M-Methyl benzyl chloride

The mixture is heated under reflux for 1 hour, the mass is cooled and a molar equivalent of m-methyl benzyl chloride is added. 

The method described is successfully used for the alkylation and aralkylation of ethyl and /-butyl phenylacetate.3 The alkylation of ethyl phenylacetate with methyl iodide, M-butyl bromide, benzyl chloride, and a-phenylethyl chloride affords the corresponding pure monoalkylation products in 69%, 91%, 85%, and 70% (erythro isomer) yields, respectively. The alkylation of /-butyl phenylacetate with methyl iodide, M-butyl bromide, a-phenylethyl chloride, and /3-phenylethyl bromide gives the corresponding pure monoalkylated products in 83%, 86%, 72-73%, and 76% yields, respectively. 

Certain of the monoalkylated ethyl phenylacetates have been further alkylated with alkyl and aralkyl halides to produce the corresponding disuhstituted phenylacetic esters.4 Ethyl 2-phenyl-propanoate has been alkylated by methyl iodide to give pure ethyl 2-methyl-2-pheny]propanoate in 81% yield. Similarly, the alkylations of ethyl 2-phenylhexanoate with methyl iodide, M-butyl bromide, and benzyl chloride gave the corresponding pure dialkylated products in 73%, 92%, and 72% yields, respectively. 

Dichloromethane solutions of some sterically congested benzyl chlorides and triethylsilane need only the addition of excess trifluoroacetic acid to promote rapid conversion of the chlorides to the related hydrocarbons.128 Thus 2,4,6-trimethylbenzyl chloride produces a 79% yield of isodurene at room temperature after 2.5 hours, 2-methyl-4,6-di-/m-bu(ylbenzyl chloride gives 50% 1, 2-di-methyl-4,6-di-tm-butylbenzene after 40 minutes at reflux, and 2,4,6-tm-butyl-benzyl chloride gives a 100% yield of 2,4,6-tri-rm-butyltoluene within 17 minutes at reflux (Eq. 54). The unsubstituted parent benzyl chloride remains unreacted under these conditions even after 30 days.128... 

Benzol hjthiophene, see Naphthalene 1,2,3-Benzotriazin-4 (3/J -one, see Azinnhos-methyl Benzotriazole, see Tetrachloroethylene Benzyl alcohol, see Benzo[a]anthracene, Benzyl butyl phthalate. Benzyl chloride, Permethrin. o-Xylene, m-Xylene, p-Xylene. Toluene 0-Benzyl alcohol, see o-Xylene m-Benzyl alcohol, see m-Xylene p-Benzyl alcohol, see p-Xylene 10-Benzyl-10-hydroanthracen-9-one, see Benzo [ a] anthracene Benzyl hydroperoxide, see Toluene Benzyl nitrate, see Toluene Benzylsuccinic acid, see Toluene... 

Hydracrylic acid, see p-Propiolactone Hydrazobenzene, see Aniline Hydriodic acid, see Methyl iodide Hydrobromic acid, see Bromodichloromethane, Bromoform, Methyl bromide, Metobromuron Hydrochloric acid, see Alachlor. Aldrin, Benzyl chloride, a-BHC, p-BHC, Bis (2-chloroethyl) ether, Bis(2-chloroisopropyl) ether, Bromacil. Bromodichloromethane, Carbon tetrachloride, Chloroethane, Chloroform, o-Chloronitrobenzene. Chloropicrin, Chloroprene, p-Chloronitrobenzene, 2,4-D, see Dalanon-sodium. p.p -DDD, p,p -DDT, Dicamba. 1,1-Dichloroethane, 1,1-Dichloroethylene, fratts-l,2-Dichloroethylene, s/m-Dichloromethyl ether, 2.3-Dichloronitrobenzene. 3.4-Dichloronitrobenzene. 1,2-Dichloropropane, cis-1,3-... 

A solution of LDAinTHF [prepared from 7.84 g (77.5 mmol) of diisopropylamine and 33.7 mL (77.5 mmol) of butyllithium (2.3 M in hexane) in 70 mL of dry I HF is added dropwise to a stirred solution of 15.9 g (77.5 mmol) of (- )-(4S.5S )-4,5-dihydro-4-methoxymethyl-2-methyl-5-phenyIo>cazolc in 200 mL of THF at — 78 C over 30 min under nitrogen. The mixture is stirred for 45 min at — 78 X and a solution of 11.77 g (93.0 mmol) of benzyl chloride in 40 mL of THF is added slowly (2-3 h). After complete addition, the mixture is stirred an additional 4 h and then allowed to slowly warm to — 50 X (to avoid poiyalkylation) and quenched by pouring into ice water. The aqueous mixture is extracted with three 150-mL portions of diethyl ether and the combined ether extract is then washed with sat. brine, dried over MgS04 or Na2S04, and concentrated. The pure 4,5-dihydrooxazole is obtained by distillation and verified by GC (>99% purity) yield 13.0 g (57%) bp 145-147 C/0.03 Torr [ ] —59.1 (c = 8.4, ethanol). 

All data obtained on the rate of reaction of [Ni(NiL2)2]Cl2 with alkyl halides— i.e., methyl iodide, benzyl bromide, benzyl chloride, p-nitrobenzyl chloride, p-chlorobenzyl chloride, ethyl bromide, ethyl iodide, n-propyl bromide, and n-propyl iodide—conform closely to a pseudo-first-order rate law. Almost all experiments were carried out in the presence of an excess of alkyl halide. Since methanol solutions of the alkylated complexes have only negligible absorption at 495 m//, rates were obtained by graphs of log A0—A vs. time. The graphs are linear over the entire time interval, which corresponds to more than two half lives in most cases, passing through the origin at zero time. The rate is essentially the same whether measured by the spectrophotometric or conductivity method. 

Methyl a-D-glucopyranoside (7.6 g), in dry pyridine (lOOmL) and benzyl chloride (7.6 g), was refluxed with a calcium chloride tube fitted to the top of the condenser for 9 h. After cooling to room temperature, acetic anhydride (20 mL) was added, and the solution allowed to stand overnight Excess water was added, and the mixture was extracted with benzene. The benzene layer was washed with, in turn, ice cold 1 M sulfuric acid, saturated aqueous sodium bicarbonate, and finally water. The benzene solution was dried over magnesium sulfate, filtered and concentrated. The dark-colored residue was recrystallized to yield methyl 2,3-di-0-acetyl-4,5-0-benzylidene-a-D-glucopyranoside 21 mp 101-104°C, [a]D +75° (c 1.0, chloroform). Part of die material was deacetylaied with 1.67% ammonia in methanol to yield methyl 4,6-0-benzylidene-a-D-glucopyranoside 19 mp 161-163°C undepressed on admixture with an authentic sample. 

Excess benzyl bromide and triethylamine in the presence of tin(II)chloride catalyst were used [91] for partial benzylation of methyl a-L-rhamnopyranoside and its 4-O-benzyl ether. Complexation of tin(II)chloride with vicinal m-disposed hydroxyl groups permitted selective benzylation at the 3- and 2-positions. Methyl 3-O-benzyl-or 3,4-di-O-benzyl-a-L-rhamnopyranoside, respectively, could be prepared in good yield by this method. No benzylation took place when benzyl chloride was used instead of benzyl bromide, or when other solvents than ethyl acetate or acetonitrile were tested. 

C7H7)+ Various including toluene, butylbenzene, benzyl chloride, xylene, benzyl alcohol, methyl anisole 29—46 g, m, P 185... 

Methylenedioxy)benzyl esters (piperonyl esters) are cleaved more readily than the 4-methoxybenzyl ester by acid hydrolysis with 2 M HBr/AcOH or TFA at room temperature within 5 minutes.3,4-(Methylenedioxy)benzyl esters are readily prepared either by transesterification of anoino acid 4-nitrophenyl esters with 3,4-(methylenedioxy)benzyl alcohol in imidazole/dioxane (rt, 12 h) or from Nps-protected amino acids with 3,4-(methyl-enedioxy)benzyl chloride/TEA in DMF at room temperature. 

To our knowledge, 46 has never been observed in solution under stable conditions, even at low temperature. Pulse radiolysis " of benzyl chloride as well as flash photolysis ° of several derivatives in HHP have allowed the observation of the electronic absorption spectra of benzyl and its 4-methyl and 4-methoxy derivatives. The and NMR spectra of the 2,4,6-trimethylbenzyl cation and other more heavily substituted benzyl cations, however, have been studied at low temperature in superacid media. In the gas phase, cold benzyl radical has been probed by two-color, resonant two-photon ionization techniques, thus providing very accurate vibrational frequencies below 650 cm for the benzyl cation. Furthermore, the adiabatic ionization energy of benzyl radical and several isotopomers in the ground state were determined from their threshold photoionization spectra using resonant two-photon excitation and detection of electrons by pulsed field ionization. This information, combined with Af//° (CgH5CH2) from Ref. 212 leads to the value of Af//°m(46) reported in Table 9. 

Hamill, Guarino, and Ronayne (II) gamma irradiated 0.18 mole % benzyl chloride in glassy 2-methyltetrahydrofuran (MTHF) at liquid nitrogen temperature and obtained a maximum ultraviolet absorption band at 320 m/x in agreement with Porter and Strachan, see Table I. They also irradiated 1.0 mole % allyl chloride, allyl bromide and allyl alcohol in 3-methylpentane (3-MP) and in all cases observed a maximum absorption band at 228 m/x which they attributed to the allyl free radical. They also irradiated 3-chloro-1-butene and 3-chlorocyclohexene in 3-MP and determined the wavelengths of the absorption band maxima of the 1-methyl allyl and 2-cyclohexen-l-yl free radicals given in Table I. 

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