4-{[6-(Methacryloyloxy)hexyl]oxy}benzenecarboxylic acid → HCID 178454691, compound

HRID 555197Notes

Reaction equation

HRID 555197 reaction equation
[C:1]([O:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][O:13][C:14]1[CH:22]=[CH:21][C:17]([C:18]([OH:20])=[O:19])=[CH:16][CH:15]=1)(=[O:5])[C:2]([CH3:4])=[CH2:3].O[C:24]1[CH:76]=[CH:75][C:27]([CH2:28][NH:29][C:30]2[C:39]3[C:34](=[CH:35][CH:36]=[CH:37][CH:38]=3)[C:33](/[N:40]=[N:41]/[C:42]3[C:51]4[C:46](=[CH:47][CH:48]=[CH:49][CH:50]=4)[C:45](/[N:52]=[N:53]/[C:54]4[CH:73]=[CH:72][C:57]([C:58]([O:60][C:61]5[CH:66]=[CH:65][C:64]([CH2:67][CH2:68][CH2:69][CH2:70][CH3:71])=[CH:63][CH:62]=5)=[O:59])=[CH:56][C:55]=4[CH3:74])=[CH:44][CH:43]=3)=[CH:32][CH:31]=2)=[CH:26][CH:25]=1>C1COCC1.C(N(CC)CC)C.CN(C1C=CN=CC=1)C>[C:1]([O:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][O:13][C:14]1[CH:15]=[CH:16][C:17]([C:18]([O:20][C:24]2[CH:76]=[CH:75][C:27]([CH2:28][NH:29][C:30]3[C:39]4[C:34](=[CH:35][CH:36]=[CH:37][CH:38]=4)[C:33](/[N:40]=[N:41]/[C:42]4[C:51]5[C:46](=[CH:47][CH:48]=[CH:49][CH:50]=5)[C:45](/[N:52]=[N:53]/[C:54]5[CH:73]=[CH:72][C:57]([C:58]([O:60][C:61]6[CH:62]=[CH:63][C:64]([CH2:67][CH2:68][CH2:69][CH2:70][CH3:71])=[CH:65][CH:66]=6)=[O:59])=[CH:56][C:55]=5[CH3:74])=[CH:44][CH:43]=4)=[CH:32][CH:31]=3)=[CH:26][CH:25]=2)=[O:19])=[CH:21][CH:22]=1)(=[O:5])[C:2]([CH3:4])=[CH2:3]

Participants

6

Reactant 2

HCID 37303444-{[6-(Methacryloyloxy)hexyl]oxy}benzenecarboxylic acidHCID 178442194HCID 178442194, compound

Product 1

HCID 178454691HCID 178454691, compoundYield 80.2%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
-30 °C

Procedure

0.68 g of 4-{[6-(methacryloyloxy)hexyl]oxy}benzoic acid (2.20 mM) were dissolved in 20 ml of THF and 2.22 g of triethylamine (22.00 mM). The solution was cooled to −30° C. and 0.25 ml of methansulfochloride (2.20 mM) were added. The mixture was stirred for 1 h at this temperature, then 1.42 g of 4-pentylphenyl 4-{(E)-[4-((E)-{4-[(4-hydroxybenzyl)-amino]1-naphthyl}-diazenyl)-1-naphthyl]diazenyl}-3-methylbenzoate (2.00 mM) were added at once, followed by 50 mg of DMAP. The reaction mixture was stirred for 1 h at −30° C. and was allowed to warm to room temperature while stirred overnight. The next day, 10 g of celite filter aid were added and the resulting suspension was stirred for 15 min., filtered, the cake was washed with THF and the filtrate was evaporated to dryness. The residue was dissolved in 10 ml of dichloromethane and to this solution was then added approx. 30 ml of methanol dropwise at 0° C. The precipitated crystals were filtered off, washed with cooled methanol and dried to give 1.60 g (1.60 mM, 80%) of 4-pentylphenyl 4-[(E)-(4-{(E)-[4-({4-[(4-{[6-(methacryloyloxy)hexyl]oxy}benzoyl)oxy]benzyl}amino)-1-naphthyl]-diazenyl}-1-naphthyl)diazenyl]-3-methylbenzoate as dark crystals; λmax=571 nm, ε=35000 (THF). For total purification, the dye might be flash chromatographed on silica gel.

Workup

  1. addition0.25 ml of methansulfochloride (2.20 mM) were added
  2. stirringThe reaction mixture was stirred for 1 h at −30° C.
  3. temperatureto warm to room temperature
  4. stirringwhile stirred overnight
  5. filtrationThe next day, 10 g of celite filter aid
  6. additionwere added
  7. stirringthe resulting suspension was stirred for 15 min.
  8. filtrationfiltered
  9. washthe cake was washed with THF
  10. customthe filtrate was evaporated to dryness
  11. dissolutionThe residue was dissolved in 10 ml of dichloromethane and to this solution
  12. additionwas then added approx. 30 ml of methanol dropwise at 0° C
  13. filtrationThe precipitated crystals were filtered off
  14. washwashed with cooled methanol
  15. customdried

Sources & evidence

ORD record
ord-453c1fed75604893a132acef1fbbb7b3
Source dataset
uspto-grants-2011_11
Patent number
US08053039B2

Reaction notes

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