Acetic Acid → 4-(3-Ethynylbenzyl)morpholine

HRID 2281756Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2281756
[C:1]([C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][CH:10]=1)[CH:6]=O)#[CH:2].[NH:11]1[CH2:16][CH2:15][O:14][CH2:13][CH2:12]1.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+].CC(O)=O>ClCCCl>[C:1]([C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][CH:10]=1)[CH2:6][N:11]1[CH2:16][CH2:15][O:14][CH2:13][CH2:12]1)#[CH:2]

Komponenten

6

Edukt 4

HCID 176Acetic AcidHCID 8083MorpholineHCID 27716443-EthynylbenzaldehydeHCID 5049666Sodium triacetoxyborohydride

Produkt 1

HCID 866588304-(3-Ethynylbenzyl)morpholineAusbeute 97,4 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 111,2-DichloroethaneLösungsmittel

Versuchsvorschrift

To a mixture of 3-ethynylbenzaldehyde (650 mg, 5 mmol) and morpholine (0.87 mL, 10 mmol) in DCE (15 mL) was added NaBH(OAc)3 (1.325 g, 6.25 mmol), followed by AcOH (0.2 mL). The resulting mixture was stirred for 2 h at rt. Aqueous workup followed by extraction with EtOAc gave crude 4-(3-ethynylbenzyl)morpholine (0.98 g) as a light brown oil. The title compound (1.75 g, quantitative yield over 2 steps) was obtained as a light brown oil using the method (PhCH3=12 mL, 1 mol % HRuCl(CO)(PPh3)3, 50° C., 2 h) for the preparation of Example A42A. 1H NMR (400 MHz, CDCl3) δ7.47 (s, 1H), 7.46-7.37 (m, 2H), 7.35-7.27 (m, 2H), 6.19 (d, J=18.4 Hz, 1H), 3.78-3.68 (m, 4H), 3.52 (s, 2H), 2.52-2.42 (m, 4H), 1.32 (s, 12H); MS ESI 330.1 [M+H]+, calcd for [C19H28BNO3+H]+ 330.2.

Aufarbeitung

  1. extractionAqueous workup followed by extraction with EtOAc

Quellen und Nachweise

ORD-Eintrag
ord-8556006d1b6d49dea0a24746638ca0ae
Quelldatensatz
uspto-grants-2015_09
Patentnummer
US09139563B2

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