Triethylamine → Diethyl[3-(1-tridecynyl)phenyl]phosphonate

HRID 265242

反応式

HRID 265242 の反応式
C([C:3]1[CH:8]=[CH:7][C:6]([P:9](=[O:12])([O-:11])[O-:10])=[C:5](CC)[C:4]=1I)C.[CH:16]#[C:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28].[C:29]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C[CH:30]=1.[CH2:48](N(CC)CC)[CH3:49]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:16]([C:4]1[CH:5]=[C:6]([P:9](=[O:12])([O:10][CH2:48][CH3:49])[O:11][CH2:29][CH3:30])[CH:7]=[CH:8][CH:3]=1)#[C:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28]

参加物

6

反応物 4

HCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 1177541-TridecyneHCID 86748802Diethyl-3-iodophenylphosphonate

生成物 1

HCID 9908538Diethyl[3-(1-tridecynyl)phenyl]phosphonate収率 17.7%

試薬・触媒・溶媒 1

HCID 167845palladium(II) acetate触媒

実験手順

Diethyl-3-iodophenylphosphonate prepared according to Example 7 (2.0 g, 5.88 mmol) and 1-tridecyne (1.79 g, 9.97 mmol) were dissolved in triethyl amine (40 ml) in a two neck round bottom flask equipped with a condenser and a nitrogen dispersing tube. The flask was inerted. Triphenylphosphine (0.047 g, 0.179 mmol) and palladium acetate (0.015 g, 0.0668 mmol) were then added and the flask was heated in an oil bath to 100° to 105° C. for 40 hours. After cooling to room temperature and filtering, the triethylamine was removed on the rotary evaporator. The residue was extracted several times with acetonitrile, and the combined extracts were stripped down to a,reddish brown liquid. Chromatography on silica eluting with 20% hexane in ethyl acetate gave the product as a pale yellow oil, 0.410 g, 1.045 mmol, 17.7% yield; 1H NMR (CDCl3) ∂0.88 (t, J=6.8 Hz, 3H), 1.18 to 1.50 (several m, 22H), 1.60 (quint, J=7.6 Hz, 2H), 2.40 (t, J=7.1 Hz, 2H), 4.11 (m, 4H), 7.38 (m, 1H), 7.55 (br d, J=7.8 Hz, 1H), 7.71 (dd, J=13.2, 7.6 Hz, 1H), 7.83 (d, J=14.1 Hz, 1H); FAB mass spectrum m/z 399 (M+Li)+.

後処理

  1. customequipped with a condenser and a nitrogen dispersing tube
  2. temperaturethe flask was heated in an oil bath to 100° to 105° C. for 40 hours
  3. filtrationfiltering
  4. customthe triethylamine was removed on the rotary evaporator
  5. extractionThe residue was extracted several times with acetonitrile

出典と根拠

ORDレコード
ord-06f4bbc50b954e189fe1343245a04a91
出典データセット
uspto-grants-1997_07
特許番号
US05648349

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