Acetamidine monohydrochloride → HCID 68312987, compound

HRID 1530722Notes

Reaction equation

HRID 1530722 reaction equation
[CH2:1]([O:8][C:9]1[CH:10]=[C:11]2[C:20](=[CH:21][C:22]=1[Br:23])[C:19]1[N:15]([CH:16]=[C:17](I)[N:18]=1)[CH2:14][CH2:13][O:12]2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl.[C:26]([NH2:29])(=[NH:28])[CH3:27].[CH3:30][C:31]1([CH3:71])C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.Cl.[CH:73]([NH:76]N)(C)C>CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2].C(O)(=O)C>[CH2:1]([O:8][C:9]1[CH:10]=[C:11]2[C:20](=[CH:21][C:22]=1[Br:23])[C:19]1[N:15]([CH:16]=[C:17]([C:73]3[N:76]([CH:31]([CH3:71])[CH3:30])[N:29]=[C:26]([CH3:27])[N:28]=3)[N:18]=1)[CH2:14][CH2:13][O:12]2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 67170Acetamidine monohydrochlorideHCID 855731-Isopropylhydrazine hydrochlorideHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 68313084HCID 68313084, compound

Product 1

HCID 68312987HCID 68312987, compoundYield 450.4%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 176Acetic AcidSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
40 °C

Procedure

A mixture of 12-(benzyloxy)-13-bromo-4-iodo-9-oxa-3,6-diazatricyclo[8.4.0.02,6]tetradeca-1(14),2,4,10,12-pentaene (6.13 g, 12.3 mmol), acetamidine hydrochloride (1.29 g, 13.6 mmol), Pd(OAc)2 (277 mg, 1.24 mmol), and Xantphos (1.43 g, 2.47 mmol) in DMF (20.0 mL) and TEA (5.0 mL) was heated at 40° C. under CO (1 atm) for 3 hrs. After cooling down, isopropylhydrazine hydrochloride (1.64 g, 14.8 mmol) and acetic acid (20.0 mL) were added. The resulting mixture was heated to 65° C. and stirred at this temperature for 1 hr. After removal of the solvent, the residue was poured into water (2000 mL). The solid was collected by filtration and washed with acetone to give the desired product (5.5 g, 90% yield) as a yellow solid. LCMS m/z [M+H]+ 494.1.

Workup

  1. temperatureAfter cooling down
  2. temperatureThe resulting mixture was heated to 65° C.
  3. customAfter removal of the solvent
  4. additionthe residue was poured into water (2000 mL)
  5. filtrationThe solid was collected by filtration
  6. washwashed with acetone

Sources & evidence

ORD record
ord-e41159ca58994cceb3e0c20da48e73f2
Source dataset
uspto-grants-2015_07
Patent number
US09090628B2

Reaction notes

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