Triphenylphosphine → 4-(3-Cyclopentyloxy-4-methoxyphenyl)-4-(2-[3-(5-methyl-[1,3,4]thiadiazol-2-yl)phenyl]ethynyl)cyclohexan-1-one

HRID 343573노트

반응식

HRID 343573 반응식
[CH:1]1([O:6][C:7]2[CH:8]=[C:9]([C:15]3([C:22]#[CH:23])[CH2:20][CH2:19][C:18](=[O:21])[CH2:17][CH2:16]3)[CH:10]=[CH:11][C:12]=2[O:13][CH3:14])[CH2:5][CH2:4][CH2:3][CH2:2]1.I[C:25]1[CH:26]=[C:27]([C:31]2[S:32][C:33]([CH3:36])=[N:34][N:35]=2)[CH:28]=[CH:29][CH:30]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(N(CC)CC)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH:1]1([O:6][C:7]2[CH:8]=[C:9]([C:15]3([C:22]#[C:23][C:29]4[CH:30]=[CH:25][CH:26]=[C:27]([C:31]5[S:32][C:33]([CH3:36])=[N:34][N:35]=5)[CH:28]=4)[CH2:16][CH2:17][C:18](=[O:21])[CH2:19][CH2:20]3)[CH:10]=[CH:11][C:12]=2[O:13][CH3:14])[CH2:2][CH2:3][CH2:4][CH2:5]1

참가 물질

6

반응물 3

HCID 11776TriphenylphosphineHCID 108289304-(3-Cyclopentyloxy-4-methoxyphenyl)-4-ethynylcyclohexan-1-oneHCID 193499822-(3-Iodophenyl)-5-methyl-1,3,4-thiadiazole

생성물 1

HCID 542762454-(3-Cyclopentyloxy-4-methoxyphenyl)-4-(2-[3-(5-methyl-[1,3,4]thiadiazol-2-yl)phenyl]ethynyl)cyclohexan-1-one수율 82.2%

시약·촉매·용매 2

HCID 178418397HCID 178418397, 화합물촉매HCID 8471Triethylamine용매

실험 절차

A stirred mixture of 4-(3-cyclopentyloxy-4-methoxyphenyl)-4-ethynylcyclohexan-1-one (0.100 g, 0.32 mmol) and 2-(3-iodophenyl)-5-methyl-[1,3,4]thiadiazole (0.097 g, 0.32 mmol) in dry triethylamine (2.5 mL) was treated under argon with a mixture of tetrakis(triphenylphosphine)palladium (0.016 g, 0.013 mmol), cuprous iodide (0.0033 g, 0.017 mmol), and triphenylphosphine (a small crystal) at 70° C. for 1 h and at 25° C. for 15 h. The reaction mixture was concentrated in vacuo and the residue was partitioned between methylene chloride and cold dilute hydrochloric acid. The organic phase was chromatographed (silica, 10 to 20% ethyl acetate in methylene chloride) and the pure fractions were combined, concentrated in vacuo and dried at 50° C. in vacuo and the brittle resin ground to afford the titled compound as a yellow powder (0.128 g, 79%). Anal. (C29H3ON2)3S.H2O) calcd: C 69.02, H 6.39, N 5.55, found: C 68.91, H 6.21, N 5.35. 1H-NMR (400 MHz, CDCl3) δ 8.06 (t, J=1.6 Hz, 1H), 7.88 (d-t, J=1.4 Hz, J=8.1 Hz, 1H), 7.58 (d-d, J=1.2 Hz, J=9.0 Hz, 1H), 7.45 (t, J=7.8 Hz), 7.21 (d, J=2.2, 1H), 7.14 (dd, J=8.4 Hz, J=2.1 Hz, 1H), 6.88 (d, J=8.5, 1H), 4.82 (p, J=4.1 Hz, 1H), 3.86 (s, 3H), 3.04 (d-t, J=6.1 Hz, J=14.2, 2H), 2.84 (s, 3H), 2.50 (d,br, J=14.9, 2H), 2.42-2.32 (m, 2H), 2.27 (d-t, J=2.8 Hz, J=14.2 Hz, 2H), 2.00-1.5 (m, 12H with H2O).

후처리

  1. concentrationThe reaction mixture was concentrated in vacuo
  2. customthe residue was partitioned between methylene chloride and cold dilute hydrochloric acid
  3. customThe organic phase was chromatographed (silica, 10 to 20% ethyl acetate in methylene chloride)
  4. concentrationconcentrated in vacuo
  5. customdried at 50° C. in vacuo

출처 및 근거

ORD 기록
ord-638ff152fe7749f4b3239135f8094fd7
출처 데이터셋
uspto-grants-1999_01
특허 번호
US05861421

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