Nucleophilic displacement on the arene oxides of phenanthrene
Bruice, PY; Bruice, TC; Yagi, H; Jerina, DM
| HERO ID | 1483125 |
|---|---|
| In Press | No |
| Year | 1976 |
| Title | Nucleophilic displacement on the arene oxides of phenanthrene |
| Authors | Bruice, PY; Bruice, TC; Yagi, H; Jerina, DM |
| Journal | Journal of the American Chemical Society |
| Volume | 98 |
| Issue | 10 |
| Page Numbers | 2973-2981 |
| Abstract | HEEP COPYRIGHT: BIOL ABS. Phenanthrene 9,10-oxide, a K-region arene oxide, undergoes nucleophilic attack by oxygen bases and a wide variety of amines as a result of its relatively slow rate of ring opening to carbonium ion and the decreased rate of rearrangement of the carbonium ion to phenol. The rate of reaction of this oxide with nucleophiles is comparable with that of ethylene oxide. The second-order rate constants for attack by primary and secondary amines give a betanuc value of 0.4. Certain tertiary amines (trimethylamine and quinuclidine amines) exhibit enhanced nucleophilic reactivity. This is suggested to be due to preequilibrium complex formation prior to nucleophilic attack. The quinuclidine amines give a betanuc value of 0.1. Oxygen bases are less reactive nucleophiles and give a betanuc value of 0.2. In the case of non-K-region arene oxides (phenanthrene 1,2-oxide, phenanthrene 3,4-oxide, benzene oxide and naphthalene oxide), nucleophilic attack by amines and oxygen bases is not sufficiently rapid to compete with the spontaneous aromatization reaction. Thiolate anions exhibit considerably greater nucleophilic reactivity than do amines and, consequently, react with both the K-region and non-K-region arene oxides. The second-order rate constants for attack by thiolate anions result in a betanuc value of 0.2 for each of the arene oxides investigated. Glutathione is no more reactive a thiol than would be predicted from its pKa. NMR studies of the nucleophilic adducts show that nucleophilic attack is stereospecific and results in trans adducts. Either direct SN2 attack or nucleophilic trapping of tight ion pairs is occurring. An index of nucleophilic susceptibility is defined for epoxides and arene oxides: ehtylene oxide = 1, phenanthrene 9,10-oxide = 0.3 and the non-K-region arene oxides are all 0.0l. (Carcinogenic behavior is discussed.) |
| Doi | 10.1021/ja00426a049 |
| Url | https://www.scopus.com/inward/record.uri?eid=2-s2.0-0347180458&doi=10.1021%2fja00426a049&partnerID=40&md5=a56e3eea92d30900fb5e6a2dcd76ec81 |
| Is Certified Translation | No |
| Dupe Override | No |
| Comments | Scopus URL: https://www.scopus.com/inward/record.uri?eid=2-s2.0-0347180458&doi=10.1021%2fja00426a049&partnerID=40&md5=a56e3eea92d30900fb5e6a2dcd76ec81 |
| Is Public | Yes |
| Language Text | English |