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| Inaccessible (Haz class 6.1), Domestic | USD 80+ |
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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
2,3-Butanediol is a butanediol derived from the bioconversion of natural resources[1].
4.5
*For Research Use Only! Not for Human Use. We Do Not Sell to Patients.
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| CAS No. : | 513-85-9 |
| Formula : | C4H10O2 |
| M.W : | 90.12 |
| SMILES Code : | CC(O)C(O)C |
| English Name : | 2,3-Butanediol |
| MDL No. : | MFCD00004523 |
| InChI Key : | OWBTYPJTUOEWEK-UHFFFAOYSA-N |
| Pubchem ID : | 262 |
| GHS Pictogram: | |
| Signal Word: | |
| Hazard Statements: | |
| Precautionary Statements: | |
| Class: | |
| UN#: | |
| Packing Group: |
* 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 |
|---|---|---|
| With sodium hydrogencarbonate at 195℃; substance, whose stereochemical homogeneity or configuration not/no known is; | ||
| With calcium hydroxide at 75℃; butanediol-(2.3); |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With water; lead(II) oxide substance, whose stereochemical homogeneity or configuration not/no known is; | ||
| With silver(I) acetate; potassium carbonate; acetic acid |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With sulfuric acid substance uncertain configuration; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 97.6% | With thionyl chloride at 10 - 20℃; for 1h; Inert atmosphere; | 2 Accurately weigh 90g of 1,2-dimethylethylene glycol in a 1000ml four-necked flask, cool to 10°C under nitrogen protection, slowly add 119g of thionyl chloride, and control the temperature at 10-20°C. After the addition is complete, keep warm for 1 hour. Obtain 132.7g of 2,3-dimethylvinyl sulfite, with a yield of 97.6%. Weigh 70.4mg of iron tetraphenylporphyrin, 400g of water, and 400g of diethyl carbonate into the reaction bottle, slowly add 270g of potassium persulfate, and control the temperature at 0-10°C. After the addition is complete, keep warm for 4 hours. Separate the liquid, take the organic phase, dry, filter, and desolventize to obtain 141.3g of 2,3-dimethylvinyl sulfate, with a GC purity of 99.3% and a total yield of 90.6%. |
| 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. | |
| With thionyl chloride In 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran at 40℃; for 2h; Inert atmosphere; | 818.A Step A. 4,5-dimethyl-L3,2-dioxathiolane 2-oxide: To a solution of butane-2,3-diol (1.00 g, 1.0 equiv) in DCM (10 mL) was added SOCh (1.72 g, 1.3 equiv). The reaction was degassed, purged with N2 for 3 times and stirred at 40 °C for 2 hours. The mixture was poured into ice-water (10 mL) and stirred for 30 minutes, and then extracted with DCM (2 x 30 mL). The combined organic layers were washed with brine (30 mL), dried over sodium sulfate and concentrated to afford the title compound (1.50 g, crude) as a yellow oil;1HNMR (400 MHz, CHLOROFORM-d) 8 = 5.16 - 4.95 (m, 2H), 1.33 - 1.28 (m, 6H). |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With mercury for 72h; Heating; Irradiation; Yield given. Yields of byproduct given; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 1: 39% 2: 31% | In methanol; chloroform for 312h; Ambient temperature; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 77% | With pyridine for 24h; Ambient temperature; | |
| In pyridine | ||
| With pyridine |
| 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 |
|---|---|---|
| 1: 20 % Spectr. 2: 13% | With triethylamine In tetrahydrofuran at 0℃; for 0.333333h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With dmap In acetonitrile at 20℃; for 0.5h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 4.95 g | With magnesium sulfate In diethyl ether at 20℃; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 99% | With magnesium sulfate In diethyl ether at 20℃; for 14h; | |
| 99% | With magnesium sulfate In diethyl ether |
| 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 |
|---|---|---|
| Stage #1: LACTIC ACID; propylene glycol; ethylene glycol; glycerol; corn oil; 2.3-butanediol at 210 - 220℃; for 3h; Stage #2: With citric acid | 4 Example 4Latex Paint FormulationIn this Example, a latex paint formulation wherein petroleum derived propylene glycol has been replaced with product mixture from the hydrogenolysis of glycerol and/or esters of the product mixture from the hydrogenolysis of glycerol.A composition enriched in compounds containing 2 hydroxyl groups was obtained by hydrogenolysis of glycerol produced by passing a 40% solution of crude glycerol through a reactor substantially as set forth in Example 1. The crude glycerol was obtained as by-product of palm biodiesel synthesis. The hydrogenolysis product was dewatered by distillation. A composite product was prepared by combining four dewatered glycerol hydrogenolysis product samples to yield a mixture of polyols containing 75.5% propylene glycol, 4.5% ethylene glycol, 18% 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 undistilled 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.Fatty acid esters of Mixture 1 were synthesized as follows. Mixture 1 (pH 8, 150 g) was mixed with corn oil (130 g) (commercially available from Archer-Daniels-Midland Company, Decatur, Ill., and other sources) and 0.98 g sodium methoxide in a Parr reactor. The reactor was purged with nitrogen and heated to ftom 210° C. to 220° for 3 hrs. After cooling, the solution was neutralized with 3.5 g citric acid. Thin layer chromatography (silica gel 60 plates developed with 1:1 ethyl ether:hexane and stained with sulfuric acid) showed spots consistent with the desired product and very little remaining starting material. The reaction product containing the fatty acid esters of Mixture 1 was mixed with ether and allowed to settle overnight, after which the ether layer had become transparent. The ether was removed from the upper layer by vacuum rotary evaporation to yield a translucent yellow liquid having the composition shown in Table 4 (“Mixture 1-FA esters”). TABLE 4 Composition of Fatty Acid Esters from Glycerol Hydrogenolysis Product Component Percent (% wt) PGME 55.46% 1,2-Propanediol 19.31% Di-PGME 10.37% Propylene glycol diester (PGDE) 5.93% Fatty acids 3.70% Glycerol 1.77% Di-PGDE 1.40% Water 0.76% Ethylene glycol 0.63% 2,3-Butanediol 0.37% Dipropylene glycol 0.30% Mixture 1 was used to replace petroleum derived propylene glycol component in the Grind portion of a latex paint formula and the composition comprising the fatty acids esters of Mixture I (Mixture 1-FA esters) was used to replace Archer RC (petroleum derived PGME, commercially available from Archer-Daniels-Midland Company, Decatur, Ill.) in the Let down portion of the latex paint formulation. Four latex paint formulations (low sheen interior/exterior white paint with <50 g/L, VOC) comprising Mixture I as a replacement for petroleum derived propylene glycol and/or Mixture 1-FA esters as a replacement for Archer RC were prepared and compared to a control comprising petroleum derived propylene glycol and Archer RC. In Formula A petroleum derived propylene glycol in the Grind portion was replaced with biobased Mixture 1. Formula B contained propylene glycol in the Grind portion but replaced the Archer RC in the Let down portion with Mixture 1-FA esters. Formula C contained propylene glycol in the Grind portion by replaced the Archer RC in the Let down portion with twice the amount of the Mixture 1-FA esters (as compared to Formula B). Formula D replaced the petroleum derived propylene glycol in the Grind portion with biobased Mixture 1 and the Archer RC in the Let down portion with twice the amount of the Mixture 1-FA esters. Table 5 presents the four latex paint formulations containing biobased products and a control formulation that contained petroleum based products.The latex paint formulations were prepared as follows. For the Grind portion, the Grind ingredients were added one at a time while mixing under low speed (200-300 rpm) with a high speed disperser (Stir Pak or Hockmeyer). When all grind ingredients were added, the speed was increased to 800-1200 rpm to completely disperse the pigment to a 5-6 NS fineness of grind. For the Let down portion, the Let down ingredients were added one at a time while mixing under medium speed (600-800 rpm) to complete the paint. After all ingredients had been added, mixing was continued for about 15 minutes. TABLE 5 Latex Paint Formulations (Grind and Let down Portions) Control Formula A Formula B Formula C Formula D Pounds Pounds Pounds Pounds Pounds Raw Material (lbs) (lbs) (lbs) (lbs) (lbs) Grind Water 70.00 70.00 70.00 70.00 70.00 Propylene glycol 12.00 - 12.00 12.00 - Mixture 1 - 12.00 - - 12.00 Tamol 1124 5.00 5.00 5.00 5.00 5.00 Omyacarb UF 165.00 165.00 165.00 165.00 165.00 Kathon LX 1.5% 1.75 1.75 1.75 1.75 1.75 LetTiO2 Slurry 260.00 260.00 260.00 260.00 260.00 Down Water 60.00 60.00 60.00 60.00 60.00 Rhoplex SG-30 440.00 440.00 440.00 440.00 440.00 Archer RC 11.27 11.27 - - - Mixture 1-FA esters - - 11.27 22.54 22.54 Aerosol OT-75 1.50 1.50 1.50 1.50 1.50 BYK 1660 2.06 2.06 2.06 2.06 2.06 Ammonia (28%) 1.50 1.50 1.50 1.50 1.50 Acrysol RM 16.00 16.00 16.00 16.00 16.00 2020NPR Acrysol SCT-275 6.00 6.00 6.00 6.00 6.00 Water 48.98 48.98 48.98 48.98 48.98 Total 1101.06 1101.06 1101.06 1112.33 1112.33 Tamol 1124 is a sodium carboxylate dispersant (Rohm & Haas, Philadelphia, PA) Omyacarb UF is a high purity, ultrafine, wet ground calcium carbonate (Omya Inc., Proctor, Vt.) Kathon LX is a biocide latex paint preservative (Rohm & Haas, Philadelphia, PA) Rhoplex SG-30 is an acrylic binder (Rohm & Haas, Philadelphia, PA) Aerosol OT-75 is an anionic surfactant (Cytec Industries, West Paterson, NJ) BYK 1660 is an emulsion of siloxylated polyethers (BYK-Chemie, Wallingford, CT) Acrylsol RM 2020NPR is a modified ethylene oxide urethane rheology modifier (Rohm & Haas, Philadelphia, PA) Acrysol SCT-275 is a rheology modifier (Rohm & Haas, Philadelphia, PA)The latex paint formulations were tested for viscosity, pH, curing, gloss, opacity, open time, color, stability, freeze-thaw stability (using ASTM D2243), scrub cycles (using ASTM D2486) and block test (using ASTM D4946). The results are presented in Table 6. TABLE 6 Properties of Latex Paint Formulations Paint Properties Control Formula A Formula B Formula C Formula D Viscosity, ku/ICI 103.3/0.80 104.6/0.75 98.1/0.746 116.6/0.746 117.7/0.738 pH 9.49 9.25 9.19 9.39 9.32 Curing (at) 40° F. passed passed failed passed passed Gloss (at) 60 deg 21.5 20.7 - 24.4 24 Opacity 96.36 96.56 - 96.7 96.55Open Time1 Standard Equal to - Equal to Equal to Standard Standard Standard Color - CIELab Lightness L 96.49 96.21 - 96.38 96.36 Yellowness b 1.67 1.65 1.66 1.69 Yellowing Index YE 2.42 2.40 2.41 2.46 Heat-aged Stability 10 days (at)140° F. Δ pH -0.19 +0.10 - -0.29 -0.15 Δ Viscosity, ku +4.90 +5.60 -7.20 -7.20 Δ Gloss (at) 60 deg 0 +1.80 +1.80 +2.60 CIELab, Δb yellowness 0.14 0.21 0.10 0.11 ΔYE, yellowing index 0.43 0.33 0.16 0.17 Freeze-thaw ASTM failed failed - failed failed D2243 (at) Cycle 1 Scrub Cycles ASTM 1600 1600 1567 1881 1975 D2486 Block Test ASTM D4946 120° F. 1 day cure 3 2 - 1 2 7 day cure 8 8 9 8 1Resin vendor in-house test procedureLatex paint in which Mixture 1 replaced petroleum derived propylene glycol in the Grind portion (Formula A) demonstrated open time, block test and scrub resistant equivalent to that of the control formulation made with petroleum derived propylene glycol. Formula A demonstrated a slight increase in yellow before and after the heat-aged stability test which may be attributed to the initial amber color of Mixture 1. The degree of failure in the freeze-thaw stability of Formula A was equal to that of the control formulation.Latex paint with which Archer RC in the Let down phase was replaced with an equal weight of Mixture 1-FA esters (Formula B) resulted in a latex paint that failed the low temperature curing test (at 40° F.). Consequently, no further evaluation was performed on this formulation.Latex paint with which Archer RC in the Let down phase was replaced with an twice the weight of Mixture 1-FA esters (Formula C) resulted in a latex paint that passed the low temperature curing test and demonstrated greater viscosity and gloss than the control formulation. Formula C also gave better scrub resistance than the control. Block resistance of Formula C after one day was less than the control formulation, but as the paint hardened during seven days of curing at elevated temperature, the paint film became harder than the control formulation. In addition, Formula C also displayed a decrease in pH and gloss after the 10-day heat-aged stability test at 140° F.For latex paint Formula D where the petroleum derived propylene glycol in the Grind phase was replaced with biobased Mixture 1 and the Archer RC in the Let down phase was replaced with Mixture 1-FA esters (at twice the weight content of the Archer RC), the resulting latex paint formulation displayed higher viscosity, gloss, and scrub resistance than the control formulation. In addition, the block resistance of Formula D was comparable with that of the control formulation.Properties of latex paint formulations in which petroleum derived propylene glycol was replaced with biobased Mixture 1 and/or petroleum derived Archer RC was replaced with biobased Mixture 1-FA esters (at twice the amount of the Archer RC) displayed properties that were equal to or substantial improvements of the properties of the control formulation. The biobased hydrogenolysis product mixtures may be used as replacement of petroleum based products in the formulation of latex paints. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 88% | With iridium chloride trihydrate; oxygen; sodium carbonate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In 1,3,5-trimethyl-benzene at 169℃; for 15h; |
[ 50-70-4 ]
[ 109-99-9 ]
[ 142-68-7 ]
[ 96-47-9 ]
[ 1003-38-9 ]
[ 67-56-1 ]
[ 71-23-8 ]
[ 1120-72-5 ]
[ 1757-42-2 ]
[ 57-55-6 ]
[ 64-17-5 ]
[ 623-37-0 ]
[ 105-30-6 ]
[ 687-47-8 ]
[ 71-41-0 ]
[ 692-45-5 ]
[ 591-78-6 ]
[ 589-38-8 ]
[ 108-21-4 ]
[ 3142-66-3 ]
[ 64-19-7 ]
[ 123-38-6 ]
[ 107-87-9 ]
[ 802294-64-0 ]
[ 5077-67-8 ]
[ 110-13-4 ]
[ 67-63-0 ]
[ 67-64-1 ]
[ 56-81-5 ]
[ 96-22-0 ]
[ 79-31-2 ]
[ 78-93-3 ]
[ 78-92-2 ]
[ 142-62-1 ]
[ 652-67-5 ]
[ 107-92-6 ]
[ 513-85-9 ]
[ 111-27-3 ]
[ 109-52-4 ]| 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 10% Pd/C; 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 |
|---|---|---|
| 1: 66 %Chromat. 2: 16 %Chromat. 3: 7 %Chromat. | With sulfuric acid at 110 - 140℃; for 10h; Dean-Stark; Green chemistry; chemoselective reaction; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 85 %Chromat. | With sulfuric acid at 110 - 140℃; for 10h; Dean-Stark; chemoselective reaction; | |
| at 90.9 - 206.3℃; for 0.4h; Reflux; Industrial scale; | 2 Esterification Implemented by Reactive Distillation (Invention) This example shows the performances of a method for esterification by reactive distillation implemented according to the invention. The reactive distillation column comprises 20 plates numbered from top to bottom. 50 kmol/h of feedstock, consisting of 2,3-BDO at 110° C., is introduced in the area of the plate 5. 150 kmol/h of acetic acid at 110° C. is injected in the area of the plate 15. The distillate reflux is reinjected at plate 1, with a molar reflux rate of 1, and the residue reflux is reinjected at plate 20, with a molar reboil rate of 5.3. The column is operated with a pressure and a temperature at the top of 0.1 MPa and 90.9° C., and a pressure and a temperature at the bottom of 0.11 MPa and 206.3° C. The dwell time in the column is 2 hours. The dwell time per reactive plate is 24 minutes. The column comprises 5 reactive plates containing an ion-exchange acid resin (Dry Amberlyst 35), with these plates being numbered 6, 8, 10, 12 and 14. The acetic acid/2,3-BDO molar ratio in the column is 3. Under these conditions, the column produces 150.0 kmol/h of distillate and 50.0 kmol/h of residue. 2,3-BDO diester with a purity of 99.3 mol % (diester flow rate in the residue/flow rate of diol+monoester+diol in the residue) is obtained, with a 2,3-BDO diester yield of 99.3 mol % (diester flow rate in the residue/flow rate of diol at the inlet). The losses in diol, monoester and diester, in the distillate are 0.4 mol % (flow rates of diol+monoester+diester in the distillate/diol flow rate at the inlet). The method according to the invention makes it possible to reduce considerably the acetic acid flow rate in relation to the 2,3-butanediol flow rate without significantly reducing the performance of the reactive distillation (purity of 99.3 mol % according to the invention versus 99.9 mol % according to the prior art; yield of 99.3 mol % according to the invention versus 99.2 mol % according to the prior art). The temperature within the column used in the method according to the invention increases significantly only at the bottom of the column, in the zone consisting only of separation stages (plates 15 to 20) that makes it possible to carry out the separation between the diol/monoester/diester radicals, on the one hand, and acetic acid/water, on the other hand. With the catalyst being located above this zone, where the temperature does not exceed 135° C., the reactions for degradation of 2,3-butanediol into MEK are very significantly limited. | |
| With TA 801 at 110℃; Sealed tube; | 1 Example 1-Esterification of 2,3-Butanediol The esterification of 2,3-butanediol is carried out in a closed stirred reactor, under the following conditions: A temperature of 110° C. (corresponds to the mean temperature of the reactive zone of the reactive distillation column al)). 6 mol of acetic acid per mol of 2,3-butanediol (corresponding to a large excess of acetic acid). Acid catalyst TA801 at 2.2 mol % in relation to 2,3-butanediol. The conversion of 2,3-butanediol into monoester and diester over time is followed by gas chromatography (FIG. 3). It should be noted that the kinetics of conversion of the RR, SS and RS forms of 2,3-butanediol are identical, and the proportions of the various diastereoisomers were added. It is possible to note that despite the presence of a large excess of acetic acid, the conversion of 2,3-butanediol is limited, which justifies carrying out reactive distillation in such a way as to shift the balance toward the formation of 2,3-butanediol diester. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 86% | With iron(II) bromide In 1,4-dioxane at 150℃; for 18h; Inert atmosphere; Sealed tube; | |
| 80% | With zinc(II) chloride In 1,2-dichloro-ethane at 84℃; for 24h; Inert atmosphere; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 98% | With tungsten hexacarbonyl at 180℃; for 1h; | |
| With tetrabutylammomium bromide at 180℃; for 0.05h; Flow reactor; | ||
| 86.6 %Chromat. | With Mg3Al0.9Ce0.1O at 150℃; Autoclave; | 2.4. Catalyst activity test General procedure: The transesterification reaction with ethylene glycol and dimethyl carbonate was carried out in a 50 mL stainless steel autoclave under self generated pressure. The reaction temperature was controlled by the SLM100 heating sleeve of Beijing Century Senlong Experimental Instrument Co, LTD. After the reaction, the product was separated in a high-speed centrifuge and then partially liquidated, ethanol and biphenyl were added as solvents and standard substances, respectively.It was quantitatively analyzed by gas chromatography (AOC-20I PLUS,30 m * 0.32 mm*1 μm) with ethanol as solvent. The conversion of ethylene glycol, the selectivity, and yield of ethylene carbonate are calculated as follows: |
| 97 %Chromat. | With cerium(IV) oxide at 130℃; for 0.5h; Autoclave; Inert atmosphere; | 2.3. Catalytic test General procedure: All transesterification reactions were carried out in a 50 mL stainless steel autoclave. In a typical experimental procedure, nitrogen purges and replaces the gas in the reactor before the experiment begins. At the end of the reaction, the reaction product was separated, and the appropriate amount of supernatant was taken and added to the internal standard to configure the standard solution. The content of each substance was quantitatively analyzed by gas chromatography (AOC-20I PLUS, 30 m*0.32 mm*1 μm) equipped with a FID detector using ethanol as solvent. The SPL1 temperature was set to 260C, the column temperature was set to 80C, the retention time was 1 min and then the temperature was increased to 240C at a rate of 15 min/C, and the retention time was again 1 min. The FID detector temperature was set to 250C. |

| 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 |
|---|---|---|
| 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 |
|---|---|---|
| 91.2% | Stage #1: 2,3-butandiol With titanium tetra-n-propoxide at 120℃; for 1.5h; Stage #2: dimethylsulfite at 64 - 150℃; | 2 Example 2 Synthesis of 4,5-Dimethyl Sulfite In a three-necked flask equipped with a condenser, an agitator, and a thermometer, 900 g of 2,3-butanediol and 13 g of anhydrous magnesium sulfate were added and reacted at 120°C for 2 hours. In order to prevent the entry of water vapor in the air(atmosphere), a drying tube was added on the top of the condenser tube, and anhydrous magnesium sulfate was added into the drying tube. It was then rapidly vacuum filtered and the moisture content measured with a trace moisture meter was 150 ppm.In a three-necked flask equipped with a stirrer, a thermometer, and a fractionation tower, 472 g of 2,3-butanediol was added after drying, 10 g of Titanium propoxide was added, and the reaction was carried out at 120°C for 1.5 hours. Then 550 g of dimethyl sulfite was added and the reaction started at 120 °C in the oil bath. The oil bath temperature was controlled to not exceed 150 °C and the temperature at the top of the fractionation tower was maintained at 64-67 °C. The reaction was stopped when the temperature of the oil bath was at 150°C and the distillation column was no longer distilling methanol. The apparatus was changed to a distillation apparatus, and a 176 -178° C. fraction was collected to obtain 620 g of 4,5-dimethyl-1,3,2-dioxathiolane 2-oxide (structure 2) in a yield of 91.2% and purity: 99% (HPLC). |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 95% | With cesiumhydroxide monohydrate In toluene at 150℃; for 24h; Inert atmosphere; Sealed tube; Green chemistry; | 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. |
| 92% | With 1,10-Phenanthroline; cesiumhydroxide monohydrate; nickel dibromide In toluene at 150℃; for 24h; Inert atmosphere; Sealed tube; | |
| 77% | With C18H24ClIrN3O(1+)*Cl(1-); potassium hydroxide In water for 24h; Schlenk technique; Reflux; Green chemistry; |
| 75% | With cesiumhydroxide monohydrate; C17H14Br2CoN4 In toluene at 150℃; for 24h; Sealed tube; Inert atmosphere; | |
| 86 % | With [Ru(p-cymene)Cl2]2; lithium monoborate; 1,4-di(diphenylphosphino)-butane at 165℃; Schlenk technique; Inert atmosphere; | 3.2. General procedure for catalytic reactions General procedure: For optimizing the homogeneous reaction condition of AAD condensation (Scheme 2), four kinds of commercially available Ru(II)-based catalysts (Cat. 1, Cat. 2, Cat. 3, or Cat. 4, Scheme 3) and three kinds of phosphine ligands (PPh3, dppe, or dppb, Scheme 3) were used to the coupling of benzene-1,2-diamine and butane-2,3-diol. Typically, benzene-1,2-diamine (0.27 g, 2.5 mmol), butane-2,3-diol (0.68 g, 7.5 mmol), Ru-based catalyst [Cat. 1 (3.125 μmol, 0.125 mol%, or Cat. 2-4 (6.25 μmol, 0.25 mol%)], phosphine ligand [PPh3, dppe, or dppb (0∼12.5 μmol, 0∼0.5 mol%)] and additive [NaB(OH)4, or LiB(OH)4 (62.5∼125 μmol, 2.5∼5.0 mol%)] were mixed in a 25 mL Schlenk tube. The reaction mixture was heated at 165°C (oil bath) for 12 h in an open system under purified nitrogen atmosphere. After cooling to room |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 93% | With cesiumhydroxide monohydrate; C17H14Br2CoN4 In toluene at 150℃; for 24h; Sealed tube; Inert atmosphere; | |
| 86% | With sodium hydroxide In toluene at 120℃; for 3h; Inert atmosphere; Sealed tube; Green chemistry; |
[ 56-81-5 ]
[ 71-23-8 ]
[ 64-17-5 ]
[ 42027-23-6 ]
[ CAS Unavailable ]
[ 78-83-1 ]
[ 78-92-2 ]
[ 513-85-9 ]| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With CuMgAl oxide at 300℃; for 4h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 98 %Spectr. | Stage #1: carbon dioxide; 2-methyl-but-3-yn-2-ol With C15H18N2O2 In acetonitrile at 25℃; for 24h; Inert atmosphere; Schlenk technique; Stage #2: 2,3-butandiol With MTBD In acetonitrile at 25℃; for 24h; Inert atmosphere; Schlenk technique; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 78 %Chromat. | With [(iPrPNHP)Fe(H)(CO)(Br)]; potassium <i>tert</i>-butylate; isopropyl alcohol In tetrahydrofuran at 140℃; for 24h; Inert atmosphere; Schlenk technique; Green chemistry; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 33.1 %Chromat. | With tetraethylammonium iodide In acetonitrile at 20℃; Electrolysis; |
| 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 |
|---|---|---|
| 94% | With sodium hydroxide In toluene at 120℃; for 3h; Inert atmosphere; Sealed tube; Green chemistry; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 58% | With pyridine; oxygen; potassium hydroxide at 110℃; for 16h; Green chemistry; chemoselective reaction; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 79% | 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 |
|---|---|---|
| 88% | With oxygen; potassium carbonate at 20℃; | |
| 74 % | Stage #1: 1,1,2,2-tetrachloroethylene; 2,3-butandiol With oxygen at 60℃; UV-irradiation; Stage #2: at 60℃; Stage #3: With potassium carbonate at 20℃; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With water; hydrogen at 179.84℃; Autoclave; regioselective reaction; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 82% | With [Ru(p-cymene)(k(2)-o-DPPBS)Cl]; sodium carbonate In toluene at 150℃; for 12h; Inert atmosphere; Autoclave; | 4.2. General procedure for quinoxalines from 1,2-dinitrobenzene derivatives and vicinal diols General procedure: Under protection of argon, 1,2-dinitrobenzene 1a (0.2 mmol, 1.0 equiv.), 2,3-butanediol 2a (1 mL), catalyst [Ru-1], base additive and solvent (1 mL) were added sequentially to a 25 mL autoclave, which was heated to the set reaction temperature on a metal block and stirred for a certain time. After the reaction finished, the autoclave was cooled down to room temperature and the pressure was carefully released and biphenyl (0.1 mmol, 0.5 equiv.) (internal standard) was added to the solution. The reaction solution was diluted with ethyl acetate (5 mL), filtered through a short silica gel column, analyzed quantitatively and qualitatively using GC and GC-MS. After removing the solvent by vacuum, the residue was directly purified by flash chromatography on silica gel (eluent: hexane/ethyl acetate =50: 1 to 20:1) to give the desired product. Caution The NMR sample preparation should avoid using plastics. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 88% | With [Ru(p-cymene)(k(2)-o-DPPBS)Cl]; sodium carbonate In toluene at 150℃; for 12h; Inert atmosphere; Autoclave; | 4.2. General procedure for quinoxalines from 1,2-dinitrobenzene derivatives and vicinal diols General procedure: Under protection of argon, 1,2-dinitrobenzene 1a (0.2 mmol, 1.0 equiv.), 2,3-butanediol 2a (1 mL), catalyst [Ru-1], base additive and solvent (1 mL) were added sequentially to a 25 mL autoclave, which was heated to the set reaction temperature on a metal block and stirred for a certain time. After the reaction finished, the autoclave was cooled down to room temperature and the pressure was carefully released and biphenyl (0.1 mmol, 0.5 equiv.) (internal standard) was added to the solution. The reaction solution was diluted with ethyl acetate (5 mL), filtered through a short silica gel column, analyzed quantitatively and qualitatively using GC and GC-MS. After removing the solvent by vacuum, the residue was directly purified by flash chromatography on silica gel (eluent: hexane/ethyl acetate =50: 1 to 20:1) to give the desired product. Caution The NMR sample preparation should avoid using plastics. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With toluene-4-sulfonic acid In toluene for 15h; Dean-Stark; Reflux; |
Tags: 2,3-Butanediol | Alcohols | Organic Building Blocks | 513-85-9
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| 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 |
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