Ammonia → 6-Iodonaphthalen-1-ol

HRID 2378552Notes

Reaction equation

HRID 2378552 reaction equation
N[C:2]1[CH:11]=[CH:10][C:9]2[C:4](=[CH:5][CH:6]=[CH:7][C:8]=2[OH:12])[CH:3]=1.N([O-])=O.[Na+].[I-:17].[K+].N>Cl>[OH:12][C:8]1[C:9]2[C:4](=[CH:3][C:2]([I:17])=[CH:11][CH:10]=2)[CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 222AmmoniaHCID 4875Potassium IodideHCID 902956-AminonaphtholHCID 23668193Sodium Nitrite

Product 1

HCID 139769956-Iodonaphthalen-1-olYield 18.2%

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent

Procedure

2-Amino-5-hydroxynaphthalene (4.80 g, TCI) was dissolved in 6 N hydrochloric acid (300 ml), added dropwise with an aqueous solution (22.5 ml) of sodium nitrite (2.25 g) over 30 minutes under ice cooling, and stirred for 30 minutes. The reaction mixture was added dropwise with an aqueous solution (75 ml) of potassium iodide (9.90 g, WAKO), stirred for 30 minutes, then warmed to room temperature, and further stirred for 3.5 hours. The reaction mixture was neutralized with aqueous ammonia, and then filtered through a Celite layer. The filtrate was added with ethyl acetate (90 ml×2) for extraction. The organic layer was washed successively with saturated aqueous sodium hydrogencarbonate, saturated aqueous ammonium chloride and saturated brine, and dried, and then the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (Quad, hexane:ethyl acetate=10:1) to obtain 1-hydroxy-6-iodonaphthalene (1.48 g). A solution of this substance (539 mg) in anhydrous THF (10 ml) was added with 60% sodium hydride (171 mg) under ice cooling, and stirred for 1 hour. The reaction mixture was cooled to −78° C. under argon gas atmosphere, added dropwise with a 1.6 M solution of n-butyllithium in hexane (3.75 ml) over 10 minutes, and stirred for 30 minutes. The reaction mixture was added dropwise with (iPrO)3B (1.16 ml) over 10 minutes, stirred for 30 minutes, then warmed to room temperature, and further stirred for 3 hours. The reaction mixture was added with water (3 ml) and 0.5 M aqueous sulfuric acid (7 ml), and extracted with diethyl ether (100 ml×3). The organic layer was washed with saturated brine and dried, and then the solvent was evaporated under reduced pressure to obtain crude 7-hydroxy-2-naphthaleneboronic acid. A solution of this substance in ethanol (1 ml), Compound No. A-1 (350 mg), 2 M aqueous sodium carbonate (2.4 ml) and (Ph3P)4Pd (116 mg) were reacted and treated according to the procedure described in the synthesis method of Compound No. V-3 with the modifications that the reaction was carried out for 14 hours, and the purification was performed by column chromatography (Quad, hexane:ethyl acetate=6:1) to obtain the title compound (Compound No. V-5, 388 mg).

Workup

  1. stirringstirred for 30 minutes
  2. stirringfurther stirred for 3.5 hours
  3. filtrationfiltered through a Celite layer
  4. additionThe filtrate was added with ethyl acetate (90 ml×2) for extraction
  5. washThe organic layer was washed successively with saturated aqueous sodium hydrogencarbonate, saturated aqueous ammonium chloride and saturated brine
  6. customdried
  7. customthe solvent was evaporated under reduced pressure
  8. customThe residue was purified by column chromatography (Quad, hexane:ethyl acetate=10:1)

Sources & evidence

ORD record
ord-a2b778c59b7f491c9568d55e6c037b58
Source dataset
uspto-grants-2008_12
Patent number
US07470807B2

Reaction notes

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