Ethylamine → Methyl 5-(3,5,5,8,8-Pentamethyl-5,6,7,8-tetrahydronaphthalen-2-ylsulphonyl)penta-2,4-diynoate

HRID 1278841

Reaktionsgleichung

Reaktionsgleichung von HRID 1278841
C(N)C.Br[C:5]#[C:6][C:7]([O:9][CH3:10])=[O:8].Cl.NO.[C:14]([S:16]([C:19]1[CH:20]=[C:21]2[C:26](=[CH:27][C:28]=1[CH3:29])[C:25]([CH3:31])([CH3:30])[CH2:24][CH2:23][C:22]2([CH3:33])[CH3:32])(=[O:18])=[O:17])#[CH:15].[Cl-].[NH4+]>O.CO.[Cu]Cl.C(OCC)(=O)C>[CH3:29][C:28]1[C:19]([S:16]([C:14]#[C:15][C:5]#[C:6][C:7]([O:9][CH3:10])=[O:8])(=[O:18])=[O:17])=[CH:20][C:21]2[C:22]([CH3:33])([CH3:32])[CH2:23][CH2:24][C:25]([CH3:30])([CH3:31])[C:26]=2[CH:27]=1

Komponenten

10

Edukt 5

HCID 6341EthylamineHCID 25517Ammonium ChlorideHCID 294619Methyl 3-bromoprop-2-ynoateHCID 443297Hydroxyamine hydrochlorideHCID 223478256-Ethynylsulphonyl-1,1,4,4,7-pentamethyl-1,2,3,4-tetrahydronaphthalene

Produkt 1

HCID 22347861Methyl 5-(3,5,5,8,8-Pentamethyl-5,6,7,8-tetrahydronaphthalen-2-ylsulphonyl)penta-2,4-diynoate

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 62652Cuprous chlorideKatalysatorHCID 887MethanolLösungsmittel2×HCID 962WaterLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

A 70% solution of ethylamine in water (563 μl) is added dropwise to a mixture of methyl 3-bromopropynoate (632 mg, 2.88 mmol), hydroxylamine hydrochloride (162 mg, 2.33 mmol) and copper (I) chloride (10 mg) in methanol. A solution of 6-ethynylsulphonyl-1,1,4,4,7-pentamethyl-1,2,3,4-tetrahydronaphthalene (Example 7(b)) (500 mg, 1.94 mmol) in methanol (5 ml) is then added dropwise. The reaction medium is stirred for 15 h at room temperature and treated with saturated aqueous ammonium chloride solution and ethyl acetate. The organic phase is washed with water, dried over magnesium sulphate and concentrated. The product is obtained in the form of an oil after purification by flash chromatography on silica (80/20 heptane/CH2Cl2). 1H NMR/CDCl3: 1.26 to 1.28 (s, 12H); 1.67 (s, 4H); 2.35 (s, 3H); 3.78 (s, 3H); 7.14 (s, 1H); 7.48 (s, 1H); 13C NMR/CDCl3: 19.7; CH3/31.8; 4*CH3/34.1; Cq/34.3; Cq/34.9; 2*CH2/52.9; CH3/71.7; CH/72.1; CH/80.2; Cq/124.5; Cq/127.6; Cq/12.8.3; CH/129.3; CH/134.8; Cq/144.6; Cq/146.2; Cq/153.4; Cq.

Aufarbeitung

  1. washThe organic phase is washed with water
  2. dry with materialdried over magnesium sulphate
  3. concentrationconcentrated
  4. customThe product is obtained in the form of an oil
  5. customafter purification by flash chromatography on silica (80/20 heptane/CH2Cl2)

Quellen und Nachweise

ORD-Eintrag
ord-0627d8b6b177464989eb15fb45861a70
Quelldatensatz
uspto-grants-2002_09
Patentnummer
US06444709B1

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