Hydrochloric Acid → HCID 22725859, compound

HRID 348228Notes

Reaction equation

HRID 348228 reaction equation
Br[C:2]1[C:19]2[C:20]3[C:5]([C:6]4[C:21]5[C:10]6=[C:11]([C:22]([N:24]([C:27]7[C:32]([CH:33]([CH3:35])[CH3:34])=[CH:31][CH:30]=[CH:29][C:28]=7[CH:36]([CH3:38])[CH3:37])[C:25](=[O:26])[C:9]6=[CH:8][CH:7]=4)=[O:23])[CH:12]=[CH:13][C:14]=5[C:15]=3[CH:16]=[CH:17][CH:18]=2)=[CH:4][CH:3]=1.[C:39]([O:42][CH2:43][CH2:44][CH2:45][CH2:46][C:47]#[CH:48])(=[O:41])[CH3:40].Cl>O1CCCC1.N1CCCCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[CH:36]([C:28]1[CH:29]=[CH:30][CH:31]=[C:32]([CH:33]([CH3:35])[CH3:34])[C:27]=1[N:24]1[C:25](=[O:26])[C:9]2[C:10]3[C:21]4[C:6](=[CH:7][CH:8]=2)[C:5]2[C:20]5[C:19]([C:2]([C:48]#[C:47][CH2:46][CH2:45][CH2:44][CH2:43][O:42][C:39](=[O:41])[CH3:40])=[CH:3][CH:4]=2)=[CH:18][CH:17]=[CH:16][C:15]=5[C:14]=4[CH:13]=[CH:12][C:11]=3[C:22]1=[O:23])([CH3:38])[CH3:37]

Participants

8

Reactant 3

HCID 313Hydrochloric AcidHCID 10219476HCID 10219476, compoundHCID 11272966HCID 11272966, compound

Product 1

HCID 22725859HCID 22725859, compoundYield 90%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 8082PiperidineSolvent

Conditions

Temperature
70 °C

Procedure

2.0 g (3.56 mmol) of 9-bromo—N-(2,6-diisopropylphenyl)perylene-3,4-dicarboximide (prepared in analogy to Example 6a of WO 96/22 332 using N-(2,6-diisopropylphenyl)perylene-3,4-dicarboximide from Example 28 of WO 97/22 607 as starting material) was dissolved in 500 ml of a mixture of one part by volume of absolute tetrahydrofuran (THF) and one part by volume of dry piperidine under inert gas, admixed in succession with 4 mol % of Pd(PPh3)4 (164 mg, 0.14 mmol), 5 mol % of CuI (32 mg, 0.18 mmol) and 1.14 g (7.12 mmol) of 6-acetoxy-1-hexyne; this mixture was slowly heated to 70° C. and held at this temperature for 1 h. After cooling to room temperature, the reaction mixture was added to three times the volume of a mixture of ice and concentrated hydrochloric acid in a volume ratio of 3:1, the organic phase was separated off, the aqueous phase was extracted with 3 times 200 ml of methylene chloride, the combined organic extracts were dried over magnesium sulfate and the solvent was removed under reduced pressure. Chromatography on silica gel using methylene chloride as eluent gave 1.98 g (90%) of N-(2,6-diisopropylphenyl)-9-(6-acetoxy-1-hexynyl)perylene-3,4-dicarboximide as a red powder having a melting point >300° C.

Workup

  1. temperatureAfter cooling to room temperature
  2. additionthe reaction mixture was added to three times
  3. customthe organic phase was separated off
  4. extractionthe aqueous phase was extracted with 3 times 200 ml of methylene chloride
  5. dry with materialthe combined organic extracts were dried over magnesium sulfate
  6. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-f416e5d79a174eadad87184a98a77404
Source dataset
uspto-grants-2007_02
Patent number
US07176255B2

Reaction notes

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