1,2-Dimethoxyethane → 3-Nitro-4-(1,4-dioxaspiro[4.5]dec-7-en-8-yl)pyridine

HRID 1523425Notes

Reaction equation

COCCOC.C(=O)([O-])[O-].[Na+].[Na+].Cl[C:14]1[CH:19]=[CH:18][N:17]=[CH:16][C:15]=1[N+:20]([O-:22])=[O:21].CC1(C)C(C)(C)OB([C:31]2[CH2:40][CH2:39][C:34]3([O:38][CH2:37][CH2:36][O:35]3)[CH2:33][CH:32]=2)O1>C(OCC)(=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl>[N+:20]([C:15]1[CH:16]=[N:17][CH:18]=[CH:19][C:14]=1[C:31]1[CH2:40][CH2:39][C:34]2([O:38][CH2:37][CH2:36][O:35]2)[CH2:33][CH:32]=1)([O-:22])=[O:21]

Participants

Conditions

Temperature: 110 °C

Procedure

A solution of DME (0.2 M) and 2M aq. sodium carbonate (1.7 equiv.) was purged with nitrogen for 20 min. Then 4-chloro-3-nitropyridine (1.6 equiv.), 4,4,5,5-tetramethyl-2-(1,4-dioxaspiro[4.5]dec-7-en-8-yl)-1,3,2-dioxaborolane (1.0 equiv.), Pd(dppf)Cl2-DCM (0.05 equiv.) were added and stirred in a sealed bomb at 110° C. The reaction was stirred at that temperature for 3.5 hours. The reaction was diluted with ethyl acetate, washed with water, dried over MgSO4, filtered, and concentrated. The residue was purified by column (ethyl acetate:hexanes=1:1 with 10% methanol) to give 3-nitro-4-(1,4-dioxaspiro[4.5]dec-7-en-8-yl)pyridine (83%). LC/MS (m/z): MH+=263.2, Rt=0.71.

Workup

stirringThe reaction was stirred at that temperature for 3.5 hours
washwashed with water
dry with materialdried over MgSO4
filtrationfiltered
concentrationconcentrated
customThe residue was purified by column (ethyl acetate:hexanes=1:1 with 10% methanol)

Sources & evidence

ORD record: ord-36570099d9e54ca1983f85664d6ba63e
Source dataset: uspto-grants-2015_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09079889B2

Reaction notes

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