Pyrrolidine → 10,12,19,21-Triacontatetraynamide

HRID 1257963노트

반응식

HRID 1257963 반응식
[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]

참가 물질

5

반응물 3

HCID 31268Pyrrolidine2회HCID 85519598HCID 85519598, 화합물HCID 85962995HCID 85962995, 화합물

생성물 1

HCID 1036570510,12,19,21-Triacontatetraynamide

시약·촉매·용매 1

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

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-3f5665f9cf334ff2b0a65482d196b3fd
출처 데이터셋
uspto-grants-2013_06
특허 번호
US08465803B2

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