HCID 18942558, compound → HCID 178467776, compound

HRID 1158600Notes

Reaction equation

HRID 1158600 reaction equation
[CH:1]([O:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][O:10][C:11]1[CH:19]=[CH:18][C:14]([C:15](O)=[O:16])=[CH:13][CH:12]=1)=[CH2:2].[OH:20][C:21]1[CH:85]=[CH:84][C:24]([CH2:25][NH:26][C:27]2[C:36]3[C:31](=[CH:32][CH:33]=[CH:34][CH:35]=3)[C:30](/[N:37]=[N:38]/[C:39]3[CH:83]=[CH:82][C:42]([C:43]([O:45][CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][O:52][C:53](=[O:81])[C:54]4[CH:59]=[CH:58][C:57](/[N:60]=[N:61]/[C:62]5[C:71]6[C:66](=[CH:67][CH:68]=[CH:69][CH:70]=6)[C:65]([NH:72][CH2:73][C:74]6[CH:79]=[CH:78][C:77]([OH:80])=[CH:76][CH:75]=6)=[CH:64][CH:63]=5)=[CH:56][CH:55]=4)=[O:44])=[CH:41][CH:40]=3)=[CH:29][CH:28]=2)=[CH:23][CH:22]=1>C1COCC1.C(N(CC)CC)C.CN(C1C=CN=CC=1)C>[CH:1]([O:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][O:10][C:11]1[CH:12]=[CH:13][C:14]([C:15]([O:20][C:21]2[CH:22]=[CH:23][C:24]([CH2:25][NH:26][C:27]3[C:36]4[C:31](=[CH:32][CH:33]=[CH:34][CH:35]=4)[C:30](/[N:37]=[N:38]/[C:39]4[CH:40]=[CH:41][C:42]([C:43]([O:45][CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][O:52][C:53](=[O:81])[C:54]5[CH:59]=[CH:58][C:57](/[N:60]=[N:61]/[C:62]6[C:71]7[C:66](=[CH:67][CH:68]=[CH:69][CH:70]=7)[C:65]([NH:72][CH2:73][C:74]7[CH:75]=[CH:76][C:77]([O:80][C:15](=[O:16])[C:14]8[CH:18]=[CH:19][C:11]([O:10][CH2:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][O:3][CH:1]=[CH2:2])=[CH:12][CH:13]=8)=[CH:78][CH:79]=7)=[CH:64][CH:63]=6)=[CH:56][CH:55]=5)=[O:44])=[CH:82][CH:83]=4)=[CH:29][CH:28]=3)=[CH:84][CH:85]=2)=[O:16])=[CH:18][CH:19]=1)=[CH2:2]

Participants

6

Reactant 2

HCID 18942558HCID 18942558, compoundHCID 178525434HCID 178525434, compound

Product 1

HCID 178467776HCID 178467776, compoundYield 55%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
-30 °C

Procedure

0.66 g of 4-{[6-(vinyloxy)hexyl]oxy}benzoic acid (2.5 mM) were dissolved in 25 ml of THF and 2.53 g of triethylamine (25.0 mM). The solution was cooled to −30° C. and 0.29 g of methansulfochloride (2.5 mM) were added dropwise. The mixture was stirred for 1 h during which the temperature was allowed to rise to −10° C. At this temperature, 0.88 g of 6-{[4-((E)-{4-[(4-hydroxybenzyl)amino]-1-naphthyl}diazenyl)benzoyl]oxy}hexyl 4-((E)-{4-[(4-hydroxybenzyl)amino]-1-naphthyl}diazenyl)-benzoate (1.0 mM) were added at once, followed by 10 mg of DMAP. The reaction mixture was allowed to warm to room temperature while stirred overnight. The next day, the mixture was filtered through a pad of celite filter aid and evaporated to dryness. The residue was dissolved in 15 ml of THF and to this solution were added dropwise 25 ml of methanol at room temperature. When addition was complete, the resulting suspension was stirred for 30 min. at room temperature and then the solids were filtered off, washed with methanol and dried to give 0.75 g (0.55 mM, 55%) of 6-[(4-{(E)-[4-({4-[(4-{[6-(vinyloxy)hexyl]oxy}benzoyl)oxy]benzyl}amino)-1-naphthyl]diazenyl}benzoyl)oxy]hexyl 4-{(E)-[4-({4-[(4-{[6-(vinyloxy)hexyl]oxy}benzoyl)oxy]benzyl}amino)-1-naphthyl]diazenyl}benzoate as red crystals, λmax=478 nm, ε=62000 (THF).

Workup

  1. addition0.29 g of methansulfochloride (2.5 mM) were added dropwise
  2. customto rise to −10° C
  3. temperatureto warm to room temperature
  4. stirringwhile stirred overnight
  5. filtrationThe next day, the mixture was filtered through a pad of celite
  6. filtrationfilter aid
  7. customevaporated to dryness
  8. dissolutionThe residue was dissolved in 15 ml of THF and to this solution
  9. additionwere added dropwise 25 ml of methanol at room temperature
  10. additionWhen addition
  11. stirringthe resulting suspension was stirred for 30 min. at room temperature
  12. filtrationthe solids were filtered off
  13. washwashed with methanol
  14. customdried

Sources & evidence

ORD record
ord-dea10401b03944b5a6c102ae38364ec5
Source dataset
uspto-grants-2010_10
Patent number
US07811642B2

Reaction notes

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