Purity | Size | Price | VIP Price | USA Stock *0-1 Day | Global Stock *5-7 Days | Quantity | |||||
{[ item.p_purity ]} | {[ item.pr_size ]} |
{[ getRatePrice(item.pr_usd, 1,1) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} |
{[ getRatePrice(item.pr_usd, 1,1) ]} | Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} {[ getRatePrice(item.pr_usd,1,item.mem_rate) ]} | {[ item.pr_usastock ]} | Inquiry - | {[ item.pr_chinastock ]} | Inquiry - |
* Storage: {[proInfo.prStorage]}
CAS No. : | 513-85-9 | MDL No. : | MFCD00004523 |
Formula : | C4H10O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | OWBTYPJTUOEWEK-UHFFFAOYSA-N |
M.W : | 90.12 | Pubchem ID : | 262 |
Synonyms : |
|
Num. heavy atoms : | 6 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 1.0 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 2.0 |
Molar Refractivity : | 23.67 |
TPSA : | 40.46 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -7.5 cm/s |
Log Po/w (iLOGP) : | 1.26 |
Log Po/w (XLOGP3) : | -0.92 |
Log Po/w (WLOGP) : | -0.25 |
Log Po/w (MLOGP) : | -0.18 |
Log Po/w (SILICOS-IT) : | -0.36 |
Consensus Log Po/w : | -0.09 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | 0.25 |
Solubility : | 159.0 mg/ml ; 1.77 mol/l |
Class : | Highly soluble |
Log S (Ali) : | 0.55 |
Solubility : | 323.0 mg/ml ; 3.58 mol/l |
Class : | Highly soluble |
Log S (SILICOS-IT) : | 0.5 |
Solubility : | 282.0 mg/ml ; 3.13 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.48 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P210-P280-P370+P378-P403+P235-P501 | UN#: | N/A |
Hazard Statements: | H227-H315-H319-H335 | 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 |
---|---|---|
91.8% | With water at 110℃; | 4 preparation of o-diol compounds (1) First, a C2-C16 monoolefin was used as a raw material, and a titanium silicate molecular sieve TS-1 having an MFI structure was used.HTS-1 as a catalyst, with an aqueous hydrogen peroxide solution as an oxidizing agent, according to the process disclosed in CN 104211665A,Oxidation to the corresponding hydrocarbon epoxide;(2) In a 100 ml jacketed stainless steel tubular reactor, 30 ml of a compound represented by the general formula (3)Substituted macroporous polystyrene season scale salt anion exchange resin catalyst, the catalyst bed at the bottom and end filled with inertball. The temperature of the reactor is controlled by an external circulation type heat transfer oil, and the reactor pressure is controlled by a back pressure valve installed on the outlet lineThe reaction material is passed through the bottom of the reactor through the bottom of the reactor and flows through the catalyst bed from the top of the reactor and is cooled by the coolerBut then flows into the reaction product tank. Time sampling, gas chromatography analysis reaction product composition. Study the concentration of reaction raw materials, reactionTemperature, pressure, liquid hourly space velocity and the type of catalyst on the reaction, the reaction materials used in Examples 1 to 10 are shown in Table1, the catalyst used has the general formula (3) structure, wherein Yi, 7, horses, 1? 6,1? 7 groups, resin crosslinking degree, resin alkali exchange capacitySee Table 2, the reaction process conditions and reaction results in Table 3. The catalyst represented by the general formula (3) has an ortho-halogenated styrene,Etine is prepared from the reaction starting material, the reaction equation is as follows: |
91.5% | With dihydrogen peroxide In water at 110℃; Molecular sieve; | 4 preparation of vicinal diol compounds (1) The mono-olefins are first oxidized to the corresponding hydrocarbon epoxides according to the process disclosed in CN104211665A , with C2-C16 mono-olefins as starting material , then using a titanium silicalite sieve TS-1 or HTS-1 as a catalyst having an MFI structure and with an aqueous solution of hydrogen peroxide as an oxidizing agent. |
90.8% | With water at 110℃; |
90.6% | With water at 110℃; | 4 In a 100 ml jacketed stainless steel tubular reactor, 30 ml of a halogen-substituted macroporous polystyrene quaternary ammonium salt type anion exchange resin catalyst having a structure represented by the general formula (3) was charged, and the upper and lower ends of the catalyst bed Filled with inert ceramic ball.The temperature of the reactor is controlled by an external circulation type heat transfer oil, which is controlled by a back pressure valve mounted on the outlet line. The reaction material is fed from the bottom of the reactor through the metering pump and flows through the catalyst bed from the top of the reactor , Cooled by the cooler and flowed into the reaction product tank.Time sampling, gas chromatography analysis reaction product composition.The reaction raw materials used in Examples 1 to 10 are shown in Table 1. The catalyst used has the structure of the general formula (3), wherein X and y are the same as those of the reaction formula, wherein the reaction temperature, pressure, liquid hourly space velocity and catalyst type change affect the reaction. , R5, R6, R7Group, resin crosslinking degree, resin alkali exchange capacity (dry basis) in Table 2, the reaction process conditions and reaction results in Table 3.The catalyst represented by the general formula (3) is prepared by preparing halogenated styrene and diene as reaction materials, and the reaction equation is as follows: |
With sulfuric acid at 90℃; substance, whose stereochemical homogeneity or configuration not/no known is; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With C30H48FeP2Rh(1+)*CF3O3S(1-); hydrogen at 20℃; for 8h; | |
100% | With 5% ruthenium on carbon; hydrogen In water monomer at 125℃; for 2.5h; Autoclave; Sealed tube; | 15 Examples 11-16 (0043) These examples further illustrate the performance of ruthenium-based catalysts on alumina and carbon supports. Reactions were performed in a semicontinuous mode using 50 g of a 20 wt % aqueous solution of acetoin at 125° C., a hydrogen pressure of 5 MPa, and variable catalyst concentrations (Ccat, wt % based on the amount of active metal relative to that of acetoin). Results are given in Table 2, with the symbols having the same meaning than in Table 1. [table-us-00002-en] TABLE 2 Performance of ruthenium-based catalysts. Reaction conditions: 20 wt % aqueous solution of acetoin at 125° C. and 5 MPa. Example Catalyst tR (h) Ccat (wt %) C (%) Y (%) 11 Ru(5%)/Al2O31 3 0.250 98 97 12 Ru(5%)/Al2O3 3 0.125 85 85 13 Ru(5%)/C2 2 0.105 100 94 14 Ru(5%)/C 2.5 0.050 100 99 15 Ru(5%)/C 2.5 0.026 100 100 16 Ru(5%)/C 2.5 0.012 100 98 (0044) Results from Table 2 indicate that ruthenium supported on carbon and alumina are both good catalysts according to the invention, with ruthenium supported on carbon having a better performance than that supported on alumina leading to conversions and yields of practically 100% even at a catalyst concentration as low as 0.012 wt %. Likewise, ruthenium concentrations into the reaction mixture were in all cases below 0.1 mg/L as determined by ICP, indicating that catalysts are stable under reactions conditions. |
89.9% | With hydrogen at 150℃; for 1h; Autoclave; Inert atmosphere; | 1 To micro autoclave (70ml), 3- hydroxy-2-butanone (acetoin) 0.5g (5.7mmol), 1.5 mass% Ru a supported activated carbon catalyst 0.1g (Ru for acetoin 0.3 mass% ), 2,3-butane diol (solvent) 3g, and a stirrer, was charged under an argon atmosphere. After sealing the micro-autoclave was pressure 3MPa at 100 vol% hydrogen gas. The micro-autoclave was placed on the reaction temperature and is 0.99 ° C. setting the electric furnace temperature was raised, and the start of the reaction time has elapsed 15 min. After 1 hour elapsed from the start of the reaction, the micro autoclave was taken out from the electric furnace, after cooling to room temperature, after purging the residual pressure, the reaction solution in the micro autoclave was total volume recovered. |
With water monomer; nickel Hydrogenation; substance, whose stereochemical homogeneity or configuration not/no known is; | ||
With glucose dehydrogenase; D-glucose; (R)-specific alcohol dehydrogenase from Candida maris IFO10003; NADH In dimethyl sulfoxide at 30℃; for 17h; aq. phosphate buffer; Enzymatic reaction; | ||
With rabbit 3-hydroxyhexobarbital dehydrogenase (AKR1C29); NADPH In aq. phosphate buffer; ethyl acetate at 37℃; for 0.5h; Enzymatic reaction; | 2.6 Product identification General procedure: The reaction was conducted at 37°C in a 2.0-mL reaction mixture, containing coenzyme (1-mM NADP+ or 0.1-mM NADPH), substrate (0.05-0.1mM), enzyme (0.1-0.3mg), and 0.1-M potassium phosphate, pH 7.4. The substrate and products were extracted into 4-mL ethyl acetate 30min after the reaction was started at 37°C. The products of oxidoreduction of steroids [25] and reduction of PGD2 [28], farnesal [29] and 4-oxo-2-nonenal [18] were analyzed by TLC, as described. The reduced products of TBE were identified by the HPLC methods [23]. The products of 3HB oxidation, 3OB reduction, 5β-androstane-3α,17β-diol oxidation and 5β-androstan-3α-ol-17-one reduction were analyzed by the liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) using a Hewlett-Packard HP 1100 Series LC/MSD system attached with a diode array detector and a column (Mightysil RP-18 GP 5μm, 4.6mm×250mm, Kanto Chemical Co., Tokyo, Japan). Separations were carried out at a flow rate of 0.5mL/min and 40°C using the following mobile phases: 25% acetonitrile aqueous solution containing 0.1% formic acid for 3OB and α/β-3HBs, and 80% acetonitrile aqueous solution containing 0.1% formic acid for the two steroids. 3OB, α-3HB, β-3HB, 5β-androstan-3α-ol-17-one and 5β-androstane-3α,17β-diol were detected by monitoring their total ions (m/z 249.1, 251.1, 251.1, 289.4 and 291.4, respectively) in the negative ESI mode, and eluted at the retention times of 20.1, 17.6, 16.8, 14.9 and 12.7min, respectively. The detection limits of 3OB, α/β-3HBs and the two steroids were 0.1, 0.1 and 1nmol, respectively. | |
With 2,3-butanediol dehydrogenase from Taiwanofungus camphorata; NADH In aq. phosphate buffer at 37℃; for 0.5h; Enzymatic reaction; | ||
83 %Chromat. | With potassium dihydrogen orthophosphate; phosphoric acid; water monomer; Sodium sulfate [anhydrous] at 20 - 25℃; for 1.9h; Electrolysis; | 4 Example 4 Example 4 (0035) A solution (60 mL) of 3-hydroxybutanone (98.5 g/L), KH2PO4 (2.5 wt %) and Na2SO4 (4 wt %) in water adjusted to pH 3.6 with phosphoric acid, was recirculated by means of a magnetic pump through an undivided filter press cell consisting of a Iridium oxide-based DSA anode (20 cm2) and a Ni foam (20 cm2 geometric area, 1.6 mm thickness, 95% porosity, 20 pores/cm, 0.45 g/cm3 apparent density) cathode separated 0.8 cm each other by means of a PP separator. An electrical current was circulated (2 A, 1000 A/m2) by applying a voltage between anode and cathode using a DC Power Supply. Electrolysis was kept at room temperature (20-25° C.) for 1.90 h (105.5% of the theoretical charge for full conversion of 3-hydroxybutanone assuming a current efficiency of 100%). Initial solution pH was 3.6 and final pH 3.4 (mean pH 3.5). After electrolysis completion, the electrolyzed solution (56.5 mL) contained a 3-hydroxybutanone concentration of 1.86 g/L and a 2,3-BDO concentration of 88.8 g/L, as shown by HPLC. Therefore, 3-hydroxybutanone conversion was 98.2% (93.1% current yield) and 2,3-BDO yield 83.0% resulting in a 2,3-BDO selectivity of 84.5%. |
92.2 %Chromat. | With NiO/SiO2; hydrogen at 150℃; Flow reactor; | 2. Experimental The vapor-phase catalytic hydrogenation of AC was performedin a fixed-bed flow reactor at atmospheric pressure.After a catalyst (typically catalyst weight, W = 0.125 g) hadbeen reduced in the reactor at a prescribed temperature for 1 h,the catalytic reaction of AC was performed at an atmosphericpressure of H2 and 150 °C. AC was fed through the reactor topat a liquid feed rate (F) of 1.35 g h1 together with an H2 flowof 1.8 dm3 h1 and continued for time on stream (TOS) oftypically 5 h. The products were collected in a dry ice-acetonetrap at 78 °C every hour. The recovered products were identifiedusing a gas chromatograph (GC) equipped with a massspectrometer(QP5050A, Shimadzu) and a capillary column(DB-WAX, a length of 30 m, JW Scientific). They were quantitativelyanalyzed with a GC (GC-8A, Shimadzu, Japan)equipped with a direct injection port, a flame ionization detector,and a 30-m capillary column of Inert Cap WAX-HT (innerdiameter of 0.53 mm, GL-Science) using 1-hexanol as an internalstandard. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 35% 2: 7% | With hydrogen; isopropyl alcohol In tetrahydrofuran at 25℃; for 20h; | |
With hydrogen; nickel at 140 - 150℃; | ||
With hydrogen In isopropyl alcohol at 79.84℃; Inert atmosphere; Sealed tube; chemoselective reaction; | Catalytic activity tests The catalytic performance of the prepared catalysts was tested in a semi-continuous stainless steel batch reactor (slurry), equipped with a magnetic stirrer and with PTFE coated internals. The catalysts were ground to a fine powder to eliminate mass transfer limitations. The reactor was charged with a solution of 2,3-butanedione (diacetyl, DC) in isopropanol (initial concentration of diacetyl, CDC = 0.188 M), and a certain mass of the activated catalyst. Then the reactor was closed. Before the reaction, the reactor was pressurized with N2 up to 5 bar and purged 3 times, to eliminate oxygen traces. The reaction begun with the hydrogen entrance into the system. During the reaction the stirring speed was maintained at 1200 rpm, the pressure was kept constant at 20 bar and the temperature at 353 K. Runs were carried out in triplicates with an experimental error of 3%. Reactants and products were analyzed by gas chromatography in a Shimadzu 2014equipment with a flame ionization detector and a 30 m J&W INNOWax 19091N-213 (cross-linked polyethyleneglycol phase) capillary column. |
With diacetyl reductase | ||
With platinum on carbon; hydrogen In cyclohexane at 79.84℃; | 2.3 Catalytic Activity Tests General procedure: The catalysts were tested with the hydrogenation reactionsof 2,3-butanedione (BD) and 2,3-pentanedione (PD).The catalytic tests were performed in a stirred tank reactor(100 mL Parr type) with PTFE-coated internals. The usedsolvents were isopropanol (Cicarelli, 99.5%) and cyclohexane(Cicarelli, 99.5%). BD was supplied by Sigma-Aldrich(Cat. N°11038, purity 99%) and PD by Fluka (Cat. N°69043,purity 99%). Reactants and solvents were distilled before thecatalytic tests. The catalysts were ground to a particle sizelower than 10 μm and the stirring rate was 1200 rpm in orderto eliminate internal and external mass transfer resistances.The reactor was operated under the following experimentalconditions: 353 K, 20 bar hydrogen pressure, 0.188 M initialreactant concentration (BD or PD), 61 mL reaction mediavolume, 50 mg catalyst mass. The catalysts were previouslyreduced for 4 h at 673 K. Reactants and products wereanalyzed by means of gas chromatography in a ShimadzuGC-2010 equipped with a flame ionization detector and a30 m long J&W InnoWax 19091 N-213 column. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With carbonylchlorohydrido(4,5-bis((diisopropylphosphino)methyl)acridine)ruthenium(II); ammonia In toluene at 150℃; for 36h; Inert atmosphere; Glovebox; | |
With aluminium oxide catalysts; ammonia at 400℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With pyridine; thionyl chloride; benzene | ||
With pyridine; thionyl chloride In chloroform | ||
With thionyl chloride In hydrogen fluoride |
With thionyl chloride | ||
With thionyl chloride In dichloromethane at 20℃; for 4h; Heating / reflux; | 1 Example 1 Preparation of 4,5-dimethyl-[1,3,2]dioxathiolane 2,2-dioxide 0.88 mol (105 g) of thionyl chloride was added dropwise at room temperature to a solution of 0.44 mol (40 g) of 2,3-dihydroxybutane (cis/trans mixture) in 200 ml of CH2Cl2 over a period of 3 hours while cooling and stirring vigorously. The HCl gas formed was passed through a wash bottle filled with NaOH solution to neutralize it. After the addition was complete, the reaction mixture was stirred under reflux for 1 hour. The solvent was removed under reduced pressure and the residue was immediately used for the further reaction. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With scandium aluminium oxide; hydrogen at 318℃; for 5h; Flow reactor; | Catalytic reaction General procedure: The dehydration of 2,3-BDO was carried out in a fixed-bed tubu-lar flow reactor under atmospheric pressure of H2with a flow rateof 45 cm3min-1at a prescribed temperature. Prior to the reaction,a catalyst (1.0 g) was preheated in an H2flow at the prescribedtemperature for 1 h. After the catalyst bed had been preheated, 2,3-BDO was fed through the reactor top at a feed rate of 1.06 g h-1(11.8 mmol h-1). The liquid effluent collected every hour was ana-lyzed by gas chromatography (GC-8A, Shimadzu, Japan) with a60-m capillary column (DB-WAX). The products were identified bygas chromatography with a mass spectrometer (GCMS-QP5050A,Shimadzu) and a 30-m capillary column (DB-WAX). Gaseous prod-ucts such as BD and butene isomers were analyzed by on-line gaschromatography (GC-8A, Shimadzu) with a 6-m packed column column(VZ-7). The catalytic activity was evaluated by averaging the con-version and selectivity data in the initial 5 h. Both the conversion of2,3-BDO and the selectivity to each product were defined as mol%.The above-mentioned description is essentially the same as thosedescribed in the previous work [32,36,37].In Section 3.4, the dehydration of MEK and 3B2OL was alsoexamined in the same way as the 2,3-BDO dehydration in order toconfirm an intermediate product in the dehydration from 2,3-BDOto BD. In Section 3.5, the dehydration of 2,3-BDO was also inves-tigated over two different catalysts packed in the tubular reactor,which consisted of 1.0 g of Al2O3placed in a lower bed with 6 mmheight and 1.0 g of Sc2O3placed in an upper bed with 4 mm height,to establish the efficient BD formation |
With water; triethylamine; 2,4-dimethylpentan-3-one at 225 - 235℃; Leiten ueber Al+SiO2+W2O5; | ||
With thorium dioxide at 350℃; unter vermindertem Druck, andere Katalysatoren; |
With scandium(III) oxide; hydrogen at 411℃; for 5h; Flow reactor; | ||
With scandium(III) oxide; hydrogen at 411℃; for 5h; Inert atmosphere; Flow reactor; | ||
With O7P2(4-)*0.5Sr(2+)*1.5Ca(2+) at 430℃; Inert atmosphere; | Dehydratation process 2,3-BDO was fed into the reactor at a rate of 0.005 mL/min, together with 20 sccm of nitrogen as a carrier gas. 0.2 g of catalyst were used (sccm = standard cubic centimeter per minute). Thus, partial pressure of 2,3-BDO was 5.78 % and WHSV was 1.48 h-1. WHSV (weight hourly space velocity) is the mass of fed 2,3-BDO per hour, divided by the catalyst mass. (0042) The catalyst screening in the present invention was carried out in a fixed bed reactor system comprising of a reactant feed, a reactor and a detector. The liquid feed to the reactor was delivered via a Shimadzu LC-20AT liquid pump while gas feed was delivered using a Brooks Instrument mass flow control system. The reactor module consisted of stainless steel tubular reactors placed vertically within a tube furnace, with a diameter of 3/8" used for packing 0.2 g of catalyst. Detection of chemical species was performed using an Agilent Technologies 7890A gas chromatography system (GC). Stainless steel tubing and fittings were used for the reactor system and procured from Swagelok. Under normal operating conditions, 2,3-BDO was fed at a rate of 0.005 mL/min, together with 20 sccm of N2 as a carrier gas and 0.2 g of catalyst. This combination gives a 2,3-BDO partial pressure composition of 5.78% and a weight hourly space velocity (WHSV) of 1.48 h-1. Chemical species were identified via their GC retention time via the flame ionization detector (FID). These values are given in Table 1. [tabl0001-en] | |
With neodymium(III) orthophosphate at 320℃; Inert atmosphere; | 9 EXAMPLE 9 (0139) The neodymium phosphate has been tested as a catalyst in the dehydration of butane-2,3-diol. (0140) The specific surface of the catalyst NdPO4 of the invention is 117 m2/g. (0141) The reaction has been carried out under the following conditions: (0142) WHSV=2.95 h-1; butane-2,3-ol/N2=1/80.3; temperature of the reactor=320° C. (0143) The catalytic results that have been obtained are shown in the following Table 7. | |
Stage #1: 2.3-butanediol With succinic acid; sulfuric acid at 130℃; for 6h; Stage #2: at 500℃; Pyrolysis; | 1.3 Preparation of 1,3-butadiene 1.3 mol of 2,3-butanediol and 1 mol of succinic acid were distilled at 130 DEG C for 6 hours in the presence of 0.1 M sulfuric acid to produce an esterified reaction intermediate.The reaction intermediate was pyrolyzed at 1 atm and 500 ° C and then separated and purified into 1,3-butadiene in gaseous state and succinic acid in solid / liquid phase.That is, the gaseous product after pyrolysis was injected into a drum cooled at 5 ° C to recover succinic acid into solid / liquid phase, and 1,3-butadiene present in the gas phase was collected and analyzed.At this time, the separated and purified succinic acid was recovered again for use in the esterification reaction. | |
With lanthanum pyrophosphate at 350℃; for 0.5h; Inert atmosphere; | 1 General procedure: 2.0 g of the catalyst obtained above was filled in a 3/8-inch reaction tube, and the reaction tube was heated in a tubular electric furnace in a nitrogen stream, and after the catalyst layer reached a predetermined temperature, nitrogen and 2, A predetermined amount of 3-butanediol was supplied and the reaction was carried out at normal pressure at a reaction temperature of 350 ° C. | |
With aluminum oxide; hydrogen at 350℃; for 5h; | 18 Examples 1 to 4 Dehydration reaction of 2,3-butanediol General procedure: Zirconium oxide (1.0 g) calcined at 900 ° C. was filled in a reaction tube,Hydrogen was flowed through the carrier gas inlet at a flow rate of 45 mL / min.The reaction temperature was set as shown in Table 1.2,3-butanediol (Tokyo Chemical Industry Co., Ltd., stereoisomer mixture)Was supplied to the vaporizer from the raw material introduction port at a flow rate of 1.06 g / hour by a syringe pump and introduced into the reaction tube together with the carrier gas. The reaction was continued for 5 hours.The average value of conversion and selectivity over 5 hours was as shown in Table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In water at 500℃; | 1 Pyroprobe Evaluation of Catalysts General procedure: The feedstock was 10 wt % BDO (Aldrich) in deionized (DI) water. The catalyst (2 mg of powder) was loaded into a quartz tube (25 mm long×1.9 mm I.D.; open at both ends), and held in position using a quartz wool plug on both ends of the powder layer. Approximately 1 μL of feed solution was subsequently dispensed onto the back quartz wool plug then loaded into the pyroprobe wand with the liquid-containing end down, so that upon heating the liquid feed vapors would be carried through the catalyst bed.After the tube was loaded into the pyroprobe wand, the end of the wand was inserted into the pyroprobe unit and sealed. Helium carrier gas flowed through the probe wand and over the quartz wool plugs and catalyst. Upon initiation of the unit, a heating coil encircling the quartz tube, rapidly heated the tube and its contents to 600° C. and maintained it at that temperature for usually 15 seconds. Carrier gas flows were typically 20 cc/m of He through the pyroprobe. Reactant and product vapors were rapidly carried out of the quartz tube and adsorbed onto a Carbopack bed at 40° C., then later desorbed from the adsorbent bed at 300° C. The desorbed products were carried into the GC/MS unit for separation and analysis. Area percent reports were generated for percent conversion of BDO and product selectivity to 1,3 butadiene, methyl vinyl carbinol, MEK, and isobutyraldehyde (IBA). Aldrich BDO was a mixture of d/l and meso isomers. Early analyses integrated over both isomers (reported as BDO) until method improvements allowed separate quantification |
85% | With hydrogen bromide; tetrabutyl phosphonium bromide at 200℃; for 0.25h; Inert atmosphere; | |
With phosphoric acid; sulfuric acid beim Destillieren; |
With magnesium chloride at 300 - 350℃; | ||
With water; magnesium chloride at 300 - 350℃; | ||
With water; magnesium sulfate at 300 - 350℃; | ||
With magnesium sulfate at 300 - 350℃; | ||
With bentonite at 225 - 275℃; | ||
With sulfuric acid beim Destillieren; | ||
With water; bentonite at 225 - 275℃; | ||
In perchloric acid Irradiation; influence of pH on radiation-chemical yield; aq. NaOH instead of aq. HClO4; | ||
With cerium(IV) oxide; hydrogen at 425℃; for 5h; Flow reactor; | Catalytic reaction General procedure: The dehydration of 2,3-BDO was carried out in a fixed-bed tubu-lar flow reactor under atmospheric pressure of H2with a flow rateof 45 cm3min-1at a prescribed temperature. Prior to the reaction,a catalyst (1.0 g) was preheated in an H2flow at the prescribedtemperature for 1 h. After the catalyst bed had been preheated, 2,3-BDO was fed through the reactor top at a feed rate of 1.06 g h-1(11.8 mmol h-1). The liquid effluent collected every hour was ana-lyzed by gas chromatography (GC-8A, Shimadzu, Japan) with a60-m capillary column (DB-WAX). The products were identified bygas chromatography with a mass spectrometer (GCMS-QP5050A,Shimadzu) and a 30-m capillary column (DB-WAX). Gaseous prod-ucts such as BD and butene isomers were analyzed by on-line gaschromatography (GC-8A, Shimadzu) with a 6-m packed column column(VZ-7). The catalytic activity was evaluated by averaging the con-version and selectivity data in the initial 5 h. Both the conversion of2,3-BDO and the selectivity to each product were defined as mol%.The above-mentioned description is essentially the same as thosedescribed in the previous work [32,36,37].In Section 3.4, the dehydration of MEK and 3B2OL was alsoexamined in the same way as the 2,3-BDO dehydration in order toconfirm an intermediate product in the dehydration from 2,3-BDOto BD. In Section 3.5, the dehydration of 2,3-BDO was also inves-tigated over two different catalysts packed in the tubular reactor,which consisted of 1.0 g of Al2O3placed in a lower bed with 6 mmheight and 1.0 g of Sc2O3placed in an upper bed with 4 mm height,to establish the efficient BD formation | |
With indium(III) oxide; hydrogen at 425℃; for 5h; Flow reactor; | Catalytic reaction General procedure: The dehydration of 2,3-BDO was carried out in a fixed-bed tubu-lar flow reactor under atmospheric pressure of H2with a flow rateof 45 cm3min-1at a prescribed temperature. Prior to the reaction,a catalyst (1.0 g) was preheated in an H2flow at the prescribedtemperature for 1 h. After the catalyst bed had been preheated, 2,3-BDO was fed through the reactor top at a feed rate of 1.06 g h-1(11.8 mmol h-1). The liquid effluent collected every hour was ana-lyzed by gas chromatography (GC-8A, Shimadzu, Japan) with a60-m capillary column (DB-WAX). The products were identified bygas chromatography with a mass spectrometer (GCMS-QP5050A,Shimadzu) and a 30-m capillary column (DB-WAX). Gaseous prod-ucts such as BD and butene isomers were analyzed by on-line gaschromatography (GC-8A, Shimadzu) with a 6-m packed column column(VZ-7). The catalytic activity was evaluated by averaging the con-version and selectivity data in the initial 5 h. Both the conversion of2,3-BDO and the selectivity to each product were defined as mol%.The above-mentioned description is essentially the same as thosedescribed in the previous work [32,36,37].In Section 3.4, the dehydration of MEK and 3B2OL was alsoexamined in the same way as the 2,3-BDO dehydration in order toconfirm an intermediate product in the dehydration from 2,3-BDOto BD. In Section 3.5, the dehydration of 2,3-BDO was also inves-tigated over two different catalysts packed in the tubular reactor,which consisted of 1.0 g of Al2O3placed in a lower bed with 6 mmheight and 1.0 g of Sc2O3placed in an upper bed with 4 mm height,to establish the efficient BD formation | |
With indium(III) oxide; hydrogen at 425℃; for 5h; Flow reactor; | ||
With cerium(IV) oxide; hydrogen at 325℃; for 5h; | 3; 13 Examples 1 to 4 Dehydration reaction of 2,3-butanediol General procedure: Zirconium oxide (1.0 g) calcined at 900 ° C. was filled in a reaction tube,Hydrogen was flowed through the carrier gas inlet at a flow rate of 45 mL / min.The reaction temperature was set as shown in Table 1.2,3-butanediol (Tokyo Chemical Industry Co., Ltd., stereoisomer mixture)Was supplied to the vaporizer from the raw material introduction port at a flow rate of 1.06 g / hour by a syringe pump and introduced into the reaction tube together with the carrier gas. The reaction was continued for 5 hours.The average value of conversion and selectivity over 5 hours was as shown in Table 1. | |
In aq. phosphate buffer; water at 25℃; for 1h; Irradiation; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | In 1,4-dioxane at 180℃; for 20h; | |
79% | With [Ru(CO)2(4,5-bis(diphenylphosphino)-9,9-dimethyl-9H-xanthene)]2; [Ru(CO)2(4,5-bis(diphenylphosphino)-9,9-dimethyl-9H-xanthene)]2; toluene-4-sulfonic acid In tert-Amyl alcohol at 120℃; for 16h; regioselective reaction; | |
65% | With toluene-4-sulfonic acid In neat (no solvent) at 175℃; for 48h; | General procedure for indole synthesis of aniline by diols catalyzed by nickel supported on silica General procedure: Diol (10.9 mmol, 1 equiv.), 65 wt% Ni/SiO2-Al2O3 (198 mg, 0.2 equiv.), aniline (21.9 mmol, 2equiv.) and PTSA (209 mg, 0.1 equiv.) were introduced in that order in a 50 mL round bottom flask, which was then equipped with an open condenser. The mixture was stirred at 175 °C for 48 h. After this duration, a sample of the crude mixture was diluted in ethyl acetate, filtered and analyzed by GC. 2-3 g of silica was added to the crude mixture, which was then concentrated under reduced pressure and purified by flash chromatography (ethylacetate/cyclohexane : 5 : 95) to afford the desired product. |
61% | With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; methanesulfonic acid at 170℃; for 48h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With [Ru(CO)2(4,5-bis(diphenylphosphino)-9,9-dimethyl-9H-xanthene)]2; [Ru(CO)2(4,5-bis(diphenylphosphino)-9,9-dimethyl-9H-xanthene)]2; toluene-4-sulfonic acid In tert-Amyl alcohol at 120℃; regioselective reaction; | |
59% | With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; methanesulfonic acid at 170℃; for 48h; Inert atmosphere; | |
48% | In 1,4-dioxane at 180℃; for 20h; |
30% | With zinc(II) oxide; Rh/Al2O3; toluene-4-sulfonic acid In 1-methyl-pyrrolidin-2-one at 175℃; Sealed tube; | |
0.905 g | With toluene-4-sulfonic acid In neat (no solvent) at 175℃; for 48h; | General procedure for indole synthesis of aniline by diols catalyzed by nickel supported on silica General procedure: Diol (10.9 mmol, 1 equiv.), 65 wt% Ni/SiO2-Al2O3 (198 mg, 0.2 equiv.), aniline (21.9 mmol, 2equiv.) and PTSA (209 mg, 0.1 equiv.) were introduced in that order in a 50 mL round bottom flask, which was then equipped with an open condenser. The mixture was stirred at 175 °C for 48 h. After this duration, a sample of the crude mixture was diluted in ethyl acetate, filtered and analyzed by GC. 2-3 g of silica was added to the crude mixture, which was then concentrated under reduced pressure and purified by flash chromatography (ethylacetate/cyclohexane : 5 : 95) to afford the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With ruthenium(III) chloride monohydrate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene at 110 - 170℃; for 25h; | |
50% | In 1,4-dioxane at 180℃; for 20h; | |
32% | With toluene-4-sulfonic acid In neat (no solvent) at 175℃; for 48h; | General procedure for indole synthesis of aniline by diols catalyzed by nickel supported on silica General procedure: Diol (10.9 mmol, 1 equiv.), 65 wt% Ni/SiO2-Al2O3 (198 mg, 0.2 equiv.), aniline (21.9 mmol, 2equiv.) and PTSA (209 mg, 0.1 equiv.) were introduced in that order in a 50 mL round bottom flask, which was then equipped with an open condenser. The mixture was stirred at 175 °C for 48 h. After this duration, a sample of the crude mixture was diluted in ethyl acetate, filtered and analyzed by GC. 2-3 g of silica was added to the crude mixture, which was then concentrated under reduced pressure and purified by flash chromatography (ethylacetate/cyclohexane : 5 : 95) to afford the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With methanesulfonic acid; oxygen In acetonitrile at 80℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With cesiumhydroxide monohydrate; C17H14Br2CoN4 In toluene at 150℃; for 24h; Sealed tube; Inert atmosphere; | |
95% | With cesiumhydroxide monohydrate In toluene at 150℃; for 24h; Inert atmosphere; Sealed tube; | 2.2 Quinoxaline synthesis from diamine General procedure: To an oven dried 9mL screw cap tube, a magnetic stir-bar, diamine (0.5mmol), vicinal diol (1.5mmol), CsOH.H2O (0.375mmol), Co-phen/C-800 (1.5mol%) and toluene (2.5mL) were added under argon atmosphere. Then, the tube was sealed and placed in a preheated oil bath at 150°C for 24h. After completion of the reaction, the tube was allowed to cool at room temperature. Then, the solvent was evaporated under reduced pressure. Finally, the product was purified by silica gel column chromatography using ethyl acetate/hexane as eluent. |
89% | With C18H24ClIrN3O(1+)*Cl(1-); potassium hydroxide In water for 24h; Schlenk technique; Reflux; Green chemistry; |
87% | In diethylene glycol dimethyl ether at 140℃; for 24h; | A generic experiment was as follows. In a two-neck roundbottomflask of 10 mL, 1,2-phenylenediamine (1a, 0.5 mmol),1,2-propyleneglycol (2a, 0.6 mmol), 1.5 mL of diethylene glycol dimethylether (diglyme), and an amount of catalyst were added.Subsequently, the reaction mixture was heated at 140 °C in a siliconebath that contains a magnetic stirrer and a temperature controller. |
85% | With 1,10-Phenanthroline; cesiumhydroxide monohydrate; nickel dibromide In toluene at 150℃; for 24h; Inert atmosphere; Sealed tube; | |
79% | With potassium hydroxide; 1-Phenylbut-1-en-3-one In diethylene glycol dimethyl ether for 20h; Heating; | |
71% | With C24H29IrN2O5(2+)*2CF3O3S(1-); caesium carbonate In 5,5-dimethyl-1,3-cyclohexadiene at 150℃; for 48h; Schlenk technique; Inert atmosphere; | General procedure for the synthesis of 3a. General procedure: The catalyst A (5% mmol, 0.05 mmol), 1,2-phenylenediamine (1 mmol, 1.0 equiv), 1,2-propanediol (1 mmol, 1.0 equiv), Cs2CO3 (3.0 equiv) and xylene (4 mL) were added to a Schlenk tube under the atmosphere of nitrogen. The mixture was heated for 48 h at 150 °C and then cooled down to room temperature. The volatile solvent was evaporated. The residue was purified by column chromatography to give the corresponding product 3a. |
65% | With potassium hydroxide In toluene at 130℃; for 24h; Inert atmosphere; | |
61% | With [Py(NP(iPr)2)(NHP(iPr)2)Ir(cod)]; potassium <i>tert</i>-butylate In tetrahydrofuran at 90℃; for 24h; Inert atmosphere; | |
43% | With bromopentacarbonylmanganese(I); N,N,N',N'',N'''-pentamethyldiethylenetriamine; potassium <i>tert</i>-butylate In toluene at 130℃; for 36h; Sealed tube; Inert atmosphere; Schlenk technique; | |
107.6 mg | With C19H34N3O2P2Re; potassium <i>tert</i>-butylate In toluene at 120℃; for 6h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With a cation exchange resin (H form) In benzene Acidic conditions; Heating / reflux; | 3 A reaction mixture: 2.0 mol of 2,3-butanediol, 2.0 mol of methyl pyruvate, 10 g of a cation exchange resin (H form), and 1 L of absolute benzene were refluxed until no more water came to be produced in a flask fitted with a Dean-Stark trap, thereby obtaining 2,4, 5-TRIMETHYL-2-CARBOXYMETHYL-1, 3-dioxolane. The yield was 75% and the boiling point of the product was 45 °C/1. 0 mmHg. 'HNMR : 1.3 ppm (6H,-CH3), 1.56 ppm (3H,-CH3), 3.77 ppm (3H, OCH3), 3.5 to 4.4 ppm (m, 2H,-OCH-). |
55% | With cation-exchange resin (H form) In benzene Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90.5% | With water at 110℃; | 4 preparation of o-diol compound General procedure: In a 100 ml jacketed stainless steel tubular reactor, 30 ml of the structure represented by the general formula (3)Halogen meta-substituted macroporous polystyrene-divinylbenzene quaternary ammonium salt anion exchange resin catalyst,The catalyst bed is filled with an inert ceramic ball on the upper and lower ends.The temperature of the reactor is controlled by an external circulation type heat transfer oil,The reactor pressure is controlled by a back pressure valve mounted on the outlet line,The reaction material is fed from the bottom of the reactor through a metering pump,Flowing through the catalyst bed from the top of the reactor,Cooled by the cooler and flowed into the reaction product tank.Timing sampling,Analysis of the reaction product by gas chromatography.To investigate the reaction concentration,Reaction temperature, pressure,Liquid hourly space velocity and catalyst type change on the reaction,The reaction materials used in Examples 1 to 10 are shown in Table 1, and the catalyst used has the structure of the general formula (3), wherein the X, y, R5, R6, R7 groups, the ion exchange resin crosslinking degree, the alkali exchange capacity ) See Table 2, the reaction process conditions and reaction results in Table 3. |
With water In acetone at 20℃; for 10h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium bicarbonate; toluene-4-sulfonic acid; In toluene; | COMPARATIVE EXAMPLE 1 Synthesis of 2,3-dimethyl-2,3-dihydro-thieno[3,4-b][1,4]dioxine via the Transetherification Reaction A solution of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> (7.2 g, 50 mmol), meso-2,3-butanediol (5.4 g, 60 mmol), and p-toluenesulphonic acid (0.2 g) in toluene (100 ml) was heated at 100° C. under a continuous argon flow for 24 h. The reaction mixture was then poured into methylene chloride (200 mL) and the organic phase washed with a 1M aqueous solution of sodium hydrogen carbonate and brine, dried with anhydrous magnesium sulphate and concentrated. This resulted in a mixture of cis and trans product that could be separated by column chromatography, yielding pure cis (2.8 g, 16percent) and trans (1.83 g, 11percent) 2,3-dimethyl-2,3-dihydro-thieno[3,4-b][1,4]dioxine. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With triethylamine In dichloromethane at 0℃; | 22 Example 22 Preparation of N-(3-(4Z,7Z,10Z,13Z,16Z,19Z)-docosa-4,7,10,13,16,19-hexaenamidobutan-2-yl)-2-hydroxybenzamide (15) To a solution of butane 2,3-diol (15 g, 0.166 mol) and Et3N (57.7 mL, 0.415 mol) in CH2Cl2 (150 mL) at 0° C. was slowly added a solution of CH3SO2Cl (32.1 mL, 0.415 mol) in CH2Cl2 (75 mL). The mixture was stirred at 0° C. for 2 h and diluted with CH2Cl2. The mixture was washed with water, 1 N HCl, 5% aqueous NaHCO3 and brine. The organic layer was dried over MgSO4, filtered and concentrated under reduced pressure to afford butane-2,3-diyl dimethanesulfonate (40 g, 98%) as a light yellow oil. 1H-NMR (CDCl3): δ4.9 (m, 2H, CH), 3.05 (s, 6H, CH3), 1.4 (m, 6H, CH3). |
With triethylamine In dichloromethane | 21.1 Step 1 Step 1 Preparation of meso-2,3-bis(methanesulfonyloxy)butane Samples of meso-2,3-butanediol (10 g, 111 mmol, Aldrich) and triethylamine (92.8 mL, 666 mmol) are dissolved in methylene chloride. The solution is cooled to -78° C., and methanesulfonyl chloride (25.8 mL, 333 mmol) is added dropwise. A precipitate forms. The mixture is diluted with additional methylene chloride, and the mixture is stirred for 20 minutes at -78° C. and at 0° C. for 2 hours. The reaction mixture is warmed to room temperature, diluted with additional solvent, and washed with H2O, aqueous NaHCO3 and aqueous NaCl. The organic solution is dried over MgSO4, and the solvent is removed to afford the title compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59.8% | With sodium hydroxide; hydrogen In ethanol; water at 181℃; | 9 Hydrogenolysis of a solution of glycerol and water (25:75) was carried out substantially as described in Example 3 except that 180 ml_ of Sd Chemie HC-1 catalyst was used. In a second experiment ethanol was added as a solvent with glycerol (glycerol: ethanol: water; 25:55:20). Results presented in Table 7 show that adding ethanol as a solvent to the glycerol feed resulted in lower formation of 2,3 BDO (0.4%) compared to hydrogenolysis without use of a solvent (0.8%).Consequently as is evident to those skilled in the art suitable conditions exist for hydrogenolysis of sorbitol or glycerol to propylene glycol wherein the yield of propylene glycol is maximized and formation of undesirable side products is minimized. Using the embodiments of this invention one skilled in the art may practice this invention to operate a reactor system and obtain high yields of propylene glycol with low concentrations of other polyhydric alcohols. Alternatively, one skilled in the art may practice this invention to obtain high concentrations of four-carbon polyhydric alcohols. |
59.2% | With sodium hydroxide; hydrogen In water at 215℃; | 9 Hydrogenolysis of a solution of glycerol and water (25:75) was carried out substantially as described in Example 3 except that 180 ml_ of Sd Chemie HC-1 catalyst was used. In a second experiment ethanol was added as a solvent with glycerol (glycerol: ethanol: water; 25:55:20). Results presented in Table 7 show that adding ethanol as a solvent to the glycerol feed resulted in lower formation of 2,3 BDO (0.4%) compared to hydrogenolysis without use of a solvent (0.8%).Consequently as is evident to those skilled in the art suitable conditions exist for hydrogenolysis of sorbitol or glycerol to propylene glycol wherein the yield of propylene glycol is maximized and formation of undesirable side products is minimized. Using the embodiments of this invention one skilled in the art may practice this invention to operate a reactor system and obtain high yields of propylene glycol with low concentrations of other polyhydric alcohols. Alternatively, one skilled in the art may practice this invention to obtain high concentrations of four-carbon polyhydric alcohols. |
57% | With sodium hydroxide; hydrogen at 166℃; | 4; 5; 6 Examples 4-7 describe methods to reduce the formation of four- carbon product BDO and maximize the conversion of polyhydric alcohol glycerol to three-carbon product propylene glycol with a solid phase catalyst such as the "G" catalyst as disclosed in US 6,479,713 or the "HC-1" catalyst available from Sd Chemie (Louisville, KY). Hydrogenolysis of a 40% solution of glycerol was carried out substantially as described in Example 3. The effect of the concentration of alkali (sodium hydroxide) in the feed at constant temperature and constant LHSV on the amount of BDO formed was investigated. Higher levels of sodium hydroxide resulted in greater formation of BDOs, thus, the formation of BDOs was minimized when the reaction was operated at lower concentrations (1- 1.9 wt %) of alkali promoter (Table 4); Hydrogenolysis of a 40% solution of the polyhydric alcohol glycerol was carried out substantially as described in Example 3. The effect of the reaction temperature at constant concentrations of alkali (sodium hydroxide) and constant LHSV on the amount of BDO formed was investigated. Higher temperatures resulted in greater formation of BDOs, thus the formation of BDOs was minimized when the reaction was operated at lower reaction temperatures (178-2050C, Table 4); Hydrogenolysis of a 40% solution of the polyhydric alcohol glycerol was carried out substantially as described in Example 3. The effect of LHSV of the feed at constant concentration of alkali (sodium hydroxide) and constant on amount of BDO formed was investigated. Higher LHSV resulted in lower levels of formation of BDOs, thus the formation of BDOs was minimized when the reaction was operated at higher LHSV (1.5-2.3, Table 4). |
56% | With sodium hydroxide; hydrogen In water at 176 - 216℃; | 5.283; 5.284; 5.285; 7.S-377; 7.S-395; 7.S-396; 7.S-397; 6.D16-M-424-03; 6.D16-M-424-04 EXAMPLE 5; Hydrogenolysis of a 40% solution of glycerol was carried out substantially as described in Example 1 except that 180 mL of Süd Chemie HC-1 catalyst was used. The effect of increasing temperature on BDO formation was investigated. Table 10 in FIG. 7 describes the conditions used in this Example, and discloses the products produced in this Example. ; EXAMPLE 7; Hydrogenolysis of a 40% solution of glycerol was carried out substantially as described in Example 1, except that 180 mL of Süd Chemie HC-1 catalyst was used. Table 12 in FIG. 9 describes the conditions used in this Example, and discloses the products produced in this Example.; EXAMPLE 6 Hydrogenolysis of a 40% solution of glycerol was carried out substantially as described in Example 1 except that 180 mL of Süd Chemie HC-1 catalyst was used. Table 11 in FIG. 8 describes the conditions used in this Example, and discloses the products produced in this Example. |
36.3% | With sodium hydroxide; hydrogen at 183 - 202℃; | 1 EXAMPLE 1.; A series of studies were conducted in a 2000ml high-pressure Stainless Steel 316 reactor. A solid catalyst similar to the "G" catalyst disclosed in US 6,479,713 or the "HC-1 " catalyst available from Sd Chemie (Louisville, KY) was loaded in the reactor to a final volume of 1000 ml of catalyst. The reactor was jacketed with a hot oil bath to provide for the elevated temperature for reactions and the feed and hydrogen lines were also preheated to the reactor temperature. A solution of a bio-based, substantially pure, 40% USP grade glycerol was fed through the catalyst bed at LHSV ranging from 0.5hr"1 to 2.5hr'1. Hydrogen was supplied at 1200-1600 psi EPO (about 83-110 bar) and was also re-circulated through the reactor at a hydrogen to glycerol feed molar ratio of 5:1. In other embodiments, the hydrogen to glycerol feed molar ratio may be between 1 :1 to 10:1. Tables 5A and 5B in FIGS. 2A and 2B describe the results with hydrogenolysis of 40% USP grade glycerol feed. Between 47.7-96.4% of the glycerol was converted and between 36.3-55.4% of propylene glycol was produced. In addition to propylene glycol, the hydrogenolysis reaction produced 0.04-2.31% unwanted BDOs, which may present a problem for recovery of pure propylene glycol (Table 6). The BDOs were measured using a known gas chromatography analysis method. EPO |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With sodium hydroxide; hydrogen at 202℃; | 4; 5; 6 Examples 4-7 describe methods to reduce the formation of four- carbon product BDO and maximize the conversion of polyhydric alcohol glycerol to three-carbon product propylene glycol with a solid phase catalyst such as the "G" catalyst as disclosed in US 6,479,713 or the "HC-1" catalyst available from Sd Chemie (Louisville, KY). Hydrogenolysis of a 40% solution of glycerol was carried out substantially as described in Example 3. The effect of the concentration of alkali (sodium hydroxide) in the feed at constant temperature and constant LHSV on the amount of BDO formed was investigated. Higher levels of sodium hydroxide resulted in greater formation of BDOs, thus, the formation of BDOs was minimized when the reaction was operated at lower concentrations (1- 1.9 wt %) of alkali promoter (Table 4); Hydrogenolysis of a 40% solution of the polyhydric alcohol glycerol was carried out substantially as described in Example 3. The effect of the reaction temperature at constant concentrations of alkali (sodium hydroxide) and constant LHSV on the amount of BDO formed was investigated. Higher temperatures resulted in greater formation of BDOs, thus the formation of BDOs was minimized when the reaction was operated at lower reaction temperatures (178-2050C, Table 4); Hydrogenolysis of a 40% solution of the polyhydric alcohol glycerol was carried out substantially as described in Example 3. The effect of LHSV of the feed at constant concentration of alkali (sodium hydroxide) and constant on amount of BDO formed was investigated. Higher LHSV resulted in lower levels of formation of BDOs, thus the formation of BDOs was minimized when the reaction was operated at higher LHSV (1.5-2.3, Table 4). |
33.2% | With sodium hydroxide; hydrogen at 154 - 229℃; | 1 EXAMPLE 1.; A series of studies were conducted in a 2000ml high-pressure Stainless Steel 316 reactor. A solid catalyst similar to the "G" catalyst disclosed in US 6,479,713 or the "HC-1 " catalyst available from Sd Chemie (Louisville, KY) was loaded in the reactor to a final volume of 1000 ml of catalyst. The reactor was jacketed with a hot oil bath to provide for the elevated temperature for reactions and the feed and hydrogen lines were also preheated to the reactor temperature. A solution of a bio-based, substantially pure, 40% USP grade glycerol was fed through the catalyst bed at LHSV ranging from 0.5hr"1 to 2.5hr'1. Hydrogen was supplied at 1200-1600 psi EPO (about 83-110 bar) and was also re-circulated through the reactor at a hydrogen to glycerol feed molar ratio of 5:1. In other embodiments, the hydrogen to glycerol feed molar ratio may be between 1 :1 to 10:1. Tables 5A and 5B in FIGS. 2A and 2B describe the results with hydrogenolysis of 40% USP grade glycerol feed. Between 47.7-96.4% of the glycerol was converted and between 36.3-55.4% of propylene glycol was produced. In addition to propylene glycol, the hydrogenolysis reaction produced 0.04-2.31% unwanted BDOs, which may present a problem for recovery of pure propylene glycol (Table 6). The BDOs were measured using a known gas chromatography analysis method. EPO |
27% | With sodium hydroxide; hydrogen at 196℃; | 3 Stainless Steel 316 reactor. As described in Figure 10, a solid catalyst was loaded in the reactor to a final volume of 1000 ml of catalyst. The reactor was jacketed with a hot oil bath to provide for the elevated temperature for reactions and the feed and hydrogen lines were also preheated to the reactor temperature. A solution of pure glycerol was fed through the catalyst bed at LHSV ranging from 0.5hr"1 to 2.5hr'1. Hydrogen was supplied at 1200 to 1600 psi (82.7 to 110.3 bar) and was also re-circulated through the reactor at a hydrogen to glycerol feed molar ratio of 1 : 1 to 10: 1 , such as at 5: 1.Table 4 describes the results with hydrogenolysis of 40% USP grade glycerol feed. Between 47.7-96.4% of the three-carbon compound glycerol was converted and between 36.3-55.4% of the three-carbon compound propylene glycol was recovered. In addition to propylene glycol, the reaction product contained 0.04-2.31% of the four-carbon butanediol compounds and other non- PG diols, which were recovered from the reaction product (Table 3). |
10% | With sodium hydroxide; hydrogen In water at 150 - 210℃; | 2.25; 2.5; 2.6; 2.27; 2.16; 2.16; 2.26; 2.21; 2.9; 3.6; 3.21; 3.25; 3.16; 3.5; 3.26; 3.27; 3.9; 4.25; 4.6; 4.16; 4.21; 4.5; 4.27; 4.26; 4.9 EXAMPLE 2; Example 2 describes a method to reduce the formation of BDOs and maximize the conversion of glycerol to propylene glycol with a solid phase catalyst such as the “G” catalyst as disclosed in U.S. Pat. No. 6,479,713 or the “HC-1” catalyst available from Sud Chemie (Louisville, Ky.). Hydrogenolysis of a 40% solution of glycerol was carried out substantially as described in Example 1. Table 7 in FIG. 4 describes the conditions used in this Example, and discloses the products produced in this Example.; EXAMPLE 3; Hydrogenolysis of a 40% solution of glycerol was carried out substantially as described in Example 1. The effect of the reaction temperature at constant concentrations of alkali (sodium hydroxide) and constant LHSV on the amount of BDO formed was investigated. Table 8 in FIG. 5 describes the conditions used in this Example, and discloses the products produced in this Example.; EXAMPLE 4; Hydrogenolysis of a 40% solution of glycerol was carried out substantially as described in Example 1. The effect of LHSV of the feed at constant concentration of alkali (sodium hydroxide) and constant on amount of BDO formed was investigated. Table 9 in FIG. 6 describes the conditions used in this Example, and discloses the products produced in this Example. |
With sodium hydroxide; hydrogen In water at 159 - 212℃; | 6.D16-M-423-01; 6.D16-M-423-02; 6.D16-M-423-03; 6.D16-M-423-04; 6.D16-M-423-05; 6.D16-M-423-06; 6.D16-M-423-07; 6.D16-M-424-01; 6.D16-M-424-02; 6.D16-M-424-05; 6.D16-M-425-01; 6.D16-M-425-02; 6.D16-M-425-03; 6.D16-M-425-04; 6.D16-M-425-05; 6.D16-M-425-06 EXAMPLE 6; Hydrogenolysis of a 40% solution of glycerol was carried out substantially as described in Example 1 except that 180 mL of Süd Chemie HC-1 catalyst was used. Table 11 in FIG. 8 describes the conditions used in this Example, and discloses the products produced in this Example. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 38% 2: 1.6% 3: 1% 4: 0.1% | With sodium hydroxide; hydrogen In water at 178 - 198℃; | 1.205 EXAMPLE 1 A series of studies were conducted in a 2000 ml high-pressure Stainless Steel 316 reactor. As described in FIG. 1, a solid catalyst similar to the “G” catalyst disclosed in U.S. Pat. No. 6,479,713 or the “HC-1” catalyst available from Sud Chemie (Louisville, Ky.) was loaded in the reactor to a final volume of 1000 ml of catalyst. The reactor was jacketed with a hot oil bath to provide for the elevated temperature for reactions and the feed and hydrogen lines were also preheated to the reactor temperature. A solution of a bio-based, substantially pure, 40% USP grade glycerol was fed through the catalyst bed at LHSV ranging from 0.5 hr-1 to 2.5 hr-1. Hydrogen was supplied at 1200-1600 psi and was also re-circulated through the reactor at a hydrogen to glycerol feed molar ratio of 5:1. In other embodiments, the hydrogen to glycerol feed molar ratio may be between 1:1 to 10:1. Tables 5A and 5B in FIGS. 2A and 2B describe the results with hydrogenolysis of 40% USP grade glycerol feed. Between 47.7-96.4% of the glycerol was converted and between 36.3-55.4% of propylene glycol was produced. In addition to propylene glycol, the hydrogenolysis reaction produced 0.04-2.31% unwanted BDOs, which may present a problem for recovery of pure propylene glycol (Table 6). The BDOs were measured using a known gas chromatography analysis method. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 47.3% 2: 2.1% 3: 0.7% 4: 0.1% 5: 0.6% | With sodium hydroxide; hydrogen In water at 154 - 229℃; | 1.250; 1.199; 1.180; 1.228; 1.240; 1.164; 1.166; 1.191 EXAMPLE 1 A series of studies were conducted in a 2000 ml high-pressure Stainless Steel 316 reactor. As described in FIG. 1, a solid catalyst similar to the “G” catalyst disclosed in U.S. Pat. No. 6,479,713 or the “HC-1” catalyst available from Sud Chemie (Louisville, Ky.) was loaded in the reactor to a final volume of 1000 ml of catalyst. The reactor was jacketed with a hot oil bath to provide for the elevated temperature for reactions and the feed and hydrogen lines were also preheated to the reactor temperature. A solution of a bio-based, substantially pure, 40% USP grade glycerol was fed through the catalyst bed at LHSV ranging from 0.5 hr-1 to 2.5 hr-1. Hydrogen was supplied at 1200-1600 psi and was also re-circulated through the reactor at a hydrogen to glycerol feed molar ratio of 5:1. In other embodiments, the hydrogen to glycerol feed molar ratio may be between 1:1 to 10:1. Tables 5A and 5B in FIGS. 2A and 2B describe the results with hydrogenolysis of 40% USP grade glycerol feed. Between 47.7-96.4% of the glycerol was converted and between 36.3-55.4% of propylene glycol was produced. In addition to propylene glycol, the hydrogenolysis reaction produced 0.04-2.31% unwanted BDOs, which may present a problem for recovery of pure propylene glycol (Table 6). The BDOs were measured using a known gas chromatography analysis method. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 33.2% 2: 1.5% 3: 0.5% 4: 0.7% | With sodium hydroxide; hydrogen In water at 185 - 205℃; | 1.242 EXAMPLE 1 A series of studies were conducted in a 2000 ml high-pressure Stainless Steel 316 reactor. As described in FIG. 1, a solid catalyst similar to the “G” catalyst disclosed in U.S. Pat. No. 6,479,713 or the “HC-1” catalyst available from Sud Chemie (Louisville, Ky.) was loaded in the reactor to a final volume of 1000 ml of catalyst. The reactor was jacketed with a hot oil bath to provide for the elevated temperature for reactions and the feed and hydrogen lines were also preheated to the reactor temperature. A solution of a bio-based, substantially pure, 40% USP grade glycerol was fed through the catalyst bed at LHSV ranging from 0.5 hr-1 to 2.5 hr-1. Hydrogen was supplied at 1200-1600 psi and was also re-circulated through the reactor at a hydrogen to glycerol feed molar ratio of 5:1. In other embodiments, the hydrogen to glycerol feed molar ratio may be between 1:1 to 10:1. Tables 5A and 5B in FIGS. 2A and 2B describe the results with hydrogenolysis of 40% USP grade glycerol feed. Between 47.7-96.4% of the glycerol was converted and between 36.3-55.4% of propylene glycol was produced. In addition to propylene glycol, the hydrogenolysis reaction produced 0.04-2.31% unwanted BDOs, which may present a problem for recovery of pure propylene glycol (Table 6). The BDOs were measured using a known gas chromatography analysis method. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Example 7Synthesis of PGME Enriched Polyol Esters of Soy OilThis Example sets forth a representative synthesis of a propylene glycol monoester from a vegetable oil and the hydrogenolysis product mixture from the hydrogenolysis of sorbitol.Sorbitol was subjected to hydrogenolysis substantially as set forth in Example 1. The hydrogenolysis product was then subjected to distillation to remove the water. The compositions of the hydrogenolysis product before and after stripping are set forth in Table 7. TABLE 7 Composition of Hydrogenolysis Product Hydrogenolysis product Hydrogenolysis product Compound before stripping (wt %) after stripping (wt %) Sorbitol 6.2% 10.0% Xylitol 2.2% 3.5% Erthyritol 0.8% 1.3% Lactate 1.0% 1.6% Glycerol 10.9% 17.6% <strong>[3068-00-6]1,2,4-Butanetriol</strong> 0.5% 0.8% Ethylene glycol 11.4% 18.4% Propylene glycol 22.3% 36.0% 2,3-Butanediol 1.4% 2.3% 1,3-Butanediol 1.0% 1.6% 1,2-Butanediol 2.5% 4.0% Ethanol 0.4% 0.6% Isopropanol 0.2% 0.3% Water 38.0% 0% Unknown 1.2% 1.9% A 1 liter autoclave reactor was charged with RBD soybean oil (refined, bleached, and deodorized soybean oil, 160 g), the hydrogenolysis product mixture from sorbitol (165 g), potassium acetate (0.08 g), and lithium hydroxide (0.02 g). The reactor headspace was purged with nitrogen. The reactor was pressurized with nitrogen at 350 psi and agitation at 800 rpm was began. The reaction mixture was heated to 240 C. over 1 hour at which time the pressure has increased to 550 psi. The reaction was held at 240 C. for 1.5 hours and then rapidly cooled to room temperature. The contents of the reactor were placed in a separatory funnel and neutralized with 0.5 g of conc. H3PO4, The mixture was extracted with hexanes and the organic layer was washed once with four times its volume of deionized water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated with a rotary evaporator under reduced pressure to give a product having a Lovibond color of 2.9R., 14.0Y. The product composition was 60-81% propylene glycol monoester and 5% propylene glycol diester with an acid value of 21.6. This material may be used as a 100% biobased polyol ester replacement for petroleum derived PGMEs, for example as a coalescent in a latex paint formulation. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Example 8Candle Wax EstersThis Example sets forth a representative synthesis of a waxy propylene glycol monoester from a hydrogenated vegetable oil and the hydrogenolysis product mixture.A 1 L three neck round bottom flask was fitted with a heating mantle, a magnetic stirrer, a reflux condenser, and nitrogen sparge. Sorbitol was subjected to hydrogenolysis to obtain a hydrogenolysis product containing polyols (before stripping) and a composition as recited in Table 7, then heated under vacuum in a rotary evaporator to remove water and lower molecular weight alkyl monohydroxyl alcohols to obtain a stripped mixed polyol sorbitol hydrogenolysis product mixture (Table 7). The reaction vessel was charged with melted soy titer (fully hydrogenated soybean oil, 150 g) and the stripped mixed polyol mixture from the hydrogenolysis of sorbitol (30 g). The mixture was heated to 150 C. with agitation and NaOH (0.18 g) was added to catalyze alcoholysis of the melted soy titer by the polyol mixture. The mixture was heated from 150 C. to 220 C. with nitrogen sparging and good agitation over 1 hour. The product mixture enriched in fatty acid esters of polyols was then quickly cooled and neutralized with cone. H3PO4 (0.55 g). The cooled, neutralized product mixture separated into an upper phase containing the fatty acid esters of polyols and remaining titer esters and an aqueous bottom phase and the top phase solidified at room temperature. The solid top phase was collected and used in as a wax in a biobased candle wax formulation. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydroxide; hydrogen;nickel-rhenium-on-carbon; In water; at 220℃; under 31029.7 - 62059.4 Torr; for 4h;Product distribution / selectivity; | Example 7Synthesis of PGME Enriched Polyol Esters of Soy OilThis Example sets forth a representative synthesis of a propylene glycol monoester from a vegetable oil and the hydrogenolysis product mixture from the hydrogenolysis of sorbitol.Sorbitol was subjected to hydrogenolysis substantially as set forth in Example 1. The hydrogenolysis product was then subjected to distillation to remove the water. The compositions of the hydrogenolysis product before and after stripping are set forth in Table 7. TABLE 7 Composition of Hydrogenolysis Product Hydrogenolysis product Hydrogenolysis product Compound before stripping (wt %) after stripping (wt %) Sorbitol 6.2% 10.0% Xylitol 2.2% 3.5% Erthyritol 0.8% 1.3% Lactate 1.0% 1.6% Glycerol 10.9% 17.6% 1,2,4-Butanetriol 0.5% 0.8% Ethylene glycol 11.4% 18.4% Propylene glycol 22.3% 36.0% 2,3-Butanediol 1.4% 2.3% 1,3-Butanediol 1.0% 1.6% 1,2-Butanediol 2.5% 4.0% Ethanol 0.4% 0.6% Isopropanol 0.2% 0.3% Water 38.0% 0% Unknown 1.2% 1.9% A 1 liter autoclave reactor was charged with RBD soybean oil (refined, bleached, and deodorized soybean oil, 160 g), the hydrogenolysis product mixture from sorbitol (165 g), potassium acetate (0.08 g), and lithium hydroxide (0.02 g). The reactor headspace was purged with nitrogen. The reactor was pressurized with nitrogen at 350 psi and agitation at 800 rpm was began. The reaction mixture was heated to 240 C. over 1 hour at which time the pressure has increased to 550 psi. The reaction was held at 240 C. for 1.5 hours and then rapidly cooled to room temperature. The contents of the reactor were placed in a separatory funnel and neutralized with 0.5 g of conc. H3PO4, The mixture was extracted with hexanes and the organic layer was washed once with four times its volume of deionized water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated with a rotary evaporator under reduced pressure to give a product having a Lovibond color of 2.9R., 14.0Y. The product composition was 60-81% propylene glycol monoester and 5% propylene glycol diester with an acid value of 21.6. This material may be used as a 100% biobased polyol ester replacement for petroleum derived PGMEs, for example as a coalescent in a latex paint formulation. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydroxide; hydrogen;nickel-rhenium-on-carbon; In water; at 220℃; under 31029.7 - 62059.4 Torr; for 4h;Product distribution / selectivity; | Example 5Polyester Polymerization ReactionThis Example sets forth a representative polyester polymerization reaction using a hydrogenolysis product mixture obtained by hydrogenolysis of glycerol or sorbitol according to certain embodiments disclosed herein.A composition enriched in compounds containing two hydroxyl groups was obtained by hydrogenolysis of glycerol by passing a 40% solution of crude glycerol obtained as a by-product of a palm biodiesel synthesis through a reactor substantially as set forth in Example 1. The reactor product was dewatered by distillation. A composite was prepared by combining four dewatered glycerol hydrogenolysis product samples to yield a mixture of polyols having the composition: 75.5% propylene glycol, 4.5% ethylene glycol, 1.8% lactic acid, 12.2% glycerol, and 0.5% water. This composition was subjected to short path distillation to reduce the water content to 0.15% and the undi stilled residue enriched in compounds containing two hydroxyl groups (Mixture 1) had the following composition: 75.8% propylene glycol, 4.7% ethylene glycol, 1.8% lactic acid, 1.3% 2,3-butanediol, and 13.8% glycerol.In one study, the composition enriched in compounds containing two hydroxyl groups is combined with an equimolar quantity of diisocyanate to make a predominantly linear polyurethane using the procedure set forth by Frisch (?Fundamental Chemistry and Catalysis of Polyirrethanes,? Frisch, K. C., in Polyurethane Technology, Paul Bruins, ed., Interscience Publishers, New York, 1969, the disclosure of which is incorporated in its entirety by reference herein).In a second study, the hydrogenolysis product from the hydrogenolysis of sorbitol containing, by weight percent, 0.25% glucose; 0.25% xylose; 0.25% arabinose; 1.74% arabitol; 1.24% erythritol; 6.47% lactate; 10.45% glycerol; 1.00% 1,2,4-butanetriol; 42.54% ethylene glycol; 32.34% propylene glycol; 1.00% 2,3-butanediol; 0.50% 1,3-butanediol; and 2.00% 1,2-butanediol is combined with a diisocyanate at 100 C. to make a branched polymer.The polymers resulting from study 1 and 2 will be suitable for use in fibers, hard and soft elastomers, coatings and adhesives, flexible and rigid foams, and thermoplastics and thermosetting plastics.; Example 6Sythesis of a Polyol EsterThis Example sets forth a representative synthesis of a polyol ester mixture from vegetable oils and the hydrogenolysis product mixture obtained by hydrogenolysis of sorbitol.A polyol sample (200 g) from the hydrogenolysis of sorbitol containing, by weight percent, 0.25% glucose; 0.25% xylose; 0.25% arabinose; 1.74% arabitol; 1.24% erythritol; 6.47% lactate; 10.45% glycerol; 1.00% 1,2,4-butanetriol; 42.54% ethylene glycol; 32.34% propylene glycol; 1.00% 2,3-butanediol; 0.5% 1,3-butanediol; and 2.00% 1,2-butanediol was combined with dried corn oil (200 g) and sodium inethoxide (1.0 g) in a 1000 mL round bottom flask. The mixture was heated with agitation at 120 C. for 4 hours. The product was cooled and neutralized with citric acid. Hexane was added and the organic layer was recovered. The hexane was removed from the product using a rotary evaporator under reduced pressure to give a residue of polyol esters of corn oil fatty acids, If desired, the product can be stripped using a wiped film evaporator/miiolecular still at 90 C., 0.6 millibars, 270 rpm and a flow rate of 4 mL/min. The resulting polyol ester composition is suitable for use as a 100% biobased replacement for a petroleum derived propylene glycol monoester. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 56% 2: 4.37% | With sodium hydroxide; hydrogen at 193 - 216℃; | 7 Hydrogenolysis of a 40% solution of the polyhydric alcohol glycerol was carried out substantially as described in Example 3 except that 180 mL of Sd Chemie HC-1 catalyst was used. The effect of increasing temperature on BDO formation was investigated. Higher temperatures resulted in formation of greater levels of BDO formation, thus the formation of BDOs was minimized when the reaction was operated at lower temperatures (176-193°C, Table 5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With iridium (III) chloride trihydrate; oxygen; sodium carbonate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In 1,3,5-trimethyl-benzene at 169℃; for 15h; | |
79% | With zinc(II) oxide; Rh/Al2O3; toluene-4-sulfonic acid In 1-methyl-pyrrolidin-2-one at 175℃; Sealed tube; | |
73% | With [Ru(CO)2(4,5-bis(diphenylphosphino)-9,9-dimethyl-9H-xanthene)]2; [Ru(CO)2(4,5-bis(diphenylphosphino)-9,9-dimethyl-9H-xanthene)]2; toluene-4-sulfonic acid In tert-Amyl alcohol at 120℃; regioselective reaction; |
72% | With ruthenium(III) chloride monohydrate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene at 110 - 170℃; for 48h; | |
72% | With tetrafluoroboric acid diethyl ether; [(PCy3)(CO)RuH]4(μ-O)(μ-OH)2}; cyclopentene In 1,4-dioxane at 130℃; for 14h; Sealed tube; Schlenk technique; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | In n-heptane for 7h; Reflux; | 1.e General acetalysation procedure of 2,2,6-trimethyl-cyclohexane carbaldehyde 2,2,6-trimethyl-cyclohexane carbaldehyde (15.4 g, 0.1 mol, 1 eq.), 1,2 or 1,3-diol (0.15 mol, 1.5 eq.), /?-ptoluene sulfonic acid monohydrate (0.1 g, 0.5 mmol, 0.005 eq.) and heptane (100 ml) were loaded altogether in a 250 ml flask equipped with a Dean- Stark apparatus and the mixture was refluxed for 7 hours. It was then cooled down, washed with water and concentrated under vacuum. The obtained crude product was then purified by distillation.According to the above general procedure, using the corresponding diol, the title compound was obtained in 89% yield.1H NMR (360.1 MHz): 5.27 (broad s), 5.15 (s), 5.14 (s), 4.90 ( broad s), 4.37-4.00 (m), 3.66-3.51 (m), 1.85-1.55 (m), 1.50-1.40 (m), 1.35-1.27 (m), 1.25-1.12 (m), 1.05- 0.92 (m), 0.90-0.82 (m) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With toluene-4-sulfonic acid In neat (no solvent) at 175℃; for 48h; | General procedure for indole synthesis of aniline by diols catalyzed by nickel supported on silica General procedure: Diol (10.9 mmol, 1 equiv.), 65 wt% Ni/SiO2-Al2O3 (198 mg, 0.2 equiv.), aniline (21.9 mmol, 2equiv.) and PTSA (209 mg, 0.1 equiv.) were introduced in that order in a 50 mL round bottom flask, which was then equipped with an open condenser. The mixture was stirred at 175 °C for 48 h. After this duration, a sample of the crude mixture was diluted in ethyl acetate, filtered and analyzed by GC. 2-3 g of silica was added to the crude mixture, which was then concentrated under reduced pressure and purified by flash chromatography (ethylacetate/cyclohexane : 5 : 95) to afford the desired product. |
51% | With ruthenium(III) chloride monohydrate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene at 110 - 170℃; for 25h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
platinum on carbon; In water; for 3h;Direct aqueous phase reforming; | Direct aqueous phase reforming (APR) experiments were conducted in 100-ml stirred reactors with draft-tube gas-induction impeller (Parr Series 4590). Reaction tests for direct bio-based feedstock aqueous phase reforming (APR) entailed filling the reactor with 60-grams of solvent (deionized water, or a mixture of DI water and isopropanol (IPA), and 3-3.5 grams of bio-based feedstock comprising biomass (bagasse, or pine sawdust)). One (1) gram of acetic acid was optionally charged to facilitate biomass hydrolysis.[0098] Bagasse was milled via a 1-mm grate. Dry, debarked Loblolly pine was ground via blender (Thomas Scientific of Swedesboro, NJ) and sieved to less than 30 mesh. Dry solids fraction was determined by vacuum drying at 80 °C to 82 °C. One gram of aqueous phase reforming catalyst (reduced 5percent Pt/C catalyst at 50percent moisture, or powdered 1.9percent Pt/A1203) was charged to the reactor, which was charged with 4200 kPa of hydrogen or nitrogen. To minimize degradation of hydrolysate to heavy ends, each reactor was typically heated with a staged temperature sequence of one hour at, 160 °C, 190 °C, 225 °C, and finally 250 °C, before leaving overnight at the final setpoint.[0099] Comparison tests were also conducted with glucose or sorbitol fed directly to the reaction in place of biomass, to simulate and quantify conversion of model hydrolysate to APR intermediates. Glucose is one of the sugars readily leached from biomass in hot water, while sorbitol is readily formed via hydrogenation of glucose, where platinum or other catalysts capable of hydrogenation are present.[00100] A batch reaction time of 20 hours under these conditions corresponds to a weight hourly space velocity (g-feed/g-catalyst/h) of about 3, for a comparable continuous flow reactor. A 0.5-micron sintered metal filter attached to a dip tube allowed liquid samples to be taken throughout the course of reaction, without loss of biomass or catalyst. Samples were analyzed by an HPLC method based on combined size and ion exclusionchromatography, to determine unreacted sorbitol, and amount of C3 and smaller polyols formed: glycerol (Gly), ethylene glycol (EG), and 1,2-propylene glycol (PG). Additional GC analysis via a moderate polarity DB-5 column were conducted to assess formation of C6 and lighter oxygenates (e.g., ketones, aldehydes, alcohols), as well as alkane and alkene products. A separate GC equipped with thermal conductivity and flame ionization (FID) detectors for refinery gas analysis, were used for detection of H2, C02, and light alkanes C1-C5. GC-mass spec was used to characterize select APR reaction product mixtures. Examples 1-3[00101] Batch APR reactions with sugar cane bagasse as biomass feed, and with a comparison of 25percent sorbitol as feed, were performed as described above. 1.7percent acetic acid was added to simulate catalysis of hydrolysis by recycle acid. Products formed from this concentration of acetic acid were subtracted from total product formation, to calculate the net production of liquid fuels from bagasse. This result shown in Table 1 shows the critical importance of concerted APR reaction with hydrolysis of biomass. In the absence of concerted aqueous phase reforming, the hydrolysate undergoes irreversible degradation (presumably to heavy ends), and cannot be reverted to liquid fuels upon subsequent APR and condensation. Converted reaction may be effected by direct inclusion of APR catalyst in the hydrolysis reactor, or via a pump around loop to recirculate liquid between a biomass contactor, and an APR catalytic reactor. Table 1: Direct APR of Biomass |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With N-chloro-succinimide; (neocuproine)Pd(OAc)2; sodium acetate In acetonitrile at 55℃; for 24h; Molecular sieve; | |
60 %Chromat. | With palladium 10% on activated carbon; oxygen; sodium acetate; potassium iodide In 1,2-dimethoxyethane at 100℃; for 8h; Autoclave; Inert atmosphere; | General procedure foroxidative carbonylation of diols:- General procedure: In a 100 mL stainless steel autoclave, diol (5mmol), catalyst (10 % Pd/C, 0.5 mol %), KI (0.09 mmol), base (1.25 mmol),solvent (10 mL) were added. The autoclave was closed, flushed with nitrogen,pressurized with O2 (33 psi) and CO (167 psi) and reaction mixturewas stirred with a mechanical starrer (520 rpm) at desired temperature forappropriate time period. After completion of reaction, the reactor was thencooled to room temperature, degassed carefully and opened. The reaction mixturewas filtered and the solvent was evaporated under vacuum. The reaction mixturewas analyzed by GC analysis (Perkin-Elmer, Clarus 400) equipped with a flameionization detector (FID) and a capillary column (Elite-1, 30 m × 0.32 mm ×0.25 μm). Purification of residue was carried out by column chromatography(silica gel 100-200 mesh, petroleum ether/ethyl acetate) to afford thecorresponding products in good to excellent yield. The prepared compounds werecharacterized by 1H NMR (Varian 200 MHz NMR Spectrometer), 13CNMR spectra (50 MHz) and GC-MS (Shimadzu GC-MS QP 2010) (Rtx-17, 30 m × 25mmID,film thickness 0.25 µm df) (column flow- 2 mL/min, 80 °C to 240 °C at 10°/min.rise.) which were consistent with those reported in the literature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With toluene-4-sulfonic acid; trimethyl orthoformate at 60℃; for 6h; Inert atmosphere; | I.1-1 No. I.1-1: Ethyl (2Z)-3-[(5-hydroxy-4,4′,5′,6-tetramethylspiro[bicyclo[4.1.0]hept-3-en-2,2′-[1,3]dioxolan]-5-yl)ethynyl]hex-2-enoate Dimethylbenzoquinone (5.00 g, 36.72 mmol) was dissolved in 2,3-butanediol (75 ml) in a round-bottom flask under argon, and trimethyl orthoformate (12.05 ml, 110.17 mmol) and p-toluenesulfonic acid (0.44 g, 2.57 mmol) were added. The resulting reaction mixture was stirred at 60° C. for 6 h. After cooling to room temperature, water and toluene were added and the aqueous phase was extracted repeatedly with toluene. The combined organic phases were dried over magnesium sulfate, filtered and concentrated under reduced pressure. By column chromatography purification of the resulting crude product (ethyl acetate/heptane gradient), 2,3,7,9-tetramethyl-1,4-dioxaspiro[4.5]deca-6,9-dien-8-one (7.00 g, 92% of theory) was obtained. |
92% | With toluene-4-sulfonic acid; trimethyl orthoformate at 60℃; for 6h; Inert atmosphere; | I.2-45 Dimethylbenzoquinone (5.00 g, 36.72 mmol) was dissolved in 2,3-butanediol (75 ml) in a round-bottom flask under argon, and trimethyl orthoformate (12.05 ml, 110.17 mmol) and p-toluenesulfonic acid (0.44 g, 2.57 mmol) were added. The resulting reaction mixture was stirred at 60° C. for 6 h. After cooling to room temperature, water and toluene were added and the aqueous phase was extracted repeatedly with toluene. The combined organic phases were dried over magnesium sulfate, filtered and concentrated under reduced pressure. By column chromatography purification of the resulting crude product (ethyl acetate/heptane gradient), 2,3,7,9-tetramethyl-1,4-dioxaspiro[4.5]deca-6,9-dien-8-one (7.00 g, 92% of theory) was obtained. |
92% | With toluene-4-sulfonic acid; trimethyl orthoformate In 1,4-dioxane at 60℃; for 6h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With toluene-4-sulfonic acid; trimethyl orthoformate In toluene at 50℃; for 7h; Inert atmosphere; | I.1-145 2,2,6-Trimethyl-1,4-cyclohexanedione (15.40 g, 101.19 mmol) was dissolved in 2,3-butanediol (90 ml) and abs. toluene (90 ml) in a round-bottom flask under argon, and trimethyl orthoformate (33.21 ml, 303.56 mmol) and p-toluenesulfonic acid (1.22 g, 7.08 mmol) were added. The resulting reaction mixture was stirred at 50° C. for 7 h. After cooling to room temperature, water and toluene were added and the aqueous phase was extracted repeatedly with toluene. The combined organic phases were dried over magnesium sulfate, filtered and concentrated under reduced pressure. By column chromatography purification of the resulting crude product (ethyl acetate/heptane gradient), 2,3,7,9,9-pentamethyl-1,4-dioxaspiro[4.5]dec-6-en-8-one (20.01 g, 88% of theory) was obtained. |
88% | With toluene-4-sulfonic acid; trimethyl orthoformate In toluene at 50℃; for 7h; Inert atmosphere; | I.1-1 No. I.1-1: Ethyl (2Z)-3-[(8-hydroxy-2,3,7,9,9-pentamethyl-1,4-dioxaspiro[4.5]dec-6-en-8-yl)ethynyl]hex-2-enoate No. I.1-1: Ethyl (2Z)-3-[(8-hydroxy-2,3,7,9,9-pentamethyl-1,4-dioxaspiro[4.5]dec-6-en-8-yl)ethynyl]hex-2-enoate In a round-bottom flask under argon, 2,2,6-trimethyl-1,4-cyclohexanedione (15.40 g, 101.19 mmol) was dissolved in 2,3-butanediol (90 ml) and abs. toluene (90 ml), and trimethyl orthoformate (33.21 ml, 303.56 mmol) and p-toluenesulfonic acid (1.22 g, 7.08 mmol) were added. The resulting reaction mixture was stirred at 50° C. for 7 h. After cooling to room temperature, water and toluene were added and the aqueous phase was extracted repeatedly with toluene. The combined organic phases were dried over magnesium sulfate, filtered and concentrated under reduced pressure. By column chromatography purification of the resulting crude product (ethyl acetate/heptane gradient), 2,3,7,9,9-pentamethyl-1,4-dioxaspiro[4.5]dec-6-en-8-one (20.01 g, 88% of theory) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With toluene-4-sulfonic acid; trimethyl orthoformate at 50℃; for 6h; Inert atmosphere; | I.1-1105 2,6-Dimethyl-6-(trifluoromethyl)cyclohex-2-ene-1,4-dione (520 mg, 2.52 mmol) was dissolved in 2,3-butanediol (4 ml) under argon, and trimethyl orthoformate (0.83 ml, 7.57 mmol) and p-toluenesulfonic acid (30 mg, 0.18 mmol) were added. The resulting reaction mixture was stirred at 50° C. for 6 h. After cooling to room temperature, water and toluene were added and the aqueous phase was extracted repeatedly with toluene. The combined organic phases were dried over magnesium sulfate, filtered and concentrated under reduced pressure. By column chromatography purification of the resulting crude product (ethyl acetate/heptane gradient), 2,3,7,9-tetramethyl-9-(trifluoromethyl)-1,4-dioxaspiro[4.5]dec-6-en-8-one (700 mg, 98% of theory) was obtained |
98% | With toluene-4-sulfonic acid; trimethyl orthoformate at 50℃; for 6h; Inert atmosphere; | I.1-521 No. I.1-521: Ethyl (2E)-5-[8-hydroxy-2,3,7,9-tetramethyl-9-(trifluoromethyl)-1,4-dioxa-spiro[4.5]dec-6-en-8-yl]-3-(trifluoromethyl)pent-2-en-4-ynoate 2,6-Dimethyl-6-(trifluoromethyl)cyclohex-2-ene-1,4-dione (520 mg, 2.52 mmol) was dissolved in 2,3-butanediol (4 ml) under argon, and trimethyl orthoformate (0.83 ml, 7.57 mmol) and p-toluenesulfonic acid (30 mg, 0.18 mmol) were added. The resulting reaction mixture was stirred at 50° C. for 6 h. After cooling to room temperature, water and toluene were added and the aqueous phase was extracted repeatedly with toluene. The combined organic phases were dried over magnesium sulfate, filtered and concentrated under reduced pressure. By column chromatography purification of the resulting crude product (ethyl acetate/heptane gradient), 2,3,7,9-tetramethyl-9-(trifluoromethyl)-1,4-dioxaspiro[4.5]dec-6-en-8-one (700 mg, 98% of theory) was obtained. |
98% | With toluene-4-sulfonic acid; trimethyl orthoformate In 1,4-dioxane at 50℃; for 6h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With rhenium oxide-modified Ir/SiO2 In water at 179.84℃; for 1h; Autoclave; Green chemistry; | ||
With hydrogen at 350℃; for 5h; Flow reactor; | 2.2. Catalytic reaction General procedure: The catalytic reaction was conducted in a fixed-bed flow reactor under atmospheric pressure of H2 carrier gas with a flow rateof 80 cm3min-1at a temperature of 300-400 °C. After the catalyst(1.0 g) bed had been heated at the prescribed reaction temperature for 1 h, the reactant 2,3-BDO was fed through the reactor top at aliquid feed rate of 11.8 mmol h-1. The liquid effluent was collected hourly at 0 °C and analyzed by gas chromatography (FID-GC-8A,Shimadzu, Japan) with a 60-m capillary column (InertCapWAX-HT). The products were identified by gas chromatography with a mass spectrometer (GCMS-QP5050A, Shimadzu, Japan) with a 30-m capillary column (DB-WAX). The catalytic activity was evaluated by averaging the conversion and selectivity, defined as mol%, dataof the initial 5 h. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Au-Pd/carbon catalyst; oxygen In water at 100℃; for 24h; | Butanediol oxidation General procedure: Reactions were carried out using a Radley’s low pressure glass reactor (50 ml). A butanediol in water (20 ml, 0.6 M) and the catalyst(butanediol/metal ratio2000) were added into the reactor,which was then pressurized with oxygen (3 bar). The reaction mixture was heated to 100 C for 24 h under constant stirring(1000 rpm), then cooled to room temperature and analyzed. 1H-NMR spectroscopy was used for product identification; spectrawere acquired over a 16 scan period using a Bruker 400 MHz DPXsystem with a 5 mm auto tune broadband probe. All samples were prepared as dilute solutions in D2O. Carbon mass balances were calculated and were between 96 and 104%. Blank reactions have also been carried out with no oxidation activity detected in the absence of catalyst or with the KB-B carbon support. | |
1: 86 %Spectr. 2: 6 %Spectr. 3: 8 %Spectr. | With oxygen In water at 100℃; for 24h; | 4.2 Butanediol oxidation General procedure: (0017) Reactions were carried out using a Radley's low pressure glass reactor (50ml). A butanediol in water (20ml, 0.6M) and the catalyst (butanediol/metal ratio=2000) were added into the reactor, which was then pressurized with oxygen (3bar). The reaction mixture was heated to 100°C for 24h under constant stirring (1000rpm), then cooled to room temperature and analyzed. 1H NMR spectroscopy was used for product identification; spectra were acquired over a 16 scan period using a Bruker 400MHz DPX system with a 5mm auto tune broadband probe. All samples were prepared as dilute solutions in D2O. Carbon mass balances were calculated and were between 96 and 104%. Blank reactions have also been carried out with no oxidation activity detected in the absence of catalyst or with the KB-B carbon support. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With oxygen In water at 100℃; for 24h; | Butanediol oxidation General procedure: Reactions were carried out using a Radley’s low pressure glass reactor (50 ml). A butanediol in water (20 ml, 0.6 M) and the catalyst(butanediol/metal ratio2000) were added into the reactor,which was then pressurized with oxygen (3 bar). The reaction mixture was heated to 100 C for 24 h under constant stirring(1000 rpm), then cooled to room temperature and analyzed. 1H-NMR spectroscopy was used for product identification; spectrawere acquired over a 16 scan period using a Bruker 400 MHz DPXsystem with a 5 mm auto tune broadband probe. All samples were prepared as dilute solutions in D2O. Carbon mass balances were calculated and were between 96 and 104%. Blank reactions have also been carried out with no oxidation activity detected in the absence of catalyst or with the KB-B carbon support. | |
1: 89 %Spectr. 2: 7 %Spectr. | With oxygen In water at 100℃; for 24h; | 4.2 Butanediol oxidation General procedure: (0017) Reactions were carried out using a Radley's low pressure glass reactor (50ml). A butanediol in water (20ml, 0.6M) and the catalyst (butanediol/metal ratio=2000) were added into the reactor, which was then pressurized with oxygen (3bar). The reaction mixture was heated to 100°C for 24h under constant stirring (1000rpm), then cooled to room temperature and analyzed. 1H NMR spectroscopy was used for product identification; spectra were acquired over a 16 scan period using a Bruker 400MHz DPX system with a 5mm auto tune broadband probe. All samples were prepared as dilute solutions in D2O. Carbon mass balances were calculated and were between 96 and 104%. Blank reactions have also been carried out with no oxidation activity detected in the absence of catalyst or with the KB-B carbon support. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 61.4% 2: 24.8% | In water at 500℃; | 22 Pyroprobe Evaluation of Catalysts General procedure: The feedstock was 10 wt % BDO (Aldrich) in deionized (DI) water. The catalyst (2 mg of powder) was loaded into a quartz tube (25 mm long×1.9 mm I.D.; open at both ends), and held in position using a quartz wool plug on both ends of the powder layer. Approximately 1 μL of feed solution was subsequently dispensed onto the back quartz wool plug then loaded into the pyroprobe wand with the liquid-containing end down, so that upon heating the liquid feed vapors would be carried through the catalyst bed.After the tube was loaded into the pyroprobe wand, the end of the wand was inserted into the pyroprobe unit and sealed. Helium carrier gas flowed through the probe wand and over the quartz wool plugs and catalyst. Upon initiation of the unit, a heating coil encircling the quartz tube, rapidly heated the tube and its contents to 600° C. and maintained it at that temperature for usually 15 seconds. Carrier gas flows were typically 20 cc/m of He through the pyroprobe. Reactant and product vapors were rapidly carried out of the quartz tube and adsorbed onto a Carbopack bed at 40° C., then later desorbed from the adsorbent bed at 300° C. The desorbed products were carried into the GC/MS unit for separation and analysis. Area percent reports were generated for percent conversion of BDO and product selectivity to 1,3 butadiene, methyl vinyl carbinol, MEK, and isobutyraldehyde (IBA). Aldrich BDO was a mixture of d/l and meso isomers. Early analyses integrated over both isomers (reported as BDO) until method improvements allowed separate quantification |
With scandium(III) oxide; hydrogen at 425℃; for 5h; Flow reactor; | Catalytic reaction General procedure: The dehydration of 2,3-BDO was carried out in a fixed-bed tubu-lar flow reactor under atmospheric pressure of H2with a flow rateof 45 cm3min-1at a prescribed temperature. Prior to the reaction,a catalyst (1.0 g) was preheated in an H2flow at the prescribedtemperature for 1 h. After the catalyst bed had been preheated, 2,3-BDO was fed through the reactor top at a feed rate of 1.06 g h-1(11.8 mmol h-1). The liquid effluent collected every hour was ana-lyzed by gas chromatography (GC-8A, Shimadzu, Japan) with a60-m capillary column (DB-WAX). The products were identified bygas chromatography with a mass spectrometer (GCMS-QP5050A,Shimadzu) and a 30-m capillary column (DB-WAX). Gaseous prod-ucts such as BD and butene isomers were analyzed by on-line gaschromatography (GC-8A, Shimadzu) with a 6-m packed column column(VZ-7). The catalytic activity was evaluated by averaging the con-version and selectivity data in the initial 5 h. Both the conversion of2,3-BDO and the selectivity to each product were defined as mol%.The above-mentioned description is essentially the same as thosedescribed in the previous work [32,36,37].In Section 3.4, the dehydration of MEK and 3B2OL was alsoexamined in the same way as the 2,3-BDO dehydration in order toconfirm an intermediate product in the dehydration from 2,3-BDOto BD. In Section 3.5, the dehydration of 2,3-BDO was also inves-tigated over two different catalysts packed in the tubular reactor,which consisted of 1.0 g of Al2O3placed in a lower bed with 6 mmheight and 1.0 g of Sc2O3placed in an upper bed with 4 mm height,to establish the efficient BD formation | |
With lutetium(III) oxide; hydrogen at 425℃; for 5h; Flow reactor; | Catalytic reaction General procedure: The dehydration of 2,3-BDO was carried out in a fixed-bed tubu-lar flow reactor under atmospheric pressure of H2with a flow rateof 45 cm3min-1at a prescribed temperature. Prior to the reaction,a catalyst (1.0 g) was preheated in an H2flow at the prescribedtemperature for 1 h. After the catalyst bed had been preheated, 2,3-BDO was fed through the reactor top at a feed rate of 1.06 g h-1(11.8 mmol h-1). The liquid effluent collected every hour was ana-lyzed by gas chromatography (GC-8A, Shimadzu, Japan) with a60-m capillary column (DB-WAX). The products were identified bygas chromatography with a mass spectrometer (GCMS-QP5050A,Shimadzu) and a 30-m capillary column (DB-WAX). Gaseous prod-ucts such as BD and butene isomers were analyzed by on-line gaschromatography (GC-8A, Shimadzu) with a 6-m packed column column(VZ-7). The catalytic activity was evaluated by averaging the con-version and selectivity data in the initial 5 h. Both the conversion of2,3-BDO and the selectivity to each product were defined as mol%.The above-mentioned description is essentially the same as thosedescribed in the previous work [32,36,37].In Section 3.4, the dehydration of MEK and 3B2OL was alsoexamined in the same way as the 2,3-BDO dehydration in order toconfirm an intermediate product in the dehydration from 2,3-BDOto BD. In Section 3.5, the dehydration of 2,3-BDO was also inves-tigated over two different catalysts packed in the tubular reactor,which consisted of 1.0 g of Al2O3placed in a lower bed with 6 mmheight and 1.0 g of Sc2O3placed in an upper bed with 4 mm height,to establish the efficient BD formation |
With scandium(III) oxide; hydrogen at 425℃; for 5h; Flow reactor; | ||
With gadolinium(III) phosphate at 300℃; Inert atmosphere; | 10 EXAMPLE 10 (0145) The phosphates of Lanthanum, Neodymium and Gadolinium have been tested as catalysts in the dehydration of butane-2,3-ol (2,3-BDO). (0146) The reaction conditions are as follows: WHSV=2.98 h-1; mcata=101 mg; contact time (W/F)=30.28 gcata·h·mol2,3-BDO-1; N2=100 ml·min-1 and a gaseous mixture butane-2,3-ol/N2=1/80.3. (0147) The catalytic results that have been obtained are shown in the following Table 8. | |
With alumina In water at 350℃; Inert atmosphere; Gas phase; | ||
With Amorphous Calcium Phosphate Catalyst (CPC-10) at 360℃; Gas phase; Flow reactor; | 1 Examples 1 to 6 and Comparative Examples 1 to 6 Examples 1 to 6 and Comparative Examples 1 to 6 (0082) Using the catalysts of Preparation Examples 1 to 6 and Comparative Preparation Examples 1 to 3, conversion reaction of 2,3-butanediol (2,3-BDO) into 1,3-butadiene (1,3-BD) according to embodiments of the present invention was carried out. (0083) Comparative Example 4 was evaluated under the same reaction conditions as in Comparative Preparation Examples 1 to 3, with the exception that a commercially available reagent calcium pyrophosphate was used after thermal treatment at 500° C., instead of the catalysts of Comparative Preparation Examples 1 to 3. (0084) Comparative Example 5 was evaluated under the same reaction conditions as in Comparative Preparation Examples 1 to 3, with the exception that a typical acid catalyst H-ZSM-5 was used, instead of the catalysts of Comparative Preparation Examples 1 to 3. (0085) Comparative Example 6 was evaluated under the same reaction conditions as in Comparative Preparation Examples 1 to 3, with the exception that a commercially available base catalyst CaO was used, instead of the catalysts of Comparative Preparation Examples 1 to 3. (0086) Dehydration of 2,3-butanediol was evaluated using a self-made continuous flow reactor having a fixed catalyst bed, and the feed before reaction was passed through a preheating zone at 300° C., and allowed to react under conditions of atmospheric pressure, N2 at 10 cc/min, 360° C., and WHSV=0.5 h-1. (0087) The results of evaluation of the prepared catalysts are shown in Table 1 below. All the products obtained after catalysis were vaporized and analyzed via on-line gas chromatography (GC). The main products were composed of 1,3-butadiene, methyl ethyl ketone (MEK) and H2O, and small amounts of byproducts included butene, 2-methylpropanealdehyde, 3-buten-2-ol, and 2-methylpropanol. The 2,3-butanediol conversion, 1,3-butadiene selectivity and methyl ethyl ketone selectivity were calculated based on mole balance. Supposing that 2,3-butanediol is 100% converted into 1,3-butadiene upon calculation based on mass %, about 40 wt % of water is theoretically produced. The amount of H2O in the evaluated catalyst was measured to be about 2030 wt %. | |
With alumina In water at 450℃; Inert atmosphere; | 2.2. Catalytic reaction The dehydration of BDO was carried out in a fixed-bed Hastelloy tube reactor of 0.30500 inner diameter. Since Hastelloy is apotential catalyst, blank tests were performed in an empty tubewith the same conditions as the actual catalytic activity tests. Forall catalyst activity experiments, 0.5 g of catalyst was placed inthe reactor between two plugs of quartz wool. Liquid phase BDO(2 g/100 mL) aqueous solution was fed at a flowrate of 0.1 mL/min through a micro pump (Eldex) to the top of the reactorthrough a nebulizer, where it was mixed with 100 mL/min of N2(regulated by a Brooks 5850E mass flow controller), which is usedas an internal standard for product analysis. The approximate residencetime is 0.14 s. The reactor was heated by heating tape. Thetemperature was measured by a K-type thermocouple, and a controllerwas used to ensure that temperature was held constant atthe desired value. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 45.4% 2: 17.6% 3: 12.6% | In water at 500℃; | 15 Pyroprobe Evaluation of Catalysts General procedure: The feedstock was 10 wt % BDO (Aldrich) in deionized (DI) water. The catalyst (2 mg of powder) was loaded into a quartz tube (25 mm long×1.9 mm I.D.; open at both ends), and held in position using a quartz wool plug on both ends of the powder layer. Approximately 1 μL of feed solution was subsequently dispensed onto the back quartz wool plug then loaded into the pyroprobe wand with the liquid-containing end down, so that upon heating the liquid feed vapors would be carried through the catalyst bed.After the tube was loaded into the pyroprobe wand, the end of the wand was inserted into the pyroprobe unit and sealed. Helium carrier gas flowed through the probe wand and over the quartz wool plugs and catalyst. Upon initiation of the unit, a heating coil encircling the quartz tube, rapidly heated the tube and its contents to 600° C. and maintained it at that temperature for usually 15 seconds. Carrier gas flows were typically 20 cc/m of He through the pyroprobe. Reactant and product vapors were rapidly carried out of the quartz tube and adsorbed onto a Carbopack bed at 40° C., then later desorbed from the adsorbent bed at 300° C. The desorbed products were carried into the GC/MS unit for separation and analysis. Area percent reports were generated for percent conversion of BDO and product selectivity to 1,3 butadiene, methyl vinyl carbinol, MEK, and isobutyraldehyde (IBA). Aldrich BDO was a mixture of d/l and meso isomers. Early analyses integrated over both isomers (reported as BDO) until method improvements allowed separate quantification |
1: 22% 2: 20.3% 3: 9.7% | With scandium(III) oxide In water at 700℃; | 97 Pyroprobe Evaluation of Catalysts General procedure: The feedstock was 10 wt % BDO (Aldrich) in deionized (DI) water. The catalyst (2 mg of powder) was loaded into a quartz tube (25 mm long×1.9 mm I.D.; open at both ends), and held in position using a quartz wool plug on both ends of the powder layer. Approximately 1 μL of feed solution was subsequently dispensed onto the back quartz wool plug then loaded into the pyroprobe wand with the liquid-containing end down, so that upon heating the liquid feed vapors would be carried through the catalyst bed.After the tube was loaded into the pyroprobe wand, the end of the wand was inserted into the pyroprobe unit and sealed. Helium carrier gas flowed through the probe wand and over the quartz wool plugs and catalyst. Upon initiation of the unit, a heating coil encircling the quartz tube, rapidly heated the tube and its contents to 600° C. and maintained it at that temperature for usually 15 seconds. Carrier gas flows were typically 20 cc/m of He through the pyroprobe. Reactant and product vapors were rapidly carried out of the quartz tube and adsorbed onto a Carbopack bed at 40° C., then later desorbed from the adsorbent bed at 300° C. The desorbed products were carried into the GC/MS unit for separation and analysis. Area percent reports were generated for percent conversion of BDO and product selectivity to 1,3 butadiene, methyl vinyl carbinol, MEK, and isobutyraldehyde (IBA). Aldrich BDO was a mixture of d/l and meso isomers. Early analyses integrated over both isomers (reported as BDO) until method improvements allowed separate quantification |
With Sc1.5Yb0.5O3; hydrogen at 411℃; for 5h; Flow reactor; | Catalytic reaction General procedure: The dehydration of 2,3-BDO was carried out in a fixed-bed tubu-lar flow reactor under atmospheric pressure of H2with a flow rateof 45 cm3min-1at a prescribed temperature. Prior to the reaction,a catalyst (1.0 g) was preheated in an H2flow at the prescribedtemperature for 1 h. After the catalyst bed had been preheated, 2,3-BDO was fed through the reactor top at a feed rate of 1.06 g h-1(11.8 mmol h-1). The liquid effluent collected every hour was ana-lyzed by gas chromatography (GC-8A, Shimadzu, Japan) with a60-m capillary column (DB-WAX). The products were identified bygas chromatography with a mass spectrometer (GCMS-QP5050A,Shimadzu) and a 30-m capillary column (DB-WAX). Gaseous prod-ucts such as BD and butene isomers were analyzed by on-line gaschromatography (GC-8A, Shimadzu) with a 6-m packed column column(VZ-7). The catalytic activity was evaluated by averaging the con-version and selectivity data in the initial 5 h. Both the conversion of2,3-BDO and the selectivity to each product were defined as mol%.The above-mentioned description is essentially the same as thosedescribed in the previous work [32,36,37].In Section 3.4, the dehydration of MEK and 3B2OL was alsoexamined in the same way as the 2,3-BDO dehydration in order toconfirm an intermediate product in the dehydration from 2,3-BDOto BD. In Section 3.5, the dehydration of 2,3-BDO was also inves-tigated over two different catalysts packed in the tubular reactor,which consisted of 1.0 g of Al2O3placed in a lower bed with 6 mmheight and 1.0 g of Sc2O3placed in an upper bed with 4 mm height,to establish the efficient BD formation |
With Sc1.5Yb0.5O3; hydrogen at 411℃; for 5h; Flow reactor; | ||
With potassium dihydrogenphosphate at 500℃; for 6h; Inert atmosphere; | ||
With scandium(III) oxide; hydrogen at 275℃; for 5h; | 1 Examples 1 to 82 The dehydration reaction of 3, 3-butanediol The reaction tube was filled with scandium oxide (1.0 g) calcined at 800 ° C, and hydrogen was flowed from the carrier gas introduction port at a flow rate of 45 mL / min. The reaction temperature was set to the temperature shown in Table 1. Using a syringe pump2,3-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.,Stereoisomer mixture) was supplied to the gasifier at a flow rate of 1.06 g / hr from the raw material inlet,The carrier gas was introduced into the reaction tube together. The reaction was continued for 5 hours. The average values of the 5-hour conversions and the selectivity values are shown in Table 1. | |
With hydrogen at 400℃; for 5h; | 1; 2 Examples 1 to 4 Dehydration reaction of 2,3-butanediol General procedure: Zirconium oxide (1.0 g) calcined at 900 ° C. was filled in a reaction tube,Hydrogen was flowed through the carrier gas inlet at a flow rate of 45 mL / min.The reaction temperature was set as shown in Table 1.2,3-butanediol (Tokyo Chemical Industry Co., Ltd., stereoisomer mixture)Was supplied to the vaporizer from the raw material introduction port at a flow rate of 1.06 g / hour by a syringe pump and introduced into the reaction tube together with the carrier gas. The reaction was continued for 5 hours.The average value of conversion and selectivity over 5 hours was as shown in Table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With cesiumhydroxide monohydrate; C17H14Br2CoN4 In toluene at 150℃; for 24h; Sealed tube; Inert atmosphere; | |
96% | With cesiumhydroxide monohydrate In toluene at 150℃; for 24h; Inert atmosphere; Sealed tube; | 2.4 Direct synthesis of quinoxaline from nitroamine General procedure: In an oven dried 9mL screw cap tube a magnetic stir-bar, nitroamine (0.5mmol), vicinal diol (2.5mmol), CsOH.H2O (0.125mmol), Co-phen/C-800 (1.5mol%) and toluene (2.5mL) were added under argon atmosphere. Then, the tube was sealed and placed in a preheated oil bath at 150°C for 24h. After completion of the reaction, the tube was allowed to cool at room temperature. Next, the solvent was evaporated under reduced pressure. Finally, the quinoxaline was purified by silica gel column chromatography using ethyl acetate/hexane as eluent. |
94% | With 1,10-Phenanthroline; cesiumhydroxide monohydrate; nickel dibromide In toluene at 150℃; for 24h; Inert atmosphere; Sealed tube; |
92% | With sodium hydroxide In toluene at 120℃; for 3h; Inert atmosphere; Sealed tube; Green chemistry; | |
90% | With C18H24ClIrN3O(1+)*Cl(1-); potassium hydroxide In water for 24h; Schlenk technique; Reflux; Green chemistry; | |
82% | With dodecacarbonyl-triangulo-triruthenium; cesiumhydroxide monohydrate; 1,3-bis-(diphenylphosphino)propane In tert-Amyl alcohol at 150℃; for 8h; Schlenk technique; Inert atmosphere; | |
80% | With trimethylamine-N-oxide; tricarbonyl(η4-1,3-bis(trimethylsilyl)-4,5,6,7-tetrahydro-2H-inden-2-one)iron In toluene at 150℃; for 24h; Green chemistry; | |
75% | With sodium sulfide hydrate; iron(III) chloride hexahydrate at 170℃; for 24h; Inert atmosphere; | Redox Condensation Reaction of o-Nitroanilines 1 with Benzyl Alcohols 2 or vic-Diols 5; General Procedure General procedure: A 20-mL test-tube equipped with a magnetic stirring bar was charged with o-nitroaniline 1 (2.5 mmol, 1 equiv), alcohol 2 or 5 (3 mmol, 1.2equiv), Na2S·nH2O (≥60%, 130 mg, 1 mmol, 40 mol%) and FeCl3·6H2O(7 mg, 0.025 mmol, 1 mol%). The resulting mixture was stirred for 24h under an argon atmosphere at the indicated temperature (see Schemes 2 and 3 and Table 2). After cooling to r.t., the mixture was purified in different ways. (i) For NH benzimidazole products, the mixture was washed with CH2Cl2 (3 × 2 mL) then dissolved in MeOH.The MeOH solution was filtered through a short pad of silica gel. The filtrate was concentrated in vacuo to afford the NH benzimidazole product. Further purification by column or recrystallization was carried out if necessary. (ii) For N-methyl-2-phenylbenzimidazole 3ha and quinoxalines 5, the crude mixture was dissolved in a minimum volume of CH2Cl2 and purified by column chromatography (silica gel or alumina, heptane-EtOAc, EtOAc, EtOAc-MeOH, hexane-Et2O). We noted that some 13C NMR signals of NH-benzimidazoles are missing or difficult to observe. |
96 %Chromat. | With cobalt supported on N,P co-doped porous carbon In toluene at 140℃; for 12h; Sealed tube; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With toluene-4-sulfonic acid In benzene Reflux; Dean-Stark; | General procedure for preparation of compounds6a-6c General procedure: A solution of 0.23 g ketone 5 (1 mmol), corresponding 1,2-diol (1.2 mmol), and p-toluenesulfonic acid (catalyticamount) in 20 cm3 benzene was refluxed in a Dean-Starkapparatus for 6 h. The reaction mixture was evaporated invacuo, quenched with aqueous solution of sodium hydrogencarbonate, filtered off, and washed with water. Theprecipitate was crystalized from i-PrOH to give oxolane6a-6c in 64-83 % yields. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 56% 2: 27.3% | In water at 500℃; | 67 Pyroprobe Evaluation of Catalysts General procedure: The feedstock was 10 wt % BDO (Aldrich) in deionized (DI) water. The catalyst (2 mg of powder) was loaded into a quartz tube (25 mm long×1.9 mm I.D.; open at both ends), and held in position using a quartz wool plug on both ends of the powder layer. Approximately 1 μL of feed solution was subsequently dispensed onto the back quartz wool plug then loaded into the pyroprobe wand with the liquid-containing end down, so that upon heating the liquid feed vapors would be carried through the catalyst bed.After the tube was loaded into the pyroprobe wand, the end of the wand was inserted into the pyroprobe unit and sealed. Helium carrier gas flowed through the probe wand and over the quartz wool plugs and catalyst. Upon initiation of the unit, a heating coil encircling the quartz tube, rapidly heated the tube and its contents to 600° C. and maintained it at that temperature for usually 15 seconds. Carrier gas flows were typically 20 cc/m of He through the pyroprobe. Reactant and product vapors were rapidly carried out of the quartz tube and adsorbed onto a Carbopack bed at 40° C., then later desorbed from the adsorbent bed at 300° C. The desorbed products were carried into the GC/MS unit for separation and analysis. Area percent reports were generated for percent conversion of BDO and product selectivity to 1,3 butadiene, methyl vinyl carbinol, MEK, and isobutyraldehyde (IBA). Aldrich BDO was a mixture of d/l and meso isomers. Early analyses integrated over both isomers (reported as BDO) until method improvements allowed separate quantification |
With Al, La and Zr mixed oxide In water at 500℃; Overall yield = 61.4 %; | Pyroprobe Evaluation of Catalysts General procedure: The feedstock was 10 wt % BDO (Aldrich) in deionized (DI) water. The catalyst (2 mg of powder) was loaded into a quartz tube (25 mm long×1.9 mm I.D.; open at both ends), and held in position using a quartz wool plug on both ends of the powder layer. Approximately 1 μL of feed solution was subsequently dispensed onto the back quartz wool plug then loaded into the pyroprobe wand with the liquid-containing end down, so that upon heating the liquid feed vapors would be carried through the catalyst bed.After the tube was loaded into the pyroprobe wand, the end of the wand was inserted into the pyroprobe unit and sealed. Helium carrier gas flowed through the probe wand and over the quartz wool plugs and catalyst. Upon initiation of the unit, a heating coil encircling the quartz tube, rapidly heated the tube and its contents to 600° C. and maintained it at that temperature for usually 15 seconds. Carrier gas flows were typically 20 cc/m of He through the pyroprobe. Reactant and product vapors were rapidly carried out of the quartz tube and adsorbed onto a Carbopack bed at 40° C., then later desorbed from the adsorbent bed at 300° C. The desorbed products were carried into the GC/MS unit for separation and analysis. Area percent reports were generated for percent conversion of BDO and product selectivity to 1,3 butadiene, methyl vinyl carbinol, MEK, and isobutyraldehyde (IBA). Aldrich BDO was a mixture of d/l and meso isomers. Early analyses integrated over both isomers (reported as BDO) until method improvements allowed separate quantification. | |
With lithium dihydrogenphosphate at 500℃; for 6h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen at 135℃; Large scale; | 1 Example 1 Example 1 [00043] Into a high pressure liquid phase fixed bed reactor system containing 60,000 kg of Ni (Raney) on Al203 (40/60 by weight) catalyst is passed 26,000 kg/hour of liquid feedstock comprising 54 % BYD and 3,000 kg/hour of hydrogen at a pressure of 300 bar. The hydrogen feedstock is from a compressed hydrogen supply system involving a hydrogen booster compressor and other unit operations required to provide quality high pressure hydrogen for the reaction. Reaction conditions maintained in the fixed bed reactor include a pressure of 300 bar and temperature of 135 C. Vent gas comprised of 96 % hydrogen is removed from the reactor and recycled to the hydrogen supply system at about 2,300kg/hour. Liquid phase product comprising approximately 54 % BDO is recovered from the reactor and passed to a first liquid phase iet down vessel via an isenthalpic pressure let down, maintained at a pressure of 80 bar at 26,000 kg/hour, along with about 50 to 100 kg/hour of hydrogen. [00044] From the first liquid phase let down vessel is recovered a first stream liquid bottoms comprising product BDO and a second stream overhead vent gas comprising mainly water vapor plus residual light organics and hydrogen. The recovered first stream liquid bottoms is passed to a second liquid phase iet down vessel, maintained at a pressure of 8 bar, at approximately 20,000 kg/hour. The recovered second stream overhead vent gas is passed to a vent gas cooler maintained at a pressure of 75 bar and temperature of 35 °C. The gas from the vent gas cooler is passed to a hydrogen recovery zone comprising a MEDAL membrane filter unit. Permeate recovered from the hydrogen recovery zone, comprising 97 % hydrogen gas of 99 % hydrogen purity (water free basis), is recycled to the hydrogen supply system. The retentate recovered from the hydrogen recovery zone comprises contaminants, such as, for example, carbon dioxide, methane, and methanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95 %Spectr. | Stage #1: carbon dioxide; 2.3-butanediol With 1,8-diazabicyclo[5.4.0]undec-7-ene In 1,2-dichloro-ethane at 25℃; Stage #2: 1-bromo-butane In 1,2-dichloro-ethane at 25℃; for 24h; | General procedure for the synthesis of cyclic carbonates 2 General procedure: Compound 1 (2.5 mmol) and DBU (20 mmol) in DCE (1mL) were placed in a 50-mL two-necked flask and CO2 gas was flowed with stirring at 25 °C until the solution was changed to a white suspension. After addition of 1-bromobutane (24 mmol), the flask was capped with a rubber septum and equipped with a CO2 balloon. The mixture was stirred at 25 °C for 24 h and then passed through a short pad of silica gel with CH2Cl2 as eluent to remove the DBU salts. The eluent was concentrated under reduced pressure and the yield of the product was determined by 1H NMR using an internal standard. The product 2 was separated by column chromatography on silica gel using hexane and/or CH2Cl2 as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
21% | at 293 - 365℃; | 1 The dehydration of 2,3-butanediol was performed in the same manner as in Example 1, with the exception that the WHSV of the first adiabatic reactor was 4.91. The reaction results are shown in Table 5 below. (0081) Each conversion was low, to a level of about 20%, from the first reactor to the third reactor due to the low retention time, and a conversion of 97.3% was obtained after the final reactor for converting the unreacted feed. However, the production reaction of 1,3-BD did not efficiently progress due to the low retention time, thus exhibiting BD selectivity of 20.9%. |
With silica-supported phosphorous at 180℃; Inert atmosphere; | ||
With alumina In water at 380℃; Inert atmosphere; Gas phase; |
With Cesium oxide- Silica composite at 400℃; for 6h; Inert atmosphere; | ||
With 1 Na phosphate on silica at 400℃; for 20h; Inert atmosphere; | Liquid BDO (97% Sigma-Aldrich) was fed by a syringe pump(0.1-0.25 cm3/h) into the empty 5 L volume kept at 180 °C to eliminateconcentration fluctuations (caused by the syringe pump delivery anddroplet evaporation into the gas phase). Nitrogen carrier gas was usedto maintain desired partial pressure of BDO. All communications weremaintained at 180 °C under the typical reaction conditions. 1 atmsystem pressure was kept constant in all the experiments |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 2,3-butanediol dehydrogenase of S. cerevisiae YAL060W In methanol for 16h; Enzymatic reaction; | Kinetic studies of biotransformations Biotransformations in shake flasks were conducted with strainsharboring one copy of the BDH1 expression cassette as determinedby quantitative real-time PCR [25]. The correspondingstrains were grown for 60 h in 200 mL BMD medium (2 Lbaffled shake flasks) and protein expression was started by theaddition of 20 mL BMM10 approximately 12 h prior to the startof the bioreduction reaction. For BDH1 catalyzed acetoinconversion, cells corresponding to 3000 OD600 units wereharvested by centrifugation (3000g, 10 min, rt) and resuspendedin 50 mL of buffered minimal medium. The reactionwas started by adding 10 mL of the substrate solution (300 mMrac-acetoin, 50% (v/v) methanol, 200 mM KPi, pH 6.0). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With dodecacarbonyl-triangulo-triruthenium; potassium <i>tert</i>-butylate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In tert-Amyl alcohol at 130℃; for 12h; Inert atmosphere; Schlenk technique; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen; sodium hydroxide; In water; at 210℃; under 45004.5 Torr; for 2h;Autoclave; | General procedure: The hydrogenolysis of sorbitol was performed in a 50 mL stainless-steel autoclave with magnetic stirring. After sorbitol aqueous solution, Ru catalyst and an appropriate amount of basewere charged into the reactor, the autoclave was purged with hydrogen four times and then pressurized to the desired pressure at room temperature. Then the reaction was performed atcertain temperature under the stirring speed of 800 r/min. After the reaction, the reactor was cooled down and the used catalystwas separated from the reaction mixture by centrifugation. Thesamples were filtered through 0.22 m-pore-size filters (Mem-brana) prior to analysis. The obtained products such as 1,2-PG,EG and GLY were determined using a gas chromatography (GC,7890A, Agilent, USA) equipped with a CP-Wax 58 (FFAP) capillarycolumn (0.25 mm × 25 m) and a flame ionization detector. Otherproducts like glucose, sugar alcohols were quantified by Anion-Exchange Chromatography (IC, Dionex ICS-3000) equipped with pulsed amperometric detector and an Aminex HPX-87H column(Bio-Rad, 7.8 × 300 mm), using 500 mM NaOH as eluent with a flowrate of 0.4 mL min-1at 30C. The obtained products in resultant solutions were also identified by GC-MS (6890N, Agilent, USA). The conversion of sorbitol and yields of products were calculated on the carbon basis and defined as follows |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen; sodium hydroxide; at 210℃; under 45004.5 Torr; for 2h; | General procedure: The hydrogenolysis of sorbitol was performed in a 50 mL stainless-steel autoclave with magnetic stirring. After sorbitol aqueous solution, Ru catalyst and an appropriate amount of basewere charged into the reactor, the autoclave was purged with hydrogen four times and then pressurized to the desired pressure at room temperature. Then the reaction was performed atcertain temperature under the stirring speed of 800 r/min. After the reaction, the reactor was cooled down and the used catalystwas separated from the reaction mixture by centrifugation. Thesamples were filtered through 0.22 m-pore-size filters (Mem-brana) prior to analysis. The obtained products such as 1,2-PG,EG and GLY were determined using a gas chromatography (GC,7890A, Agilent, USA) equipped with a CP-Wax 58 (FFAP) capillarycolumn (0.25 mm × 25 m) and a flame ionization detector. Otherproducts like glucose, sugar alcohols were quantified by Anion-Exchange Chromatography (IC, Dionex ICS-3000) equipped with pulsed amperometric detector and an Aminex HPX-87H column(Bio-Rad, 7.8 × 300 mm), using 500 mM NaOH as eluent with a flowrate of 0.4 mL min-1at 30C. The obtained products in resultant solutions were also identified by GC-MS (6890N, Agilent, USA). The conversion of sorbitol and yields of products were calculated on the carbon basis and defined as follows |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With cesiumhydroxide monohydrate In toluene at 150℃; for 24h; Inert atmosphere; Sealed tube; | 2.2 Quinoxaline synthesis from diamine General procedure: To an oven dried 9mL screw cap tube, a magnetic stir-bar, diamine (0.5mmol), vicinal diol (1.5mmol), CsOH.H2O (0.375mmol), Co-phen/C-800 (1.5mol%) and toluene (2.5mL) were added under argon atmosphere. Then, the tube was sealed and placed in a preheated oil bath at 150°C for 24h. After completion of the reaction, the tube was allowed to cool at room temperature. Then, the solvent was evaporated under reduced pressure. Finally, the product was purified by silica gel column chromatography using ethyl acetate/hexane as eluent. |
84% | With C18H24ClIrN3O(1+)*Cl(1-); potassium hydroxide In water for 24h; Schlenk technique; Reflux; Green chemistry; | |
66% | With C24H29IrN2O5(2+)*2CF3O3S(1-); caesium carbonate In 5,5-dimethyl-1,3-cyclohexadiene at 150℃; for 48h; Schlenk technique; Inert atmosphere; | General procedure for the synthesis of 3a. General procedure: The catalyst A (5% mmol, 0.05 mmol), 1,2-phenylenediamine (1 mmol, 1.0 equiv), 1,2-propanediol (1 mmol, 1.0 equiv), Cs2CO3 (3.0 equiv) and xylene (4 mL) were added to a Schlenk tube under the atmosphere of nitrogen. The mixture was heated for 48 h at 150 °C and then cooled down to room temperature. The volatile solvent was evaporated. The residue was purified by column chromatography to give the corresponding product 3a. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With cesiumhydroxide monohydrate; C17H14Br2CoN4 In toluene at 150℃; for 24h; Sealed tube; Inert atmosphere; | |
56% | With C24H29IrN2O5(2+)*2CF3O3S(1-); caesium carbonate In 5,5-dimethyl-1,3-cyclohexadiene at 150℃; for 48h; Schlenk technique; Inert atmosphere; | General procedure for the synthesis of 3a. General procedure: The catalyst A (5% mmol, 0.05 mmol), 1,2-phenylenediamine (1 mmol, 1.0 equiv), 1,2-propanediol (1 mmol, 1.0 equiv), Cs2CO3 (3.0 equiv) and xylene (4 mL) were added to a Schlenk tube under the atmosphere of nitrogen. The mixture was heated for 48 h at 150 °C and then cooled down to room temperature. The volatile solvent was evaporated. The residue was purified by column chromatography to give the corresponding product 3a. |
55% | With cesiumhydroxide monohydrate In toluene at 150℃; for 28h; Inert atmosphere; Sealed tube; | 2.2 Quinoxaline synthesis from diamine General procedure: To an oven dried 9mL screw cap tube, a magnetic stir-bar, diamine (0.5mmol), vicinal diol (1.5mmol), CsOH.H2O (0.375mmol), Co-phen/C-800 (1.5mol%) and toluene (2.5mL) were added under argon atmosphere. Then, the tube was sealed and placed in a preheated oil bath at 150°C for 24h. After completion of the reaction, the tube was allowed to cool at room temperature. Then, the solvent was evaporated under reduced pressure. Finally, the product was purified by silica gel column chromatography using ethyl acetate/hexane as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With C24H29IrN2O5(2+)*2CF3O3S(1-); caesium carbonate In 5,5-dimethyl-1,3-cyclohexadiene at 150℃; for 48h; Schlenk technique; Inert atmosphere; | General procedure for the synthesis of 3a. General procedure: The catalyst A (5% mmol, 0.05 mmol), 1,2-phenylenediamine (1 mmol, 1.0 equiv), 1,2-propanediol (1 mmol, 1.0 equiv), Cs2CO3 (3.0 equiv) and xylene (4 mL) were added to a Schlenk tube under the atmosphere of nitrogen. The mixture was heated for 48 h at 150 °C and then cooled down to room temperature. The volatile solvent was evaporated. The residue was purified by column chromatography to give the corresponding product 3a. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 99 %Chromat. 2: 94 %Chromat. | With potassium phosphate; C62H63N5OPRu(1+)*Cl(1-); hydrogen In tetrahydrofuran at 140℃; for 24h; Glovebox; Autoclave; | |
With potassium <i>tert</i>-butylate; hydrogen; C39H37N2OP2Ru(1+)*Cl(1-) In tetrahydrofuran at 140℃; for 18h; Glovebox; Autoclave; | 14 Example 14: Hydrogenation of cyclic carbonate catalyzed by ruthenium complex 1a General procedure: In the glove box,To a 125 mL autoclave, add ruthenium complex 1a (7.5 mg, 0.01 mmol), potassium tert-butoxide (2.3 mg, 0.02 mmol), tetrahydrofuran (20 mL),Cyclic carbonate (20 mmol).After sealing the autoclave, remove it from the glove box,Fill with 50atm hydrogen. The reaction kettle was heated and stirred in a 140°C oil bath for a specific period of time. After cooling the reaction kettle in an ice water bath for 1.5 hours, the excess hydrogen was slowly released.With p-xylene as the internal standard, use gas chromatography (using the standard curve method, that is, with p-xylene as the internal standard, for cyclic carbonate,Methanol and diol are used as standard curves on the gas chromatography with the ratio of the peak area to the peak area of para-xylene. By measuring the ratio of the peak area in the reaction system, the cyclic carbonate contained in the reaction system mixture after the reaction is determined , The quality of methanol and glycol.The same gas chromatography method as in Example 9 was used to determine the conversion of cyclic carbonate and the yield of methanol and diol. The results are shown in Table 6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | Stage #1: 2,4-diferrocenyl-1,3-dithiadiphosphetane-2,4-disulfide; 2.3-butanediol With triethylamine In acetonitrile at 20℃; for 24h; Inert atmosphere; Stage #2: With iodine In acetonitrile at 20℃; for 4h; Inert atmosphere; | 3.2.1. General Procedure for the Reaction of FcLR with Alkenyl-diols and I2 in the Presence of Triethylamine General procedure: A mixture of alkenyl-diol (1.0 mmol) and FcLR (0.56 g, 1.0 mmol) in dry acetonitrile (40 mL) was stirring in the presence of triethylamine (0.202 g, 2.0 mmol) at room temperature overnight. I2 solution (0.254 g, 1.0 mmol) in acetonitrile (15 mL) was added dropwise during 2 h and the mixture was continued stirring for another 2 h. Upon removing solvent, the residue was extracted with dichloromethane (20 mL x 3). After removal of the solvent, the crude product was purified by silica column (dichloromethane as eluent) to give the di-phosphorus species 1-6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With cesiumhydroxide monohydrate; In toluene; at 150℃; for 24h;Inert atmosphere; Sealed tube; | General procedure: In an oven dried 9mL screw cap tube a magnetic stir-bar, nitroamine (0.5mmol), vicinal diol (2.5mmol), CsOH.H2O (0.125mmol), Co-phen/C-800 (1.5mol%) and toluene (2.5mL) were added under argon atmosphere. Then, the tube was sealed and placed in a preheated oil bath at 150C for 24h. After completion of the reaction, the tube was allowed to cool at room temperature. Next, the solvent was evaporated under reduced pressure. Finally, the quinoxaline was purified by silica gel column chromatography using ethyl acetate/hexane as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With sodium hydroxide In 1,2-dichloro-benzene at 10℃; for 2h; Irradiation; | 5,6-Dihydro[C70-D5h(6)][5,6](1,4-dioxano)fullerene(2). General procedure: Diol 1a-1c, 40 mmol (2.9 mL of 1a, 3.6 mL of1b, or 4.7 g of 1c), and 0.1 g (2.5 mmol) of solidsodium hydroxide were added to 10 mL (35 mg,0.04 mmol) of a solution of C70 in o-dichlorobenzene.The resulting heterogeneous mixture was placed ina reactor equipped with a cooling jacket and subjectedto ultrasonic irradiation for 2 h at 10°C. The originally dark red fullerene solution turned dark brown. It wasseparated from the yellow layer of α-diol 1a or 1b andpassed through a column charged with a ~4-cm layerof silica gel. The product was isolated by preparativeHPLC. Removal of the solvent under reduced pressuregave dark brown powder. Yield 23.3 (62%, from 1a),19.9 (53%, from 1b), 11.6 mg (31%, from 1c);mp >300°C. UV spectrum (CHCl3), λmax, nm: 313-318, 379, 394, 462. IR spectrum, ν, cm-1: 2918-2849(C-H), 2920 (C-H), 1460, 1427, 1098 (C-O-C), 793,727, 671, 633, 577, 533. 1H NMR spectrum (CDCl3); δ4.35 ppm, s (4H, CH2). 13C NMR spectrum (CDCl3),δC, ppm: 56.93 (CH2), 74.64 (2C, Csp3, C70), 130.82,131.27, 137.24, 137.97, 142.41, 142.79, 143.12,144.91, 145.32, 145.45, 145.53, 146.41, 146.73,147.34, 148.017, 148.41, 148.71, 150.22, 152.38,153.44, 156.79, 158.56. Mass spectrum, m/z (Irel, %):900.025 (83.8) [M]+, 900.044 (79.4) [M]-. C72H4O2.Calculated: M 900.021. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dihydrogen peroxide In acetone at 50℃; for 8h; Autoclave; | 4 2. Preparation of o-diol compounds General procedure: In a 500ml autoclave, a solvent, an olefin, an oxidant and a particulate titanium silicalite catalyst are distributed, and the catalyst is fixed on the side of the cooling coil of the autoclave by a hanging basket.After the completion of the feeding, nitrogen was flushed into the reaction vessel to set the initial pressure of the reaction, and the stirring was started to examine the effects of different olefin raw materials, solvents, temperature, pressure, reaction time, feed ratio, and catalyst on the reaction.After the reaction started, the oxidant partially decomposed, so the reactor pressure gradually increased.After the reaction was terminated, sampling was carried out, and the product composition was analyzed by gas chromatography.The reaction olefin raw materials used in Examples 1 to 10 are shown in Table 1.The catalyst titanium silicate molecular sieve raw powder, the nano SiO2 and the heteropoly acid mass distribution used in the examples, the titanium silicon molar ratio in the titanium silicon molecular sieve raw powder,Reaction charge molar ratio, solvent, oxidant mass concentration,The types of heteropolyacids are shown in Table 2.The batch reaction process conditions and results are shown in Table 3.The conditions and results of the continuous bed continuous reaction process are shown in Table 4. | |
With diboron trioxide; γ-Al2O3 ; dihydrogen peroxide In methanol at 70℃; for 6h; Molecular sieve; | ||
With dihydrogen peroxide In acetone at 130℃; Molecular sieve; | 5 Example 5 20 g of titanium-silicon molecular sieves were loaded into the fluidized bed reactor. The molar ratio of acetone and hydrogen peroxide is 10:1, the mass concentration of hydrogen peroxide is 60%, and the mol ratio of 2-butene and hydrogen peroxide is 2:1. After mixing acetone and hydrogen peroxide, the reactor is injected into the reactor by a metering pump, and the 2-butene is injected into the reactor by a metering pump. It is injected into the reactor, and the material is contacted and reacted with the catalyst to synthesize 2,3-butanediol. Reaction conditions: the reaction temperature is 130°C, the reaction pressure is 1.0MPa, and the liquid space velocity of the reaction bed is 2.3h-1. The resulting product was analyzed,The selectivity of 2,3-butanediol was 94.6%, and the conversion rate of hydrogen peroxide was 99.1%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86.2% | With sodium bromate; sodium hydrogensulfite In acetonitrile at 50℃; | 2.1 S1, Synthesis of S1, 3-benzenesulfonylhydrazino-2-butanol 9.02 g of 2,3-butanediol was dissolved in 40 ml of acetonitrile, and 12.6 g of sodium bromate and 8.24 g of sodium hydrogensulfite were slowly added to the solution, and the temperature was raised to 50 ° C. 18.62 g of benzenesulfonyl hydrazide was added in portions over 1 hour under stirring. At the same time, HPLC was used to detect the progress of the reaction until the peak area of 2,3-butanediol in the HPLC was less than 0.2%, and a 10% by mass aqueous solution of sodium hydroxide was added to the reaction solution until the pH of the solution was 7, The reaction solution was concentrated to half volume and cooled to room temperature. The precipitated inorganic salt was filtered, and the filtrate was distilled under reduced pressure to give an intermediate, which was 3-benzenesulfonylhydrazino-2-butanol, the mass was 21.5 g, and the molar yield was 86.2%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87.9% | With sodium bromate; sodium hydrogensulfite In 1,2-dichloro-ethane at 40℃; | 1.1 S1 Synthesis of 3-p-toluenesulfonylhydrazino-2-butanol 9.03 g of 2,3-butanediol was dissolved in 40 ml of dichloroethane, and 11.5 g of sodium bromate and 7.81 g of sodium hydrogensulfite were slowly added to the solution, and the temperature was raised to 40 ° C. 19.57 g of p-toluenesulfonylhydrazide was added in portions over 1 hour with stirring. At the same time, HPLC traces the progress of the reaction until the peak area of 2,3-butanediol in HPLC is less than 0.2%. A 10% by mass aqueous sodium hydroxide solution was added to the reaction solution until the pH of the solution was 7, and the reaction solution was concentrated to half volume and cooled to room temperature. The precipitated inorganic salt was filtered, and the filtrate was distilled under reduced pressure to give an intermediate, which was 3-p-toluenesulfonyl hydrazino-2-butanol, and the mass was 22.7 g, and the molar yield was 87.9%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With cesiumhydroxide monohydrate In toluene at 150℃; for 28h; Inert atmosphere; Sealed tube; | 2.4 Direct synthesis of quinoxaline from nitroamine General procedure: In an oven dried 9mL screw cap tube a magnetic stir-bar, nitroamine (0.5mmol), vicinal diol (2.5mmol), CsOH.H2O (0.125mmol), Co-phen/C-800 (1.5mol%) and toluene (2.5mL) were added under argon atmosphere. Then, the tube was sealed and placed in a preheated oil bath at 150°C for 24h. After completion of the reaction, the tube was allowed to cool at room temperature. Next, the solvent was evaporated under reduced pressure. Finally, the quinoxaline was purified by silica gel column chromatography using ethyl acetate/hexane as eluent. |
78% | With C18H24ClIrN3O(1+)*Cl(1-); potassium hydroxide In water for 24h; Schlenk technique; Reflux; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With cesiumhydroxide monohydrate In toluene at 150℃; for 24h; Inert atmosphere; Sealed tube; | 2.2 Quinoxaline synthesis from diamine General procedure: To an oven dried 9mL screw cap tube, a magnetic stir-bar, diamine (0.5mmol), vicinal diol (1.5mmol), CsOH.H2O (0.375mmol), Co-phen/C-800 (1.5mol%) and toluene (2.5mL) were added under argon atmosphere. Then, the tube was sealed and placed in a preheated oil bath at 150°C for 24h. After completion of the reaction, the tube was allowed to cool at room temperature. Then, the solvent was evaporated under reduced pressure. Finally, the product was purified by silica gel column chromatography using ethyl acetate/hexane as eluent. |
55% | With 1,10-Phenanthroline; cesiumhydroxide monohydrate; nickel dibromide In toluene at 150℃; for 24h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With 1,10-Phenanthroline; cesiumhydroxide monohydrate; nickel dibromide In toluene at 150℃; for 24h; Inert atmosphere; Sealed tube; | |
82% | With cesiumhydroxide monohydrate In toluene at 150℃; for 24h; Inert atmosphere; Sealed tube; | 2.2 Quinoxaline synthesis from diamine General procedure: To an oven dried 9mL screw cap tube, a magnetic stir-bar, diamine (0.5mmol), vicinal diol (1.5mmol), CsOH.H2O (0.375mmol), Co-phen/C-800 (1.5mol%) and toluene (2.5mL) were added under argon atmosphere. Then, the tube was sealed and placed in a preheated oil bath at 150°C for 24h. After completion of the reaction, the tube was allowed to cool at room temperature. Then, the solvent was evaporated under reduced pressure. Finally, the product was purified by silica gel column chromatography using ethyl acetate/hexane as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With cesiumhydroxide monohydrate In toluene at 150℃; for 24h; Inert atmosphere; Sealed tube; | 2.4 Direct synthesis of quinoxaline from nitroamine General procedure: In an oven dried 9mL screw cap tube a magnetic stir-bar, nitroamine (0.5mmol), vicinal diol (2.5mmol), CsOH.H2O (0.125mmol), Co-phen/C-800 (1.5mol%) and toluene (2.5mL) were added under argon atmosphere. Then, the tube was sealed and placed in a preheated oil bath at 150°C for 24h. After completion of the reaction, the tube was allowed to cool at room temperature. Next, the solvent was evaporated under reduced pressure. Finally, the quinoxaline was purified by silica gel column chromatography using ethyl acetate/hexane as eluent. |
82% | With sodium hydroxide In toluene at 120℃; for 3h; Inert atmosphere; Sealed tube; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With sodium hydroxide In toluene at 120℃; for 3h; Inert atmosphere; Sealed tube; Green chemistry; | |
82% | With cesiumhydroxide monohydrate In toluene at 150℃; for 28h; Inert atmosphere; Sealed tube; | 2.4 Direct synthesis of quinoxaline from nitroamine General procedure: In an oven dried 9mL screw cap tube a magnetic stir-bar, nitroamine (0.5mmol), vicinal diol (2.5mmol), CsOH.H2O (0.125mmol), Co-phen/C-800 (1.5mol%) and toluene (2.5mL) were added under argon atmosphere. Then, the tube was sealed and placed in a preheated oil bath at 150°C for 24h. After completion of the reaction, the tube was allowed to cool at room temperature. Next, the solvent was evaporated under reduced pressure. Finally, the quinoxaline was purified by silica gel column chromatography using ethyl acetate/hexane as eluent. |
77% | With trimethylamine-N-oxide; tricarbonyl(η4-1,3-bis(trimethylsilyl)-4,5,6,7-tetrahydro-2H-inden-2-one)iron In toluene at 150℃; for 24h; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen In 1,4-dioxane at 20 - 140℃; for 20h; Autoclave; | 52 Example 51 General procedure: A stirrer chip, 300 mg of the catalyst (ReOX-Au / CeO2) obtained in Production Example 21 weighed, 4 g of 1,4-dioxane, and 500 mg of glycerin were placed in a glass inner cylinder for autoclave.The inner cylinder for the autoclave was placed in a 190 mL autoclave (high-pressure batch reactor) and covered.Next, the operation of filling 1 MPa of hydrogen into the autoclave and then exhausting the gas was repeated three times to expel the air inside the autoclave. The autoclave was filled so as to exhibit 8 MPa at 140 ° C. and 5 MPa at room temperature.Subsequently, the autoclave is set in a magnetic stirrer additional heating device, heated so that the temperature inside the reactor (inside the autoclave) becomes 140 ° C., and the reaction temperature is maintained at 140 ° C. for 32 hours at 250 rpm (Reaction time). = 32h) Stirred.Then, the mixture was cooled to room temperature, the hydrogen inside the autoclave was released, and the pressure was released.The analysis of the solution after the reaction was carried out in the same manner as in Example 1.From this, the conversion rate of glycerin and the selectivity of the product were calculated. The analysis results are shown in Table 9. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With modified zirconium superacid In water at 120℃; | 1.2; 1 (2) Preparation of 1,3-BG: General procedure: The synthesis reaction of 1,3-BG is carried out in a rectification tower filled with catalyst. The inner diameter of the rectification tower is 25mm and the length is 1000mm. The middle of the rectification tower is filled with 400g catalyst-1, and the upper and lower ends of the catalyst bed are filled with θ rings.Keep the bed temperature of the rectification tower at 120°C, feed the reaction liquid containing the intermediate (I) prepared in step (1) at the upper end of the catalyst bed, and enter it continuously through the feed pump. The liquid space velocity WHSV=2.0g/ gcat/h, at the same time, water is fed at the lower end of the catalyst bed and continuously enters through the feed pump. The molar ratio of intermediate I to water is 1:3. The top of the tower extracts low-boiling aldehydes and ketone compounds and water, and the bottom of the tower contains 1,3-Butanediol reaction solution. The reaction liquid was analyzed by GC, and the reaction conversion rate reached 99.90%, and the 1,3-BG selectivity reached 99.00%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With pyridine; oxygen; potassium hydroxide at 110℃; for 16h; Green chemistry; chemoselective reaction; | |
68% | With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 12h; Schlenk technique; | 7 Add 0.25 mmol of cyclopropyl amidine hydrochloride, 0.375 mmol of 2,3-butanediol, 0.75 mmol of potassium carbonate, and 60 mg of manganese dioxide supported cobalt catalyst into the schlenk tube (the mass fraction of manganese dioxide is 3%) and 1ml of N,N-dimethylformamide. After stirring and reacting at 120°C and air for 12 hours, stop heating and stirring, cool to room temperature, remove the solvent by rotary evaporation under reduced pressure, and pass through thin layer chromatography. Separation and purification by method to obtain the target product. The stationary phase of thin-layer chromatography is silica gel, and the eluent is a mixed solvent of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate = 6:1, v/v). The yield of 68%. |
Tags: 513-85-9 synthesis path| 513-85-9 SDS| 513-85-9 COA| 513-85-9 purity| 513-85-9 application| 513-85-9 NMR| 513-85-9 COA| 513-85-9 structure
Precautionary Statements-General | |
Code | Phrase |
P101 | If medical advice is needed,have product container or label at hand. |
P102 | Keep out of reach of children. |
P103 | Read label before use |
Prevention | |
Code | Phrase |
P201 | Obtain special instructions before use. |
P202 | Do not handle until all safety precautions have been read and understood. |
P210 | Keep away from heat/sparks/open flames/hot surfaces. - No smoking. |
P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
P223 | Keep away from any possible contact with water, because of violent reaction and possible flash fire. |
P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
P235 | Keep cool |
P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
Home
* Country/Region
* Quantity Required :
* Cat. No.:
* CAS No :
* Product Name :
* Additional Information :