There will be a HazMat fee per item when shipping a dangerous goods. The HazMat fee will be charged to your UPS/DHL/FedEx collect account or added to the invoice unless the package is shipped via Ground service. Ship by air in Excepted Quantity (each bottle), which is up to 1g/1mL for class 6.1 packing group I or II, and up to 25g/25ml for all other HazMat items.
Type
HazMat fee for 500 gram (Estimated)
Excepted Quantity
USD 0.00
Limited Quantity
USD 15-60
Inaccessible (Haz class 6.1), Domestic
USD 80+
Inaccessible (Haz class 6.1), International
USD 150+
Accessible (Haz class 3, 4, 5 or 8), Domestic
USD 100+
Accessible (Haz class 3, 4, 5 or 8), International
USD 200+
Structure of 111-27-3 * Storage: {[proInfo.prStorage]}
* 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.
General procedure: Alcohols (50 mmol, 1 equiv.) and 11.08 mL Et3N (80 mmol, 1.6 equiv.) was dissolved in 60 mL CH2Cl2, and the solution was cooleddown to 0 °C, then 4.33 mL methanesulfonyl chloride (56 mmol, 1.12 equiv.) was introduced by syringe successively. The mixture is stirredfor 30 min at 0 °C, and then stirred overnight at room temperature. The organic layer is washed successively with 1M hydrochloric acid solution, saturated aqueous sodium bicarbonate solution, and brine. The organic layer is dried over Na2SO4, filtered, and concentrated under reduced pressure. The product was purified by column chromatography with silica gel (EtOAc: petroleum=1: 2).
Reference:
[1] Organic and Biomolecular Chemistry, 2018, vol. 16, # 41, p. 7753 - 7759
[2] Journal of the American Chemical Society, 1985, vol. 107, # 18, p. 5210 - 5219
[3] Journal of Fluorine Chemistry, 2018, vol. 214, p. 35 - 41
[4] Journal of the Electrochemical Society, 2010, vol. 157, # 9, p. F124-F129
[5] European Journal of Organic Chemistry, 2018, vol. 2018, # 35, p. 4850 - 4856
[6] Canadian Journal of Chemistry, 1956, vol. 34, p. 757,760
[7] Journal of the American Chemical Society, 1954, vol. 76, p. 2984,2986
[8] Journal of Medicinal Chemistry, 1990, vol. 33, # 10, p. 2807 - 2813
[9] Tetrahedron Letters, 1990, vol. 31, # 17, p. 2457 - 2460
[10] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1991, # 8, p. 1201 - 1208
[11] Synthetic Communications, 1984, vol. 14, # 5, p. 469 - 476
[12] Green Chemistry, 2009, vol. 11, # 12, p. 1955 - 1960
[13] Physical Chemistry Chemical Physics, 2009, vol. 11, # 39, p. 8939 - 8948
[14] Catalysis Communications, 2010, vol. 11, # 5, p. 470 - 475
[15] Tetrahedron Letters, 2017, vol. 58, # 1, p. 59 - 62
EXAMPLE 4 In a 500 ml flask fitted with thermometer, mechanical stirrer, addition funnel, and a Dean-Stark trap, with attached condenser is placed 110g of resorcinol and 71.4g of 1-hexanol. The reaction mixture was heated at 160-200 C for 4 hours with no apparent reaction taking place. Alumina (15g) was added and the mixture heated gradually to 255 C over a period of 4 hours, 1.8 ml of water having been produced. Hexanol was removed from the reaction by drawing off through the Dean-Stark trap to allow the temperature to reach 255 C. Refluxing was continued at 240-255 C with the reflux temperature being controlled by the periodic addition of hexanol (that which had been removed) back to the reaction mixture. This procedure was continued over a period of about 8 hours, during which time all of the original hexanol had been added back to the reaction mixture, and during which 16.7 ml of produced water had been collected in the Dean-Stark trap. The reaction mixture was analyzed at this point (using o-cresol as an external standard) and was found to have the following composition, as determined by area under a gas chromatograph curve. A part of the crude reaction product (ca 90g was taken up in 500 ml of diisopropyl ether and washed with one 300 ml portion of 1N sulfuric acid and then with five 300 ml portions of water. The combined aqueous phases were back-extracted with 100 ml of diisopropyl ether, and this was combined with the other organic phase. Isopropyl ether was mostly removed from the organic material on a rotary evaporator. The residue 142.g was charged to a 4-foot spinning band fractional distillation column and distilled, the results shown in Table 1. The individual cuts were analyzed by gas chromatography. Cut 1 was essentially pure diisopropyl ether with about 8 percent hexenes. The compositions of the other cuts are listed in Table 2. The isolated yield of 4-n-hexylresorcinol amounts to about 24 wt %. A portion of cut 4, 5g. was recrystallized from petroleum ether to yield light yellow platelets, m.p. 57 C (m.p. of 4-n-hexylresorcinol is 61 C). The proton magnetic resonance spectrum of the recrystallized material was identical with that of a known sample of 4-n-hexylresorcinol.
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