4-Allyl-2-methoxyphenol (Eugenol) [RRAFCDWBNXTKKO-UHFFFAOYSA-N] to Isoeugenol by Asch

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Date

27 reactions in Reaxys

2017-11-05 09h:20m:29s (EST)

Search as: As drawn, No salts, No mixtures

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Rx-ID: 133204 View in Reaxys 1/27 Yield 82 %

Conditions & References With Grubb's 2nd generation catalyst, polydimethylsiloxane in methanol, water, Time= 20h, T= 100 °C Brett Runge; Mwangi, Martin T.; Bowden, Ned B.; Journal of Organometallic Chemistry; vol. 691; nb. 24-25; (2006); p. 5278 - 5288 View in Reaxys

78 %

With potassium fluoride on basic alumina in ethylene glycol, Time= 1.5h, T= 200 °C Radhakrishna, A.S.; Suri, S.K.; Rao, K.R.K.Prasad; Sivaprakash, K.; Singh, B.B.; Synthetic Communications; vol. 20; nb. 3; (1990); p. 345 - 348 View in Reaxys With platinum on activated charcoal, T= 300 °C , im Kohlendioxyd-Strom Lewina; Zhurnal Obshchei Khimii; vol. 6; (1936); p. 1092,1094; Chem. Zentralbl.; vol. 108; nb. I; (1937); p. 586 View in Reaxys With potassium hydroxide, diethylene glycol, T= 160 - 180 °C West; Journal of the Society of Chemical Industry, London; vol. 59; (1940); p. 275 View in Reaxys Patent; Allen and Sons; GB525705; (1939) View in Reaxys With potassium hydroxide, glycerol, T= 180 °C Priester; ; vol. 5; (1930); p. 83,108 View in Reaxys With potassium hydroxide, pentan-1-ol, T= 140 °C Tiemann; Chemische Berichte; vol. 24; (1891); p. 2881 View in Reaxys Patent; Haarmann; Reimer; DE57808; Fortschr. Teerfarbenfabr. Verw. Industriezweige; vol. 3; p. 862 View in Reaxys With potassium hydroxide, T= 130 - 140 °C Eijkman; Chemische Berichte; vol. 23; (1890); p. 862 View in Reaxys Ciamician; Silber; Chemische Berichte; vol. 23; (1890); p. 1165 View in Reaxys Tiemann; Chemische Berichte; vol. 27; (1894); p. 2580 View in Reaxys Patent; Haarmann; Reimer; DE57808; Fortschr. Teerfarbenfabr. Verw. Industriezweige; vol. 3; p. 862 View in Reaxys With pentan-1-ol, sodium Gassmann; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 124; (1897); p. 38 View in Reaxys With potassium hydroxide, T= 220 °C Einhorn; Frey; Chemische Berichte; vol. 27; (1894); p. 2457 View in Reaxys With potassium hydroxide, water, T= 220 °C , Loesen in Wasser und Ansaeuern Patent; Einhorn; DE76982; Fortschr. Teerfarbenfabr. Verw. Industriezweige; vol. 3; p. 863

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View in Reaxys Einhorn; Frey; Chemische Berichte; vol. 27; (1894); p. 2457 View in Reaxys With potassium hydroxide, beim Schmelzen McLang; Chem. Zentralbl.; vol. 97; nb. I; (1926); p. 515 View in Reaxys McLang; ; vol. 77; p. 3,180; Chem. Zentralbl.; vol. 96; nb. II; (1925); p. 1562 View in Reaxys Gokhale; Sudborough; Watson; Journal of the Indian Institute of Science; vol. 6; (1923); p. 246; Chem. Zentralbl.; vol. 95; nb. II; (1924); p. 324 View in Reaxys With potassium hydroxide, sodium hydroxide, beim Schmelzen McLang; Chem. Zentralbl.; vol. 97; nb. I; (1926); p. 515 View in Reaxys McLang; ; vol. 77; p. 3,180; Chem. Zentralbl.; vol. 96; nb. II; (1925); p. 1562 View in Reaxys Gokhale; Sudborough; Watson; Journal of the Indian Institute of Science; vol. 6; (1923); p. 246; Chem. Zentralbl.; vol. 95; nb. II; (1924); p. 324 View in Reaxys With 10 KOH/alumina Merchan Arenas, Diego R.; Rojas Ruiz, Fernando A.; Kouznetsov, Vladimir V.; Tetrahedron Letters; vol. 52; nb. 12; (2011); p. 1388 - 1391 View in Reaxys With hexaaquaruthenium(II) tosylate in ethanol, T= 20 °C Kuo, Louis Y.; Delaney, Frances E.; Inorganica Chimica Acta; vol. 435; (2015); p. 335 - 339 View in Reaxys 99 %Chromat.

With [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][2-[[(2-methylphenyl)imino]methyl]phenolyl][3-phenyl-1Hinden-1-ylidene](chloro)ruthenium(II), [Pd(µ-Br)(tBu3P)]2 in toluene, Time= 1h, T= 50 °C , Inert atmosphere Trita; Over; Pollini; Baader; Riegsinger; Meier; Gooßen; Green Chemistry; vol. 19; nb. 13; (2017); p. 3051 - 3060 View in Reaxys

Rx-ID: 1770372 View in Reaxys 2/27 Yield 99 %

Conditions & References With [CpRu(2-PiPr2-4-tBu-1-Me-imidazole)(MeCN)]PF6 in [(2)H6]acetone, Time= 0.0666667h, T= 25 °C , Inert atmosphere, Glovebox, Reagent/catalyst, Temperature, Solvent, stereoselective reaction Erdogan, Gulin; Grotjahn, Douglas B.; Organic Letters; vol. 16; nb. 11; (2014); p. 2818 - 2821 View in Reaxys

96 %

With platinum(II) chloride in methanol Zhao, Huiping; Brandt, Gary E.; Galam, Lakshmi; Matts, Robert L.; Blagg, Brian S.J.; Bioorganic and Medicinal Chemistry Letters; vol. 21; nb. 9; (2011); p. 2659 - 2664 View in Reaxys

95.9 %

Eugenol to (E)-Isoeugenol In a glove box, a 50 mL round bottomed flask equipped with a magnetic stir bar was added eugenol (16.43 g, 0.1 mol), capped with a rubber septum, and removed from the glove box. In an inert atmosphere glove box, catalyst 1(60.5 mg, 0.101 mmol, 0.1 molpercent) was measured into a scintillation vial, capped, and brought out of the glove box. The septum was removed from the reaction flask and thecatalyst was quickly added, followed by bubbling nitro-

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gen through the liquid to remove any air that had entered. Aliquots (ca. 5 μL) were removed from the reaction at 5, 10,and 20 minutes using a gastight syringe and analyzed by 1H NMR for completion. Full conversion of eugenol to (E)-isoeugenol occurred after 20 minutes, and the product was isolated by vacuum distillation (2 torr, 98 oC) to afford 15.76 g (95.9percent) of (E)-isoeugenolas a clear, colorless oil. To accurately determine amount of starting material remaining,105.1 mg of the distillate was weighed out in an NMR tube containing 0.5-0.7 mL CDCl3and analyzed by 1H NMR; percentages were calculated assuming a two-component mixture (eugenol/isoeugenol), using residual chloroform peak as internal standard. Peaks used: eugenol 5.11 ppm (2H), 3.34 ppm (2H); isoeugenol 6.36 ppm (1H), 6.12 ppm (1H), 1.90 ppm (3H). With [CpRu(2-PiPr2-4-tBu-1-Me-imidazole)(MeCN)]PF6, Time= 0.333333h, T= 20 °C , Glovebox, Inert atmosphere, Green chemistry, Catalytic behavior, Reagent/catalyst, diastereoselective reaction Larsen, Casey R.; Paulson, Erik R.; Erdogan, Gulin; Grotjahn, Douglas B.; Synlett; vol. 26; nb. 17; (2015); p. 2462 - 2466; Art.No: ST-2015-B0231-L View in Reaxys 90 %

With palladium dichloride in methanol, Time= 24h, Inert atmosphere Nielsen, Alex J.; Jenkins, Hilary A.; McNulty, James; Chemistry - A European Journal; vol. 22; nb. 27; (2016); p. 9111 - 9115 View in Reaxys

86 %

With C21H35N3PRu*F6P(1-), T= 20 °C , Inert atmosphere, neat (no solvent), stereoselective reaction Larsen, Casey R.; Grotjahn, Douglas B.; Journal of the American Chemical Society; vol. 134; nb. 25; (2012); p. 10357 - 10360 View in Reaxys

85 %

With palladium dichloride in methanol, Time= 24h, T= 20 °C Curti, Claudio; Zanardi, Franca; Battistini, Lucia; Sartori, Andrea; Rassu, Gloria; Pinna, Luigi; Casiraghi, Giovanni; Journal of Organic Chemistry; vol. 71; nb. 22; (2006); p. 8552 - 8558 View in Reaxys

81 %

With di-μ-bromobis(tri-tertbutylphosphine)dipalladium(I) in toluene, Time= 2h, T= 50 °C , Inert atmosphere, optical yield given as percent de Mamone, Patrizia; Gruenberg, Matthias F.; Fromm, Andreas; Khan, Bilal A.; Goossen, Lukas J.; Organic Letters; vol. 14; nb. 14; (2012); p. 3716 - 3719 View in Reaxys

22 %

2.3. Catalytic procedure General procedure: In a 3 mL vial were introduced the surfactant followed by water(1 mL). The mixture was stirred until complete dissolution and formation of a clear solution. To this, catalyst 1 (0.005 mmol) was added and the mixture was stirred for 10 min, followed by allylbenzene(50 eq. with respect to 1). The mixture was heated at 95 C under stirring at 750 rpm. After 18 h the aqueous reaction mixture was extracted two times with ethyl acetate and the organic phase was analyzed by GC and GC–MS. The structure ofthe isomerized products were confirmed by GC–MS and 1H NMR. With [Ru(η5-C5Me5)(CH3CN){P(OEt)3}2]BPh4 in water, Time= 18h, T= 95 °C Sperni, Laura; Scarso, Alessandro; Strukul, Giorgio; Inorganica Chimica Acta; vol. 455; (2017); p. 535 - 539 View in Reaxys

15 %

With C44H58Cl2N4Pd in methanol, toluene, Time= 3h, T= 20 °C Spallek, Markus J.; Stockinger, Skrollan; Goddard, Richard; Trapp, Oliver; Advanced Synthesis and Catalysis; vol. 354; nb. 8; (2012); p. 1466 - 1480 View in Reaxys

99 % Spectr.

With hexaaquaruthenium(II) in ethanol-d6, water-d2, Time= 24h, T= 24.9 °C , ΔH(excit.), ΔS(excit.), Thermodynamic data, Rate constant Karlen, Thomas; Ludi, Andreas; Helvetica Chimica Acta; vol. 75; nb. 5; (1992); p. 1604 - 1606 View in Reaxys

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99 % Spectr.

With hexaaquaruthenium(II) in ethanol-d6, water-d2, Time= 24h, T= 24.9 °C Karlen, Thomas; Ludi, Andreas; Helvetica Chimica Acta; vol. 75; nb. 5; (1992); p. 1604 - 1606 View in Reaxys With H2 activated polymer-supported (pC6H4-PPh2)2Ir(+)(COD)PF6(-), hydrogen in tetrahydrofuran, Time= 24h, T= 20 °C Lee, Ai-Lan; Ley, Steven V; Organic and biomolecular chemistry; vol. 1; nb. 22; (2003); p. 3957 - 3966 View in Reaxys Reaction Steps: 2 1: 90 percent / Ag2O / CCl4 / 65 °C 2: NaBH4 / CCl4; methanol / Ambient temperature With sodium tetrahydroborate, silver(l) oxide in methanol, tetrachloromethane Zanarotti, Antonio; Journal of Organic Chemistry; vol. 50; nb. 7; (1985); p. 941 - 945 View in Reaxys With RuCl2(η6-C6H5OCH2CH2OH){P(Ph)3} in ethanol, Time= 0.666667h, T= 80 °C , Inert atmosphere, Reagent/catalyst, pH-value, Solvent, diastereoselective reaction Lastra-Barreira, Beatriz; Diaz-Alvarez, Alba E.; Menendez-Rodriguez, Lucia; Crochet, Pascale; RSC Advances; vol. 3; nb. 43; (2013); p. 19985 - 19990 View in Reaxys

100 With [CpRu(PN)(MeCN)]PF6 in toluene, Time= 0.5h, T= 20 °C , Inert atmosphere, Glovebox, diastereoselective re%Chromat. action Higman, Carolyn S.; De Araujo; Fogg, Deryn E.; Catalysis Science and Technology; vol. 6; nb. 7; (2016); p. 2077 - 2084 View in Reaxys With palladium (II) acetate, bis(pinacol)diborane, tricyclohexylphosphine in toluene, Time= 12h, T= 80 °C , Sealed tube, Inert atmosphere Ojha, Devi Prasan; Gadde, Karthik; Prabhu, Kandikere Ramaiah; Journal of Organic Chemistry; vol. 82; nb. 9; (2017); p. 4859 - 4865 View in Reaxys

Rx-ID: 28954246 View in Reaxys 3/27 Yield

Conditions & References With potassium fluoride on basic alumina in ethylene glycol, Time= 0.15h, Neat (no solvent), Microwave irradiation, optical yield given as percent de Luu, Thi Xuan Thi; Lam, Trinh To; Le, Thach Ngoc; Duus, Fritz; Molecules; vol. 14; nb. 9; (2009); p. 3411 - 3424 View in Reaxys With tri-tert-butyl phosphine, isobutyryl chloride, bis(dibenzylideneacetone)-palladium(0) in toluene, Time= 24h, T= 80 °C , Inert atmosphere, optical yield given as percent de, stereoselective reaction Gauthier, Delphine; Lindhardt, Anders T.; Olsen, Esben P. K.; Overgaard, Jacob; Skrydstrup, Troels; Journal of the American Chemical Society; vol. 132; nb. 23; (2010); p. 7998 - 8009 View in Reaxys With ruthenium containing hydrotalcite, Time= 2h, T= 210 °C , Inert atmosphere, optical yield given as percent de Sharma, Sumeet K.; Parikh, Parimal A.; Jasra, Raksh V.; Journal of Molecular Catalysis A: Chemical; vol. 317; nb. 1-2; (2010); p. 27 - 33 View in Reaxys

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With [(dppb)Pt(C6F5)(H2O)]OTf in chloroform, Time= 24h, T= 50 °C , optical yield given as percent de, diastereoselective reaction Scarso, Alessandro; Colladon, Marco; Sgarbossa, Paolo; Santo, Claudio; Michelin, Rino A.; Strukul, Giorgio; Organometallics; vol. 29; nb. 6; (2010); p. 1487 - 1497 View in Reaxys With RuCl2(η6-C6H5OCH2CH2OH){P(OEt)3} in ethanol, Time= 6h, T= 80 °C , Inert atmosphere, Reagent/catalyst, pH-value, Solvent, diastereoselective reaction Lastra-Barreira, Beatriz; Diaz-Alvarez, Alba E.; Menendez-Rodriguez, Lucia; Crochet, Pascale; RSC Advances; vol. 3; nb. 43; (2013); p. 19985 - 19990 View in Reaxys With C51H41P2Ru(1+)*C32H12BF24 (1-) in neat (no solvent), Time= 16h, T= 110 °C , Sealed tube, stereoselective reaction Manzini, Simone; Nelson, David J.; Nolan, Steven P.; ChemCatChem; vol. 5; nb. 10; (2013); p. 2848 - 2851 View in Reaxys With aluminium(III) triflate, palladium diacetate, Time= 4h, T= 30 °C , Reagent/catalyst Senan, Ahmed M.; Qin, Shuhao; Zhang, Sicheng; Lou, Chenling; Chen, Zhuqi; Liao, Rong-Zhen; Yin, Guochuan; ACS Catalysis; vol. 6; nb. 7; (2016); p. 4144 - 4148 View in Reaxys 2 : Method for synthesizing isoeugenol A three-necked flask were successively added 70.0 g of 1,2-propanediol, 26.0 g of potassium hydroxide, stir mixing, 30.0 g of eugenol was added under nitrogen, and stirring was continued mixing;. B The reaction was placed under nitrogen over 20 minutes to quickly warmed to 165 , reflux for 8 hours, the reaction was blocking reaction;. C cooled to 50-60 , acidified with 50percent sulfuric acid was added to a solution of pH = 3 ~ 4;. D was added 200 ml of toluene was stirred uniformly, filtered and the solid washed with a small amount of toluene;. E The filtrate was allowed to stand, the organic phase was separated, the aqueous phase was extracted with toluene, and the combined organic phase;f. washing the organic phase with water to neutral, toluene was removed by rotary evaporator, vested crude, the crude vacuum distillation to obtain the product.g. Connect steps e and f in the aqueous phases were combined, neutralized potassium hydroxide, the water was distilled off at atmospheric pressure, and then distilled under reduced pressure to recover the solvent.Product quality: 25.5 g.2, the products were determined by gas content of 99.45percent, which cis-isoeugenol accounted for 8.14percent, trans-isoeugenol accounted for 91.31percent. With pentylene glycol, potassium hydoxide in toluene, Time= 8h, T= 50 - 165 °C , Inert atmosphere, Industrial scale Patent; Chongqing Xinxiang Xiangrong Fine Chemical Co., Ltd; Zhao, Huawen; Ji, Weigang; Gan, Jianqiang; Tang, Ling; Hong, Wei; (9 pag.); CN103408407; (2016); (B) Chinese View in Reaxys With palladium (II) acetate, water, bis(pinacol)diborane, PCy3 in toluene, Time= 12h, T= 20 °C , Sealed tube, Inert atmosphere Ojha, Devi Prasan; Gadde, Karthik; Prabhu, Kandikere Ramaiah; Journal of Organic Chemistry; vol. 82; nb. 9; (2017); p. 4859 - 4865 View in Reaxys

HO O

Rx-ID: 45315026 View in Reaxys 4/27 Yield 25 %Spectr., 72 %

Conditions & References With trimethylaluminum, cesium fluoride, (5-diphenylphosphanyl-9,9-dimethyl-xanthen-4-yl)-diphenyl-phosphane, cobalt acetylacetonate in N,N-dimethyl acetamide, toluene, Time= 12h, T= 60 °C , p= 760.051Torr , Inert atmosphere, Sealed tube, regioselective reaction

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Michigami, Kenichi; Mita, Tsuyoshi; Sato, Yoshihiro; Journal of the American Chemical Society; vol. 139; nb. 17; (2017); p. 6094 - 6097 View in Reaxys

HO O

Rx-ID: 45724741 View in Reaxys 5/27 Yield

Conditions & References

64 %Chromat., 24 %Chromat., 10 %Chromat.

With [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro[[2-(1-methyl-2-oxopropoxy)phenyl]methylene]ruthenium(II), [Pd(µ-Br)(tBu3P)]2 in dichloromethane, Time= 1h, T= 50 °C , Inert atmosphere Trita; Over; Pollini; Baader; Riegsinger; Meier; Gooßen; Green Chemistry; vol. 19; nb. 13; (2017); p. 3051 - 3060 View in Reaxys

HO O

Rx-ID: 45724742 View in Reaxys 6/27 Yield

Conditions & References

90 %Chro- With [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro[[2-(1-methyl-2-oxopropoxy)phenyl]methylmat., 5 ene]ruthenium(II), [Pd(µ-Br)(tBu3P)]2 in tetrahydrofuran, Time= 1h, T= 50 °C , Inert atmosphere %Chromat. Trita; Over; Pollini; Baader; Riegsinger; Meier; Gooßen; Green Chemistry; vol. 19; nb. 13; (2017); p. 3051 - 3060 View in Reaxys

Rx-ID: 41597187 View in Reaxys 7/27 Yield

Conditions & References

35 %Spectr.

With hydrogen in methanol, Time= 18h, T= 180 °C , p= 30003Torr , Sealed tube Petitjean, Laurene; Gagne, Raphael; Beach, Evan S.; Xiao, Dequan; Anastas, Paul T.; Green Chemistry; vol. 18; nb. 1; (2016); p. 150 - 156 View in Reaxys

HO C

Rx-ID: 39885845 View in Reaxys 8/27 Yield

Conditions & References 2.2. Catalytic runs General procedure: The catalytic runs were performed in a mechanically stirredstainless steel Parr 4560 bomb coupled with a 4282 control mod-ule with a PDI temperature controller, tachometer, and a pressuretransducer connected to a field logger apparatus. In a typical exper-iment the catalyst precursor [Rh(COD)(-OMe)]2(2.5 × 10−6mol),TPPTS (5.0 × 10−5mol) and the phase transfer agent cetyltrimethy-lammonium bromide (CTAB, 0.0–2.0 × 10−4mol) were dissolvedin 20 mL of deoxygenated water in a Schlenk tube under argon.The solution was transferred into the bomb,

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and the substrate(1.0–2.0 × 10−2mol) was placed in a pressure-equalized reservoiron the top of the bomb. The reactor was pressurized with thedesired carbon monoxide pressure (5–20 bar) and then with hydro-gen (5–20 bar) up to the desired total pressure. The bomb washeated to the desired temperature (80–120C) and kept for onehour under mechanical stirring (750 rpm). The substrate was thenadded and the register of the syngas pressure drop was initiated.After pressure drop stopped, the reactor was cooled, vented, theorganic phase was extracted with toluene (20 mL) and analysed by GC. With methoxy(cyclooctadiene)rhodium(I) dimer, trisodium tris(3-sulfophenyl)phosphine, hydrogen, cetyltrimethylammonim bromide in water, Time= 1h, T= 100 °C , p= 15001.5Torr , Autoclave, Schlenk technique, Inert atmosphere, Catalytic behavior, Kinetics, Pressure, Solvent, Temperature, Reagent/catalyst, regioselective reaction Baricelli, Pablo J.; Rodriguez, Mariandry; Melean, Luis G.; Alonso, Maria Modroño; Borusiak, Margarita; Rosales, Merlin; Gonzalez, Beatriz; De Oliveira, Kelley C. B.; Gusevskaya, Elena V.; Dos Santos, Eduardo N.; Applied Catalysis A: General; vol. 490; (2015); p. 163 - 169 View in Reaxys

HO C

Rx-ID: 32101448 View in Reaxys 9/27 Yield 6 %Chromat., 32 %Chromat., 62 %Chromat. 6 %Chromat., 62 %Chromat., 31 %Chromat.

Conditions & References With C44H34N4O8P2Rh2S2 (2-)*2Na(1+), hydrogen, cetyltrimethylammonium chloride in water, toluene, Time= 8h, T= 80 °C , p= 15526.6Torr , chemoselective reaction Melean, Luis G.; Rodriguez, Mariandry; Romero, Marynell; Alvarado, Maria L.; Rosales, Merlin; Baricelli, Pablo J.; Applied Catalysis A: General; vol. 394; nb. 1-2; (2011); p. 117 - 123 View in Reaxys With C44H34N4O8P2Rh2S2 (2-)*2Na(1+), hydrogen, cetyltrimethylammonium chloride in water, toluene, Time= 3h, T= 80 °C , p= 15526.6Torr , chemoselective reaction Melean, Luis G.; Rodriguez, Mariandry; Romero, Marynell; Alvarado, Maria L.; Rosales, Merlin; Baricelli, Pablo J.; Applied Catalysis A: General; vol. 394; nb. 1-2; (2011); p. 117 - 123 View in Reaxys 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 hydrogen in toluene, Time= 17h, T= 70 °C , p= 45603.1Torr , Inert atmosphere, Schlenk technique, Catalytic behavior, Pressure Carvalho, Glenda A.; Gusevskaya, Elena V.; Santos, Eduardo N. Dos; Journal of the Brazilian Chemical Society; vol. 25; nb. 12; (2014); p. 2370 - 2377 View in Reaxys

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Rx-ID: 39166463 View in Reaxys 10/27 Yield

Conditions & References

11 %Chro- With Rh/Al2O3, hydrogen in α-n-hexadecene, Time= 6h, T= 249.84 °C , p= 22502.3Torr mat., 13 Deepa, Ayillath K.; Dhepe, Paresh L.; ChemPlusChem; vol. 79; nb. 11; (2014); p. 1573 - 1583 %ChroView in Reaxys mat., 59 %Chromat., 4 %Chromat., 1 %Chromat. 10 %Chro- With hydrogen in α-n-hexadecene, Time= 6h, T= 249.84 °C , p= 22502.3Torr mat., 3 Deepa, Ayillath K.; Dhepe, Paresh L.; ChemPlusChem; vol. 79; nb. 11; (2014); p. 1573 - 1583 %ChroView in Reaxys mat., 44 %Chromat., 15 %Chromat., 3 %Chromat.

HO C

N H

N O

Rx-ID: 34577049 View in Reaxys 11/27 Yield

Conditions & References 2.2 Catalytic runs#10; 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, trifluorormethanesulfonic acid, hydrogen, triphenylphosphine in toluene, Time= 24h, T= 120 °C , p= 30003Torr Oliveira, Kelley C.B.; Santos, Alexandra G.; Dos Santos; Applied Catalysis A: General; vol. 445-446; (2012); p. 204 - 208 View in Reaxys

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HO C

N H

N O

N N

N O

O OH

Rx-ID: 34577050 View in Reaxys 12/27 Yield

Conditions & References 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, Time= 24h, T= 120 °C , p= 30003Torr Oliveira, Kelley C.B.; Santos, Alexandra G.; Dos Santos; Applied Catalysis A: General; vol. 445-446; (2012); p. 204 - 208 View in Reaxys

HO C

Rx-ID: 32101446 View in Reaxys 13/27 Yield 7 %Chromat., 13 %Chromat., 32 %Chromat., 48 %Chromat. 19 %Chromat., 40 %Chromat., 27 %Chro-

Conditions & References With BF4 (1-)*C57H46NO10P3RuS3 (2-)*3Na(1+), hydrogen, cetyltrimethylammonium chloride in water, toluene, Time= 10h, T= 100 °C , p= 46579.7Torr , chemoselective reaction Melean, Luis G.; Rodriguez, Mariandry; Romero, Marynell; Alvarado, Maria L.; Rosales, Merlin; Baricelli, Pablo J.; Applied Catalysis A: General; vol. 394; nb. 1-2; (2011); p. 117 - 123 View in Reaxys With C44H34N4O8P2Rh2S2 (2-)*2Na(1+), hydrogen in water, toluene, Time= 3h, T= 80 °C , p= 11401.1Torr , chemoselective reaction Melean, Luis G.; Rodriguez, Mariandry; Romero, Marynell; Alvarado, Maria L.; Rosales, Merlin; Baricelli, Pablo J.; Applied Catalysis A: General; vol. 394; nb. 1-2; (2011); p. 117 - 123 View in Reaxys

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mat., 14 %Chromat.

HO C

Rx-ID: 29466869 View in Reaxys 14/27 Yield

Conditions & References

21 %Chromat., 60 %

With [rhodium(I)(carbonyl)2(acetylacetonate)], phosphoric acid, hydrogen, methoxybenzene, triphenylphosphine in dichloromethane, Time= 2h, T= 110 °C , p= 15514.9Torr , Autoclave Alhaffar, Mouheddin; Suleiman, Rami; Ali, Bassam El; Catalysis Communications; vol. 11; nb. 8; (2010); p. 778 782 View in Reaxys

HO C

O O

Rx-ID: 24877165 View in Reaxys 15/27 Yield

Conditions & References 1 With hydrogen, rhodium(II)bis(2-ethylhexanoate) in water, toluene, Time= 10h, T= 125 °C , p= 18751.9Torr Patent; Celanese Chemicals Europe GmbH; EP1719752; (2006); (A1) German View in Reaxys

Rx-ID: 1770369 View in Reaxys 16/27 Yield

Conditions & References

88 %

With potassium hydroxide, Aliquat, Time= 0.2h, Irradiation, other basic system, other additives, var. microwave power and time, Product distribution Loupy; Le Ngoc; Synthetic Communications; vol. 23; nb. 18; (1993); p. 2571 - 2577 View in Reaxys

Ru3 (CO)12

HO Ru

Rx-ID: 25462627 View in Reaxys 17/27 Yield

Conditions & References 2 : EXAMPLE 2 EXAMPLE 2 A mixture of 200 g. of eugenol and 10 mg. of Ru3 (CO)12 (i.e. 0.0023percent of elementary ruthenium) is heated to 130° C. for 1 hour 55 minutes. By distilling the reaction mass, 198 g. of isoeugenol are recovered. The yield based on the eugenol used is 99percent (conversion rate 100percent).

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Patent; Rhone-Poulenc S. A.; US4138411; (1979); (A1) English View in Reaxys

Cl Os

(v3)

Rx-ID: 25462628 View in Reaxys 18/27 Yield 85.2%

Conditions & References 16 : EXAMPLE 16 EXAMPLE 16 A mixture of 73 g. of eugenol and 5.7 mg. of osmium trichloride is brought for 4 hours 25 minutes to 130° C. After distillation, 65.2 g. of a mixture, containing (as measured by gas-liquid chromatography) 13.8percent of eugenol, 6.8percent of cis-isoeugenol and 79.4percent of trans-isoeugenol are obtained. The conversion rate is 88percent and the yield is 85.2percent, based on the converted eugenol. Patent; Rhone-Poulenc S. A.; US4138411; (1979); (A1) English View in Reaxys

cinnamon leaves-oil

Rx-ID: 7161289 View in Reaxys 19/27 Yield

Conditions & References With potassium hydroxide, paraffin oil, T= 244 °C Patent; Jemac A.G.; CH175671; (1934) View in Reaxys With potassium hydroxide, phenol, T= 150 - 170 °C Patent; Verona Chem. Co.; US1787036; (1928) View in Reaxys

clove-oil

Rx-ID: 7161290 View in Reaxys 20/27 Yield

potassium hydroxide

Rx-ID: 6675068 View in Reaxys 21/27 Yield

Conditions & References durch Schmelzen

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Gokhale; Sudborough; Watson; Journal of the Indian Institute of Science; vol. 6; (1923); p. 246; Chem. Zentralbl.; vol. 95; nb. II; (1924); p. 324 View in Reaxys

potassium hydroxide

sodium hydroxide

Rx-ID: 6675071 View in Reaxys 22/27 Yield

Conditions & References durch Schmelzen Gokhale; Sudborough; Watson; Journal of the Indian Institute of Science; vol. 6; (1923); p. 246; Chem. Zentralbl.; vol. 95; nb. II; (1924); p. 324 View in Reaxys

potassium hydroxide

lead peroxide

Rx-ID: 6675070 View in Reaxys 23/27 Yield

Conditions & References beim Verschmelzen Graebe; Kraft; Chemische Berichte; vol. 39; (1906); p. 799 View in Reaxys

sodium

Rx-ID: 6675072 View in Reaxys 24/27 Yield

Conditions & References Gassmann; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 124; (1897); p. 38 View in Reaxys

ethanolic KOH-solution

Rx-ID: 6675066 View in Reaxys 25/27 Yield

Conditions & References T= 130 - 140 °C , unter Druck Eijkman; Chemische Berichte; vol. 23; (1890); p. 862 View in Reaxys Ciamician; Silber; Chemische Berichte; vol. 23; (1890); p. 1165 View in Reaxys Tiemann; Chemische Berichte; vol. 27; (1894); p. 2580 View in Reaxys Patent; Haarmann and Reimer; DE57808; Fortschr. Teerfarbenfabr. Verw. Industriezweige; vol. 3; p. 862 View in Reaxys

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HO H

potash

Rx-ID: 6675067 View in Reaxys 26/27 Yield

Conditions & References T= 200 - 230 °C , beim Schmelzen Patent; Einhorn; DE76982; Fortschr. Teerfarbenfabr. Verw. Industriezweige; vol. 3; p. 863 View in Reaxys Einhorn; Frey; Chemische Berichte; vol. 27; (1894); p. 2457 View in Reaxys

potassium hydroxide

Rx-ID: 6675069 View in Reaxys 27/27 Yield

Conditions & References T= 140 °C Tiemann; Chemische Berichte; vol. 24; (1891); p. 2881 View in Reaxys Patent; Haarmann and Reimer; DE57808; Fortschr. Teerfarbenfabr. Verw. Industriezweige; vol. 3; p. 862 View in Reaxys

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