Pyrrolidine → 10,12,19,21-Triacontatetraynamide

HRID 1257963ノート

反応式

HRID 1257963 の反応式
[C:1]([NH2:13])(=[O:12])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][C:10]#[CH:11].N1CCCC1.I[C:20]#[C:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][C:27]#[C:28][C:29]#[C:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH3:38]>[Cu]I>[C:1]([NH2:13])(=[O:12])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][C:10]#[C:11][C:20]#[C:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][C:27]#[C:28][C:29]#[C:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH3:38]

参加物

5

反応物 3

HCID 31268Pyrrolidine2 回HCID 85519598HCID 85519598、化合物HCID 85962995HCID 85962995、化合物

生成物 1

HCID 1036570510,12,19,21-Triacontatetraynamide

試薬・触媒・溶媒 1

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒

実験手順

CuI (0.126 g, 0.66 mmol) and 10-undecynoic acid amide (0.29 g, 1.59 mmol) were added to a flask and inerted with nitrogen. Pyrollidine (5 mL) was then added. In a separate flask 1-Iodo-nonadeca-1,8,10-triyne (0.5 g, 1.3 mmol) was mixed with pyrollidine (5 mL) and subsequently added slowly to the amide solution. The reaction mix was left in darkness under nitrogen for 48 hours, then quenched with aqueous 1M NH4Cl (10 mL), and worked up with CH2Cl2 and 1 M HCl. The organic was dried over anhydrous MgSO4. Organic products were concentrated by rotary evaporation, although polymer formed, decreasing yield. Hexanes trituration removed unreacted 1-Iodo-nonadeca-1,8,10-triyne. Desired product was obtained by several crystallizations from hexanes/ethyl acetate, again under dark conditions. All handling of the solid was done under red light. Final product triaconta-10,12,19,21-tetraynoic acid amide was made up of white crystals (0.377 g, 0.86 mmol) and was stored frozen (liquid nitrogen) in methylene chloride. 65% yield; 1H NMR (CDCl3) δ: 5.31 (s, 2H, NH2), 2.22-2.26 (m, 10H, CH2—C≡C & CH2—CO), 1.58-1.66 (quin, 2H, J=7, CH2—C—CO), 1.45-1.56 (m, 8H, CH2—C—C≡C), 1.28-1.4 (m, 20H, C—CH2—C), 0.86-0.91 (t, 3H, CH3); 13C NMR (CDCl3) δ 175.69, 77.98, 77.84, 77.34, 65.69, 69.45, 65.37, 57.68, 53.63, 38.37, 38.35, 33.80, 32.97, 32.92, 32.03, 29.34, 29.27, 29.07, 28.94, 28.55, 28.47, 28.26, 28.26, 28.06, 27.17, 25.67, 22.86, 19.39, 19.32 14.30. MS (ESI) [M+H]+ calc. 436.3574. Found 436.3560.

後処理

  1. additionThe reaction mix
  2. customquenched with aqueous 1M NH4Cl (10 mL)
  3. dry with materialThe organic was dried over anhydrous MgSO4
  4. concentrationOrganic products were concentrated by rotary evaporation, although polymer
  5. customformed
  6. customdecreasing yield
  7. customHexanes trituration removed unreacted 1-Iodo-nonadeca-1,8,10-triyne

出典と根拠

ORDレコード
ord-3f5665f9cf334ff2b0a65482d196b3fd
出典データセット
uspto-grants-2013_06
特許番号
US08465803B2

反応ノート

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