2,2,4,4-Tetramethyl-1,3-cyclobutanedione → 2,2,4,4-Tetramethylcyclobutane-1,3-diol

HRID 591101Notes

Reaction equation

[CH3:1][C:2]1([CH3:10])[C:5](=[O:6])[C:4]([CH3:8])([CH3:7])[C:3]1=[O:9]>[Ru]>[CH3:7][C:4]1([CH3:8])[CH:5]([OH:6])[C:2]([CH3:10])([CH3:1])[CH:3]1[OH:9]

Participants

Conditions

Temperature: 120 °C

Procedure

A 300 mL Parr autoclave was charged with 25 grams of 2,2,4,4-tetramethylcyclobutane-1,3-dione, 100 grams Isopar™ G, and 12.5 grams of 2% ruthenium on alumina (surface area=10 m2/g, purchased from BASF Catalysts). The autoclave was pressure purged three times with nitrogen and three times with hydrogen, and the pressure was increased to 3.5 MPa (500 psig) with hydrogen. The autoclave was heated to 120° C. with stirring at approximately 1400 rpm and held for 70.8 hours at 3.5 MPa (500 psig). Analysis of the product by gas chromatography indicated that complete conversion of the 2,2,4,4-tetramethylcyclobutane-1,3-dione was obtained with 97.4% selectivity to 2,2,4,4-tetramethycyclobutane-1,3-diol with a cis:trans ratio of 8.19:1. The main by-products are 2,2,4-trimethyl-3-pentanol at 1.40%, and 2,2,4-trimethyl-1,3-pentanediol at 0.92%.

Workup

custompurged three times with nitrogen and three times with hydrogen
temperaturethe pressure was increased to 3.5 MPa (500 psig) with hydrogen

Sources & evidence

ORD record: ord-4cb5c0b5ee614f0d975b26d247787545
Source dataset: uspto-grants-2016_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09238602B1

Reaction notes

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