Aluminium lithium hydride → HCID 86696514, compound

HRID 1615918Notes

Reaction equation

[C:1]([C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[CH:9]1[CH2:11][CH:10]1[C:12](N(OC)C)=[O:13])#[N:2].[H-].[H-].[H-].[H-].[Li+].[Al+3]>C1COCC1>[CH:12]([CH:10]1[CH2:11][CH:9]1[C:4]1[CH:5]=[CH:6][CH:7]=[CH:8][C:3]=1[C:1]#[N:2])=[O:13]

Participants

Conditions

Temperature: -30 °C

Procedure

A solution of 2-(2-cyanophenyl)-N-methoxy-N-methylcyclopropanecarboxamide (250 mg, 1.086 mmol) in THF (5 mL) was stirred, maintaining the temperature below −40° C., as a suspension of LAH (82 mg, 2.171 mmol) in THF (20 mL) at −50° C. was added. After the addition was complete, the reaction was slowly allowed to warm to −30° C., and then cooled to below −40° C. The reaction was quenched with a EtOAc, followed by 1 N sodium hydroxide (1 mL). The reaction was stirred at rt for 30 min. The solution was diluted with EtOAc, filtered through celite, then concentrated. The material was purified on silica gel using 5-40% EtOAc/hexanes as the eluent to give 2-(2-formylcyclopropyl)benzonitrile (135 mg, 72.6%) as an oil. 1H NMR (400 MHz, CHLOROFORM-d) δ 9.42 (d, J=4.3 Hz, 1H), 7.67 (dd, J=7.8, 1.0 Hz, 1H), 7.56 (td, J=7.8, 1.3 Hz, 1H), 7.36 (td, J=7.6, 1.1 Hz, 1H), 7.12 (d, J=8.0 Hz, 1H), 2.95 (ddd, J=9.2, 6.6, 4.3 Hz, 1H), 2.27 (ddt, J=8.5, 5.3, 4.3 Hz, 1H), 1.87 (dt, J=9.3, 5.3 Hz, 1H), 1.67-1.49 (m, 1H). LCMS: M+1=171.1.

Workup

temperaturemaintaining the temperature below −40° C.
additionwas added
additionAfter the addition
temperaturecooled to below −40° C
customThe reaction was quenched with a EtOAc
additionThe solution was diluted with EtOAc
filtrationfiltered through celite
concentrationconcentrated
customThe material was purified on silica gel using 5-40% EtOAc/hexanes as the eluent

Sources & evidence

ORD record: ord-d1a2a1d497de40538417778c77559c4e
Source dataset: uspto-grants-2014_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08765767B2

Reaction notes

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