2,2,4,4-Tetramethyl-1,3-cyclobutanediol

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In one embodiment, the present invention provides processes for producing 2,2,4,4-tetramethylcyclobutane-1,3-diol, comprising contacting 2,2,4,4-tetramethylcyclobutane-1,3-dione, a promoted copper-based catalyst, a non-protic solvent, and hydrogen in a hydrogenation zone under conditions of temperature and pressure sufficient to form 2,2,4,4-tetramethylcyclobutane-1,3-diol. In one such embodiment, the 2,2,4,4-tetramethylcyclobutane-1,3-dione and hydrogen are continuously fed into the hydrogenation zone. In one such embodiment, the hydrogenation zone has a temperature ranging from 75° C. to 250° C. In one such embodiment, the pressure ranges from 689 kPa (100 psi) to 41,368 kPa (6000 psi). In one embodiment, the present invention provides processes for producing 2,2,4,4-tetramethylcyclobutane-1,3-diol, comprising contacting 2,2,4,4-tetramethylcyclobutane-1,3-dione, a promoted copper-based catalyst, a non-protic solvent, and hydrogen in a hydrogenation zone under conditions of temperature and pressure sufficient to form 2,2,4,4-tetramethylcyclobutane-1,3-diol, and further comprising continuously recovering an effluent comprising the 2,2,4,4-tetramethylcyclobutane-1,3-diol and the solvent from the hydrogenation zone. In one such embodiment, the process further comprises continuously recycling a portion of the effluent to the hydrogenation zone. In one such embodiment, the process further comprises continuously recovering the effluent from the hydrogenation zone and recovering at least a portion of the 2,2,4,4-tetramethylcyclobutane-1,3-diol from the effluent to form a depleted 2,2,4,4-tetramethylcyclobutane-1,3-diol stream. In one such embodiment, at least a portion of the depleted 2,2,4,4-tetramethylcyclobutane-1,3-diol stream is recycled to the hydrogenation zone. The term “depleted 2,2,4,4-tetramethylcyclobutane-1,3-diol stream” means that the depleted stream has less 2,2,4,4-tetramethylcyclobutane-1,3-diol in it than the effluent from which the depleted stream is derived. In one such embodiment, the hydrogenation zone comprises a tubular, fixed bed, or trickle bed reactor. In one such embodiment, the hydrogenation zone comprises a stirred tank, a continuous stirred tank, or a slurry reactor. In one such embodiment, the 2,2,4,4-tetramethylcyclobutane-1,3-diol has a cis/trans molar ratio of 1.3 or less. In one such embodiment, the 2,2,4,4-tetramethylcyclobutane-1,3-diol has a cis/trans molar ratio of 0.3 or more. ranging from 75° C. to 250° C In one embodiment, the present invention provides processes

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

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%. purged three times with nitrogen and three times with hydrogen the pressure was increased to 3.5 MPa (500 psig) with hydrogen

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

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 130° C. with stirring at approximately 1400 rpm and held for 16.75 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 96.1% selectivity to 2,2,4,4-tetramethycyclobutane-1,3-diol with a cis:trans ratio of 4.31:1. The main by-products are 2,2,4-trimethyl-3-pentanol at 1.59%, and 2,2,4-trimethyl-1,3-pentanediol at 2.01%. purged three times with nitrogen and three times with hydrogen the pressure was increased to 3.5 MPa (500 psig) with hydrogen

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

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 130° C. with stirring at approximately 1400 rpm and held for 16.75 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 96.1% selectivity to 2,2,4,4-tetramethycyclobutane-1,3-diol with a cis:trans ratio of 4.31:1. The main by-products are 2,2,4-trimethyl-3-pentanol at 1.59%, and 2,2,4-trimethyl-1,3-pentanediol at 2.01%. purged three times with nitrogen and three times with hydrogen the pressure was increased to 3.5 MPa (500 psig) with hydrogen

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2 liter Parr autoclave was charged with 100 grams of 2,2,4,4-tetramethylcyclobutane-1,3-dione, 375 grams Isopar™ G, 25 grams dionized water, and 50 grams of 2% ruthenium on alumina (surface area=10 m2/g, purchased from BASF Catalysts) placed under a screen in the bottom of the autoclave. 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 100° C. with stirring at approximately 1200 rpm and held for 4 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 100% selectivity to 2,2,4,4-tetramethycyclobutane-1,3-diol with a cis:trans ratio of 19.8:1. purged three times with nitrogen and three times with hydrogen the pressure was increased to 3.5 MPa (500 psig) with hydrogen

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 300 mL Parr autoclave was charged with 25 grams of 2,2,4,4-tetramethylcyclobutane-1,3-dione, 87.50 grams Isopar™ G, 12.50 grams of water, 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 100° C. with stirring at approximately 1400 rpm and held for 4 hours at 3.5 MPa (500 psig). Analysis of the product by gas chromatography indicated that complete conversion of the 2,2,4,4-tetramethyl-1,3-cyclobutanedione was obtained with 99.9% selectivity to 2,2,4,4-tetramethycyclobutane-1,3-diol with a cis:trans ratio of 17.2:1. purged three times with nitrogen and three times with hydrogen the pressure was increased to 3.5 MPa (500 psig) with hydrogen

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2 liter Parr autoclave was charged with 100 grams of 2,2,4,4-tetramethylcyclobutane-1,3-dione, 300 grams Isopar™ G, 100 grams of dionized water, and 50 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 80° C. with stirring at approximately 1377 rpm and held for 6 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 100% selectivity to 2,2,4,4-tetramethycyclobutane-1,3-diol with a cis:trans ratio of 21.1:1. purged three times with nitrogen and three times with hydrogen the pressure was increased to 3.5 MPa (500 psig) with hydrogen

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 300 mL Autoclave Engineers autoclave was charged with 25 grams of 2,2,4,4-tetramethylcyclobutane-1,3-dione, 87.50 grams Isopar™ G, 12.50 grams of water, and approximately 8 grams of washed raney nickel catalyst. 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 100° C. with stirring at approximately 1400 rpm and held for 5 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 97.3% selectivity to 2,2,4,4-tetramethycyclobutane-1,3-diol with a cis:trans ratio of 0.6:1. purged three times with nitrogen and three times with hydrogen the pressure was increased to 3.5 MPa (500 psig) with hydrogen

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2 liter Parr autoclave was charged with 100 grams of 2,2,4,4-tetramethylcyclobutane-1,3-dione, 300 grams Isopar™ G, 100 grams of isopropyl alcohol, and 50 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 80° C. with stirring at approximately 1400 rpm and held for 6 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 100% selectivity to 2,2,4,4-tetramethycyclobutane-1,3-diol with a cis:trans ratio of 1.44:1. purged three times with nitrogen and three times with hydrogen the pressure was increased to 3.5 MPa (500 psig) with hydrogen

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2 liter Parr autoclave was charged with 100 grams of 2,2,4,4-tetramethylcyclobutane-1,3-dione, 300 grams of 4-methyl-2-pentanol, and 50 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 100° C. with stirring at approximately 1300 rpm and held for 6 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 99.5% selectivity to 2,2,4,4-tetramethycyclobutane-1,3-diol with a cis:trans ratio of 1.54:1. purged three times with nitrogen and three times with hydrogen the pressure was increased to 3.5 MPa (500 psig) with hydrogen

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2 liter Parr autoclave was charged with 100 grams of 2,2,4,4-tetramethylcyclobutane-1,3-dione, 300 grams of 4-methyl-2-pentanol, and 50 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 100° C. with stirring at approximately 1300 rpm and held for 6 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 99.5% selectivity to 2,2,4,4-tetramethycyclobutane-1,3-diol with a cis:trans ratio of 1.54:1. purged three times with nitrogen and three times with hydrogen the pressure was increased to 3.5 MPa (500 psig) with hydrogen

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2 liter Parr autoclave was charged with 100 grams of 2,2,4,4-tetramethylcyclobutane-1,3-dione, 300 grams of isopropyl alcohol, and 50 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 100° C. with stirring and held for 6 hours at 3.5 MPa (500 psig). Analysis of the product by gas chromatography indicated that 99.8% conversion of the 2,2,4,4-tetramethylcyclobutane-1,3-dione was obtained with 99.9% selectivity to 2,2,4,4-tetramethycyclobutane-1,3-diol with a cis:trans ratio of 1.54:1. purged three times with nitrogen and three times with hydrogen the pressure was increased to 3.5 MPa (500 psig) with hydrogen