Acetonitrile, 2,2-diethoxy- → 1,3-Propanediol

HRID 2204444Notes

Reaction equation

HRID 2204444 reaction equation
[CH2:1]([O:3][CH:4]([O:7][CH2:8][CH3:9])C#N)C.C[O:11][CH:12]([C:15]([CH:17](OC)[O:18]C)=O)OC>C1C=CC=CC=1.CC1C=CC(S(O)(=O)=O)=CC=1>[CH2:17]([OH:18])[CH2:15][CH2:12][OH:11].[O:3]1[CH2:1][CH2:9][CH2:8][O:7][CH2:4]1

Participants

5

Reactant 2

HCID 80223Acetonitrile, 2,2-diethoxy-HCID 85736988HCID 85736988, compound

Product 2

HCID 104421,3-PropanediolHCID 104501,3-Dioxane

Reagents, catalysts & solvents 1

HCID 22637252HCID 22637252, compoundSolvent

Procedure

The new route to Michael acceptors enabled expansion of the structural diversity of these intermediates. Diethoxymethyl Michael acceptor 1b was prepared from commercially available diethoxyacetonitrile in analogy with the synthesis of 1a. Transacetalization of diethoxyacetal 1b with 1,3-propanediol in benzene/TsOH afforded 1,3-dioxane 1c in 64% yield. On the other hand, attempted transacetalization of 1b with ethylene glycol gave an inseparable mixture consisting of 1,3-dioxolane 1d and a by-product assumed to be bis(1,3-dioxolane) C (Scheme 6). Transacetalization of diethoxyacetonitrile with ethylene glycol in the presence of TsOH also did not proceed. Therefore, we considered an alternative approach to 1d.

Sources & evidence

ORD record
ord-842dbdcf0dd5418d83c56ad55316b140
Source dataset
uspto-grants-2016_06
Patent number
US09365722B2

Reaction notes

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