Potassium Bromide → 7-N-chloroacetyldemethyllavendamycin isoamyl ester

HRID 727116Notes

Reaction equation

HRID 727116 reaction equation
[Cl:1][CH2:2][C:3]([NH:5][C:6]1[C:15](=[O:16])[C:14]2[N:13]=[C:12]([CH:17]=O)[CH:11]=[CH:10][C:9]=2[C:8](=[O:19])[CH:7]=1)=[O:4].[CH2:20]([O:25][C:26](=[O:39])[C@H:27]([CH2:29][C:30]1[C:38]2[C:33](=[CH:34][CH:35]=[CH:36][CH:37]=2)[NH:32][CH:31]=1)[NH2:28])[CH2:21][CH:22]([CH3:24])[CH3:23].[K+].[Br-].COC(=O)[C@H](C(C)C1C2C(=CC=CC=2)NC=1)N>>[CH3:24][CH:22]([CH2:21][CH2:20][O:25][C:26]([C:27]1[CH:29]=[C:30]2[C:31](=[C:17]([C:12]3[CH:11]=[CH:10][C:9]4[C:8](=[O:19])[CH:7]=[C:6]([NH:5][C:3]([CH2:2][Cl:1])=[O:4])[C:15](=[O:16])[C:14]=4[N:13]=3)[N:28]=1)[NH:32][C:33]1[CH:34]=[CH:35][CH:36]=[CH:37][C:38]2=1)=[O:39])[CH3:23]

Participants

5

Reactant 4

HCID 253877Potassium BromideHCID 115726897-Chloroacetamido-2-Formylquinoline-5.8-DioneHCID 11594264L-tryptophan isoamyl esterHCID 14284053beta-Methyltryptophan methyl ester

Product 1

HCID 116422667-N-chloroacetyldemethyllavendamycin isoamyl esterYield 27%

Conditions

Temperature
76 °C

Procedure

In a 100 ml. three-necked, round-bottomed flask equipped with a reflux condenser, flowing argon and a magnetic bar, 7-chloro-acetamido-2-formylquinoline-5,8-dione (24) (prepared as described in Example 24) (0.0500 g., 0.18 mmol), L-tryptophan isoamyl ester (37) (prepared as described in Example 37) (0.0490 g., 0.18 mmol), and 75 ml. of dried and distilled xylene were slowly heated to 76° C. over a five-hour period. Upon the first detection of the formation of a light-colored precipitate, the mixture was filtered hot. The filtrate was concentrated under reduced pressure to about 10 ml. The filtrate was stored in a refrigerator overnight during which a considerable amount of a dark orange-brown solid formed. This was filtered and washed with cold ethyl acetate giving 25.5 mg. of the crude product (a yield of 27%). The filtrate was further concentrated which, upon cooling, yielded an additional 15 mg. of the product (16% yield, total yield 43%): mp. 280-284° C.; 1H NMR (CDCl3) δ 1.05 (6H, d, J=6.3 Hz., (CH3)2), 1.76-1.95 (3H, m, COOCH2CH2CH), 4.29 (2H, s, C-7NHCOCH2Cl), 4.52 (2H, t, J=6.8 Hz., COOCH2), 7.39 (1H, dd, J=8.0 Hz., J=8.0 Hz., C-11'H), 7.66 (1H, dd, J=8.0 Hz., J=8.0 Hz., C-10'H), 7.78 (1H, d, J=8.0 Hz., C-9'H), 7.95 (1H, s, C-6H), 8.23 (1H, d, J=8.0 Hz., C-12'H), 8.54 (1H, d, J=8.3 Hz., C-3H), 8.93 (1H, s, C-3'H), 9.18 (1H, d, J=8.3 Hz., C-4H), 9.56 (1H, br s, C-7NH), 11.76 (1H, br s, NH); IR (KBr) vmax 3336, 2957, 2929, 2908, 2871, 1713, 1680, 1651, 1588, 1520, 1337, 1308, 1265, 1219, 1119, 738 cm1 ; EIMS, m/e (relative intensity) 530/532 (M+, 2.4/1, 45), 496 (58), 480 (6), 454 (39), 416 (83), 382 (95), 366 (15), 340 (base); HRMS, m/e for C28 H23ClN4O5 calculated 530.135698, found 530.135781.

Workup

  1. customthree-necked, round-bottomed flask equipped with a reflux condenser
  2. customof dried
  3. distillationdistilled xylene
  4. filtrationUpon the first detection of the formation of a light-colored precipitate, the mixture was filtered hot
  5. concentrationThe filtrate was concentrated under reduced pressure to about 10 ml
  6. customwas stored in a refrigerator overnight during which
  7. customformed
  8. filtrationThis was filtered
  9. washwashed with cold ethyl acetate giving 25.5 mg
  10. concentrationThe filtrate was further concentrated which
  11. temperatureupon cooling
  12. customyielded an additional 15 mg

Sources & evidence

ORD record
ord-b1a075f3b52b461c8f14d2d08b40db96
Source dataset
uspto-grants-1998_01
Patent number
US05712289

Reaction notes

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