Trichloroacetonitrile → HCID 86658274, compound

HRID 74835Notes

Reaction equation

HRID 74835 reaction equation
[C:1]([O:9][C@H:10]1[C@@H:15]([O:16][C:17](=[O:24])[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C@H:14]([O:25][C:26](=[O:33])[C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C@@H:13]([CH2:34][O:35][C:36](=[O:43])[C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[O:12][C@@H:11]1[O:44][C@H:45]1[C@@H:51]([O:52][C:53](=[O:60])[C:54]2[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=2)[C@H:50]([O:61][C:62](=[O:69])[C:63]2[CH:68]=[CH:67][CH:66]=[CH:65][CH:64]=2)[C@@H:49]([CH2:70][O:71][C:72](=[O:79])[C:73]2[CH:78]=[CH:77][CH:76]=[CH:75][CH:74]=2)[O:48][CH:46]1[OH:47])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Cl:80][C:81]([Cl:85])([Cl:84])[C:82]#[N:83].CCCCCC.CCOC(C)=O>C(Cl)Cl.C1CCN2C(=NCCC2)CC1>[Cl:80][C:81]([Cl:85])([Cl:84])[C:82](=[NH:83])[O:47][CH:46]1[O:48][C@H:49]([CH2:70][O:71][C:72](=[O:79])[C:73]2[CH:74]=[CH:75][CH:76]=[CH:77][CH:78]=2)[C@@H:50]([O:61][C:62](=[O:69])[C:63]2[CH:64]=[CH:65][CH:66]=[CH:67][CH:68]=2)[C@H:51]([O:52][C:53](=[O:60])[C:54]2[CH:55]=[CH:56][CH:57]=[CH:58][CH:59]=2)[C@@H:45]1[O:44][C@H:11]1[O:12][C@H:13]([CH2:34][O:35][C:36](=[O:43])[C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[C@@H:14]([O:25][C:26](=[O:33])[C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=2)[C@H:15]([O:16][C:17](=[O:24])[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C@@H:10]1[O:9][C:1](=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 11011TrichloroacetonitrileHCID 21226206Ethyl acetate hexaneHCID 86658272HCID 86658272, compound

Product 1

HCID 86658274HCID 86658274, compoundYield 77%

Reagents, catalysts & solvents 2

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

To a pre-cooled (0° C.) solution of 29 (609 mg, 0.569 mmol) in anhydrous DCM (2.8 mL, 0.2 M) was added trichloroacetonitrile (114 μL, 1.138 mmol, 2 eq). A solution of DBU (4.3 μL, 0.05 eq, 0.0285 mmol) in anhydrous DCM (0.3 mL) was added. The mixture was stirred at 0° C. for 4 h and TLC (hexane-EtOAc=65:35) indicated complete conversion. The crude mixture was evaporated onto silica gel and purified by silica column chromatography (2.5×14 cm, gradient elution with hexane-EtOAc-Et3N 210:20:0.5, 200:50:0.5, 180:60:0.5, 150:70:0.5). The product fractions were combined, evaporated and dried in a vacuum desiccator over P2O5 o/n to give the trichloroacetimidate 30 as white foam (530 mg, 77%), used without further purification in the next step.

Workup

  1. customThe crude mixture was evaporated onto silica gel
  2. custompurified by silica column chromatography (2.5×14 cm, gradient elution with hexane-EtOAc-Et3N 210:20:0.5, 200:50:0.5, 180:60:0.5, 150:70:0.5)
  3. customevaporated
  4. dry with materialdried in a vacuum desiccator over P2O5 o/n

Sources & evidence

ORD record
ord-e985e81bec0c4735b7575a7351061dec
Source dataset
uspto-grants-2014_09
Patent number
US08828952B2

Reaction notes

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