Triethylamine → HCID 11684347, compound

HRID 218297Notes

Reaction equation

HRID 218297 reaction equation
P(Br)(Br)Br.O[CH2:6][C:7]1[CH:12]=[C:11]([N:13]=[N:14][C:15]2[CH:20]=[CH:19][C:18]([N+:21]([O-:23])=[O:22])=[CH:17][CH:16]=2)[CH:10]=[CH:9][C:8]=1[OH:24].CC[N:27]([CH2:30][CH3:31])[CH2:28][CH3:29]>CC#N>[N+:21]([C:18]1[CH:19]=[CH:20][C:15]([N:14]=[N:13][C:11]2[CH:10]=[CH:9][C:8]3[O:24][C:30]4([C:31]5[CH:19]=[CH:20][CH:15]=[CH:16][CH:17]=5)[C:11]([CH3:12])([CH3:10])[C:29]5[C:28]([N:27]4[CH2:6][C:7]=3[CH:12]=2)=[CH:9][CH:8]=[CH:7][CH:6]=5)=[CH:16][CH:17]=1)([O-:23])=[O:22]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 24614Phosphorus tribromideHCID 135977780155850-91-2

Product 1

HCID 11684347HCID 11684347, compoundYield 51%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of PBr3 in MeCN (1:10 v/v, 190 μL) was added over 20 min to a solution of 4 (185 mg, 0.6 mmol) in MeCN (25 mL) maintained at 0° C. under Ar. After addition of Et3N (80 μL), the mixture was stirred for a further one hour at 0° C. and then heated under reflux for 4 h. At this point, 6 (400 mg, 1.8 mmol) was added and the temperature was allowed to lower to ambient conditions. After 36 h, the solvent was evaporated under reduced pressure and the residue was purified by column chromatography [SiO2, hexane/CH2Cl2 (1:1 v/v)] to give 8a (135 mg, 51%) as an orange-red solid. HPLC [analytical, MeCN/H2O (90:10 v/v)]: RT=4.1 min, PA=1.6, APP=303.2±1.0 nm; mp=200° C.; FABMS: m/z=476 [M]+; 1H-NMR (400 MHz, chloroform-d): δ=0.85 (3H, s), 1.60 (3H, s), 4.57 (1H, d, 11 Hz), 4.67 (1H, d, 11 Hz), 6.75 (1H, d, 8 Hz), 6.90 (1H, t, 7 Hz), 6.97 (1H, d, 9 Hz), 7.16-7.19 (2H, m), 7.35-7.42 (3H, m), 7.64-7.73 (4H, m), 7.93 (2H, d, 9 Hz), 8.34 (2H, d, 9 Hz); 13C-NMR (100 MHz, chloroform-d): δ=22.9, 31.8, 41.2, 49.8, 104.8, 109.2, 118.7, 120.6, 120.7, 122.4, 122.6, 123.3, 124.3, 124.9, 127.8, 128.3, 128.7, 129.0, 137.0, 138.0, 146.6, 147.5, 148.4, 156.2, 157.9.

Workup

  1. temperatureheated
  2. temperatureunder reflux for 4 h
  3. waitAfter 36 h
  4. customthe solvent was evaporated under reduced pressure
  5. customthe residue was purified by column chromatography [SiO2, hexane/CH2Cl2 (1:1 v/v)]

Sources & evidence

ORD record
ord-4a0085fff45742b7af4a7aaeba225b99
Source dataset
uspto-grants-2012_06
Patent number
US08198436B2

Reaction notes

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