Hydrochloric Acid → 3-Bromophenanthrene-9-carboxylic acid

HRID 1084319Notes

Reaction equation

N[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8](=[CH:12][C:13]1[CH:18]=[CH:17][C:16]([Br:19])=[CH:15][CH:14]=1)[C:9]([O-:11])=[O:10].[Na+].N(OCCC(C)C)=O.Cl>C(O)C.OS(O)(=O)=O.O.[Cu]>[Br:19][C:16]1[CH:15]=[CH:14][C:13]2[CH:12]=[C:8]([C:9]([OH:11])=[O:10])[C:3]3[C:4]([C:18]=2[CH:17]=1)=[CH:5][CH:6]=[CH:7][CH:2]=3

Participants

Conditions

Temperature: 0 °C

Procedure

A suspension of the amino-carboxylate 2 (13.3 g, 39.1 mmol) in 155 ml of ethanol was cooled to 0° C. and isoamyl nitrite (18.0 ml, 134 mmol) was added followed by dropwise addition of 15% ethanolic HCl (125 ml) during 1 hour. The resulting brown slurry was stirred at 0° C. for 2 hours more, and was then added gradually to a vigorously stirred suspension of copper powder (1.8 g) in a solution of NaH2PO2.H2O (41.4 g, 391 mmol) and conc. H2SO4 (3 drops) in 63 ml of water which was maintained at 40° C. After the addition was complete, the mixture was stirred at 40° C. for 1 hour and was then cooled to 0° C. and the solid was isolated by filtration, washing with water. Drying in vacuo gave 9.9 g of a brown solid which was taken-up in CH2Cl2 -THF, filtered to remove some inorganic material, and evaporated to yield 7.28 g (62%) of the title compound as a tan solid. This compound was used in the next reaction without purification.

Workup

temperaturewas maintained at 40° C
additionAfter the addition
stirringthe mixture was stirred at 40° C. for 1 hour
temperaturewas then cooled to 0° C.
customthe solid was isolated by filtration
washwashing with water
customDrying in vacuo

Sources & evidence

ORD record: ord-18820a24d319412b88d0a92eb70c0ee5
Source dataset: uspto-grants-1991_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05004740

Reaction notes

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