Trifluoroacetic acid → HCID 86663609, compound

HRID 1520748Notes

Reaction equation

HRID 1520748 reaction equation
[C:1]([C:3]1[CH:4]=[C:5]([NH:9][C:10]2[C:11]3[CH:19]=[C:18]([NH:20]CC4C=CC(OC)=CC=4)[N:17]=[CH:16][C:12]=3[N:13]=[CH:14][N:15]=2)[CH:6]=[CH:7][CH:8]=1)#[CH:2].FC(F)(F)C(O)=O.C1(OC)C=CC=CC=1>C(Cl)Cl>[C:1]([C:3]1[CH:4]=[C:5]([NH:9][C:10]2[C:11]3[CH:19]=[C:18]([NH2:20])[N:17]=[CH:16][C:12]=3[N:13]=[CH:14][N:15]=2)[CH:6]=[CH:7][CH:8]=1)#[CH:2]

Participants

5

Reactant 3

HCID 6422Trifluoroacetic acidHCID 7519AnisoleHCID 86663608HCID 86663608, compound

Product 1

HCID 86663609HCID 86663609, compoundYield 101.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred homogeneous solution of compound 167 (12.3 g, 32.3 mmol) in dry DCM (325 mL) was added trifluoroacetic acid (24.5 mL, 323 mmol), followed by anisole (7.11 mL, 64.6 mmol). The resultant mixture was stirred at room temperature for 70 h and then poured into petroleum ether (1 L) and stirred at room temperature for ca. 30 min. The petroleum ether layer was decanted and discarded. This process was repeated with more petroleum ether (800 mL). The residue left behind was dissolved in acetone/water (1:1, 200 mL) and stirred with 5M NH3 (500 mL) at room temperature for 1 h. The solid was collected by filtration and washed successively with acetone/water (1:4, 5×100 mL) and then petroleum ether/ethyl acetate (3:1, 5×100 mL) before being dried in vacuo to give N4-(3-ethynylphenyl)pyrido[3,4-d]pyrimidine-4,6-diamine (169) (8.56 g, 98%), mp 220-225° C. (decomp); 1H NMR δ [(CD3)2SO] 9.69 (s, 1H), 8.70 (s, 1H), 8.38 (s, 1H), 8.08 (t, J=1.7 Hz, 1H), 7.95-7.89 (m, 1H), 7.40 (t, J=7.9 Hz, 1H), 7.34 (br d, J=7.7 Hz, 1H), 7.16 (s, 1H), 6.25 (s, 2H), 4.17 (s, 1H). Anal. Calcd for C15H11N5.2H2O.0.2CH3COCH3: C, 60.65; H, 5.29; N, 22.67%. Found C, 60.54; H, 5.01; N, 22.56%.

Workup

  1. customThe petroleum ether layer was decanted
  2. waitThe residue left
  3. dissolutionbehind was dissolved in acetone/water (1:1, 200 mL)
  4. stirringstirred with 5M NH3 (500 mL) at room temperature for 1 h
  5. filtrationThe solid was collected by filtration
  6. washwashed successively with acetone/water (1:4, 5×100 mL)
  7. dry with materialpetroleum ether/ethyl acetate (3:1, 5×100 mL) before being dried in vacuo

Sources & evidence

ORD record
ord-900eb1df572547879f40731e009081c1
Source dataset
uspto-grants-2015_07
Patent number
US09073916B2

Reaction notes

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