US EPA

8375460 

Journal Article 

Factors influencing the course and mechanism of grignard reactions. XXI. the reaction of haloalkyl phenyl ethers with grignard reagents in the presence of cobaltous halides 

Kharasch, MS; Stampa, G; Nudenberg, W 

1953 

Yes 

Journal of Organic Chemistry
ISSN: 0022-3263
EISSN: 1520-6904 

18 

5 

575-581 

English 

10.1021/jo01133a014 

1. The reaction of haloalkyl phenyl ethers C6H5O(CH2)nBr or C6H5O(CH2)nCl with Grignard reagents (in ethyl ether) in the presence of cobaltous bromide gave the following results: (a) n = 2. Phenol (58-90%), ethylene and C6H5O(CH)2H (3-4%); (b) n = 3. Phenol (59-70%) and cyclopropane (70%) containing about 5-10% of propylene, and a trace of C6H5O(CH2)6OC6H5 and C6H5O(CH2)3H (17-27%); (c) n = 4. Phenol (up to 8%), a mixture (74-85%) of C6H5O(CH2)4 + h and C6H5O(CH2)4T−h (11% of unsaturated ether in the case of the bromoalkyl phenyl ether and 26% of the unsaturated ether in the case of chloroalkyl phenyl ether) and a trace of the ether C6H5O(CH2)8OC6H5; (d) n = 5. Traces of phenol, a mixture (87%) of C6H5O(CH2)5 + h and C6H5(CH2)5 − h (30% of the unsaturated ether C6H5O(CH2)5 − h) and a trace of the ether C6H5O(CH2)10OC6H5; (e) n = 6. Phenol (7%), a mixture (70%) of C6H5O(CH2)6 + h and C6H5O(CH2)6 − h (12 % of the unsaturated ether), and 25 % of the ether C6H5O(CH2)12OC6H5. 2. It was established that n-hexylmagnesium bromide (in ethyl ether) reacts with methyl bromide in the presence of cobaltous bromide to give hexane and hexene and a small amount of a nonane. A careful but unsuccessful search for the hydrocarbon C12H26 was made. 3. Methylmagnesium bromide in ethyl ether reacts with methyl bromide and dodecanal, in the presence of cobaltous bromide, to give CH3(CH2)10CHOHCH3, a small amount of unidentified oil, and a gas. The composition of the gas was 78% methane, 15% ethylene, and 7% ethane. © 1953, American Chemical Society. All rights reserved.