Dimethylformamide → 4-azido-2-nitrophenyl-N'-(N-((2-hydroxyethyldithio)-2-ethylamidosuccinimido)-3-aminopropyl)-N'-methyl-1,3-propanediamine

HRID 1460043Notes

Reaction equation

HRID 1460043 reaction equation
[OH:1][CH2:2][CH2:3][S:4][S:5][CH2:6][C:7]([NH:9][CH:10]([CH2:14][C:15]([OH:17])=O)[C:11]([OH:13])=O)=[O:8].NCCCN(C)CCCN[C:27]1[CH:32]=[CH:31][C:30]([N:33]=[N+:34]=[N-:35])=[CH:29][C:28]=1[N+:36]([O-:38])=[O:37].[CH2:40]([N:42]([CH2:45][CH3:46])[CH2:43][CH3:44])C.F[P-](F)(F)(F)(F)F.[N:54]1(OC(N(C)C)=[N+](C)C)[C:58]2C=CC=CC=2N=[N:55]1.[CH3:71][N:72](C=O)C>C(Cl)Cl>[N:33]([C:30]1[CH:31]=[CH:32][C:27]([CH:71]([NH2:72])[CH2:44][CH2:43][N:42]([CH2:45][CH2:46][CH2:58][NH:54][N:55]2[C:15](=[O:17])[CH2:14][CH:10]([NH:9][C:7](=[O:8])[CH2:6][S:5][S:4][CH2:3][CH2:2][OH:1])[C:11]2=[O:13])[CH3:40])=[C:28]([N+:36]([O-:38])=[O:37])[CH:29]=1)=[N+:34]=[N-:35]

Participants

7

Reactant 5

HCID 6228Dimethylformamide2×HCID 8471TriethylamineHCID 2733084Methanaminium, N-((1H-benzotriazol-1-yloxy)(dimethylamino)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 54090062(2-Hydroxyethyldithio)ethylamidosuccinic acidHCID 54562181N-(3-aminopropyl)-N'-(4-azido-2-nitrophenyl)-N-methyl-1,3-propanediamine

Product 1

HCID 867534994-azido-2-nitrophenyl-N'-(N-((2-hydroxyethyldithio)-2-ethylamidosuccinimido)-3-aminopropyl)-N'-methyl-1,3-propanediamine

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

The reaction was carried out in the dark. A one necked flask was charged with 95.0 mg (1 eq., 0.375 mmole) (2-hydroxyethyldithio)ethylamidosuccinic acid in 1.5 ml DMF and this solution was then sequentially treated with 0.1154 g (1 eq., 0.375 mmole) N-(3-aminopropyl)-N'-(4-azido-2-nitrophenyl)-N-methyl-1,3-propanediamine in 2 ml methylene chloride, 57.5 μl, (1.1 eq., 41.74 mg, 0.4125 mmole) triethylamine (neat), and then 156.4 mg (1.1 eq., 0.4175 mmole) O-benzotriazol-1-yl-N,N,N',N'-tetramethyluronium hexafluorophosphate in 1 ml DMF. The reaction was monitored by TLC and found to be complete after 15 min at which time the solvents were removed via vacuum transfer (bath temp. 40° C.). The residue was purified by flash chromatography. 1H NMR (CD3CN/TMS) δ: 1.17 (2H, J=7.29 Hz, CH2), 1.71 (2H, m, J=6.88 Hz, CH2), 1.89 (2H, t, J=6.99 Hz, CH2), 2.37 (2H, t, J=3.10 Hz, CH2), 2.40 (3H, s, CH3), 2.64 (2H, t, J=7.45 Hz, CH2), 2.69 (2H, t, J=7.27 Hz, CH2), 2.76 ((2H, t, J=6.69 Hz, CH2), 2.80 (2H, t, J=5.33 Hz, CH2), 3.01 (2H, q, J=7.31 Hz, CH2), 3.16 (2H, q, J=6.42 Hz, CH2), 3.40 (4H, m, J=6.48 Hz, 2×CH2), 3.70 (2H, t, J=6.30 Hz, CH2), 6.97 (2H, d, ArH), 7.18 (2H, dd, ArH), 7.77 (2H, d, NH). 13C NMR (CD3CN/TMS) δ: 27.2 (CH2), 27.8 (CH2), 32.25 (CH2), 32.28 (CH2), 38.60 (CH2), 38.80 (CH2), 39.7 (CH2), 42.2 (CH3), 42.4 (CH2), 42.5 (CH2), 56.3 (CH2), 56.4 (CH2), 61.4 (CH2), 116.6 (ArH), 117.3 (Ar), 128.9 (Q), 129.3 (Ar), 132.7 (Q), 144.6 (Q), 174.6 (C=O), 174.8 (C=O).

Workup

  1. customthe solvents were removed via vacuum transfer (bath temp. 40° C.)
  2. customThe residue was purified by flash chromatography

Sources & evidence

ORD record
ord-2010a42635b242adaa49e455720c4d81
Source dataset
uspto-grants-1998_12
Patent number
US05854409

Reaction notes

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