Triethylamine → [6-Chloro-4-(3,3-dimethyl-but-1-ynyl)-pyridin-3-yl]-carbamic acid tert-butyl ester

HRID 513069

Reaktionsgleichung

Reaktionsgleichung von HRID 513069
[C:1]([O:5][C:6](=[O:16])[NH:7][C:8]1[CH:9]=[N:10][C:11]([Cl:15])=[CH:12][C:13]=1I)([CH3:4])([CH3:3])[CH3:2].[CH3:17][C:18]([CH3:22])([CH3:21])[C:19]#[CH:20].C(N(CC)CC)C>C1(C)C=CC=CC=1.O.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:1]([O:5][C:6](=[O:16])[NH:7][C:8]1[CH:9]=[N:10][C:11]([Cl:15])=[CH:12][C:13]=1[C:20]#[C:19][C:18]([CH3:22])([CH3:21])[CH3:17])([CH3:4])([CH3:3])[CH3:2]

Komponenten

8

Edukt 3

HCID 8471TriethylamineHCID 135123,3-Dimethyl-1-butyneHCID 53415320tert-Butyl (6-chloro-4-iodopyridin-3-yl)carbamate

Produkt 1

HCID 57908146[6-Chloro-4-(3,3-dimethyl-but-1-ynyl)-pyridin-3-yl]-carbamic acid tert-butyl esterAusbeute 78 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

To a deoxygenated solution of (6-chloro-4-iodo-pyridin-3-yl)-carbamic acid tert-butyl ester (23.3 g, 65.6 mmol), 3,3-dimethyl-but-1-yne (53.8 g, 0.656 mol), CuI (623 mg, 3.3 mmol) and triethylamine (13.3 g, 0.13 mol) in toluene (150 mL) and water (50 mL) was added Pd(PPh3)2Cl2 (2.30 g, 3.28 mmol) under N2. The mixture was heated at 70° C. and stirred for 24 hours. The solid was filtered off and washed with ethyl acetate (200 mL×3). The filtrate was evaporated under reduced pressure to obtain a residue, which was purified by column (petroleum ether/ethyl acetate=10/1) to give [6-chloro-4-(3,3-dimethyl-but-1-ynyl)-pyridin-3-yl]-carbamic acid tert-butyl ester (15.8 g, 78%). 1H NMR (300 MHz, CDCl3) δ 9.10 (br s, 1H), 7.21 (s, 1H), 6.98 (br s, 1H), 1.53 (s, 9H), 1.36 (s, 9H).

Aufarbeitung

  1. filtrationThe solid was filtered off
  2. washwashed with ethyl acetate (200 mL×3)
  3. customThe filtrate was evaporated under reduced pressure
  4. customto obtain a residue, which
  5. customwas purified by column (petroleum ether/ethyl acetate=10/1)

Quellen und Nachweise

ORD-Eintrag
ord-625d21f062fd45b0ae63ef512db8e683
Quelldatensatz
uspto-grants-2015_08
Patentnummer
US09102672B2

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