Fumaric Acid → HCID 131715076, compound

HRID 1906512Notes

Reaction equation

HRID 1906512 reaction equation
[CH3:1][C:2]([NH:5][CH2:6][CH:7]([OH:17])[CH2:8][O:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1I)([CH3:4])[CH3:3].[C:18]([C:20]1[CH:25]=[CH:24][C:23]([C:26]#[CH:27])=[CH:22][CH:21]=1)#[N:19].[C:28]([OH:35])(=[O:34])/[CH:29]=[CH:30]/[C:31]([OH:33])=[O:32]>C(N(CC)CC)C.C1COCC1.CO.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>[OH2:9].[C:28]([OH:35])(=[O:34])/[CH:29]=[CH:30]/[C:31]([OH:33])=[O:32].[CH3:1][C:2]([NH:5][CH2:6][CH:7]([OH:17])[CH2:8][O:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[C:27]#[C:26][C:23]1[CH:24]=[CH:25][C:20]([C:18]#[N:19])=[CH:21][CH:22]=1)([CH3:4])[CH3:3]

Participants

9

Reactant 3

HCID 444972Fumaric AcidHCID 45472454-EthynylbenzonitrileHCID 13823543HCID 13823543, compound

Product 1

HCID 131715076HCID 131715076, compoundYield 75%

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Procedure

A solution of 6.6 g (19 mmoles) of 1-[(1,1-dimethylethyl)amino]-3-(2-iodophenoxy)-2-propanol, the product of Example 12b., 2.5 g (19.7 mmoles) of p-cyanophenylacetylene, 0.44 g (0.38 mmole) of (Ph3P)4Pd and 0.07 g (0.78 mmole) of copper (I) iodide in 40 ml of deoxygenated triethylamine and 20 ml of deoxygenated THF was stirred under nitrogen for 18 hr. A precipitate was removed by filtration and discarded. The solvent was evaporated from the filtrate in vacuo. Trituration of the residue with ether gave a crystalline solid which was collected by filtration. Evaporation of the ether filtrate gave a second crop of crystalline product. The combined crystalline material was dissolved in MeOH and fumaric acid (0.5 equivalent) was added. There was obtained 5.6 g (75%) of crystalline 4-[2-[3-[(1,1-dimethylethyl)amino]-2-hydroxypropoxy]phenylethynyl]benzonitrile (E)-2-butenedioate hydrate (50:25:17), mp 198°-200° C.

Workup

  1. customA precipitate was removed by filtration
  2. customThe solvent was evaporated from the filtrate in vacuo
  3. customTrituration of the residue with ether gave a crystalline solid which
  4. filtrationwas collected by filtration
  5. customEvaporation of the ether filtrate
  6. customgave a second crop of crystalline product

Sources & evidence

ORD record
ord-c09b46e6c6ba478ea9d11f4f2f15a662
Source dataset
uspto-grants-1987_03
Patent number
US04652584

Reaction notes

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