, Hive-unknown? : Beilstein reaction possibilities.
3base (Stranger) 02-07-02 10:51 No 266531 |
Hive-unknown? : Beilstein reaction possibilities. (Rated as: excellent) |
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---------------------------------------- piperonylalcohol --> piperonal Reagent: MnO2, molecular sieves; Solvent hexane; Time 2h; Heating; Yield given J.Chem.Res.Synop.; EN; 6; 1998; 308-309; Hirano, Masao; Yakabe, Sigetaka; Chikamori, Hideki; Clark, James H.; Morimito, Takashi ---------------------------------------- piperonylalcohol --> piperonal Reagent: MnO2 (CMD); Solvent CH2Cl2; Time 24h; Ambient temperature; Yield 95% Syn.Lett.; EN; 1; 1998; 35-36; Journal; Aoyama, Toyohiko; Sonoda, Naoko; Yamauchi, Mariko; Toriyama, Kyoko; Anzai, Masahiro; et al. ---------------------------------------- piperonylalcohol --> piperonal Solvent CH2Cl2; Time 3h; Yield: 96% J.Chem.Soc.Dalton Trans.; EN; 1989; 901-906; El-Hendawy, Ahmed M.; Griffith, William P.; Taha, Fatma I.; Moussa, Mahmoud N. ---------------------------------------- piperonylalcohol --> piperonal Reagent H2O2; Catalyst: ligninase; Ambient temperature; pH 3.0; Subject Studied; Product distribution Phytochemistry; EN; 30; 1; 1991; 121-126; Ageorges, Agnes; Pelter, Andrew; Ward, Robert S. ---------------------------------------- + + + + + + + + + + + + + + + + + + + + + demorol (Hive Bee) 02-06-02 15:55 No 266091 Re: piperonylalcohol --> piperonal I'm sure all these syntheses work, but the piperonylalcohol is not very easy to get. ---------------------------------------- Life without chemistry would be a mistake. + + + + + + + + + + + + + + + + + + + + + ---------------------------------------- benzylchloride --> benzaldehyde Reactant: hexamethylenetetramine J.Chem.Soc.; 1949; 2704; Angyal et al. C.R.Hebd.Seances Acad.Sci.; 157; 1913; 852; Sommelet Patent DE 268786; Fabr. de Laire Fortschr.Teerfarbenfabr.Verw.Industriezw ---------------------------------------- benzylchloride --> benzaldehyde Reactant: aqueous Ca(NO3)2 solution Zh.Prikl.Khim.(Leningrad); 3; 1930; 721, 725; Schorygin; Kisber; Ssmoljaninowa Chem.Zentralbl.; GE; 101; II; 1930; 3397 ---------------------------------------- benzylchloride --> benzaldehyde Reagent: diluted nitric acid or aqueous lead nitrate Lauth; Grimaux; Bull.Soc.Chim.Fr.; <2> 7; 1867; 106 ---------------------------------------- benzylchloride --> benzaldehyde Reagent: copper nitrate Other Conditions: Reaktion ueber mehrere Stufen Book Review / Secondary Ref.; Fischer,E.; Anleitung zur Darstellung organischer Praeparate, 9. Aufl. <Braunschweig 1920>, S. 41 ---------------------------------------- benzylchloride --> benzaldehyde Reactant: potassium nitrite anthracene; Temperature: 150 C Chem.Ber.; 9; 1876; 1745; Brunner ---------------------------------------- benzylchloride --> benzaldehyde Reactant: nickel-powder, air ; Temperature: 160 C Korczynski; Reinholz; Schmidt; ROCHAC; Rocz.Chem.; 9; 1929; 731,738 Chem.Zentralbl.; GE; 101; I; 1930; 2075 ---------------------------------------- benzylchloride --> benzaldehyde Reagent: DMSO, NaHCO3 J.Org.Chem.; 24; 1959; 1792; Nace; Monagle ---------------------------------------- benzylchloride + benzalchloride --> benzaldehyde 2 C5H5.CH2.Cl + C5H5.CH.Cl2 + 2 MnO2 --> 3 C6H5.CHO + 2 MnCL2 + H2O Patent DE 20909, Schmidt Fortschr.Teerfarbenfabr.Verw.Industriezw ---------------------------------------- hi, here are some refs again. the first with MnO2/Microwaves is very nice. the first sentence of the description of the procedure is: " MnO2 'doped' silica ... " that's music in my ears ! the article doesn't mention how the obtained benzaldehyde was further treated, but with regard to the writingstyle, i could imagine that they've done a microwave assisted Knoevenagel condensation and so on ... ---------------------------------------- benzylalcohol --> benzaldehyde Active Manganese Dioxide on Silica: Oxidation of Alcohols under Solvent-free Conditions Using Microwaves Abstract: Alcohols are rapidly and selectively oxidized to the corresponding carbonyl compounds by silica supported active manganese dioxide under solvent-free conditions using microwaves. Tetrahedron Letters, Vol38, Issue 45, Nov-10-1997, 7823-7824; Varma, Rajender S.; Saini, Rajesh K.; Dahiya, Rajender ---------------------------------------- benzylalcohol --> benzaldehyde silica gel supported ferric nitrate reagent Solvent hexane; Time 4h; Other Conditions: Heating Synth.Commun.; EN; 28; 2; 1998; 207-212; Khadilkar, Bhushan; Borkar, Shobha ---------------------------------------- benzylalcohol --> benzaldehyde Chromat; Reagent MnO2/bentonite; Time 1 min; Temp 175C Other Conditions: Irradiation; Yield 40% Tetrahedron Lett.; FR; 34; 33; 1993; 5293-5294; Martinez, Luis A.; Garcia, Olivia; Delgado, Francisco; Alvarez, Cecilio; Patino, Rocio ---------------------------------------- benzylalcohol --> benzaldehyde Reagent HBr, H2O2; Solvent CH2Cl2; Time 4h; Temp 60C; Yield 84% Bull.Soc.Chim.Fr.; EN; 4; 1988; 756; Dakka, Jihad; Sasson, Yoel ---------------------------------------- benzylalcohol --> benzaldehyde Reagent manganese dioxide, benzyl alcohol; Turnov; Solvent hexane; Temp 20C; Yield 60% J.Chem.Soc.Perkin Trans.1; EN; 7; 1990; 1937-1943 Cavaleiro, Jose A. S.; Neves, Maria G. P. S.; Hewlins, Michael J. E.; Jackson, Anthony H. ---------------------------------------- |
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Rhodium (Chief Bee) 02-08-02 05:43 No 266901 |
Re: benzylchloride --> benzaldehyde | Bookmark | ||||||
3base: You are doing an excellent work by donating your time in front of Beilstein for our purposes. Suggested search areas: nitroalkene reductions w/o LAH or catalytic hydrogenation under pressure, ways of making 2,6-dimethoxy-4-bromo-PEA (and other things in the 4-position), phenylacetonitrile and cyanohydrin reductions to phenethylamines, with the same limitations as above. |
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foxy2 (Distinctive Doe) 02-08-02 11:11 No 267008 |
Phenylacetonitrile to phenylethylamine (Rated as: excellent) |
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Phenylacetonitrile to phenylethylamine Reductions Reduction of some functional groups with zirconium tetrachloride/sodium borohydride. Itsuno, Shinichi; Sakurai, Yoshiki; Ito, Koichi. Synthesis (1988), (12), 995-6. Abstract A novel reducing agent prepd. from ZrCl4 and NaBH4 reduces various functional groups including C:O, C:N, and C.tplbond.N bonds in excellent yield (85-96%) under mild conditions. Supported nickel-catalyzed hydrogenation of aromatic nitriles under low pressure conditions. Takamizawa, Satoshi; Wakasa, Noriko; Fuchikami, Takamasa. Synlett (2001), (10), 1623-1625. Abstract Hydrogenation of arom. nitriles takes place under the mild conditions using supported Ni catalysts to afford aminomethyl-substituted aroms. in good yields. Convenient synthesis of protected primary amines from nitriles. Caddick, Stephen; Haynes, Alexandra K. De K.; Judd, Duncan B.; Williams, Meredith R. V. Tetrahedron Lett. (2000), 41(18), 3513-3516. Abstract Investigations into the use of nickel chloride and sodium borohydride for the redn. of nitriles showed the secondary amine dimers to be the major products under normal conditions. The addn. of a suitable trapping agent, such as di-tert.-Bu dicarbonate, allowed the isolation of the protected primary amines. Electrocatalytic reduction of nitriles on Raney nickel. Muthukumaran, A.; Krishnan, V. Bull. Electrochem. (1991), 7(9), 410-11. Abstract An electrochem. method for the prepn. of primary amines from org. nitriles using a Raney nickel cathode is reported. It has been obsd. that it is possible to reduce benzyl cyanide to b-phenylethylamine with an yield efficiency of 85% and to reduce benzonitrile to benzylamine with an yield efficiency of 20%. b-Phenylethylamine by electrolytic reduction of benzyl cyanide using deposited iron black cathode. Udupa, Handady Venkatakrishna; Krishnan, Venkatasubramanian; Muthukumaran, Arunachalam. Indian (1984), 6 pp. IN 153683 A 19840804 Abstract In this improved process Fe black cathode deposited an a graphite substrate is used as the cathode in a diaphragm cell. The catholyte is aq. ethanolic (NH4)2SO4 contg. benzyl cyanide and the anolyte 10% H2SO4. The anode is a hollow perforated cylinder of Pb-Ag alloy and the reaction vessel is PVC. Electrolysis was carried out at 5 A/dm2 using 500 A at 10-12 V with a current efficiency of 28% and a yield of 56%. The use of Fe black cathodes decreased the cost of b-phenylethylamine considerably. Fully Informed Jury! (http://www.fija.org/) |
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3base (Stranger) 02-09-02 01:52 No 267367 |
nitroalkene reductions | Bookmark | ||||||
> Suggested search areas: nitroalkene reductions w/o LAH > or catalytic hydrogenation under pressure rhodium: this is exactly what i've searched already some months ago ! for those interessted in catalytic hydrogenation WITHOUT(!) overpressure under mild conditions, i highly recomend: "Synthesis of PEA's by Hydrogenation of b-nitrostyrenes" Bull.Chem.Soc.Jpn., Vol.63, No.4, 1990, pp.1252-1254 Masahiko Hohno, Shigehiro Sasao and Shun-Ichi Murahashi never fear, it's in english ! a general procedure is describe using H2, Pd/C and HCl(aq) in EtOH. Stirring at 0°C for 3h followed by a classical workup. they've prepared several PEA's and their HCL-salts like: - mescaline (yield 65%) - 3,4-methylenedioxyPEA (yield 71%) shulgin's alkyloxy-substituted-PEA's like IP, E, ASB are surley also accessible by this procedure. it won't get easier Edit: the full article has been uploaded to ../rhodium /ns.hydr |
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