4,7-Phenanthroline → 5-methoxy-4,7-phenanthroline

HRID 1648128Notes

Reaction equation

HRID 1648128 reaction equation
[C:1]1(=[O:14])C2C(C3C(C=2)=CC=CC=3)=CN=N1.[CH:15]1[C:28]2[C:19](=[CH:20][CH:21]=[C:22]3[C:27]=2[CH:26]=[CH:25][CH:24]=[N:23]3)[N:18]=[CH:17][CH:16]=1>>[CH3:1][O:14][C:20]1[CH:21]=[C:22]2[C:27]([CH:26]=[CH:25][CH:24]=[N:23]2)=[C:28]2[C:19]=1[N:18]=[CH:17][CH:16]=[CH:15]2

Participants

3

Reactant 2

HCID 674724,7-PhenanthrolineHCID 69079878HCID 69079878, compound

Product 1

HCID 2853595-methoxy-4,7-phenanthroline

Procedure

Some phenanthrolines are very reluctant to undergo the usual basic oxidative rearrangement to the corresponding diazafluorenone. This is true of 4,7-phenanthroline, for instance. In this case, one uses 2-methoxyparaphenylenediamine in a double Skraup synthesis to produce the enolether, 5-methoxy-4,7-phenanthroline (150). Reaction of it with concentrated sulfuric acid and fuming nitric acid yields 4,7-phenanthrolin-5,6-quinone (151). The quinone undergoes oxidative rearrangerent to produce 1,8-diazafluoren-9-one (152). Hydrazine reduction produces 1,8-diazafluorene (153) which is alkylated to the target compound, 9,9-bis(4-pyridinylmethyl)-1,8-diazafluorene (154). Other diazafluorenes produced by this method include 1,5-diazafluorene, (Scheme 67, 157), 1,6-diazafluorene, 2,5-diazafluorene, 3,5-diazafluorene, and 4,5-diazafluorene. See references for Scheme 64 and: French patent 382 542; French patent 1,369,626, U.S. Pat. No. 2,640,830, Swiss patent 275,433. ##STR87##

Workup

  1. customIn this case, one uses 2-methoxyparaphenylenediamine in a double Skraup synthesis

Sources & evidence

ORD record
ord-33cd315eee9447e0889d3c200878eb96
Source dataset
uspto-grants-1995_07
Patent number
US05434264

Reaction notes

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