Methyl iodide propyl ether

N-Phenyl-N-isopropylacrylamide refluxed overnight with 2 equivalents 1,1-di-methylhydrazine, coned, in vacuo, and treated with methyl iodide in ether 2- [ (2-isopropylphenylcarbamoyl) ethyl] -1,1,1-trimethylhydrazinium iodide (Y ca. 100%) refluxed IShrs. with Na-methoxide in ethanol N-phenyl-N-iso-propyl-2-aziridinecarboxamide (Y 57%). F. e. s. G. R. Harvey, J. Org. Chem. 33, 887 (1968). 

Repeat this analysis for the reaction of phenyl methyl ether with HI leading to phenol and methyl iodide or methanol and phenyl iodide and involving protonated phenyl methyl ether as an intermediate. (Note In this case, the appropriate empty molecular orbital is LUMO+2 the LUMO is concentrated primarily on the CO bond.) Which reaction, with ethyl propyl ether or phenyl methyl ether, appears to be more likely to give selective ether cleavage ... 

Alkyl halides, acyl halides, anhydrides, and related substances. It was discovered as early as 1861 by Rcboul and Luurenool<4t> that epicblorohydrin may be caused to react with ethyl bromide on heating in a sealed tube to an elevated temperature. The product isolated from this condensation was ]-broJHo-3-chloro-2-ethoxyprt>pane. Some year later Paalli6 extended this reaction to include also methyl iodide, ethyl iodide, n-propyl iodide, and isopropyl iodide do2-propunol was formed. 

Asymmetric a-alkylatlon of ketones (7, 10-11 8, 16-17). Enders and Eichenauer have now obtained almost complete asymmetric a-alkylation of acyclic ketones by way of hydrazones formed with 1. An example is the synthesis of (+)-(S)-4-methyl-3-heptanone (4), an ant alarm pheromone, from diethyl ketone. The hydrazone 2 was metalated and alkylated with n-propyl iodide in ether to give 3. 

Acetone -f isobutylchloride ethyl iodide butyl bromide propyl mercaptan methyl acetate diallyl n-hexane cyclohexane ethyl propyl ether... 

Explain why methyl propyl ether forms both methyl iodide and propyl iodide when it is heated with excess HI. 

Butylthiomethylenecycloheptanone in ether added dropwise at 0° under N, during 15 min. to 3 moles stirred ethereal Li-dimethyIcuprate, after 0.5 hr. at 0° almost all of the solvent cautiously removed by distillation under reduced pressure, the residue dissolved in 1,2-dimethoxyethane, cooled to 0°, 10 moles methyl iodide added quiddy, and the product isolated after 5 min. at 0° -> 2-iso-propyl-2-methylcycloheptanone. Y 93%. F. e., also from a,/ -ethyleneketones by 1,4-addition-alkylation with incorporation of 2 alkyl groups, s. R. M. Coates and L. O. Sandefur, J. Org. Chem. 39, 275 (1974). 

Preferential formation. 1-Methyl-2-(I -diethylamino -2 -hydroxy -2 -propyl)-3-(dimethylaminomethyl) indole in ether treated with excess methyl iodide-> 1-methyl -2- (I -diethylamino - 2 -hydroxy - 2 - propyl) -3- (trimethylammoniummethyl) -indole iodide. Y ca. 100%. J. Kebrle, A. Rossi, and K. Hoffmann, Helv. 42, 907 (1959). 

A mixture of 10 parts of 7-chloro-4-fluorobutyrophenone, 5.5 parts of 1-(1,2,3,6-tetrahydro-4-pyridyl)-2-benzimidazolinone, 4 parts of sodium carbonate, and 0.1 part of potassium iodide in 176 parts of 4-methyl-2-pentanone is stirred and refluxed for 64 hours. The cooled reaction mixture is filtered and the solvent is evaporated from the filtrate to leave an oily residue which is dissolved in toluene. The toluene solution is filtered and the solvent is evaporated. The resultant residue is recrystallized from a mixture of 32 parts of ethyl acetate and 32 parts of diisopropyl ether to give 1-[1-[(4-fluorobenzoyl)propyll-1,2,3,6-tetrahydro-4-pyridyl]-2-benzimidazolinone hydrate melting at about 145°-146.5°C. 

CLEAVAGE OF ETHERS Aluminum chloride. Boron tribromide. Bromine. Dimethylformamide. Methylmagnesium iodide. Triphenylphosphine dibromide. a-GLYCOLS Silver iododibenzoate KETOXIMES Chromous acetate METHYL ESTERS Lithium n-propyl mercaptide. 

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