Formic Acid → sodium (3S,5R,6R)-6-formamido-2,2-dimethylpenam-3-carboxylate

HRID 329240

反応式

HRID 329240 の反応式
[NH2:1][C@@H:2]1[C:13](=[O:14])[N:4]2[C@@H:5]([C:10]([OH:12])=[O:11])[C:6]([CH3:9])([CH3:8])[S:7][C@H:3]12.C[Si](C)(C)Cl.C(N(CC)CC)C.[C:27](OC=O)(=[O:29])C.C(O)=O.C(Cl)(=O)C.Cl.C(N(CC)CC)C.C(C(CCCC)C([O-])=O)C.[Na+:58]>O1CCCC1.CCOCC>[CH:27]([NH:1][C@@H:2]1[C:13](=[O:14])[N:4]2[C@@H:5]([C:10]([O-:12])=[O:11])[C:6]([CH3:9])([CH3:8])[S:7][C@H:3]12)=[O:29].[Na+:58]

参加物

11

反応物 8

HCID 284Formic AcidHCID 6367Acetyl chlorideHCID 6397ChlorotrimethylsilaneHCID 8471Triethylamine3 回HCID 110826-Aminopenicillanic acidHCID 11130Triethylamine hydrochlorideHCID 75269Acetic-formic anhydrideHCID 23672331Sodium 2-ethylhexanoate

生成物 1

HCID 86733807sodium (3S,5R,6R)-6-formamido-2,2-dimethylpenam-3-carboxylate

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒HCID 8028Tetrahydrofuran溶媒3 回

実験手順

A mixture of (3S,5R,6R)-6-amino-2,2-dimethylpenam-3-carboxylic acid (6ApA, 2.2056 g., 10.21 mmole), trimethyl chlorosilane (2.615 ml., 20.42 mmole), and triethylamine (2.84 ml., 20.3 mmole) in tetrahydrofuran, (50 ml.) was stirred for 1 hour at +20 to +25° and then cooled to -70°. To this solution at -70° was added a cold (-60 to -70°) solution of formic-acetic anhydride [generated by stirring formic acid (470 mg., 10.2 mmole), acetyl chloride (0.726 ml., 10.2 mmole) and triethylamine (1.42 ml., 10.2 mmole) at -60 to -70° in tetrahydrofuran (40 ml.). The solution contained suspended triethylamine hydrochloride] and triethylamine (1.42 ml., 10.2 mmole). The temperature of the mixture was allowed to rise to +20° over ca. 1 hour and the mixture was then filtered. The filtrate and washings were stirred and a solution of sodium 2-ethylhexanoate (2 g., 12 mmole) in tetrahydrofuran (2ml.) and ether (18 ml.) was added. The white precipitate was isolated by filtration, washed with ether and dried to give sodium (3S,5R,6R)-6-formamido-2,2-dimethylpenam-3-carboxylate as a white powder (1.6127 g., 6.06 mmole), 59.4%); m.p. 238° to 242° (dec.); [α]D + 281° (H2O); νmax. 3412 (NH), 1790 (azetidin-2-one), 1677 and 1505 (CONH), 1602 cm.-1 (CO2 -); τ 1.28 (1H, d, J 9 Hz, NH), 1.90 (1H, s, HCO), 4.40 to 4.60 (2H, m, C5 -H and C6 -H), 6.01 (1H, s, C3 -H), 8.42 (3H, s) and 8.50 (3H, s) (C[CH3 ]2). (Found : C, 40.7; H, 4.3; N, 10.3; Na, 8.6; S, 11.7. C9H11N2NaO4S (266.3) requires C, 40.5; H, 4.1; N, 10.5; Na, 8.6; S, 12.0%).

後処理

  1. temperaturecooled to -70°
  2. waitto rise to +20° over ca. 1 hour
  3. filtrationthe mixture was then filtered
  4. stirringThe filtrate and washings were stirred
  5. customThe white precipitate was isolated by filtration
  6. washwashed with ether
  7. customdried

出典と根拠

ORDレコード
ord-a4d26e3ba95f42608431a695268b6dec
出典データセット
uspto-grants-1977_04
特許番号
US04020077

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