* 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.
With lithium chloride In <i>N</i>,<i>N</i>-dimethyl-aniline at 190℃; for 3 h; Inert atmosphere
To a 500 ml 3 necked RBF equipped with an overhead stirrer, N2 inlet and a water condenser, were charged 5-allyl-3-methoxysalicylic acid (100 g, 0.48 mol., obtained above), N,N-dimethylaniline (20 ml, SRL 99.5percent pure) and anhydrous lithium chloride (0.750 g, 0.0176 mol., SRL 99percent pure). The above mixture was then heated gradually to 190 °C. The mixture begins to melt slowly as the bath temperature reaches 130 °C, becomes stirrable slurry at 150 °C and eventually a homogeneous liquid as the temperature approaches 190 °C. The reaction mixture was maintained at 190 °C for about 3h. Progress of the reaction was monitored by quenching aliquot sample with dilute hydrochloric acid followed by extraction with solvent (EDC or ether) and analyzing by HPLC (area percent) for the conversion of acid to eugenol. Having ensured the complete conversion of acid by HPLC, the reaction mixture was cooled to room temperature (25 °C) and diluted with 200 ml of 1,2- dichloroethane. To this dil. HC1 (28 ml of 35percent HC1 in 67 ml of water) was added such that the temperature of the reaction mixture does not shoot beyond 25 °C. The resultant mixture was then stirred for lh at room temperature followed by separation of the organic and aqueous layer. The resultant organic layer was passed through a bed of acidic sulphonated polystyrene resin cross linked with divinyl benzene (commonly known as Ion exchange resin, IER) to remove the residual N,N-dimethylaniline (Spec: <2 parts per million by weight (ppm). [0136] The solvent was distilled under vacuum (recovered) and the resultant dark brown liquid was purified by high vacuum distillation to give 71 g (Yield: 90percent) of pure para- eugenol (distilled at 112-116 °C at -10-12 mbar) with purity 99.7percent.
Reference:
[1] Patent: WO2015/15445, 2015, A2, . Location in patent: Paragraph 0135-0136
[2] Justus Liebigs Annalen der Chemie, 1919, vol. 418, p. 102
[3] Justus Liebigs Annalen der Chemie, 1863, vol. 125, p. 19
2
[ 143654-03-9 ]
[ 97-53-0 ]
Yield
Reaction Conditions
Operation in experiment
96%
With toluene-4-sulfonic acid In neat (no solvent, solid phase) at 20℃; for 0.583333 h; Green chemistry
General procedure: MOM ether (5 mmol) and pTSA.H2O (7.7 mmol) weretriturated well in a mortar for 5 min (in the case of entry 10trituration time was about 15 min), reaction mixture was leftat room temperature for another 30 min. After completion ofthe reaction (monitored by TLC), cold water (4oC) wasadded. The products were separated by centrifugation. Theyields of the products ranged from 85-98percent. The purities andthe identities of the products were established by direct comparisonwith known compounds (TLC, Mp and IR). See supplementaryinformation for further details.
89%
With bismuth(III) chloride In water; acetonitrile at 50℃; for 1 h;
General procedure: BiCl3 (30 molpercent) was added to a stirred solution of MOM-protected phenol (1 mmol) in MeCN/H2O (5:0.1 mL; 5:0.1 v/v) and the mixture was stirred at 50 °C until reaction was complete (TLC control). The mixture was filtered over a pad of celite using CH2Cl2 (10 mL), and the resulting filtrate was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. Flash column chromatography of the residue over silica gel (hexane/EtOAc mixture) afforded the desired pure phenol (76–95percent). All phenolic products were analyzed by IR and NMR spectroscopy and by comparison with authentic samples.
Reference:
[1] Letters in Organic Chemistry, 2017, vol. 14, # 4, p. 231 - 235
[2] Synthetic Communications, 2016, vol. 46, # 7, p. 586 - 593
3
[ 214330-24-2 ]
[ 97-53-0 ]
Yield
Reaction Conditions
Operation in experiment
87%
With sodium tetrachloroaurate (III) dihydrate In methanol at 20℃; for 7 h;
NaAuCl4·2 H2O (39.8 mg, 0.1 mmol, 0.05 equiv) was added to a solution of silyl ether 1030 (557 mg, 2 mmol) in MeOH (4 mL) at r.t., and the mixture was stirred at r.t. for 7 h. The mixture was then diluted with EtOAc (10 mL), filtered through activated alumina, and concentrated in vacuo. The residue was purified by flash column chromatography[silica gel, EtOAc–PE (1:5)] to give a pale-yellow oil; yield: 286mg (87percent). 1H NMR (300 MHz, CDCl3): δ = 6.86–6.83 (m, 1 H), 6.69–6.67 (m, 2 H),5.99–5.88 (m, 1 H), 5.49 (s, 1 H), 5.10–5.04 (m, 2 H), 3.87 (s, 3 H), 3.32(d, J = 6.6 Hz, 2 H).13C NMR (75 MHz, CDCl3): δ = 146.44, 143.92, 137.80, 131.89, 121.17,115.45, 114.26, 111.14, 55.83, 39.84.MS (ESI, MeOH): m/z = 187 [M + Na]+.HRMS-ESI: m/z [M + Na]+ calcd for C10H12NaO2: 187.0735; found:187.0735.
Reference:
[1] Patent: WO2015/15445, 2015, A2, . Location in patent: Paragraph 0119-0121
[2] Patent: CN105294409, 2016, A, . Location in patent: Paragraph 0042; 0043; 0044; 0045; 0046
5
[ 4125-45-5 ]
[ 97-53-0 ]
Reference:
[1] Synlett, 2008, # 13, p. 1957 - 1960
[2] Catalysis Science and Technology, 2013, vol. 3, # 10, p. 2541 - 2545
6
[ 50-00-0 ]
[ 56521-01-8 ]
[ 97-53-0 ]
Yield
Reaction Conditions
Operation in experiment
59.51 %Chromat.
With formic acid; zinc In ethanol at 65℃; for 4.5 h;
A mixture of nitroeugenol (0.72mmol), formaldehyde (0.72 mmol) and Zn powder (7.32mmol) was dissolved in 25 mL of ethanol. Formic acid (4.5mmol) was then added to the mixture. Reaction was heated at 65 °C for approximately 4.5 h and filtered while hot. Filtrate was extracted with dichloromethane (3 × 25 mL) and the organic phases were combined, which then dried with Na2SO4. Mixture was filtered and evaporated. Afterwards, the obtained product was analyzed by using GC-MS.
Reference:
[1] Asian Journal of Chemistry, 2017, vol. 29, # 4, p. 867 - 869
7
[ 85614-43-3 ]
[ 97-53-0 ]
Reference:
[1] Justus Liebigs Annalen der Chemie, 1919, vol. 418, p. 102
[2] Patent: WO2015/15445, 2015, A2, . Location in patent: Paragraph 0138
8
[ 81391-19-7 ]
[ 97-53-0 ]
Reference:
[1] Journal of Organic Chemistry, 1982, vol. 47, # 10, p. 1983 - 1984
9
[ 4125-43-3 ]
[ 97-53-0 ]
Reference:
[1] Tetrahedron Letters, 1986, vol. 27, # 41, p. 4945 - 4948
[2] Zhurnal Obshchei Khimii, 1941, vol. 11, p. 722,725[3] Chem.Abstr., 1942, p. 430
To a 5ml_ Biotage® microwave vial fitted with a magnetic stirrer, was charged with calcium bis-triflimide (16 mg, 26.7 μιτιοΙ) and O-allylguaiacol (438 mg, 2.67 mmol). The vial was then sealed and the resultant homogeneous mixture was stirred for 2 minutes at the temperature of 200°C, under an autogenous pressure and a microwave irradiation generated by the Biotage® microwave instrument. After cooling to room temperature, the resulting reaction mixture was analysed by 1H NMR to determine the conversion ratio (100percent) and isomeric composition (76percent of ortho- eugenol and 24percent of para- eugenol).
Reference:
[1] Tetrahedron, 2007, vol. 63, # 45, p. 10949 - 10957
[2] Synthetic Communications, 2004, vol. 34, # 8, p. 1433 - 1440
[3] Journal of Chemical Research, Miniprint, 1991, # 7, p. 1758 - 1770
[4] Synlett, 2000, # 5, p. 615 - 618
[5] Advanced Synthesis and Catalysis, 2002, vol. 344, # 3-4, p. 434 - 440
[6] Patent: WO2016/4632, 2016, A1, . Location in patent: Paragraph 0041
With hydrogen In 2,2,4-trimethylpentane at 180℃; for 0.166667h; Inert atmosphere;
General procedure: Hydrogenation/deoxygenation experiments were carried out in a 500 ml batch stirred reactor (PPI). The reactor vessel wasfilled with 1.00 g of not calcined catalyst and flushed with nitrogen and hydrogen. Before each experiment, catalyst was heated at 200 C in presence of hydrogen. After reactor cooling to ambient temperature, the vessel was filled with 300 ml of isooctane containing 0.125 mol of substrate. Reactor free space was gradually flushed first with nitrogen and then with hydrogen and pressurized to 1 MPa. Reactor was then heated under slow stirring (lessthan 50 rpm) for promoting heat transfer until the desired reaction temperature (180°C) was reached. After reaching the reaction temperature, hydrogen pressure was set at 5 MPa and the stirrer rotation was increased to 1500 rpm. The reaction was carriedout under the set reaction conditions for 90 min. Samples of reaction products were taken at defined reaction times and analyzed off-line by GC. As constant amount of reactant and catalyst were used in each experiment, the determined conversions correspond to catalyst activity, i.e. rate of disappearance of reactant per mass of catalyst. For catalyst activity study, o-, m- and p-cresols were used for studying the effect of isomer type, i.e. of the methyl position relative to the hydroxyl group, on substrate hydrogenation and deoxygenation.Eugenol was used as a model compound for pyrolysis oil stabilization (allyl hydrogenation). Guaiacol represents a modelcompound for studying the effect of methoxy substitution that istypical in products of lignin pyrolysis. Samples of products and substrates were analyzed by gas chromatography, using HP-PONAcolumn with temperature ramp starting at 35 C for 15 min and5 C/min up to 250 C.
100%
With sodium formate; sodium hydroxide In water at 120℃;
2.4. General procedure for the flow hydrogenation
General procedure: A premixed mixture of phenolic compound (1a-h) and sodium formate (2, 3 equiv.) in H2O (0.1 M) was prepared in a flask with the function of the reservoir, and the mixture was adjusted to pH 12.0 with the addition of 5 M aq NaOH. POLITAG-Pd(0)-L1 (8 wt%, 0.54 mmol,718.3 mg) was dispersed in solid glass beads and glass powder and was charged in a stainless-steel reactor; the equipment was connected byusing the appropriate valves, and a back pressure regulator was placedon the outlet tube. The packed reactor was placed into a thermostated box, and the mixture was pumped through the catalyst columns at120 °C. The conversion of 1a-i and its selectivity were periodically monitored by GLC analysis.
99%
With 4,4'-di-tert-butylbiphenyl; lithium; isopropyl alcohol; nickel dichloride In tetrahydrofuran at 20 - 76℃; Inert atmosphere; chemoselective reaction;
99.1%
With hydrogen In dodecane at 200℃; for 1.5h;
98%
With hydrogen In ethanol at 20℃; for 5h;
97%
With hydrogen In ethanol; ethyl acetate at 60℃; Flow reactor;
97%
With palladium 10% on activated carbon; hydrogen In ethanol at 20℃; for 16h;
96%
With hydrogen In methanol at 180℃; for 18h; Sealed tube; Green chemistry; chemoselective reaction;
95%
With hydrogen In water for 24h; Ambient temperature;
95%
With Wilkinson's catalyst; hydrogen In dichloromethane at 125℃;
95%
With hydrogen at 80℃; for 1h; Autoclave;
94%
With hydrogen In ethanol Ambient temperature;
93%
With palladium 10% on activated carbon; hydrogen In ethanol at 20℃; for 16h;
93%
With triethylsilane; sulfuric acid; 5%-palladium/activated carbon In tetrahydrofuran at 20℃; for 0.5h;
91%
With crithmene; palladium 10% on activated carbon; silica gel In ethyl acetate at 140℃; for 0.025h; Flow reactor;
89%
With cobalt In tetrahydrofuran at 20℃;
84%
With palladium (II) acetate; water; bis(pinacol)diborane; tricyclohexylphosphine In toluene at 27℃; for 12h; Inert atmosphere;
80%
With dimethylamine borane In toluene at 20℃; for 6h; Schlenk technique; Green chemistry;
78%
With air; hydrazine hydrate In ethanol at 25℃; for 4h;
15.5%
With hydrogen In dodecane at 250℃; for 8h; Autoclave;
With ethanol; hydrogen
With nickel at 20 - 65℃; Hydrogenation;
With ethanol; nickel at 20 - 65℃; Hydrogenation;
With ethanol; nickel at 20℃; Hydrogenation;
With ethanol; platinum at 20℃; Hydrogenation;
With palladium Hydrogenation;
With tetralin; palladium at 115 - 120℃;
With palladium on activated charcoal; ethanol Hydrogenation;
With palladium; acetic acid Hydrogenation;
With diethyl ether; platinum Hydrogenation;
With nickel at 92℃; Hydrogenation.unter erhoehtem Druck;
With hydrogen In ethyl acetate
With hydrogen In ethanol at 20℃;
With hydrogen In tetrahydrofuran at 20℃; for 24h;
With hydrogen In isopropyl alcohol at 50℃; for 4.5h;
76 %Chromat.
With hydrazine hydrate In chloroform at 25℃; for 24h;
92 %Chromat.
With Pt/γ-Al2O3; hydrogen In Hexadecane at 249.84℃; for 1h; Autoclave;
With riboflavin 2’,3’,4’,5’-tetraoctadecanoate; hydrazine hydrate at 30℃; for 4.5h;
With hydrogen In methanol at 20℃; for 1h;
With Lindlar's catalyst; hydrogen In ethanol at 20℃; for 24h;
3.4. Synthesis of Compounds 5-7, 10a and b
General procedure: The hydrogenation of 2-4, eugenol, and 2-allyl phenol (0.5 mmol) was carried out employingabsolute EtOH (7 mL) and Pd/CaCO3 (10%w/w; 17.4 mg) as catalyst. The reaction flask was filled withH2(1 atm) and stirred at rt for 24 h. The catalyst was removed by filtration on Celite 545. In these conditionsthe expected products have been obtained quantitatively without further purification. The spectroscopicdata of 30,5-dipropyl-(1,10-biphenyl)-2,40-diol (5) [42] 2,40-dimethoxy-30,5-dipropyl-1,10-biphenyl(7) [42] 2-methoxy-4-propylphenol (10a) [45] and 2-propylphenol (10b) [46] were in agreement withliterature data.
100 %Chromat.
With rhodium-meso-tetrakis(4-carboxyphenyl)porphyrin; hydrogen In isopropyl alcohol at 100℃; for 12h; Schlenk technique; Autoclave;
With hydrogen; 1-butyl-3-methylimidazolium Tetrafluoroborate In hexane at 80℃; for 8h; Autoclave;
Biphasic hydrogenation of eugenol
General procedure: Biphasic eugenol hydrogenations were performed using the nanostructured rhodium and ruthenium catalysts: Rh/ IL1, Rh/ IL2, Ru/ IL1 and Ru/ IL2. The methodology carried out by Melean et al 14 was modified, such that the substrate was reacted with hydrogen in the presence of the nanostructured system stabilized with ionic liquid, an organic solvent was used to ensure the separation of the reaction products and the catalytic phase. In this sense, a Parr reactor was charged under inert atmosphere, with 6 mmol of eugenol, 3 ml of n-hexane, 0.5 ml of ionic liquid (IL1 and IL2) and 5 mg of each of the Ru catalysts (nanoparticles). of Ru/ IL1 and Ru/ IL2) and Rh (nanoparticles of Rh/ IL1 and Rh/ IL2) with 100 psi of H2 at a temperature of 80 C. The catalytic evaluations were carried out between 0.5 and 8 hours. At the end of the reaction time, the phases were separated for analysis by gas chromatography and mass spectroscopy
96.5 %Chromat.
With 5% active carbon-supported ruthenium; ethylene glycol at 185℃; for 0.5h;
97 %Spectr.
With hydrogen In methanol at 25 - 27℃; for 8h; Autoclave;
With rhodium(III) chloride; ethanol at 140 - 145℃;
2 (2) isomerization of eugenol: the isomerization reaction of eugenol by preparing isoeugenol
In a 25 ml flask was added4.2 mg of rhodium trichloride (RhCl3),And add about 3 drops of absolute ethanol to dissolve,Then 20.0 mmol (3.284 g)The eugenol obtained in step (1)The reaction at 140-145 ° C for 3-5h,The reaction liquid gradually changed from pale yellow to bright orange then dark orange,Detection of each section of the reaction liquid,Structural analysis with UV - Vis spectroscopy,After the reaction, stop heating,Cooled to room temperature; suction filtered,Rhodium trichloride catalyst was separated and recovered; Extraction of isoeugenol in the filtrate with ether,The combined organic layers,Evaporate the ether in the water bath,Get isoeugenol,The yield of isoeugenol is about 99%;
99%
With tris(triphenylphosphine)ruthenium(II) chloride at 50 - 60℃; for 4h;
1.1; 2.1; 3.1 Heterogeneous reaction:
500g of eugenol and 4.0g of triphenylphosphine ruthenium chloride as a catalyst are added into the reaction kettle and mixed uniformly, heated to 50-60°C and kept at the temperature for 4h until the eugenol content is less than 1%. Then, it was directly distilled under reduced pressure to obtain 495 g of isoeugenol with a content of 98.5%, with a mass yield of 99%.
82%
In methanol; water at 100℃; for 20h;
78%
With potassium fluoride on basic alumina In ethylene glycol at 200℃; for 1.5h;
69.72%
With potassium hydroxide at 140℃; for 4h;
64%
With cholin hydroxide; potassium hydroxide In water at 220℃; for 2.5h;
1.1; 2.1 step 1: Preparation of isoeugenol (3a) form eugenol (2a)
(a) In a round bottom flask, eugenol (0.1 g, 0.61 mmol), choline hydroxide (46% assay w/win aqueous solution, 0.5 g, 4.27 mmol), and potassium hydroxide (0.2 g, 3.65 mmol) was taken and was allowed to reflux for 2.5 h at temp 220°C. The progress of the reaction was monitored by GC analysis. After completion of the reaction, the reaction mixture was neutralized with con. HC1 (0.5 mL) followed by its extraction with ethyl acetate and water. The organic layer was dried over anhydrous sodium sulfate and concentrated to an oily crude material. The crude material was purified by column chromatography on silica gel (100-200 mesh size) using ethyl acetate-hexane as eluent which yielded pure isoeugenol (3a, a mixture of cis and trans) as oil. The conversion from eugenol to isoeugenol was 64% (GC analysis; cis: trans = 21:43).
With platinum on activated charcoal at 300℃; im Kohlendioxyd-Strom;
With potassium hydroxide; diethylene glycol at 160 - 180℃;
With potassium hydroxide; glycerol at 180℃;
With potassium hydroxide; pentan-1-ol at 140℃;
With potassium hydroxide at 130 - 140℃;
With pentan-1-ol; sodium
With potassium hydroxide at 220℃;
With potassium hydroxide; water at 220℃; Loesen in Wasser und Ansaeuern;
With potassium hydroxide beim Schmelzen;
With potassium hydroxide; sodium hydroxide beim Schmelzen;
With 10% KOH/alumina
With hexaaquaruthenium(II) tosylate In ethanol at 20℃;
99 %Chromat.
With [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][2-[[(2-methylphenyl)imino]methyl]phenolyl][3-phenyl-1H-inden-1-ylidene](chloro)ruthenium(II); di-μ-bromobis(tri-tertbutylphosphine)dipalladium(I) In toluene at 50℃; for 1h; Inert atmosphere;
With potassium hydroxide at 130 - 140℃;
With potassium hydroxide; pentan-1-ol at 140℃;
With MCM-22 zeolites dispersed on palladium In N,N-dimethyl-formamide at 200℃; for 6h; Autoclave;
2.3a Isomerisation of Eugenol
To understand thesurface basicity, the cations exchanged MCM-22 catalystswere studied for the isomerization of eugenol in a liquid phaseautoclave reactor at 200 °C for 6 h. All the alkali metal ionexchangedsamples were applied for the isomerisation ofeugenol. Prior to the reaction, the catalysts were activated byheating in an air oven at 70 °C for 1 h. Approximately 0.2 g ofeugenol (*0.188 mL) was introduced into the autoclavereactor having 2.5 mL of DMF as a solvent. Then, 0.05 g ofthe alkali and alkaline earth metal-containing MCM-22catalyst was added into the reactor. The temperature of thereactor was set to 200 °C and the reaction was continued for6 h. After the reaction, the catalyst was separated by filtrationand the products were analysed by gas chromatography (GC)equipped with ZB-5 capillary column (non-polar column)and a flame ionization detector. The products were confirmedbased on the retention time of the authentic samples receivedcommercially.
A 100 mL three-neck flask equipped with condenser and magnetic stirrer was charged with eugenol (5 g) was then added NaOH (2 g in 20 mL of distilled water) and stirred for 15 min. 4 mL of dimethyl sulfate was added drop-wise and stirring for 0.5 h. The mixture was refluxed at 103 C for 1 h.
With potassium carbonate; In acetone; at 20℃; for 12h;
To a solution of the eugenol (1) (4.1 g, 25 mmol) in acetone (25 mL), K2CO3 (10.2 g, 75 mmol) and CH3I (10.5 g, 75 mmol) were added. After 12 h, the reaction mixture was filtered and the solvent was removed to afford product 2 in 95% of yield (4.227 g), brownish oil. IR (KBr, cm-1): 3062, 2908, 2835, 1639, 1591, 1517, 1417, 1261, 1153, 1139, 1029, 995, 914, 850, 765, 740, 707, 650; 1H NMR (400 MHz, CDCl3) delta 3.33 (d, J = 7.02 Hz, 2H, CH2-CH=CH2), 3.86 (s, 3H, -OCH3), 3.85 (s, 3H, -OCH3), 5.07 (m, 2H, CH2-CH=CH2), 5.95 (m, 1H, CH2-CH=CH2), 6.77 (m, 3H, Ar-H3,5,6); 13C NMR (100 MHz, CDCl3) delta 39.61 (CH2-CH=CH2), 55.56 (-OCH3), 55.69 (-OCH3), 111.03 (Ar-C6), 111.62 (Ar-C3), 115.40 (CH2-CH=CH2), 120.21 (Ar-C5), 132.40 (Ar-C4), 137.50 (CH2-CH=CH2), 147.15 (Ar-C1), 148.66 (Ar-C2) ppm.
78.2%
A pear bottomed flask (200 mL) equipped with a magnetic stir bar was charged with eugenol (2.257 g, 0.0137 mmol, 1 equiv) and acetone (60 mL) was added. Potassium carbonate (3.800 g, 0.0275 mmol, 2 equiv) was added to the stirring mixture which turned a vibrant yellow color. Methyl iodide wasa dded (2.342 g, 0.0165 mmol, 1.20 equiv). The flask was equipped with a reflux condenser and N2 adaptor, and was placed in an oil bath (62 oC) for 19 hours. The volatiles were removed and methylene chloride (90 mL) and H2O (75 mL) were added to wash the organic layer, followed by an extraction of the aqueous layer using CH2Cl2(45 mL). The organic fractions were combined and washed with 1M NaOH (6 x 65 mLeach), saturated brine solution (2 x 50 mL), and dried over MgSO4. After filtration, the volatiles were removed and the residue purified on a column (3 inch x 1 inchdimensions) packed with basic alumina and eluted using pentane to afford 1.92 g(78.2% yield) of methyl eugenol.
With 2,2'-azobis(isobutyronitrile) In toluene at 80℃; for 48h;
16
Example 16: Preparation of a mixture of compounds 116 A and 1 16 B.; A mixture of 6.40 g (38.7 mmol) of 4-allyl-2-methoxyphenol, 18.6 g (38.7 mmol) of 1 H,1 H,2H,2H-perfluorodecane-1-thiol and 0.32 g (1.94 mmol) of AIBN [2,2'-azo-bis-(2- methylbutyronitrile)] in 50 ml of dry toluene is heated at 800C for 2 days. Each 2-3 hours, an additional quantity of AIBN (0.32 g) is added. The reaction mixture is evaporated to dryness to give 27.3 g of a white wax. The crude material is purified by distillation (175°C/0.05 mbar) to give 14.7 g of a mixture of regioisomers 1 16A and 116B (GC: appr. 80%/20%) as white solid, m.p. 65-67°C. 1H NMR: (300 MHz, CDCI3): major regioisomer 116A: δ = 6.95-6.80 (m, ArH, 1 H); 6.75-6.65 (m, ArH, 2H); 5.49 (s, OH, 1 H); 3.90 (s, OCH3, 3H); 2.80-2.50 (m, ArCH2CH2CH2SCH2, 6H); 2.50-2.20 (m, SCH2CH2CF2, 2H); 2.00-1.85 (m, ArCH2CH2, 2H). Significant peaks of the minor isomer 116B : 5.53 (s, OH, 1 H); 3.05- 2.80 (m, 2H); 1.28 (d, J = 6.6 Hz, CH3, 3H). 13C-NMR (100 MHz, CDCI3): 146.46; 144.32; 143.89; 133.06; 130.93; 121.92; 121.00; 1 14.28; 11 1.62; 1 10.92; 55.80; 43.36; 42.20 (minor); 34.30; 32.30; 32.08; 31.86; 31.41 ; 31.06; 22.53; 21.22; 20.71 (minor). HPLC-UV/APCI-MS: [M-I]+ = 644.07
With lithium chloride; In N,N-dimethyl-formamide; for 12h;Reflux; Inert atmosphere;
To a solution of the ester (1.0 g) in N,N-dimethylformamide (2 ml), taken in a 2 necked RB fitted with a water condenser and a nitrogen inlet, lithium chloride (0.190 g) was added and the reaction mixture was heated to reflux for 12h. At the end of 12 h the reaction mixture was quenched with water and the organics were extracted with diethyl ether and were analyzed by HPLC. Conversion was 98% and the purity of crude para-eugenol was 93.4 % (HPLC area %).
2
A four-neck flask equipped with a stirrer was filled with 287.4 g (0.86 mol) of l,l,555-tetramethyl-3,3-diphenyltrisiloxane, 160 g of toluene, and 0.06 g of a platinum- 1,3- divinyl-l,l,3,3-tetramethyldisiloxane complex (concentration of metal platinum was 4 wt.%). The contents were heated to 80°C, and 312.6 g (1.90 mol) of eugenol were added dropwise. A reaction was carried out for 2 hours at 1200C. After the reaction mixture was stripped under a reduced pressure, 564 g of a brown transparent liquid having a viscosity of 2,700 mPa-s were produced with yield of 98.7%. 13C-NMR and 29Si-NMR analyses showed that the product was an organotrisiloxane represented by the following formula:
With potassium hydroxide In water; toluene at -78 - 50℃; for 4h;
82%
With potassium hydroxide In water; toluene at 50℃; for 4h; Inert atmosphere; Sealed tube;
General procedures:
Under a N2 atmosphere, compounds S1,S3, or S5 (1.0 mmol), KOH (0.8 mL, 25 wt%, ca. 4.5 mmol) were added into a pressure tube at room temperature (rt). The reactant mixture was cooled to -78 oC, then TMSCF2Cl (395 mg, 2.5 mmol) in toluene (2.0 mL) was added. The tube was sealed? and heated at 50 oC for 4 h (NOTE: The reaction conditions were not optimized). After being cooled to rt, the reaction mixture was quenched by adding water (5 ml), and extracted wiyh Et2O (3 x 15 mL). The organic layers were dried over anhydrous MgSO4, concentrated in vacuo, and purified by column chromatography (silica gel; petroleum ether/ethyl acetate) to afford the desired products S2, S4, S6, or S7 (see Table S-1). All the characterization data were in consistence with the previous report [1].
With phosphoric acid; 5% Pd(II)/C(eggshell); hydrogen In water at 249.84℃; for 0.5h; Autoclave;
Aqueous-phase HDO of bio-derived phenolic compounds
General procedure. The HDO reactions were optimized by varying the pH of the aqueous solution (neutral, acidic, basic), the metal (Pd, Pt, Ru, Rh), the catalyst support (C, Al2O3, SiO2, ASA), as well as by varying the reaction temperature (423, 473, 523 K). The reaction conditions used are noted in the footnotes of the tables. In a typical experiment, phenol or other lignin-derived monomers (0.0106 mol), H3PO4-H2O solution (80 ml, 0.5 wt.%, pH = 2.1), and Pd/C (0.040 g, 5 wt.%) were added into an autoclave (Parr, Series 4843, 300 ml). Then, the autoclave was pressured with 5 MPa H2 (ambient temperature). Reactions were conducted at 473 K for 0.5 h with a stirring speed of 1000 rpm. After cooling to ambient temperature, the organic products were extracted by ethyl acetate. The organic phase and aqueous phase were both analyzed by a gas chromatograph (GC, Shimadzu 2010, flame ionization detector) with a HP-5 capillary column (30 m × 250 μm). A gas chromatograph-mass spectrometer combination (GC-MS, Shimadzu QP 2010S) was used to identify the organic compounds. Internal standards (i.e., 2-isopropylphenol for the organic phase and acetone for the aqueous phase) were used to determine the liquid product concentration and carbon balance. The calculations of conversion and selectivity were based on carbon mole basis. Conversion = (the amount of aromatic ring change during reaction/total amount of aromatic ring) × 100%. Selectivity = (C atoms in each product/total C atoms in the products) × 100%. The carbon balance in the liquid phase for all reported experiments was better than 95 +/- 3% in this work.The composition of the gas phase was determined by GC (HP 6890) equipped with a plot Q capillary column (30 m × 250 μm) with thermal conductivity detector (TCD). We found 99% hydrogen and trace amounts of CO2 and methanol in the gas phase, so in this work only the changes in the liquid phase were considered.
With 4-methyl-morpholine; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In N,N-dimethyl-formamide; at 25℃;Inert atmosphere;
To a solution of 4[(pyridine-3-carbonyl)-amino]-butyric acid (0.6g, 2.8 mmol) in DMF (lOmL) were added N-methyl morpholine (0.9 mL, 8.6 mmol), EDCI.HC1 (l.lg, 5.7mmol) and eugenol (0.4 mL, 4.8 mmol). The mixture was allowed to stir at room temperature (25 C) over night under nitrogen atmosphere. The resulting mixture was diluted with ethylacetate (200mL), washed with water (4X100 mL j and dried over sodium sulphate. The crude product obtained upon evaporation of the solvent was further purified by preparative HPLC to obtain required product as colorless solid.LCMS (ESI) m/z: 355.1 ([M+H]+).Nature of the compound: colorless solid
With platinum/carbon xerogel catalyst; hydrogen In water monomer at 280℃; for 6h;
94 %Chromat.
With carbon nanotubes-supported ruthenium; hydrogen In dodecane; water monomer at 220℃; for 3h; Autoclave;
With hydrogen In hexane at 249.84℃; for 2h; Autoclave;
2.3. Catalytic tests
General procedure: Catalytic HDO reaction was performed in a stainless steelautoclave with an internal volume of 100 mL. Typically, reactant(1 g), solvent (40 mL), and catalyst (0.2 g) were added into anautoclave reactor. After flushing the reactor with H2for threetimes, reactions were conducted at 523 K for 2 h with a stir-ring rate of 700 rpm. After cooled to ambient temperature, theorganic products were extracted by ethyl acetate (Aladdin, ≥99.0%)while water was the solvent and the liquid products were sepa-rated from the catalyst directly while n-hexane (Aladdin, ≥98.0%)was the solvent. All products were analyzed by GC-MS (Agilent7890A/5975C) using p-cresol (Aladdin, ≥99.7%) as an internalstandard. This instrument was equipped with a capillary column(HP-5, 30 m × 250 m × 0.25 m) and a flame ionization detector(FID). The calculations of conversion and selectivity were based oncarbon mole basis. Because of the excellent hydrogenation per-formance of Ni based catalyst, eugenol (Aladdin, 99%) was firstlyconverted into 4-propylguaiacol rapidly and completely. Therefore,the conversion was calculated by regarding 4-propylguaiacol as thereactant in this research. Conversion = (total C atoms in the prod-ucts except 4-propylguaiacol/total C atoms in all products) × 100%.Selectivity = (C atoms in each product/total C atoms in the productsexcept 4-propylguaiacol) × 100%.
With C44H34N4O8P2Rh2S2(2-)*2Na(1+); hydrogen; cetyltrimethylammonium chloride In water; toluene at 80℃; for 8h; chemoselective reaction;
1: 62 %Chromat.
2: 31 %Chromat.
3: 6 %Chromat.
With C44H34N4O8P2Rh2S2(2-)*2Na(1+); hydrogen; cetyltrimethylammonium chloride In water; toluene at 80℃; for 3h; chemoselective reaction;
With hydrogen In toluene at 70℃; for 17h; Inert atmosphere; Schlenk technique;
Catalytic runs
General procedure: A mechanically stirred stainless steel Parr 4560 bomb coupled with a 4282 control module with a PID temperature controller and tachometer was employed as the reaction vessel. The bomb was loaded with the solid catalyst and three cycles of vacuum/argon were made. The solvent (15 mL) and the substrate (5 mmol) were introduced with a syringe through a valved port under argon. The vessel was pressurized with carbon monoxide followed by hydrogen up to the reported pressure. Stirring and heating were then started, and the desired temperature was attained in about 5 min. At appropriate time intervals, stirring was stopped and liquid samples were taken through a valved dip tube after quick catalyst settling. Recycling experiments were performed maintaining the catalyst in the vessel and washing it with the same solvent employed in the reaction before a new cycle to remove product residues.
With methoxy(cyclooctadiene)rhodium(I) dimer; hydrogen In toluene at 80℃; for 0.5h; Autoclave; Inert atmosphere; regioselective reaction;
With methoxy(cyclooctadiene)rhodium(I) dimer; trifluorormethanesulfonic acid; hydrogen; triphenylphosphine In toluene at 120℃; for 24h;
2.2 Catalytic runs
The pre-catalyst [Rh(cod)(μ-OMe)]2 (5.0 × 10-3 mmol), the phosphorus ancillary (if any) and a PTFE-covered magnetic stirring bar were placed in a stainless steel bomb, which was closed and purged with three cycles of vacuum and argon. In a Schlenk tube, a solution was prepared by adding toluene (30 mL), eugenol (10 mmol), di-n-butylamine (10 mmol) and then the acid (if any). The solution was transferred under inert atmosphere to the bomb, which was pressurized with carbon monoxide (10-20 atm) and then with hydrogen (to 40-80 atm). The bomb was placed in a pre-heated silicone bath over magnetic stirring. Liquid samples were taken periodically through a dip tube.
With methoxy(cyclooctadiene)rhodium(I) dimer; sulfuric acid; hydrogen; triphenylphosphine In toluene at 120℃; for 24h;
2.2 Catalytic runs
The pre-catalyst [Rh(cod)(μ-OMe)]2 (5.0 × 10-3 mmol), the phosphorus ancillary (if any) and a PTFE-covered magnetic stirring bar were placed in a stainless steel bomb, which was closed and purged with three cycles of vacuum and argon. In a Schlenk tube, a solution was prepared by adding toluene (30 mL), eugenol (10 mmol), di-n-butylamine (10 mmol) and then the acid (if any). The solution was transferred under inert atmosphere to the bomb, which was pressurized with carbon monoxide (10-20 atm) and then with hydrogen (to 40-80 atm). The bomb was placed in a pre-heated silicone bath over magnetic stirring. Liquid samples were taken periodically through a dip tube.
With potassium hydroxide; In water; acetonitrile; at 20℃; for 0.0333333h;
General procedure: Into a 20 mL vial was placed the phenol or thiophenols (0.5 mmol, 1.0 equiv), acetonitrile (1.0 mL) and 6M aqueous KOH (1.0 mL). The mixture was stirred rapidly at room temperature and HCF2OTf (210 μ, 1.5 mmol, 3.0 equiv) was added at once. Note: the reactions are exothermic. The mixture was stirred vigorously for 2 minutes. The reaction was diluted with FLO (8 mL) and extracted with ether (2 x 8 mL). The combined organic layers were dried over MgSC , concentrated, and purified by silica gel chromatography.
3-(2-methoxy-4-allylphenoxy)-1,2-dicyanobenzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
90%
With potassium carbonate; In dimethyl sulfoxide; at 150℃; for 0.166667h;Microwave irradiation;
Eugenol (0.625 g, 3.81 mmol) and <strong>[51762-67-5]3-nitrophthalonitrile</strong> (0.640 g, 3.69 mmol) was dissolved in dry dimethylsulphoxide (3 ml). After stirring for 15 min, newly ground anhydrous K2CO3 (0.76 g, 5.50 mmol) was added to this solution. The reaction flask was heated under microwave irradiation at 150 C for 10 min, with stirring and air-jet cooling. After reaction completed, the mixture was filtered and poured in ice. The formed solid material was filtered off and the crude product was purified by recrystallization from dry ethanol. Yield: 240 mg (85%); m.p. 101 C. Single crystals were obtained by slow evaporation from ethanol. Yield: 770 mg (% 90); m.p. 89-90 C. FTIRnumax/cm-1. 3070 (Ar-CH), 2966, 2939, 2917, 2227 (CN), 1636, 1599, 1583, 1570, 1506, 1465, 1417, 1279, 1257, 1155, 1034, 794. 1H NMR (DMSO-d6) delta, ppm: 7.746-7.729 (2H, m, ArCH), 7.204-7.184 (1H, d, ArCH), 7.069-7.065(1H, d, ArCH), 7.069-6.965 (1H, m, ArCH), 6.872-6.847 (1H, d.d, ArCH), 6.026-5.958 (1H, m, =CH), 5.145-5.059 (2H, m, =CH2), 3.71 (3H, s, OCH3), 3.412-3.395 (2H, d, -CH). 13C NMR (DMSO-d6) delta, ppm: 160.993, 151.105, 140.157, 139.696, 137.684, 136.335, 127.810, 122.656, 121.596, 120.217, 116.682, 116.104, 115.967, 114.255 (CN), 113.843 (CN), 103.452, 56,260 (OCH3), 39.706. Anal. Calcd. For C18H14O2N2: C, 74.46; H, 4.86; N, 9.64 Found: C, 74.50; H, 4.58; N, 9.50.
With 5% active carbon-supported ruthenium; hydrogen In dodecane; water at 220℃; for 3h; Autoclave;
With hydrogen In hexane at 249.84℃; for 2h; Autoclave;
2.3. Catalytic tests
General procedure: Catalytic HDO reaction was performed in a stainless steelautoclave with an internal volume of 100 mL. Typically, reactant(1 g), solvent (40 mL), and catalyst (0.2 g) were added into anautoclave reactor. After flushing the reactor with H2for threetimes, reactions were conducted at 523 K for 2 h with a stir-ring rate of 700 rpm. After cooled to ambient temperature, theorganic products were extracted by ethyl acetate (Aladdin, ≥99.0%)while water was the solvent and the liquid products were sepa-rated from the catalyst directly while n-hexane (Aladdin, ≥98.0%)was the solvent. All products were analyzed by GC-MS (Agilent7890A/5975C) using p-cresol (Aladdin, ≥99.7%) as an internalstandard. This instrument was equipped with a capillary column(HP-5, 30 m × 250 m × 0.25 m) and a flame ionization detector(FID). The calculations of conversion and selectivity were based oncarbon mole basis. Because of the excellent hydrogenation per-formance of Ni based catalyst, eugenol (Aladdin, 99%) was firstlyconverted into 4-propylguaiacol rapidly and completely. Therefore,the conversion was calculated by regarding 4-propylguaiacol as thereactant in this research. Conversion = (total C atoms in the prod-ucts except 4-propylguaiacol/total C atoms in all products) × 100%.Selectivity = (C atoms in each product/total C atoms in the productsexcept 4-propylguaiacol) × 100%.
2-methoxy-4-(prop-2-en-1-yl)phenyl 4-ethylbenzenesulfonate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80%
With pyridine Reflux;
Synthesis of Eugenol-tosylate and its congeners
General procedure: All the compounds E1-E6 were synthesized from 2-methoxy-4-(prop-2-en-1-yl)phenol (1) bytreating with different phenyl and substituted phenylsulfonyl chlorides in refluxing pyridinefor 18-24 h (completion of reaction was monitored by TLC) (Fig 1). After the completion ofreaction the reaction mass was quenched with distilled water and extracted with dichloromethane.Finally the combined organic layer was washed with distilled water again and driedover anhydrous Na2SO4. All the compounds were obtained as pure oil after removal of the solventin vacuum.
With (2,4,6-trimethylbenzoyl)diphenylphosphine oxide; In 1,4-dioxane; ethanol; at 40℃; for 30h;UV-irradiation;
100g eugenol, 200g<strong>[1074-36-8]4-mercapto benzoic acid</strong>, 35g2, 4, 6-trimethyl benzoyl diphenyl phosphine oxide, is dissolved in dioxane, and the mixed solution of ethanol, in 40 C lower 365 nm ultraviolet lamp irradiation 30 hours, pressure reducing rotary evaporated to remove the mixed solvent, water washing and drying to obtain eugenol-mercapto benzoic acid compound, the yield is 92%.
2-((4-allyl-2-methoxyphenoxy)methyl)benzo[d]thiazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
41.8%
With potassium carbonate; In acetone; for 4h;Reflux;
General procedure: To a solution of various substituted phenols (1 mmol) in dry acetone (30 mL) K2CO3 (1 mmol)and compound 3 or 4 (1 mmol) were added. After being stirred for 4 h at reflux temperature, thereaction mixture was cooled, filtered, and concentrated under vacuum. Then the residue was dilutedwith 30 mL ethyl acetate and sequentially washed with 30 mL 1 M HCl, aq. NaHCO3 solution andbrine in order. The organic layer was dried over MgSO4 and concentrated in vacuo. Purification of theresidue by chromatography on silica gel furnished target compounds. 1H-NMR, 13C-NMR and massspectroscopy (MS) of compounds 5a-m and 6a-m are shown in Supplementary Materials.
2-((4-allyl-2-methoxyphenoxy)methyl)benzo[d]oxazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
68%
With potassium carbonate; In acetone; for 4h;Reflux;
General procedure: To a solution of various substituted phenols (1 mmol) in dry acetone (30 mL) K2CO3 (1 mmol)and compound 3 or 4 (1 mmol) were added. After being stirred for 4 h at reflux temperature, thereaction mixture was cooled, filtered, and concentrated under vacuum. Then the residue was dilutedwith 30 mL ethyl acetate and sequentially washed with 30 mL 1 M HCl, aq. NaHCO3 solution andbrine in order. The organic layer was dried over MgSO4 and concentrated in vacuo. Purification of theresidue by chromatography on silica gel furnished target compounds. 1H-NMR, 13C-NMR and massspectroscopy (MS) of compounds 5a-m and 6a-m are shown in Supplementary Materials.
Stage #1: 4-allylguaiacol; epichlorohydrin at 120℃; for 4h;
Stage #2: 1,1,5,5-tetramethyl-3,3-diphenyl-trisiloxane With dihydrogen hexachloroplatinate at 80℃; for 3h;
5
0.1 mol of benzyldiethylamine, 0.1 mol of γ-chloropropyltriethoxysilane, 200 mL of ethanol, 0.05 mol ofpotassium iodide, heated to 70 ° C under nitrogen atmosphere, reacted for 2 hours, and the product wasfiltered to obtain a quaternary ammonium salt mother liquor. 100 mL of quaternary ammonium salt was added to 120 mL of distilled water/ethanol (40 ml of water, 80 ml of ethanol), and the pH of the solution was adjusted to4.5 with glacial acetic acid. After standing for 3 hours, 60 g of halloysite nanotubes were placed therein. After fullyimmersing for 2.5 hours, the water is removed by evaporation, and the obtained product is a quaternaryammonium salt functionalized halloysite nanotube. Eugenol and epichlorohydrin (molar ratio 1:1) were added under normal pressure, and the quaternaryammonium salt functionalized halloysite nanotubes prepared in this example were added as a catalyst(benzyltriethylammonium chloride). The molar ratio of eugenol to 0.05:1), etherification ring-opening reactionat 120 ° C, the reaction time is 4 hours, to obtain chlorohydrin ether; to cool the system to about 60 ° C to addsodium hydroxide to the system (Molar ratio of sodium hydroxide to eugenol = 1.05:1), added in batches within3 hours, and the reaction was kept for 10 hours; the system was allowed to stand for cooling and layering, and theobtained organic phase product was epoxidized eugenol. The yield (calculated as phenolic hydroxyl compound)was 95%. The epoxidized eugenol prepared in the present example was tested to have a hydrolyzable chlorinecontent of 60 ppm and an inorganic chlorine content of 3 ppm. to 120 mL of distilled water/ethanol (40 ml of water, 80 ml of ethanol), and the pH of the solution was adjusted to4.5 with glacial acetic acid. After standing for 3 hours, 60 g of halloysite nanotubes were placed therein. After fullyimmersing for 2.5 hours, the water is removed by evaporation, and the obtained product is a quaternaryammonium salt functionalized halloysite nanotube. Eugenol and epichlorohydrin (molar ratio 1:1) were added under normal pressure, and the quaternaryammonium salt functionalized halloysite nanotubes prepared in this example were added as a catalyst(benzyltriethylammonium chloride). The molar ratio of eugenol to 0.05:1), etherification ring-opening reactionat 120 ° C, the reaction time is 4 hours, to obtain chlorohydrin ether; to cool the system to about 60 ° C to addsodium hydroxide to the system (Molar ratio of sodium hydroxide to eugenol = 1.05:1), added in batches within3 hours, and the reaction was kept for 10 hours; the system was allowed to stand for cooling and layering, and theobtained organic phase product was epoxidized eugenol. The yield (calculated as phenolic hydroxyl compound)was 95%. The epoxidized eugenol prepared in the present example was tested to have a hydrolyzable chlorinecontent of 60 ppm and an inorganic chlorine content of 3 ppm. Chloroplatinic acid (30 ppm) was added to epoxidized eugenol, and hydrosilylation reaction with 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane was carried out at 80 °C. (The molar ratio of epoxidized eugenol to 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane is 2:1), the reaction time is 3 hours, and the reaction is completed to obtainthe organism. Base epoxy resin. It can be seen from the nuclear magnetic test that the structural formula of the bio-based epoxy resin prepared inthis embodiment is as shown in (I-3).
With hydrogen; benzene at 350℃; for 2h; Autoclave;
3 Example 3: Demethoxylation of 2-methoxy-4-propylphenol using Parr autoclave (Figure 7):
A Parr autoclave with a volume of 100 ml was used for the 2-methoxy- 4-propylphenol demethoxylation reactions. Typically, 100 mg of catalyst and 3000 mg of feedstock were added to the reactor together with 30 ml benzene solvent. After sealing, purging with H2and checking for leaks, the autoclave was brought to 50 bar by introducing H2. Then the reactor was heated to 350 °C in ca. 60 min and maintained at that temperature for 2h. A small amount of sample was taken via a sampling valve after 1 h and 2h reaction time. An aliquot amount of 1 ml sample was accurately taken from the reaction mixture. After adding an amount of 10 ul dodecane internal standard, the sample was measured by GC-MS for product identification and quantification. After reaction, the reactor was allowed to naturally cool down by removing the heating oven.
With hydrogen In Hexadecane at 250℃; for 1h; Autoclave;
1 Test Example 1
Hydrodeoxygenation reaction was carried out using the catalysts prepared in Example 1 and a batch reactor. Eugenol (CAS 97-53-0) was used as a reactant. 0.003 mol of eugenol, 30 mL of n-hexadecane, and 0.05 g of a catalyst were introduced into an autoclave reactor (internal volume of about 160 mL) at room temperature, which was then filled with 50 bar of hydrogen gas at room temperature. The reactor was heated to 250° C., followed by stirring at 800 rpm for 1 hour to carry out the reaction. The reactor was cooled back to room temperature and then the liquid reaction product was analyzed. FIG. 1 shows the reactants and products of the hydrodeoxygenation reaction. A product having no oxygen atom (0-O), a product having one oxygen atom (1-0), and a product having two oxygen atoms (2-O) were obtained from eugenol, which has two oxygen atoms. As shown in FIG. 3, when CaCO3 was used as the carrier, the yield of the product having two oxygen atoms (2-O) was lower and the yield of the product having no oxygen atom (0-O) was higher than the various basic carriers, including MgO, Mg-Al mixed oxide (MgAlOx), hydrotalcite (HT), and zirconia (ZrO2), which indicates that the carrier significantly increased the hydrodeoxygenation reaction activity. When CaCO3 was used as the carrier, the yield of 1-0 was about 25% higher than the case of using a zirconia carrier, and the yield of 2-0, which did not go through hydrodeoxygenation reaction, was about 30% lower than the case of using a zirconia carrier, which indicates that the carrier increased the hydrodeoxygenation reaction efficiency. Also, when the catalyst, after reaction, was washed, dried and reused, the hydrodeoxygenation reaction activity was maintained without a significant change even in the third use of the catalyst, and the hydrodeoxygenation reaction activity was remarkably higher than those of fresh catalysts using a carrier of MgO, Mg-Al mixed oxide (MgAlOx) or hydrotalcite (HT) (see FIG. 4).
With hydrogen In Hexadecane at 250℃; for 1h; Autoclave;
1 Test Example 1
Hydrodeoxygenation reaction was carried out using the catalysts prepared in Example 1 and a batch reactor. Eugenol (CAS 97-53-0) was used as a reactant. 0.003 mol of eugenol, 30 mL of n-hexadecane, and 0.05 g of a catalyst were introduced into an autoclave reactor (internal volume of about 160 mL) at room temperature, which was then filled with 50 bar of hydrogen gas at room temperature. The reactor was heated to 250° C., followed by stirring at 800 rpm for 1 hour to carry out the reaction. The reactor was cooled back to room temperature and then the liquid reaction product was analyzed. FIG. 1 shows the reactants and products of the hydrodeoxygenation reaction. A product having no oxygen atom (0-O), a product having one oxygen atom (1-0), and a product having two oxygen atoms (2-O) were obtained from eugenol, which has two oxygen atoms. As shown in FIG. 3, when CaCO3 was used as the carrier, the yield of the product having two oxygen atoms (2-O) was lower and the yield of the product having no oxygen atom (0-O) was higher than the various basic carriers, including MgO, Mg-Al mixed oxide (MgAlOx), hydrotalcite (HT), and zirconia (ZrO2), which indicates that the carrier significantly increased the hydrodeoxygenation reaction activity. When CaCO3 was used as the carrier, the yield of 1-0 was about 25% higher than the case of using a zirconia carrier, and the yield of 2-0, which did not go through hydrodeoxygenation reaction, was about 30% lower than the case of using a zirconia carrier, which indicates that the carrier increased the hydrodeoxygenation reaction efficiency.
With HY-1 zeolite In ethanol; water at 200℃; for 0.5h; Microwave irradiation;
1. General procedure for reactions of model compounds with zeolites in vial
General procedure: A 2-5 mL microwave vial (Biotage) equipped with a stir bar was loaded with the corresponding model compound and catalyst. Solvent (standard solution of dodecane in Ethanol/ water) was added and the vial was sealed. The reaction mixture was stirring for specified time at specified temperature. After the completing of the reaction the reaction mixture was filtrated and analyzed by GC-FID and GC-MS.
With beta-1 zeolite In ethanol; water at 200℃; for 0.5h; Microwave irradiation;
1. General procedure for reactions of model compounds with zeolites in vial
General procedure: A 2-5 mL microwave vial (Biotage) equipped with a stir bar was loaded with the corresponding model compound and catalyst. Solvent (standard solution of dodecane in Ethanol/ water) was added and the vial was sealed. The reaction mixture was stirring for specified time at specified temperature. After the completing of the reaction the reaction mixture was filtrated and analyzed by GC-FID and GC-MS.
With beta-1 zeolite In water; isopropyl alcohol at 200℃; for 0.5h; Microwave irradiation; Overall yield = 70 percentChromat.;
1. General procedure for reactions of model compounds with zeolites in vial
General procedure: A 2-5 mL microwave vial (Biotage) equipped with a stir bar was loaded with the corresponding model compound and catalyst. Solvent (standard solution of dodecane in Ethanol/ water) was added and the vial was sealed. The reaction mixture was stirring for specified time at specified temperature. After the completing of the reaction the reaction mixture was filtrated and analyzed by GC-FID and GC-MS.
With methoxy(cyclooctadiene)rhodium(I) dimer; hydrogen; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In toluene at 80℃; for 4h; Autoclave; Inert atmosphere; regioselective reaction;
With methoxy(cyclooctadiene)rhodium(I) dimer; hydrogen; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene at 80℃; for 4h; Autoclave; Inert atmosphere; regioselective reaction;
With Candida antarctica lipase B immobilized on a macroporous acrylic resin at 40℃; for 48h; Green chemistry; Enzymatic reaction;
General experiment for the optimised acetylation of alcohols, according to Scheme 2:
General procedure: Lipozyme 435 (2% wt) was added to a solution of an alcohol (1 equiv) in EGDA (2 equiv).The reaction mixture was incubated in an orbital shaker (40 °C, 150 rpm) and the reaction progress wasmonitored by GC-FID (see Table 1).
With hydrogen In hexane at 80℃; for 8h; Autoclave;
Biphasic hydrogenation of eugenol
General procedure: Biphasic eugenol hydrogenations were performed using the nanostructured rhodium and ruthenium catalysts: Rh/ IL1, Rh/ IL2, Ru/ IL1 and Ru/ IL2. The methodology carried out by Melean et al 14 was modified, such that the substrate was reacted with hydrogen in the presence of the nanostructured system stabilized with ionic liquid, an organic solvent was used to ensure the separation of the reaction products and the catalytic phase. In this sense, a Parr reactor was charged under inert atmosphere, with 6 mmol of eugenol, 3 ml of n-hexane, 0.5 ml of ionic liquid (IL1 and IL2) and 5 mg of each of the Ru catalysts (nanoparticles). of Ru/ IL1 and Ru/ IL2) and Rh (nanoparticles of Rh/ IL1 and Rh/ IL2) with 100 psi of H2 at a temperature of 80 C. The catalytic evaluations were carried out between 0.5 and 8 hours. At the end of the reaction time, the phases were separated for analysis by gas chromatography and mass spectroscopy
With sodium formate; sodium hydroxide In water at 120℃;
2.4. General procedure for the flow hydrogenation
General procedure: A premixed mixture of phenolic compound (1a-h) and sodium formate (2, 3 equiv.) in H2O (0.1 M) was prepared in a flask with the function of the reservoir, and the mixture was adjusted to pH 12.0 with the addition of 5 M aq NaOH. POLITAG-Pd(0)-L1 (8 wt%, 0.54 mmol,718.3 mg) was dispersed in solid glass beads and glass powder and was charged in a stainless-steel reactor; the equipment was connected byusing the appropriate valves, and a back pressure regulator was placedon the outlet tube. The packed reactor was placed into a thermostated box, and the mixture was pumped through the catalyst columns at120 °C. The conversion of 1a-i and its selectivity were periodically monitored by GLC analysis.