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CAS No. : | 933-52-8 | MDL No. : | MFCD00001331 |
Formula : | C8H12O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | RGCDVHNITQEYPO-UHFFFAOYSA-N |
M.W : | 140.18 | Pubchem ID : | 13617 |
Synonyms : |
|
Num. heavy atoms : | 10 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.75 |
Num. rotatable bonds : | 0 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 38.34 |
TPSA : | 34.14 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.91 cm/s |
Log Po/w (iLOGP) : | 1.74 |
Log Po/w (XLOGP3) : | 1.75 |
Log Po/w (WLOGP) : | 1.19 |
Log Po/w (MLOGP) : | 0.65 |
Log Po/w (SILICOS-IT) : | 2.12 |
Consensus Log Po/w : | 1.49 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -1.81 |
Solubility : | 2.16 mg/ml ; 0.0154 mol/l |
Class : | Very soluble |
Log S (Ali) : | -2.08 |
Solubility : | 1.15 mg/ml ; 0.00824 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -2.27 |
Solubility : | 0.76 mg/ml ; 0.00542 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.35 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P302+P352-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 20℃; for 6.0h; | High purity (99.9%) condensation in the primary trap By dimerizing dimethyl ketone in air at room temperature for 6 hours, More than 99% of 2,2,4,4-tetramethyl-1,3-cyclobutanedione (2,2,4,4-tetramethyl-1,3-butanedione, CBDK) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(reduction); | ||
(i) semicarbazide*HCl, aq. NaOAc, (ii) (heating), Na, HOCH2CH2OH, (iii) aq. oxalic acid; Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen; at 180℃; under 30003 Torr; | 2, 2,4,4-tetramethyl-1,3-cyclobutanedione was hydrogenated using a known fixed bed hydrotreating apparatus,Preparation 2, 2,4,4-tetramethyl-1,3-cyclobutanediol, catalyst selection Example 3. Catalyst, catalyst loading: 3 ml, reaction pressure: 4. OmPa, reaction temperature: 180 C, raw material: 8.8 g 2, 2,4,4-tetramethyl-1,3-cyclobutanedione / 100 ml 1,4-cyclohexanedicarboxylic acid dimethyl ester, feed rate: 9 Ml / hour, Eta2: 1.4 liters / min, the results are listed in Table 1. | |
With hydrogen; In butan-1-ol; at 80℃; under 26252.6 Torr; | General procedure: 6 mL of the catalyst D (20 to 30 mesh) was put into a fixed bed reactor and tested in a continuous trickle-bed mode. 4 wt % of 2,2,4,4-tetramethyl-1,3-cyclobutanediketone was hydrogenated in the above reactor with hydrogen. The hydrogenation factors are listed below: the solvent was n-butanol (BuOH), the WHSV of the feed was 0.24 hr-1, the liquid hourly space velocity (LHSV) of the feed was 4 hr-1, the hydrogenation temperature was 135 C., the hydrogenation pressure was 50 kg/cm2, in which the hydrogen and the 2,2,4,4-tetramethyl-1,3-cyclobutanediketone had a molar ratio of 69. The hydrogenation result was analyzed by gas chromatography (GC) as indicated below: the conversion rate of the 2,2,4,4-tetramethyl-1,3-cyclobutanediketone was 99.8%, and the selectivity of the CBDO in the products was 10%, as shown in Table 3. Example 7-3 was similar to Example 7-2, except that the reaction temperature was lowered to 80 C. The other reaction factors in Example 7-3 were similar to those in Example 7-2. The hydrogenation result was analyzed by GC as indicated below: the conversion rate of the 2,2,4,4-tetramethyl-1,3-cyclobutanediketone was 99.9%, and the selectivity of the CBDO in the products was 97.2%, as shown in Table 3. | |
With hydrogen; In isopropyl alcohol; at 120℃; under 15001.5 Torr; for 2.0h;Autoclave; | To compare the catalytic activity according to the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanediol via <strong>[933-52-8]2,2,4,4-tetramethyl-1,3-cyclobutanedione</strong> hydrogenation, 4 g of <strong>[933-52-8]2,2,4,4-tetramethyl-1,3-cyclobutanedione</strong> in a batch reactor (500 mL Autoclave), 4 g of ruthenium-based catalyst (the ruthenium-based catalyst is a catalyst including ruthenium (Ru), tin (Sn), and platinum (Pt) in parts by weight of 1, 1, and 1.8, respectively, based on 100 parts by weight of the silica carrier), 40 mL of isopropyl alcohol and 20 bar of hydrogen were reacted at 120 C. for 2 hours to prepare 2,2,4,4-tetramethyl-1,3-cyclobutanediol. |
With hydrogen; In isopropyl alcohol; at 120℃; under 15001.5 Torr; for 2.0h;Autoclave;Catalytic behavior; | <strong>[933-52-8]2,2,4,4-tetramethyl-1,3-cyclobutanedione</strong> hydrogenation To compare the catalytic activity according to the preparation of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4 g of <strong>[933-52-8]2,2,4,4-tetramethyl-1,3-cyclobutanedione</strong> and 4 g of ruthenium-based catalyst in a batch reactor (500 mL Autoclave) (The ruthenium-based catalyst is ruthenium (Ru), Tin (Sn), platinum (Pt) is a catalyst containing 1, 1 and 1.8 parts by weight, respectively), 40 mL of isopropyl alcohol and 20 bar of hydrogen, and then reacted at 120 C. for 2 hours to give 2,2,4,4-tetramethyl-1,3-cyclobutanediol was prepared. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen;cobalt-promoted copper on silica catalyst; In isobutyl isobutanoate; at 135 - 165℃; under 75007.5 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 5; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a cobalt-promoted copper on silica catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The cobalt-promoted copper on silica catalyst was prepared from a copper on silica catalyst purchased from Engelhard Corporation as follows:The copper on silica catalyst was ground and sieved, retaining the 0.2-0.4 mm sieve fraction. 500 mg of this fraction of the copper on silica catalyst were wetted with 500 mul of a 17.3 wt % solution of Co(NO3)2-6H2O in water and then dried in air, first at 50 C. for 16 hr and then at 110 C. for 4 hr. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C. at a rate of 2 C./min, and then maintaining the catalyst at 400 C. for 2 hr.The results of the hydrogenation of TMCB using the cobalt-promoted copper catalyst thus prepared are shown in Table 5. | |
With hydrogen;ruthenium-promoted KL1970-T3 copper on barium chromate catalyst; In isobutyl isobutanoate; at 135℃; under 25877.6 - 75007.5 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 6; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a ruthenium-promoted copper on barium chromate catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The ruthenium-promoted copper on barium chromate catalyst was prepared from a KL1970-T3 copper on barium chromate catalyst purchased from CRI KataLeuna as follows:The KL1970-T3 catalyst was ground and sieved, retaining the 0.2-0.4 mm sieve fraction. 500 mg of this fraction of the KL1970-T3 catalyst were wetted with 500 mul of a 3.5 wt % solution of Ru(NO)(NO3)2 in water and then dried in air, first at 50 C. for 16 hr and then at 110 C. for 4 hr. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C. at a rate of 2 C./min, and then maintaining the catalyst at 400 C. for 2 hr.The results of the hydrogenation of TMCB using the ruthenium-promoted copper catalyst thus prepared are shown in Table 6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In benzene at 220℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In dichloromethane; for 3.0h;Reflux; | Example 2. Preparation of 3-(methacryloyloxy)-2,2-dimethylpropyl 2,2,4-trimethyl- 3-oxopentanoate [0082] To a 1-L flask was charged 2, 2, 4, 4-tetramethyl-l, 3-cyclobutanedione (140.2 g, 1.0 moles), neopentyl glycol (208.3 g, 2 moles), potassium carbonate (138 g, 1.0 moles) and methylene chloride (500 g). The batch was refluxed for three hours then clarified to remove salts. The methylene chloride was removed with a rotary evaporator. Toluene (250 g) was added to the residue and the organic layer washed six times with 150 mL demineralized water. The organic layer was dried with sodium sulfate and the solvent removed with a rotary evaporator at 75 C/3 mmHg to provide 3-hydroxy-2,2-dimethylpropyl 2,2,4-trimethyl-3-oxopentanoate (244 g, 96.3% GC assay). To a 2-L flask was charged 3-hydroxy-2,2-dimethylpropyl 2,2,4- trimethyl-3-oxopentanoate (97.6 g, 0.4 moles), methylene chloride (600 g), DMAP (0.04 g) and triethylamine (50.4 g, 0.504 moles) and the resulting mixture cooled to 0-5 C. Added dropwise over an hour was methacryloyl chloride (50 g, 0.48 moles). After the addition was complete, the reaction was held at <10 C for 30 minutes then heated to reflux and held for six hours. GC analysis indicated starting material remained so additional methacryloyl chloride (6 g) and triethylamine (6 g) were added. After one hour at reflux, the reaction was cooled and 600 mL demineralized water added. Lower product layer decanted and upper water layer discarded.Water wash was repeated four times. Organic layer dried with sodium sulfate and then removed with a rotary evaporator to provide 123 g crude product (93.7% GC assay). Material distilled in a Kugelrohr apparatus to provide the desired product in 96% GC assay and 94.9% NMR assay. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 2% ruthenium on alumina; hydrogen; In water; at 100℃; under 26618.1 Torr; for 6.0h;Autoclave; | Comparative Example 2 Hydrogenation of <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> with 2,2,4,4-tetramethylcyclobutane-1,3-diol soluble in water at 100 C. (0166) A 2 liter Parr autoclave was charged with 100 grams of <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>, 600 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 100 C. with stirring at approximately 1000 rpm and held for 6 hours at 3.5 MPa (500 psig). Analysis of the product by gas chromatography indicated that 98.5% conversion of the <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was obtained with 100% selectivity to 2,2,4,4-tetramethycyclobutane-1,3-diol with a cis:trans ratio of 2.15:1. | |
With hydrogen; In water; at 100℃; under 26618.1 Torr; for 6.0h;Autoclave; | Comparative Example 9 Using Nickel as a Catalyst in Place of Ruthenium (0173) A 300 mL Autoclave Engineers autoclave was charged with 25 grams of <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>, 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 <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was obtained with 97.3% selectivity to 2,2,4,4-tetramethycyclobutane-1,3-diol with a cis:trans ratio of 0.6:1. | |
With hydrogen; In water; at 100℃; under 26252.6 Torr; for 5.0h;Autoclave; | A 300 mE Autoclave Engineers autoclave was chargedwith 25 grams of <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>,87.50 grams IsoparTM 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 threetimes with hydrogen, and the pressure was increased to 3.5MPa (500 psig) with hydrogen. The autoclave was heated to100 C. with stirring at approximately 1400rpm and held for5 hours at 3.5 MPa (500 psig). Analysis of the product by gas chromatography indicated that complete conversion of the2,2,4,4-tetramethylcyclobutane- 1 ,3-dione was obtained with97.3% selectivity to 2,2,4,4-tetramethycyclobutane-1,3-diolwith a cis:trans ratio of 0.6:1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With pyridine; tetraphosphorus decasulfide; | General procedure: 2,2,4,4-Tetramethyl-3-thioxocyclobutanone 1a, 3,3-dichloro-2,2,4,4-tetramethylcyclobutanethione 1b, and adamantanethione 1c were obtained by thionation of the corresponding ketones with P2S10 in pyridine according to literature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 70% 2: 6.4% 3: 8.3% 4: 5.3% 5: 8.3% | With tetrabutyl ammonium fluoride In 1,2-dimethoxyethane at -20℃; for 0.0333333h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
135 g (89%) | With chloro-trimethyl-silane; sodium methylate; In tetrahydrofuran; | Methyl 2,2,4-Trimethyl-3-silyloxypent-3-enecarboxylate 84 g (0.6 mol) of <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> and 32.4 g (0.6 mol) of sodium methylate were mixed together in 320 ml of tetrahydrofuran. 65.1 g (0.6 mol) of trimethylsilyl chloride were added dropwise and the mixture was stirred. The reaction mixture was then concentrated and the residue was taken up with diethyl ether. The solid was filtered off with suction and the mother liquor was concentrated. Yield: 135 g (89%). 1H-NMR (CDCl3): delta=0.3 (s, 9H), 1.3 (s, 6H), 1.5 (s, 3H), 1.7 (s, 3H), 3.6 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen;A280 cobalt on alumina catalyst; In isobutyl isobutanoate; at 165℃; under 25877.6 - 75007.5 Torr; for 2h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in Examples 1-6 unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa or 1450 psig). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure.The 2,2,4,4-tetramethylcyclobutane-1,3-dione used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The 2,2,4,4-tetramethylcyclobutane-1,3-dione/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Comparative Example 1; Using the general procedure described above, 2,2,4,4-tetramethylcyclobutane-1,3-dione was hydrogenated using a non-promoted supported cobalt catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The catalyst used was an A280 cobalt on alumina catalyst obtained from Engelhard Corporation.The results are shown in Table 1. | |
With hydrogen;A280 cobalt on alumina catalyst promoted with Ir(OAc)x; In isobutyl isobutanoate; at 135 - 165℃; under 25877.6 - 75007.5 Torr; for 2h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in Examples 1-6 unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa or 1450 psig). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure.The 2,2,4,4-tetramethylcyclobutane-1,3-dione used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The 2,2,4,4-tetramethylcyclobutane-1,3-dione/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 2; Using the general procedure described above, 2,2,4,4-tetramethylcyclobutane-1,3-dione was hydrogenated using an iridium-promoted cobalt on alumina catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The iridium-promoted cobalt on alumina catalyst was prepared from a cobalt on alumina catalyst obtained from Engelhard Corporation (A280) as follows:The cobalt on alumina catalyst was ground and sieved to obtain the 0.2-0.4 mm sieve fraction. 500 mg of the cobalt on alumina catalyst were wetted with 500 mul of a 6.83 wt % solution of Ir(OAc)x in water, and then dried in air at 50 C. for 16 hr and at 110 C. for 4 hr. The Ir(OAc)x was obtained from Heraeus. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C., at a rate of 2 C./min, and maintaining the catalyst at 400 C. for 2 hr. The results of the hydrogenation of TMCB using the iridium-promoted cobalt catalyst thus prepared are shown in Table 2. | |
With hydrogen;G-96B-RS 62percent nickel on kieselguhr catalyst; In isobutyl isobutanoate; at 160℃; under 46504.7 Torr; for 3h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.30.2 g of 2,2,4,4-tetramethylcyclobutane-1,3-dione, 1.0 g of a catalyst (either promoted or non-promoted, as necessary), and 171 g of isobutyl isobutyrate were charged into a 300 ml autoclave fitted with a magnetic stirrer, nitrogen gas purge, cooling coil, and temperature-controlled heater. The autoclave was sealed, purged with nitrogen, pressurized to 32 bar (6,200 kPa) of hydrogen, and heated to 160 C. After stirring the mixture for 3 hr at 160 C., the solution was cooled and the pressure was released. The catalyst was removed by hot filtration. The filtrate product samples were analyzed by capillary GLC analysis as follows:The filtrate product samples were heated to 100 C. 20-25 drops of the liquid sample were transferred to a 2 ml autoinjector vial, which was then filled to the 1 ml mark with DMSO. The samples were analyzed by capillary gas-liquid chromatography (?GC?) using an Agilent Model 6890 Gas Chromatograph with an FID detector. The GC samples were injected onto a 0.25 mum (30 m×0.5 mm) DB Wax fused silica capillary column. For each analysis, the initial temperature of the column was set at 5 C., held for 4 minutes, ramped to 125 C. at a rate of 12 C./min, held for 5 minutes, ramped to 165 C. at a rate of 3 C./min, then ramped to 240 C. at a rate of 15 C./min and held for 5 minutes at 240 C. Results are given as area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Comparative Example 1; 2,2,4,4-Tetramethylcyclobutane-1,3-dione was hydrogenated in the presence of a G-96B-RS 62% nickel on kieselguhr catalyst from Sued-Chemie using the general procedure described previously.The results of the hydrogenation of TMCB using the G-96B-RS 62% nickel on kieselguhr catalyst are shown in Table 1. |
With hydrogen;A280 cobalt on alumina catalyst; In isobutyl isobutanoate; at 165℃; under 25877.6 - 75007.5 Torr; for 2h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours, which was considered to be the reaction time.The 2,2,4,4-tetramethylcyclobutane-1,3-dione used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The 2,2,4,4-tetramethylcyclobutane-1,3-dione/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 1; Using the general procedure described above, 2,2,4,4-tetramethylcyclobutane-1,3-dione was hydrogenated using a supported cobalt catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The catalyst used was an A280 cobalt on alumina catalyst obtained from Engelhard Corporation. The results are shown in Table 1. | |
With hydrogen;A281 cobalt on alumina catalyst; In isobutyl isobutanoate; at 165℃; under 25877.6 - 75007.5 Torr; for 2h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours, which was considered to be the reaction time.The 2,2,4,4-tetramethylcyclobutane-1,3-dione used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The 2,2,4,4-tetramethylcyclobutane-1,3-dione/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 2; Using the general procedure described above, 2,2,4,4-tetramethylcyclobutane-1,3-dione was hydrogenated using a supported cobalt catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The catalyst used was an A281 cobalt on alumina catalyst obtained from Engelhard Corporation. The results are shown in Table 2. | |
With hydrogen;G-67A 20percent cobalt on silica catalyst; In isobutyl isobutanoate; at 135 - 165℃; under 25877.6 - 75007.5 Torr; for 2h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours, which was considered to be the reaction time.The 2,2,4,4-tetramethylcyclobutane-1,3-dione used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The 2,2,4,4-tetramethylcyclobutane-1,3-dione/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 3; Using the general procedure described above, 2,2,4,4-tetramethylcyclobutane-1,3-dione was hydrogenated using a supported cobalt catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The catalyst used was a G-67A 20% cobalt on silica catalyst obtained from Sud-Chemie. The results are shown in Table 3. | |
With hydrogen;KL1970-T3 copper on barium chromate catalyst; In isobutyl isobutanoate; at 165℃; under 25877.6 - 75007.5 Torr; for 2h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The 2,2,4,4-tetramethylcyclobutane-1,3-dione used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The 2,2,4,4-tetramethylcyclobutane-1,3-dione/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Comparative Example 2; Using the general procedure described above, 2,2,4,4-tetramethylcyclobutane-1,3-dione was hydrogenated using a KL1970-T3 copper on copper on barium chromate catalyst from CRI KataLeuna at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The results are shown in Table 2. | |
With hydrogen;KL2015-T5 copper on zinc oxide catalyst; In isobutyl isobutanoate; at 165℃; under 25877.6 - 75007.5 Torr; for 2h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The 2,2,4,4-tetramethylcyclobutane-1,3-dione used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The 2,2,4,4-tetramethylcyclobutane-1,3-dione/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Comparative Example 3; Using the general procedure described above, 2,2,4,4-tetramethylcyclobutane-1,3-dione was hydrogenated using a KL2015-T5 copper on copper on zinc oxide catalyst from CRI KataLeuna at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The results are shown in Table 3. | |
With hydrogen;chromium-promoted KL2015-T5 copper on zinc oxide catalyst; In isobutyl isobutanoate; at 135℃; under 25877.6 Torr; for 2h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The 2,2,4,4-tetramethylcyclobutane-1,3-dione used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The 2,2,4,4-tetramethylcyclobutane-1,3-dione/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 8; Using the general procedure described above, 2,2,4,4-tetramethylcyclobutane-1,3-dione was hydrogenated using a chromium-promoted copper on zinc oxide catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The chromium-promoted copper on zinc oxide catalyst was prepared from a KL2015-T5 copper on zinc oxide catalyst purchased from CRI KataLeuna as follows:The KL2015-T5 catalyst was ground and sieved, retaining the 0.2-0.4 mm sieve fraction. 500 mg of this fraction of the KL2015-T5 catalyst were wetted with 500 mul of a 26.9 wt % solution of Cr(NO3)3-9H2O in water and then dried in air, first at 50 C. for 16 hr and then at 110 C. for 4 hr. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C. at a rate of 2 C./min, and then maintaining the catalyst at 400 C. for 2 hr.The results of the hydrogenation of TMCB using the chromium-promoted copper catalyst thus prepared are shown in Table 8. | |
With hydrogen;rhenium-promoted KL2015-T5 copper on zinc oxide catalyst; In isobutyl isobutanoate; at 165℃; under 75007.5 Torr; for 2h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The 2,2,4,4-tetramethylcyclobutane-1,3-dione used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The 2,2,4,4-tetramethylcyclobutane-1,3-dione/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 7; Using the general procedure described above, 2,2,4,4-tetramethylcyclobutane-1,3-dione was hydrogenated using a rhenium-promoted copper on zinc oxide catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The rhenium-promoted copper on zinc oxide catalyst was prepared from a KL2015-T5 copper on zinc oxide catalyst purchased from CRI KataLeuna as follows:The KL2015-T5 catalyst was ground and sieved, retaining the 0.2-0.4 mm sieve fraction. 500 mg of this fraction of the KL2015-T5 catalyst were wetted with 500 mul of a 75 wt % solution of HReO4 in water and then dried in air, first at 50 C. for 16 hr and then at 110 C. for 4 hr. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C. at a rate of 2 C./min, and then maintaining the catalyst at 400 C. for 2 hr.The results of the hydrogenation of TMCB using the rhenium-promoted copper catalyst thus prepared are shown in Table 7. | |
With hydrogen;A280 cobalt on alumina catalyst; In isobutyl isobutanoate; at 165℃; under 25877.6 - 75007.5 Torr; for 2h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in Examples 1-6 unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure.The 2,2,4,4-tetramethylcyclobutane-1,3-dione used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The 2,2,4,4-tetramethylcyclobutane-1,3-dione/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.; Comparative Example 1; Using the general procedure described above, 2,2,4,4-tetramethylcyclobutane-1,3-dione was hydrogenated using a non-promoted supported cobalt catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The catalyst used was an A280 cobalt on alumina catalyst obtained from Engelhard Corporation. The results are shown in Table 1. | |
With hydrogen;ruthenium promoted A280 cobalt on alumina catalyst; In isobutyl isobutanoate; at 165℃; under 75007.5 Torr; for 2h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in Examples 1-6 unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure.The 2,2,4,4-tetramethylcyclobutane-1,3-dione used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The 2,2,4,4-tetramethylcyclobutane-1,3-dione/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.; Example 2; Using the general procedure described above, 2,2,4,4-tetramethylcyclobutane-1,3-dione was hydrogenated using a ruthenium-promoted cobalt on alumina catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The ruthenium-promoted cobalt on alumina catalyst was prepared from an A280 cobalt on alumina catalyst obtained from Engelhard Corporation as follows:The cobalt on alumina catalyst was ground and sieved to obtain the 0.2-0.4 mm sieve fraction. 500 mg of the cobalt on alumina catalyst were wetted with 500 mul of a 11 wt % solution of Ru(NO)(NO3)2 in water, and then dried in air at 50 C. for 16 hr and at 11 0 C. for 4 hr. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C., at a rate of 2 C./min, and maintaining the catalyst at 400 C. for 2 hr. The results of the hydrogenation of TMCB using the ruthenium-promoted cobalt catalyst thus prepared are shown in Table 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen;A280 cobalt on alumina catalyst; In isobutyl isobutanoate; at 135℃; under 25877.6 - 75007.5 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in Examples 1-6 unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa or 1450 psig). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Comparative Example 1; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a non-promoted supported cobalt catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The catalyst used was an A280 cobalt on alumina catalyst obtained from Engelhard Corporation.The results are shown in Table 1. | |
With hydrogen;zirconium-promoted G-96B-RS 62percent nickel on kieselguhr catalyst; In isobutyl isobutanoate; at 160℃; under 46504.7 Torr; for 3.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.30.2 g of <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>, 1.0 g of a catalyst (either promoted or non-promoted, as necessary), and 171 g of isobutyl isobutyrate were charged into a 300 ml autoclave fitted with a magnetic stirrer, nitrogen gas purge, cooling coil, and temperature-controlled heater. The autoclave was sealed, purged with nitrogen, pressurized to 32 bar (6,200 kPa) of hydrogen, and heated to 160 C. After stirring the mixture for 3 hr at 160 C., the solution was cooled and the pressure was released. The catalyst was removed by hot filtration. The filtrate product samples were analyzed by capillary GLC analysis as follows:The filtrate product samples were heated to 100 C. 20-25 drops of the liquid sample were transferred to a 2 ml autoinjector vial, which was then filled to the 1 ml mark with DMSO. The samples were analyzed by capillary gas-liquid chromatography (?GC?) using an Agilent Model 6890 Gas Chromatograph with an FID detector. The GC samples were injected onto a 0.25 mum (30 m×0.5 mm) DB Wax fused silica capillary column. For each analysis, the initial temperature of the column was set at 5 C., held for 4 minutes, ramped to 125 C. at a rate of 12 C./min, held for 5 minutes, ramped to 165 C. at a rate of 3 C./min, then ramped to 240 C. at a rate of 15 C./min and held for 5 minutes at 240 C. Results are given as area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 2; 2,2,4,4-Tetramethylcyclobutane-1,3-dione was hydrogenated in the presence of a zirconium-promoted G-69B-RS 62% nickel on kieselguhr catalyst from Sued-Chemie using the general procedure described previously.The results of the hydrogenation of TMCB using the zirconium-promoted nickel catalyst are shown in Table 2. | |
With hydrogen;A280 cobalt on alumina catalyst; In isobutyl isobutanoate; at 135℃; under 25877.6 - 75007.5 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours, which was considered to be the reaction time.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 1; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a supported cobalt catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The catalyst used was an A280 cobalt on alumina catalyst obtained from Engelhard Corporation. The results are shown in Table 1. |
With hydrogen;A281 cobalt on alumina catalyst; In isobutyl isobutanoate; at 135℃; under 25877.6 - 75007.5 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours, which was considered to be the reaction time.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 2; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a supported cobalt catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The catalyst used was an A281 cobalt on alumina catalyst obtained from Engelhard Corporation. The results are shown in Table 2. | |
With hydrogen;T4405 57percent cobalt on silica/alumina catalyst; In isobutyl isobutanoate; at 135 - 165℃; under 25877.6 - 75007.5 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours, which was considered to be the reaction time.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 4; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a a supported cobalt catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The catalyst used was a T4405 57% cobalt on silica/alumina catalyst obtained from Sued-Chemie. The results are shown in Table 4. | |
With hydrogen;copper on silica catalyst; In isobutyl isobutanoate; at 135 - 165℃; under 25877.6 - 75007.5 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Comparative Example 1; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a copper on silica catalyst from Engelhard Corporation at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The results are shown in Table 1. | |
With hydrogen;KL1970-T3 copper on barium chromate catalyst; In isobutyl isobutanoate; at 135℃; under 25877.6 - 75007.5 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Comparative Example 2; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a KL1970-T3 copper on copper on barium chromate catalyst from CRI KataLeuna at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The results are shown in Table 2. | |
With hydrogen;KL2015-T5 copper on zinc oxide catalyst; In isobutyl isobutanoate; at 135℃; under 75007.5 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Comparative Example 3; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a KL2015-T5 copper on copper on zinc oxide catalyst from CRI KataLeuna at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The results are shown in Table 3. | |
With hydrogen;rhenium-promoted KL2015-T5 copper on zinc oxide catalyst; In isobutyl isobutanoate; at 135℃; under 25877.6 - 75007.5 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 7; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a rhenium-promoted copper on zinc oxide catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The rhenium-promoted copper on zinc oxide catalyst was prepared from a KL2015-T5 copper on zinc oxide catalyst purchased from CRI KataLeuna as follows:The KL2015-T5 catalyst was ground and sieved, retaining the 0.2-0.4 mm sieve fraction. 500 mg of this fraction of the KL2015-T5 catalyst were wetted with 500 mul of a 75 wt % solution of HReO4 in water and then dried in air, first at 50 C. for 16 hr and then at 110 C. for 4 hr. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C. at a rate of 2 C./min, and then maintaining the catalyst at 400 C. for 2 hr.The results of the hydrogenation of TMCB using the rhenium-promoted copper catalyst thus prepared are shown in Table 7. | |
With hydrogen;ruthenium-promoted KL1970-T3 copper on barium chromate catalyst; In isobutyl isobutanoate; at 165℃; under 25877.6 - 75007.5 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 6; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a ruthenium-promoted copper on barium chromate catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The ruthenium-promoted copper on barium chromate catalyst was prepared from a KL1970-T3 copper on barium chromate catalyst purchased from CRI KataLeuna as follows:The KL1970-T3 catalyst was ground and sieved, retaining the 0.2-0.4 mm sieve fraction. 500 mg of this fraction of the KL1970-T3 catalyst were wetted with 500 mul of a 3.5 wt % solution of Ru(NO)(NO3)2 in water and then dried in air, first at 50 C. for 16 hr and then at 110 C. for 4 hr. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C. at a rate of 2 C./min, and then maintaining the catalyst at 400 C. for 2 hr.The results of the hydrogenation of TMCB using the ruthenium-promoted copper catalyst thus prepared are shown in Table 6. | |
With hydrogen;A280 cobalt on alumina catalyst; In isobutyl isobutanoate; at 135℃; under 25877.6 - 75007.5 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in Examples 1-6 unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.; Comparative Example 1; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a non-promoted supported cobalt catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The catalyst used was an A280 cobalt on alumina catalyst obtained from Engelhard Corporation. The results are shown in Table 1. | |
With hydrogen;ruthenium promoted A280 cobalt on alumina catalyst; In isobutyl isobutanoate; at 135 - 165℃; under 25877.6 - 75007.5 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in Examples 1-6 unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.; Example 2; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a ruthenium-promoted cobalt on alumina catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The ruthenium-promoted cobalt on alumina catalyst was prepared from an A280 cobalt on alumina catalyst obtained from Engelhard Corporation as follows:The cobalt on alumina catalyst was ground and sieved to obtain the 0.2-0.4 mm sieve fraction. 500 mg of the cobalt on alumina catalyst were wetted with 500 mul of a 11 wt % solution of Ru(NO)(NO3)2 in water, and then dried in air at 50 C. for 16 hr and at 11 0 C. for 4 hr. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C., at a rate of 2 C./min, and maintaining the catalyst at 400 C. for 2 hr. The results of the hydrogenation of TMCB using the ruthenium-promoted cobalt catalyst thus prepared are shown in Table 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen;A280 cobalt on alumina catalyst promoted with Ir(OAc)x; In isobutyl isobutanoate; at 135℃; under 75007.5 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in Examples 1-6 unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa or 1450 psig). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 2; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using an iridium-promoted cobalt on alumina catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The iridium-promoted cobalt on alumina catalyst was prepared from a cobalt on alumina catalyst obtained from Engelhard Corporation (A280) as follows:The cobalt on alumina catalyst was ground and sieved to obtain the 0.2-0.4 mm sieve fraction. 500 mg of the cobalt on alumina catalyst were wetted with 500 mul of a 6.83 wt % solution of Ir(OAc)x in water, and then dried in air at 50 C. for 16 hr and at 110 C. for 4 hr. The Ir(OAc)x was obtained from Heraeus. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C., at a rate of 2 C./min, and maintaining the catalyst at 400 C. for 2 hr. The results of the hydrogenation of TMCB using the iridium-promoted cobalt catalyst thus prepared are shown in Table 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.2%Chromat. | With hydrogen;T4405 57percent cobalt on silica/alumina catalyst; In isobutyl isobutanoate; at 135℃; under 75007.5 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours, which was considered to be the reaction time.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 4; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a a supported cobalt catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The catalyst used was a T4405 57% cobalt on silica/alumina catalyst obtained from Sued-Chemie. The results are shown in Table 4. |
0.3%Chromat. | With hydrogen;KL2015-T5 copper on zinc oxide catalyst; In isobutyl isobutanoate; at 135℃; under 25877.6 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Comparative Example 3; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a KL2015-T5 copper on copper on zinc oxide catalyst from CRI KataLeuna at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The results are shown in Table 3. |
2.5%Chromat. | With hydrogen;rhenium-promoted KL2015-T5 copper on zinc oxide catalyst; In isobutyl isobutanoate; at 165℃; under 25877.6 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 7; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a rhenium-promoted copper on zinc oxide catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The rhenium-promoted copper on zinc oxide catalyst was prepared from a KL2015-T5 copper on zinc oxide catalyst purchased from CRI KataLeuna as follows:The KL2015-T5 catalyst was ground and sieved, retaining the 0.2-0.4 mm sieve fraction. 500 mg of this fraction of the KL2015-T5 catalyst were wetted with 500 mul of a 75 wt % solution of HReO4 in water and then dried in air, first at 50 C. for 16 hr and then at 110 C. for 4 hr. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C. at a rate of 2 C./min, and then maintaining the catalyst at 400 C. for 2 hr.The results of the hydrogenation of TMCB using the rhenium-promoted copper catalyst thus prepared are shown in Table 7. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen;G-67A 20percent cobalt on silica catalyst; In isobutyl isobutanoate; at 135℃; under 25877.6 Torr; for 2h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours, which was considered to be the reaction time.The 2,2,4,4-tetramethylcyclobutane-1,3-dione used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The 2,2,4,4-tetramethylcyclobutane-1,3-dione/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 3; Using the general procedure described above, 2,2,4,4-tetramethylcyclobutane-1,3-dione was hydrogenated using a supported cobalt catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The catalyst used was a G-67A 20% cobalt on silica catalyst obtained from Sud-Chemie. The results are shown in Table 3. | |
With hydrogen;cesium-promoted copper on silica catalyst; In isobutyl isobutanoate; at 135℃; under 75007.5 Torr; for 2h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The 2,2,4,4-tetramethylcyclobutane-1,3-dione used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The 2,2,4,4-tetramethylcyclobutane-1,3-dione/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 4; Using the general procedure described above, 2,2,4,4-tetramethylcyclobutane-1,3-dione was hydrogenated using a cesium-promoted copper on silica catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The cesium-promoted copper on silica catalyst was prepared from a copper on silica catalyst purchased from Engelhard Corporation as follows:The copper on silica catalyst was ground and sieved, retaining the 0.2-0.4 mm sieve fraction. 500 mg of this fraction of the copper on silica catalyst were wetted with 500 mul of a 1.47 wt % solution of CsNO3 in water and then dried in air, first at 50 C. for 16 hr and then at 110 C. for 4 hr. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C. at a rate of 2 C./min, and then maintaining the catalyst at 400 C. for 2 hr.The results of the hydrogenation of TMCB using the cesium-promoted copper catalyst thus prepared are shown in Table 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen;chromium-promoted KL2015-T5 copper on zinc oxide catalyst; In isobutyl isobutanoate; at 135℃; under 25877.6 - 75007.5 Torr; for 2h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The 2,2,4,4-tetramethylcyclobutane-1,3-dione used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The 2,2,4,4-tetramethylcyclobutane-1,3-dione/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 8; Using the general procedure described above, 2,2,4,4-tetramethylcyclobutane-1,3-dione was hydrogenated using a chromium-promoted copper on zinc oxide catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The chromium-promoted copper on zinc oxide catalyst was prepared from a KL2015-T5 copper on zinc oxide catalyst purchased from CRI KataLeuna as follows:The KL2015-T5 catalyst was ground and sieved, retaining the 0.2-0.4 mm sieve fraction. 500 mg of this fraction of the KL2015-T5 catalyst were wetted with 500 mul of a 26.9 wt % solution of Cr(NO3)3-9H2O in water and then dried in air, first at 50 C. for 16 hr and then at 110 C. for 4 hr. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C. at a rate of 2 C./min, and then maintaining the catalyst at 400 C. for 2 hr.The results of the hydrogenation of TMCB using the chromium-promoted copper catalyst thus prepared are shown in Table 8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen;cesium-promoted copper on silica catalyst; In isobutyl isobutanoate; at 135℃; under 25877.6 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 4; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a cesium-promoted copper on silica catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The cesium-promoted copper on silica catalyst was prepared from a copper on silica catalyst purchased from Engelhard Corporation as follows:The copper on silica catalyst was ground and sieved, retaining the 0.2-0.4 mm sieve fraction. 500 mg of this fraction of the copper on silica catalyst were wetted with 500 mul of a 1.47 wt % solution of CsNO3 in water and then dried in air, first at 50 C. for 16 hr and then at 110 C. for 4 hr. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C. at a rate of 2 C./min, and then maintaining the catalyst at 400 C. for 2 hr.The results of the hydrogenation of TMCB using the cesium-promoted copper catalyst thus prepared are shown in Table 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen;cesium-promoted copper on silica catalyst; In isobutyl isobutanoate; at 165℃; under 25877.6 - 75007.5 Torr; for 2h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The 2,2,4,4-tetramethylcyclobutane-1,3-dione used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The 2,2,4,4-tetramethylcyclobutane-1,3-dione/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 4; Using the general procedure described above, 2,2,4,4-tetramethylcyclobutane-1,3-dione was hydrogenated using a cesium-promoted copper on silica catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The cesium-promoted copper on silica catalyst was prepared from a copper on silica catalyst purchased from Engelhard Corporation as follows:The copper on silica catalyst was ground and sieved, retaining the 0.2-0.4 mm sieve fraction. 500 mg of this fraction of the copper on silica catalyst were wetted with 500 mul of a 1.47 wt % solution of CsNO3 in water and then dried in air, first at 50 C. for 16 hr and then at 110 C. for 4 hr. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C. at a rate of 2 C./min, and then maintaining the catalyst at 400 C. for 2 hr.The results of the hydrogenation of TMCB using the cesium-promoted copper catalyst thus prepared are shown in Table 4. | |
With hydrogen;chromium-promoted KL2015-T5 copper on zinc oxide catalyst; In isobutyl isobutanoate; at 135 - 165℃; under 75007.5 Torr; for 2h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The 2,2,4,4-tetramethylcyclobutane-1,3-dione used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The 2,2,4,4-tetramethylcyclobutane-1,3-dione/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 8; Using the general procedure described above, 2,2,4,4-tetramethylcyclobutane-1,3-dione was hydrogenated using a chromium-promoted copper on zinc oxide catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The chromium-promoted copper on zinc oxide catalyst was prepared from a KL2015-T5 copper on zinc oxide catalyst purchased from CRI KataLeuna as follows:The KL2015-T5 catalyst was ground and sieved, retaining the 0.2-0.4 mm sieve fraction. 500 mg of this fraction of the KL2015-T5 catalyst were wetted with 500 mul of a 26.9 wt % solution of Cr(NO3)3-9H2O in water and then dried in air, first at 50 C. for 16 hr and then at 110 C. for 4 hr. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C. at a rate of 2 C./min, and then maintaining the catalyst at 400 C. for 2 hr.The results of the hydrogenation of TMCB using the chromium-promoted copper catalyst thus prepared are shown in Table 8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen;cobalt-promoted copper on silica catalyst; In isobutyl isobutanoate; at 135℃; under 25877.6 Torr; for 2.0h;Product distribution / selectivity; | General; The following is a general description of the reactor system, catalyst preparation, hydrogenation process, and analytical methods used henceforward in the Examples described below unless otherwise specified.The experiments were performed in a nanoflow parallel fixed bed reactor system under continuous trickle phase conditions in co-current downstream mode utilizing a tubular reactor that has an internal diameter of 2 mm. The reactor is made by Advantium Technologies B.V. The reactor was loaded with solid catalyst to fill a volume of 150 mul. The catalyst was reduced with hydrogen in-situ prior to testing. The catalyst reduction was carried out in the presence of isobutyl isobutyrate at 100 barg (10,000 kPa). Temperature was increased at a rate of 0.5 C./min from ambient temperature to 180 C. and held for 2 hours. All pressures are gauge pressure unless otherwise specified as absolute pressure. The pressures in the tables are in unit of barg unless otherwise specified.The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> used in the experiments was diluted with isobutyl isobutyrate to a concentration of 10 wt % and heated to 85 C. The <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong>/isobutyl isobutyrate feed mixture was fed at the top of the reactor vessel along with hydrogen and contacted with the catalyst. After the system reached the correct process conditions, the system was held at these conditions for 2 hours, which was considered to be the reaction time. The reactor effluent stream containing crude 2,2,4,4-tetramethylcyclobutane-1,3-diol product was removed from the bottom of the reactor.The reactor effluent stream was sampled using a Gilson 233 liquid sampler. 30 mul of the reaction sample was diluted with 970 mul isopropanol and analyzed by capillary gas-liquid chromatography (?GC?) using a TraceGC from Thermo Finnigan with a CombiPal autosampler from CTC Analytics, with a FID detector. The GC samples were injected onto a 0.25 micron (30 m×0.32 mm) Varian CP Wax 52 CB column. For each analysis, the initial temperature of the column was set at 80 C., held for 2 minutes, ramped to 90 C. at a rate of 5 C./min, ramped to 240 C. at a rate of 20 C./min, and then held for 3.5 min at 240 C. Results are given as GC area percentages, normalized for isobutyl isobutyrate.The following abbreviations apply throughout the working examples and tables:; Example 5; Using the general procedure described above, <strong>[933-52-8]2,2,4,4-tetramethylcyclobutane-1,3-dione</strong> was hydrogenated using a cobalt-promoted copper on silica catalyst at temperatures of 135 C. and 165 C., reactor pressures of 34.5 barg (3450 kPa) and 100 barg (10,000 kPa), and a liquid space velocity of 25 hr-1. The cobalt-promoted copper on silica catalyst was prepared from a copper on silica catalyst purchased from Engelhard Corporation as follows:The copper on silica catalyst was ground and sieved, retaining the 0.2-0.4 mm sieve fraction. 500 mg of this fraction of the copper on silica catalyst were wetted with 500 mul of a 17.3 wt % solution of Co(NO3)2-6H2O in water and then dried in air, first at 50 C. for 16 hr and then at 110 C. for 4 hr. After drying, the catalyst was calcined in air by heating from ambient temperature to 400 C. at a rate of 2 C./min, and then maintaining the catalyst at 400 C. for 2 hr.The results of the hydrogenation of TMCB using the cobalt-promoted copper catalyst thus prepared are shown in Table 5. | |
With dimethyl 1,4-cyclohexane dicarboxylate; hydrogen;copper chromite; at 150℃; under 258581 Torr;Product distribution / selectivity; | Using the general procedure described above, a 15 wt % solution of TMCB in DMCD was hydrogenated at temperatures ranging from 150 C. to 225 C. and pressures ranging from 500 to 5000 psi. The feed rate ranged from 0.6 to 1.3 L/hr. The results are shown in Table 2. | |
With isobutyl isobutanoate; hydrogen;3 wt percent Ru on carbon nanotube; at 20 - 140℃; under 20702.1 Torr; for 1.0h;Autoclave; Inert atmosphere; | A 3 wt % Ru on carbon nanotube catalyst (0.5 g, surface area=244 m2/g) was loaded in a 100 mL stainless steel autoclave in a stainless steel catalyst basket with 6 g of dione and 54 g of IBIB. The autoclave was agitated, purged twice with helium (0.69 MPa, 100 psig) at ambient temperature, and purged with hydrogen (0.69 MPa, 100 psig). The autoclave was then heated to 140 C. and pressurized with hydrogen (2.76 MPa, 400 psig). After 1 hour, a product sample was taken and analyzed by GC. The conversion of dione was 100% and the selectivity to diol was 87%. The cis:trans isomer ratio of the diol was 1.08. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; at 50 - 60℃; for 1.0h; | Example 1. Preparation of 2-(methacryloyloxy)ethyl 2,2,4-trimethyl-3- oxopentanoate [0081] To a 2-L flask was charged ethylene glycol (900 mL) and 2, 2, 4, 4- tetramethyl-1, 3-cyclobutanedione (210.3 g, 1.5 moles). While using good mixing, potassium carbonate (103.5 grams, 0.75 moles) was added. An exothermic reaction resulted and the batch temperature rose to approximately 60 C. The reaction was held for 1 hour between 50-60 C. The batch was then drowned into 1500 mL demineralized water and extracted with 500 mL ethyl acetate. The ethyl acetate was evaporated at 75 C under 6 mm Hg vacuum. The resulting crude product was distilled through a 0.5 x 6 inch Penn-State packed column and the vapor boiling point recorded as 94 C (<1 mmHg). The total recovery of 2-hydroxyethyl 2,2,4-trimethyl- 3-oxopentanoate was 71% with an assay of 99.5% (GC). To a 2-L flask was charged N,N-dimethylacetamide (636 g), 2-hydroxyethyl-2,2,4-trimethyl-3-oxopentanoate (318 g, 1.57 moles), DMAP (0.31 g) and triethylamine (183.2 g). The reaction was cooled to 0-5 C and methacryloyi chloride (194.4 g, 1.88 moles) was added dropwise at <10 C over three hours. Once addition was complete, the reaction was stirred for an additional hour at <10 C and then warmed to 40 C for one hour. The reaction slurry was drowned into 763 mL of demineralized water and extracted at 40 C with 763 mL of ethyl acetate. Acetic acid (25 g) was used to aid separation of layers. The lower aqueous layer was decanted and discarded and the organic layer washed with demineralized water (763 mL). The organic layer was dried with sodium sulfate and removed with a rotary evaporator at 60 C / 5 mmHg. The crude product (GC assay 82.5%) was distilled in a Kugelrohr apparatus twice at 124 C / 0.05 mmHg to provide the desired product (220 g, 93% GC assay). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
3.57 g | With pyridine; hydroxylamine hydrochloride; at 20℃; for 72.0h; | A mixture of hydroxylamine HC1 (5.95 g, 86 mmol) and 2,2,4,4-tetramethyl- 1 ,3-cyclobutanedione (3.00 g, 21.4 mmol) in pyridine (15 ml) was stirred for 3 days at RT. Water was added, the precipitate was filtered off and washed with water yielding 3.57 g of the title compound. NMR (400 MHz, DMSO-^): 1.27 (3H, s), 1.37 (6H, s), 1.49 (3H, s), 10.26 (IH, s), 10.31 (IH, s) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 440℃; under 22.5023 Torr;Inert atmosphere; Pyrolysis; | 100g of isobutyric acid to 4ml / min feed rate through the feed pump feed nitrogen to 20ml / min feed rate of the feed, both in the mixer after mixing by cracking reactor, pyrolysis temperature 440 , 3KPa reaction pressure is, the reaction product after the reaction was rapidly through the condenser cooling temperature control 10 , the gas-liquid mixture after separation by cooling separation tank, gas-phase products enters the first polymerizer polymerization, adipic absorbing liquid dimethyl ester and 1,4-dimethyl cyclohexane 1: 1 mixture, control the temperature 90 , polymerization 60min.By absorbing liquid by gas chromatography can be obtained with respect to the solvent 5% (WT) content of 2,2,4,4-tetramethyl-1,3-cyclobutane-dione. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 480℃; under 225.023 Torr;Inert atmosphere; Pyrolysis; | The isobutyric anhydride in 120g 6ml / min by the feed rate of the feed pump feed nitrogen at 48ml / min feed rate of the feed, both in the mixer after mixing cleavage reaction by means cracking temperature 480 , the reaction pressure was 30KPa process, the reaction product after the reaction was rapidly through a condenser, controlling the cooling temperature 20 , the gas-liquid mixture after separation by cooling separation tank, gas-phase products enters the polymerization vessel first reaction.Polymerization vessel has been added dimethyl adipate and dimethyl 1,4-cyclohexane 1: 2 mixture, control the temperature 120 , polymerization 80min.By absorbing liquid was subjected to gas chromatography, 15% can be obtained with respect to the solvent (WT) content of 2,2,4,4-tetramethyl-1,3-cyclobutane-dione | |
With 0.25 wt% lanthanum metal supported on 75 wt% silica-25 wt% alumina porous particles; at 300 - 400℃; under 37.5038 Torr; | After vaporizing at 300 C by introducing isobutyric acid (IBA) at a vacuum velocity of 0.05 bar at 200 cc / min and a velocity of 3.15 h-1 (LHSV), 2,2,4,4-tetramethyl-1,3-cyclobutanedione was prepared by contacting isobutyric acid with a catalyst at a pyrolysis temperature of 400 C. The catalyst is a heterogeneous solid acid catalyst comprising silica-alumina porous particles consisting of 75% by weight silica and 25% by weight alumina and lanthanum metal supported at 0.25% by weight on the porous particles. The quantity is 20cc. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With ytterbium(III) triflate; In 1,3,5-trimethyl-benzene; at 60℃; for 24.0h;Inert atmosphere; | General procedure: 2-aminobenzamide (1, 1.0 mmol), 1,3-diketone (2, 1.5 mmol), Yb(OTf)3 (0.050 mmol, 5.0 mol%),and mesitylene (2.0 mL) was placed in a 20-mL Pyrex flask equipped with a magnetic stirring bar and a reflux condenser under a flow of argon. The reaction was carried out at 60C (bath temp.) for 24 h with stirring. The reaction mixture was then cooled to room temperature and analyzed by GLCand GC-MS. The product 3 was isolated by medium-pressure column chromatography on silica gel(eluent: EtOAc/hexane = 30/70 ~ EtOAc 100%. For 3j, eluent: MeOH/CHCl3 = 30/70 ~ 50/50) andrecrystallization from MeOH/hexane. The products 3l and 3m were isolated by recrystallizationfrom EtOAc/hexane. 1H NMR spectra were recorded at 400 MHz, and 13C NMR spectra wererecorded at 100 MHz in DMSO-d6 (For 3j, in a mixture of DMSO-d6 and methanol-d4). Elemental analyses were performed at the Microanalytical Center of Kyoto University. The analytical and spectral data of 3a,10 3b-c,11 3d,12 3e,13 3f,14 3g-h,10 and 3j-l,7 are fully consistent with those reported previously. The products 3i,15 and 3m16 were characterized below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen; In ethyl acetate; at 80℃; under 26252.6 Torr; | 6 mL of the catalyst C (20 to 30 mesh) was put into a fixed bed reactor and tested in a continuous trickle-bed mode. 4 wt % of 2,2,4,4-tetramethyl-1,3-cyclobutanediketone was hydrogenated in the above reactor with hydrogen. The hydrogenation factors are listed below: the solvent was EA, the WHSV of the feed was 0.24 hr-1, the hydrogenation temperature was 80 C., the hydrogenation pressure was 35 kg/cm2, in which the hydrogen and the 2,2,4,4-tetramethyl-1,3-cyclobutanediketone had a molar ratio of 69. The hydrogenation result was analyzed by GC as indicated below: the conversion rate of the 2,2,4,4-tetramethyl-1,3-cyclobutanediketone was 61.8%, and the selectivity of the CBDO in the products was 1.7%, as shown in Table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen; In ethyl acetate; at 80℃; under 26252.6 Torr; | 6 mL of the catalyst A (20 to 30 mesh) was put into a fixed bed reactor and tested in a continuous trickle-bed mode. 4 wt % of 2,2,4,4-tetramethyl-1,3-cyclobutanediketone was hydrogenated in the above reactor with hydrogen. The hydrogenation factors are listed below: the solvent was ethyl acetate (EA), the weight hourly space velocity (WHSV) of the feed was 0.24 hr-1, the hydrogenation temperature was 80 C., the hydrogenation pressure was 35 kg/cm2, in which the hydrogen and the 2,2,4,4-tetramethyl-1,3-cyclobutanediketone had a molar ratio of 69. The hydrogenation result was analyzed by gas chromatography (GC) as indicated below: the conversion rate of the 2,2,4,4-tetramethyl-1,3-cyclobutanediketone was 99.9%, and the selectivity of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO) in the products was 77.6%, as shown in Table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen; In butan-1-ol; at 100℃; under 26252.6 Torr; | General procedure: 6 mL of the catalyst D (20 to 30 mesh) was put into a fixed bed reactor and tested in a continuous trickle-bed mode. 4 wt % of 2,2,4,4-tetramethyl-1,3-cyclobutanediketone was hydrogenated in the above reactor with hydrogen. The hydrogenation factors are listed below: the solvent was n-butanol (BuOH), the WHSV of the feed was 0.24 hr-1, the liquid hourly space velocity (LHSV) of the feed was 4 hr-1, the hydrogenation temperature was 135 C., the hydrogenation pressure was 50 kg/cm2, in which the hydrogen and the 2,2,4,4-tetramethyl-1,3-cyclobutanediketone had a molar ratio of 69. The hydrogenation result was analyzed by gas chromatography (GC) as indicated below: the conversion rate of the 2,2,4,4-tetramethyl-1,3-cyclobutanediketone was 99.8%, and the selectivity of the CBDO in the products was 10%, as shown in Table 3. Example 7-2 was similar to Example 7-1, except that the reaction pressure was changed to 35 kg/cm2, in which the hydrogen and the 2,2,4,4-tetramethyl-1,3-cyclobutanediketone had a molar ratio of 69, the WHSV of the feed being lowered to 0.12 hr-1, the LHSV of the feed being lowered to 2 hr-1, and the reaction temperature being lowered to 100 C. The other reaction factors in Example 7-2 were similar to those in Example 7-1. The hydrogenation result was analyzed by GC as indicated below: the conversion rate of the 2,2,4,4-tetramethyl-1,3-cyclobutanediketone was 99.9%, and the selectivity of the CBDO in the products was 77.3%, as shown in Table 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen; In butan-1-ol; at 135℃; under 37503.8 Torr; | 6 mL of the catalyst D (20 to 30 mesh) was put into a fixed bed reactor and tested in a continuous trickle-bed mode. 4 wt % of 2,2,4,4-tetramethyl-1,3-cyclobutanediketone was hydrogenated in the above reactor with hydrogen. The hydrogenation factors are listed below: the solvent was n-butanol (BuOH), the WHSV of the feed was 0.24 hr-1, the liquid hourly space velocity (LHSV) of the feed was 4 hr-1, the hydrogenation temperature was 135 C., the hydrogenation pressure was 50 kg/cm2, in which the hydrogen and the 2,2,4,4-tetramethyl-1,3-cyclobutanediketone had a molar ratio of 69. The hydrogenation result was analyzed by gas chromatography (GC) as indicated below: the conversion rate of the 2,2,4,4-tetramethyl-1,3-cyclobutanediketone was 99.8%, and the selectivity of the CBDO in the products was 10%, as shown in Table 3. |
Tags: 933-52-8 synthesis path| 933-52-8 SDS| 933-52-8 COA| 933-52-8 purity| 933-52-8 application| 933-52-8 NMR| 933-52-8 COA| 933-52-8 structure
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