Diisopropylethylamine → Methyl 2-(3-methoxy-4-((4-((((4-nitrophenoxy)carbonyl)oxy)methyl)phenyl)diazenyl)phenoxy)acetate

HRID 526268Notes

Reaction equation

HRID 526268 reaction equation
[OH:1][CH2:2][C:3]1[CH:8]=[CH:7][C:6]([N:9]=[N:10][C:11]2[CH:22]=[CH:21][C:14]([O:15][CH2:16][C:17]([O:19][CH3:20])=[O:18])=[CH:13][C:12]=2[O:23][CH3:24])=[CH:5][CH:4]=1.CCN(C(C)C)C(C)C.Cl[C:35]([O:37][C:38]1[CH:43]=[CH:42][C:41]([N+:44]([O-:46])=[O:45])=[CH:40][CH:39]=1)=[O:36]>C(Cl)Cl.CN(C1C=CN=CC=1)C>[CH3:24][O:23][C:12]1[CH:13]=[C:14]([CH:21]=[CH:22][C:11]=1[N:10]=[N:9][C:6]1[CH:7]=[CH:8][C:3]([CH2:2][O:1][C:35]([O:37][C:38]2[CH:39]=[CH:40][C:41]([N+:44]([O-:46])=[O:45])=[CH:42][CH:43]=2)=[O:36])=[CH:4][CH:5]=1)[O:15][CH2:16][C:17]([O:19][CH3:20])=[O:18]

Participants

6

Reactant 3

HCID 81531DiisopropylethylamineHCID 821294-Nitrophenyl chloroformateHCID 86675387HCID 86675387, compound

Product 1

HCID 86675388Methyl 2-(3-methoxy-4-((4-((((4-nitrophenoxy)carbonyl)oxy)methyl)phenyl)diazenyl)phenoxy)acetate

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Procedure

Compound 4 (0.1 g, 0.0302 mmol) was dissolved in DCM (15 mL) and freshly activated 4° A M.S (0.15 g) was added and reaction mixture stirred for 10 minutes. DIPEA (0.215 mL, 1.2 mmol) and DMAP (0.05 g) were added and reaction mixture cooled to 0° C. p-Nitrophenyl chloroformate (0.15 g, 0.0757 mmol) in DCM was added slowly and reaction mixture stirred at 0° C. for 1 hour, followed by an additional 4 hours at room temperature. The remaining procedure was followed as described for compound 5 to obtain compound 6 (E:Z isomers). Yield: 0.11 g (76%). 1H NMR (500 MHz, CDCl3) δ 3.79 (s, 3H, Hn (OMe), for Z), 3.82 (s, 3H, Hn (OMe), for E), 3.99 (s, 3H, aromatic-OMe for Z), 4.00 (s, 3H, aromatic-OMe for E), 4.58 (s, 2H, Hf for Z), 4.71 (s, 2H, Hf for E), 5.21 (s, 2H, Hl for Z), 5.34 (s, 2H, Hi for E), 6.22-6.28 (m, 1H, Hb for Z), 6.44-6.50 (m, 2H, Hb for E), 6.52-6.60 (m, 1H, He for Z), 6.64-6.70 (m, 1H, He for E), 6.84-6.95 (m, 2H, He for Z), 7.30-7.40 (m, 2H, He for E), 7.42-7.50 (m, 1H, Ha for Z), 7.50-7.54 (m, 1H, Ha for E), 7.54-7.58 (m, 2H, Hn for Z), 7.68-7.75 (m, 2H, Hn for E), 7.80-7.90 (m, 4H, Hd for Z and E), 8.08-8.14 (m, 2H, Ho for Z), 8.22-8.30 (m, 2H, Ho for E). 13C NMR (125 MHz, CD3SOCD3) δ 52.3, 52.44 (Cn), 55.4, 56.34 (aromatic-OMe), 65.2, 65.2 (Cf), 67.3, 67.4 (Cl), 70.1, 70.4, 100.2 (Cc), 104.2, 105.3 (Cb), 115.62, 116.9 (Ci), 118.0, 120.04, 121.5, 121.7, 121.75, 122.8, 122.9, 125.3, 126.0, 128.7, 128.9, 129.2, 135.9, 137.3, 145.3, 152.3, 154.4, 155.4, 158.7, 161.7, 168.7 (CO). ESI-MS: [M+H]+ C24H22N3O9 calcd 496.1356, obsd 496.12.

Workup

  1. additionwas added
  2. customreaction mixture
  3. customreaction mixture
  4. additionwas added slowly
  5. customreaction mixture
  6. stirringstirred at 0° C. for 1 hour
  7. waitfollowed by an additional 4 hours at room temperature

Sources & evidence

ORD record
ord-c692aface75a465d98cf1fdd09b439c9
Source dataset
uspto-grants-2016_05
Patent number
US09345781B2

Reaction notes

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