboethoxy-3-azabicyclo[3.2.0]heptanes 7 and of allylic alcohols to the corresponding hydroxy-substituted bicyclo[3.2.0]heptanes.8 9 Examples of such reactions are summarized below. 

The oxidation of various secondary alcohols, including the allylic alcohols carveol (5) and P-ionol (4), leads to the corresponding ketones in 70-80 % yield (Eq. (3), Table 7). Oxidation of (—)-carveol (J) with nickel peroxide (2.5 eq., 50 °C, benzene) yielded only 33 % ketone. 

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