N,N,N',N'-Tetramethylazodicarboxamide → 1,3-Bis-(tert-butyl-dimethyl-silanyloxy)-5-[2-(2-{2-[2-(2-trityloxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-benzene

HRID 2075646Notes

Reaction equation

HRID 2075646 reaction equation
[C:1]([O:20][CH2:21][CH2:22][O:23][CH2:24][CH2:25][O:26][CH2:27][CH2:28][O:29][CH2:30][CH2:31][O:32][CH2:33][CH2:34][OH:35])([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(P(CCCC)CCCC)CCC.[C:49]([Si:53]([CH3:71])([CH3:70])[O:54][C:55]1[CH:56]=[C:57](O)[CH:58]=[C:59]([O:61][Si:62]([C:65]([CH3:68])([CH3:67])[CH3:66])([CH3:64])[CH3:63])[CH:60]=1)([CH3:52])([CH3:51])[CH3:50].N(C(N(C)C)=O)=NC(N(C)C)=O>C1(C)C=CC=CC=1.C(OCC)(=O)C>[C:65]([Si:62]([CH3:64])([CH3:63])[O:61][C:59]1[CH:58]=[C:57]([O:35][CH2:34][CH2:33][O:32][CH2:31][CH2:30][O:29][CH2:28][CH2:27][O:26][CH2:25][CH2:24][O:23][CH2:22][CH2:21][O:20][C:1]([C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)[CH:56]=[C:55]([O:54][Si:53]([C:49]([CH3:52])([CH3:51])[CH3:50])([CH3:71])[CH3:70])[CH:60]=1)([CH3:68])([CH3:67])[CH3:66]

Participants

7

Reactant 4

HCID 4278N,N,N',N'-TetramethylazodicarboxamideHCID 13831TributylphosphineHCID 230808033,5-Bis-(tert-butyl-dimethyl-silanyloxy)-phenolHCID 54298879Tr-PEG6

Product 1

HCID 670892321,3-Bis-(tert-butyl-dimethyl-silanyloxy)-5-[2-(2-{2-[2-(2-trityloxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-benzeneYield 39%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a solution of Compound 2 (4.3 g, 8.9 mmol) in toluene (20 ml), tributylphosphine (2.35 g, 8.92 mmol) was added at room temperature; this was followed by stirring for 1 hour. This was gradually added to a solution of Compound 43 (3.3 g, 11.6 mmol) and 1,1′-azobis(N,N-dimethylformamide) (2.0 g, 11.6 mmol) in toluene (20 ml), and this was followed by overnight stirring at room temperature. Ethyl acetate (100 ml) was added; the resulting insoluble matter was removed by Celite filtration and washed with ethyl acetate. The combined organic phases were concentrated under reduced pressure; the residue obtained was purified by silica gel column chromatography (Yamazen YFLC Gel, eluent (n-hexane:ethyl acetate 3:1-2:1)) to yield Compound 44 (colorless oil 2.8 g, 39%).

Workup

  1. waitthis was followed by overnight
  2. stirringstirring at room temperature
  3. customthe resulting insoluble matter was removed by Celite filtration
  4. washwashed with ethyl acetate
  5. concentrationThe combined organic phases were concentrated under reduced pressure
  6. customthe residue obtained
  7. customwas purified by silica gel column chromatography (Yamazen YFLC Gel, eluent (n-hexane:ethyl acetate 3:1-2:1))

Sources & evidence

ORD record
ord-95dccbf0e6964569b851efd3dd9e4603
Source dataset
uspto-grants-2011_04
Patent number
US07919653B2

Reaction notes

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