Water → 1,3-bis(4-[N-(2,4-bis(N-octylamino)-1,3,5-triazin-6-yl)amino]phenoxy)-2,2-bis[(4-[N-(2,4-bis(N-octylamino)-1,3,5-triazin-6-yl)amino]phenoxy)methyl]propane

HRID 1372551Notes

Reaction equation

HRID 1372551 reaction equation
[N:1]1[C:8](Cl)=[N:7][C:5](Cl)=[N:4][C:2]=1Cl.[NH2:10][C:11]1[CH:46]=[CH:45][C:14]([O:15][CH2:16][C:17]([CH2:36][O:37][C:38]2[CH:43]=[CH:42][C:41]([NH2:44])=[CH:40][CH:39]=2)([CH2:27][O:28][C:29]2[CH:34]=[CH:33][C:32]([NH2:35])=[CH:31][CH:30]=2)[CH2:18][O:19][C:20]2[CH:25]=[CH:24][C:23]([NH2:26])=[CH:22][CH:21]=2)=[CH:13][CH:12]=1.[CH2:47]([NH2:55])[CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH3:54].O>O1CCCC1>[CH2:47]([NH:55][C:2]1[N:4]=[C:5]([NH:55][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH3:54])[N:7]=[C:8]([NH:44][C:41]2[CH:40]=[CH:39][C:38]([O:37][CH2:36][C:17]([CH2:18][O:19][C:20]3[CH:21]=[CH:22][C:23]([NH:26][C:2]4[N:4]=[C:5]([NH:55][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH3:54])[N:7]=[C:8]([NH:55][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH3:54])[N:1]=4)=[CH:24][CH:25]=3)([CH2:27][O:28][C:29]3[CH:34]=[CH:33][C:32]([NH:35][C:2]4[N:4]=[C:5]([NH:55][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH3:54])[N:7]=[C:8]([NH:55][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH3:54])[N:1]=4)=[CH:31][CH:30]=3)[CH2:16][O:15][C:14]3[CH:13]=[CH:12][C:11]([NH:10][C:2]4[N:4]=[C:5]([NH:55][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH3:54])[N:7]=[C:8]([NH:55][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH3:54])[N:1]=4)=[CH:46][CH:45]=3)=[CH:43][CH:42]=2)[N:1]=1)[CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH3:54]

Participants

6

Reactant 4

HCID 962WaterHCID 7954Cyanuric chlorideHCID 8143OctylamineHCID 220154304,4'-((2,2-Bis((4-aminophenoxy)methyl)propane-1,3-diyl)bis(oxy))dianiline

Product 1

HCID 220154331,3-bis(4-[N-(2,4-bis(N-octylamino)-1,3,5-triazin-6-yl)amino]phenoxy)-2,2-bis[(4-[N-(2,4-bis(N-octylamino)-1,3,5-triazin-6-yl)amino]phenoxy)methyl]propaneYield 70.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of cyanuric chloride (36.9 grams, 200 mmol; obtained from Aldrich Chemical Co., Milwaukee, Wis.) in 100 milliliters of dry tetrahydrofuran was added dropwise to a solution of 1,3-bis(4-aminophenoxy)-2,2-bis[(4-aminophenoxy)methyl]propane (25 grams, 50.0 mmol, prepared as described in Part C of Example I) in 500 milliliters of dry tetrahydrofuran at −78° C. The mixture was stirred and allowed to warm up to room temperature for 2 hours. Octylamine (165 milliliters, 1.00 mol; obtained from Aldrich Chemical Co.) was then added and the mixture was stirred at reflux for 3 hours. The mixture was subsequently cooled to room temperature, water was added, and a gummy precipitate (like glue) was filtered. The precipitate was dissolved in hot dimethylformamide, ethanol was added (3 liters), and trituration was done until the product became a fine solid. The solid was then filtered, washed with methanol, and dried for 2 days under reduced pressure to afford tetrakis[(4-[N-[4,6-bis(N-octylamino)-1,3,5-triazin-2-yl]amino]phenoxy)methyl]methane (65.0 grams, 35.4 mmol, 70 percent yield) as a white solid: softening point 94–96° C.; IR (KBr) 3434, 3274, 2925, 2854, 1579, 1506, 1421, 1367, 1226, 1030, 810 cm−1; 1H NMR (400 MHz, DMSO-d6, 373° K.) δ 8.11 (s, 4H), 7.60 (d, 8H, 3J=8.9 Hz), 6.84 (d, 8H, 3J=8.9 Hz), 6.12 (s, 8H), 4.25 (s, 8H), 3.26 (td, 16H, 3Jt=6.6 Hz, 3Jd=6.6 Hz), 1.53 (m, 16H), 1.29 (m, 80H), 0.86 (t, 24H, 3J=7.1 Hz); 13C NMR (100 MHz, DMSO-d6, 373° K.) δ 165.54, 163.77, 153.31, 133.96, 120.76, 114.27, 67.15, 44.47, 39.61, 30.56, 28.87, 28.14, 27.96, 25.90, 21.29, 13.00; MS (FAB, 3-nitrobenzyl alcohol) m/e 1834.6; Anal. Calcd for C105H172N24O4: C, 68.74; H, 9.45; N, 18.32. Found: C, 68.31; H, 9.58; N, 18.34.

Workup

  1. stirringthe mixture was stirred
  2. temperatureat reflux for 3 hours
  3. temperatureThe mixture was subsequently cooled to room temperature
  4. filtrationa gummy precipitate (like glue) was filtered
  5. dissolutionThe precipitate was dissolved in hot dimethylformamide
  6. additionethanol was added (3 liters), and trituration
  7. filtrationThe solid was then filtered
  8. washwashed with methanol
  9. customdried for 2 days under reduced pressure

Sources & evidence

ORD record
ord-16cc584677124554a4e06695864ca723
Source dataset
uspto-grants-2007_01
Patent number
US07157601B2

Reaction notes

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