java (Hive Bee) 07-31-04 18:32 No 523004 |
Hydrogenolysis of Phenylalaninol..... (Rated as: excellent) |
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In mining through the large archives here at the hive I read Post 108597 (dormouse: "drone's amphetamine synthesis contest -drone 342", Novel Discourse) from which psychokitty contributes to the amphetamine contest where she introduces her way to Methamphetamine starting with Phenylalanine .....anyway read it yourself but the point is a reference which she gives , Hydrogenolysis of Diaryl and Aryl Alkyl Ketones and Carbinols by sodium Borohydride and anhydrous Aluminum(III) chloride AoiOno, Nobuko Suzuki, Junko Kamimura for which deals with the reduction, to the respective Hydrocarbons, of Phenylalaninol alcohols but it also works for the benzylic alcohols in ephedrine and Pseudoephedrine and phenylpropanolamine. One thing also she discusses the acylation of the amine prior to reduction to the alcohol in order to obtain at the end methamphetamine. Thank you psychokitty for your research........java Just hold on to the thread...that keeps us going http://www.chiapaslink.ukgateway.net/ |
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java (Hive Bee) 08-01-04 13:18 No 523116 |
Syntheses of amino alcohols..... | |||||||
Syntheses of Amino Alcohols and Chiral C2-Symmetric Bisoxazolines Derived from O-Alkylated R-4-Hydroxyphenylglycine and S-Tyrosine Vesna ^aplar,a,* Zlata Raza,b Darinka Kataleni},a and Mladen @ini}a CROATICA CHEMICA ACTA CCACAA 76 (1) 23-36 (2003) ISSN-0011-1643 CCA-2849 Abstract Chiral C2-symmetric bisoxazolines 1b–f and 2b,c, derived from 4’-O-alkylated R-4-hydroxyphenylglycine or S-tyrosine, were prepared. As intermediates, a series of chiral amino alcohols possessing substituted phenolic groups was prepared and fully characterized. CONCLUSION Chiral amino alcohols with free and substituted (alkyl,benzyl) phenolic groups have been prepared in high yields, using easily available reagents and mild conditions. They served as precursors for the preparation of either macrocyclic or acyclic chiral C2-symmetric bisoxazolines, designed as ligands for metal-catalyzed enantioselective transformations. Just hold on to the thread...that keeps us going http://www.chiapaslink.ukgateway.net/ |
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josef_k (Hive Bee) 08-02-04 05:33 No 523222 |
Re: for which deals with the reduction, to the | |||||||
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java (Hive Bee) 08-02-04 09:46 No 523245 |
Hydrogenolysis...... | |||||||
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armageddon (Hive Bee) 08-05-04 18:36 No 523910 |
Pd/C and solvents | |||||||
Java: Water is out of the question because of thionyl violent reaction to water , hence I need something that will put the alcohol in solution so it can react with the acid. I thought of using chloroform, as I've used this in the reduction of ephedrine and pseudoephedrine to a chloroephedrine, but not sure that the alcohol will work in this solvent. I guess I will try a small sample for solubility. For dehalogenations, DCM and chloroform are a good choice - but for hydrogenations, alcohols (maybe with additional acetic acid) are the solvents to be used with Pd/C... http://www.strem.com/code/degussakit.htm Greetz A Pleased to meet you hope you get my name. But whats puzzlin you is the nature of my game! |
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java (Hive Addict) 08-13-04 17:20 No 525336 |
Alpha-methyl-Aminoacids ..... | |||||||
Noted in the post listed under Chapter 3 "Ligans for Asymmetric Catalysed Cross Coupling Reactions" Post 525324 (java: "ENANTIOSELECTIVE CROSS COUPLING REACTIONS", Chemistry Discourse)
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java (Hive Addict) 08-18-04 18:10 No 526168 |
Summary of Phenylalanine to Amphetamine | |||||||
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java (Hive Addict) 08-19-04 11:47 No 526326 |
Phenylalanine to amphetamine continuation..... | |||||||
I have a question which I need some help answering , in the hydrogenolysis of OH to CH3 of Phenylalaninol as mentioned in my last post where Assholium proved that RP/I would reduce the alcohol to the respective hydrocarbon, keeping in mind that Phenylalaninol is slightly soluble in water. Now water is needed for the chemistry of RP and I to work into making HI and catalyse it to reduce the OH to CH3. As noted and mentioned by Rhodium Post 521414 (Rhodium: "Note the formation of HCl salts in the reaction", Serious Chemistry) on this thread the solubility of phenylalaninol and most amino alcohols are soluble in chloroform and DMF. But does that mean that the reaction solvent will be chloroform? Doubtful, hence it would be nice to find out the solvent Assholium used in his method which he showed this reduction of the alcohol to hydrocarbon. So if there is anyone out there that has the answer, since I wrote to Assholium and no response, It would be nice to add to this project.......java It is better to die on your feet than to live on your knees....... -Emiliano Zapata- |
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java (Hive Addict) 08-19-04 15:02 No 526340 |
RP/I in the reduction of Phenylalaninol.... | |||||||
I found this info as to using RP/I .....
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Organikum (Wonderful Personality) 08-20-04 06:43 No 526466 |
Deoxygenation of benzhydrols | |||||||
There are more methods available some of which have not been talked about by now: I except those which for sure only work on alpha-alcohols like the Li/ammonia (Birch)and those already mentioned. Here we go: 1. Fe(CO)5 2. Diiododimethylsilane 3. Zinc iodide/sodium cyanoborohydride 4. Triphenylsilane in trifluoroacetic acid/methylene chloride 5. Sodium borohydride/trifluoroacetic acid 1. Alper, H.; Salisova, M. J. Org. Chem. 1980, 21, 801. (this one would 9interest me in special as I have never heard of Fe(CO)5 as reducing reagent before - very curious I am! 2. Ando W.; Ikeno M. Tetrahedron Lett. 1979, 1979. 3. Lau C. K.; Dufresne C.; Belanger C. P.; Pietre S.; Scheigetz J. J. Org. Chem. 1986, 51, 3038. 4. Olah G. H.; Tremper H. S. J. Am. Chem. Soc. 1968, 90, 2578. 5. Gribble G. W.; Leese W. M.; Evans B. E. Synthesis 1977, 763. And onto the RP/I a remark: Acetic or phosphoric acid are the solvents of choice here. The low solubility of the substrate is not really important - the reaction is heterogenous anyways and the solid substrate being where the HI is formed - at the bottom where the RP is - might even be favorable. btw. I am rather sure that a suitable noble metal catalyst reduces ANY alcohol when trifluoroacetic acid is used as solvent and perchloric acid as moderator. Also there was a post times ago by "chicken" AFAIK, where it was told that triethylsilane/aluminiumchloride in trifluoroacetic acid reduces aminoalcohols in yields up to 100%. No reference was given, the post has vanished like so many useful posts did. Looking at the reagents used in the above references it seems very probable that this works. Silanes have become a mass-product in the last years, not too expensive and not watched by now. They are produced in tons over tons by Wacker-Chemie Burghausen in Germany. (thats no source, you cant buy it from them directly, but your industrial chem-supplier can do so) ORG so near, so far...... |
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java (Hive Addict) 08-20-04 11:47 No 526494 |
Other methods..... | |||||||
Organikum...check the reference Alper, H.; Salisova, M. J. Org. Chem. 1980, 21, 801. it doesn't seem to be the right date or page , anyway check so I can find it. Here is one that I found.... Reactions of Sodium Borohydride in Acidic Media; VII. Reduction of Diaryl Ketones in Trifluoroacetic Acid GRIBBLE, Gordon W.; KELLY, William J.; EMERY, Sanford E.: Will look for ........... Carbonium ion-silane hydride transfer reactions. I. Scope and stereochemistry Francis A. Carey and Henry S. Tremper J. Am. Chem. Soc. 1968, 90, 2578. Reductive deoxygenation of aryl aldehydes and ketones and benzylic, allylic, and tertiary alcohols by zinc iodide-sodium cyanoborohydride C. K. Lau, Claude Dufresne, Patrice C. Belanger, Sylvie Pietre, and John Scheigetz Org. Chem. 1986, 51, 3038. Copper-complexes of pyridazine N-oxides; The synthesis and x-ray studies Akio Ohsawa, , Toshio Akimoto, Akio Tsuji and Hiroshi Igeta Tetrahedron Letters Volume 19, Issue 23, (1978)Pages 1979-1982 It is better to die on your feet than to live on your knees....... -Emiliano Zapata- |
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Organikum (Wonderful Personality) 08-20-04 16:07 No 526529 |
Uhh ? | |||||||
Alper, H.; Salisova, M. J. Org. Chem. 1980, 21, 801. This is exactly how its referenced in the article from which I quoted this, with italics and bold...... Cant help it, sorry. Any chance to get hold of it by the authors or the reagent, Fe(CO)5 ? Damn. so near, so far...... |
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gsus (Hive Bee) 08-20-04 18:57 No 526537 |
Alper and Salisova | |||||||
right year/volume/page, wrong journal, i think. try Tet Lett. http://www.mindstates.org/mindstatesoaxa |
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java (Hive Addict) 08-20-04 20:44 No 526546 |
The correct Reference on FE(CO)5 | |||||||
The iron carbonyl induced deoxygenation of alcohols Howard Alper* and Marta Saliová Tetrahedron Letters volume 21 773-890 1980 Abstract Alcohols, able to form stable carbanions, are deoxygenated to hydrocarbons by treatment with potassium, iron pentacarbonyl, and then hydrochloric acid. Use of an alkyl halide in place of HCl results in reductive alkylation. It is better to die on your feet than to live on your knees....... -Emiliano Zapata- |
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7is (Hive Bee) 08-20-04 20:50 No 526547 |
Articles | |||||||
A convenient reduction of amino acids and their derivatives Marc J. McKennon, A. I. Meyers, Karlheinz Drauz, and Michael Schwarm JOC 1993,58,3568-3571 Organometallic compounds of Group III. 49. Reductive deoxygenation of ketones and secondary alcohols by organoaluminum Lewis acids John J. Eisch, Zhi Rong Liu, and Marek P. Boleslawski JOC 1992, 57, 2143-2147 Carbonium ion-silane hydride transfer reactions. I. Scope and stereochemistry Francis A. Carey and Henry S. Tremper J. Am. Chem. Soc. 1968, 90, 2578. Copper-complexes of pyridazine N-oxides; The synthesis and x-ray studies Akio Ohsawa, , Toshio Akimoto, Akio Tsuji and Hiroshi Igeta Tetrahedron Letters Volume 19, Issue 23, (1978)Pages 1979-1982 The iron carbonyl induced deoxygenation of alcohols Howard Alper and Marta Salisova Tetrahedron Letters 1980, 21, 801. |
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java (Hive Addict) 08-21-04 14:26 No 526633 |
Phenylalaninol reduction ....... | |||||||
Organikum...maybe it's this article that you mentioned that dissapeared.... Selectivities in ionic reductions of alcohols and ketones with triethylsilane/trifluoroacetic acid Herbert Mayr*a) and Barbara Doganb) Tetrahedron Letters Volume 38, Issue 6 , 10 February 1997, Pages 1013-1016 DOI::10.1016/S0040-4039(96)02484-7 Abstract The relative rates of reduction of alcohols and ketones by Et3SiH/CF3CO2H have been determined by competition experiments in order to derive scope and selectivities of these reactions. ---------------------------------------- As for the articles mentioned in the removal of OH groups I think the Fe(CO)5 has the most viability as the others seem to get busy real fast. Thanks to 7is there is a chance to read all of them and evaluate for one self.
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Organikum (Wonderful Personality) 08-25-04 11:03 No 527294 |
not found | |||||||
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java (Hive Addict) 08-25-04 13:08 No 527307 |
The missing Tetrahedral article.... | |||||||
Here it is, it was already uploaded .....but was not found easy with the search ......java Post 514666 (scarmani: "Et3SiH / TFA Reduction - Improvements?", Serious Chemistry) edit: I underestand the article is not found on the bord, so heere is the copy.....java Selectivities in Ionic Reductions of Alcohols and Ketones with Triethylsilane / Trifluoroacetic Acid Tetrahedron Letters, Vol. 38, No. 6, pp. 1013-1016, 1997 It is better to die on your feet than to live on your knees....... -Emiliano Zapata- |
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java (Hive Addict) 09-03-04 13:58 No 529405 |
phenylalaninol reduction RP/I....... | |||||||
After searching through the archives here at the Hive and asking questions from knowledgeable bee's I've been able to deduce the following which can be found and read from this thread, 1. Phenylalaninol can be reduced with the RP/I method , only increasing the reactants 1.5 as much as regularly used in the reduction of ( Pseudo) Ephedrine and at least a 24 hr. reflux as recomended by Rhodium 2.The solubility of the alcohol is slight in water, hence recomended acidic acid or Phosphoric acid. 3. There is a concern brought to my attention as to cyclozation producing cycloamines, but I wonder if by running the reaction with 1.5 in excess of the reactants will create a strong acidic environment , as recomended to avoid this. 4. there is out there a post by Assholium where he gave details of the reaction and proof of its viability.....one quoted by Labrat Note: Trying to complete this reaction with availabe methods already know here at the hive. Yes there is the NaBh4 Al(111), the hydrogenation methods the halogenation & hydrogenation methods , the few introduced by Organikum on this thread and those by Psychokitty Will be looking for the elusive post to bring to light any possible complications with this procedure....java It is better to die on your feet than to live on your knees....... -Emiliano Zapata- |
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java (Hive Addict) 09-05-04 15:41 No 529757 |
Another primary -OH reduction method... | |||||||
More recently this was posted by Kinetic and thought this to fit nicely in this thread in dealing with the reduction of Phenylalaninol to a hydrocarbon........ Post 529529 (Kinetic: "More reductions with triethylsilane/boranes", Chemistry Discourse) It is better to die on your feet than to live on your knees....... -Emiliano Zapata- |
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nightshade 09-09-04 10:22 |
Reducing Phenylalaniol to what using RP/I...
(Rated as: UTFSE!) |
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Rhodium (Chief Bee) 09-23-04 10:35 No 532870 |
L-Phenylalanine to d-Amphetamine (Rated as: good read) |
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Überführung optisch aktiver α-Aminocarbonsäuren in optisch aktive Amine mit gleichem Kohlenstoffskelett P. Karrer & K. Erhardt Helv. Chim. Acta 34, 2202-2210 (1951) (../rhodium/pdf /pha2amph.ehr Summary: This is one of the first published methods for the conversion of L-Phenylalanine to d-Amphetamine. First phenylalanine is condensed with methanol to form phenylalanine methyl ester, which is reduced with LiAlH4 to L-Phenylalaninol. This aminoalcohol is reacted with tosyl chloride in pyridine to give L-Phenylalaninol O,N-ditosylate. The O-tosylester was reduced to the hydrocarbon with LiAlH4 to yield D-Amphetamine N-tosylamide, which finally was cleaved to give D-Amphetamine. The same scheme was applied to L-Tyrosine, transforming it into 4-Hydroxy-Amphetamine. The Hive - Clandestine Chemists Without Borders |
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java (Hive Addict) 09-25-04 17:49 No 533189 |
Question on Tosyls.....on route to Amphetamine.... | |||||||
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Rhodium (Chief Bee) 09-26-04 14:43 No 533293 |
Catalytic de-tosylation | |||||||
They do not offer any such procedure in that publication, but I'm sure that it would work, somehow. Someone just needs to perform a literature search for it. The Hive - Clandestine Chemists Without Borders |
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java (Hive Addict) 09-27-04 13:03 No 533429 |
phenylalaninol reduction RP/I....... (Rated as: good read) |
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In searching for a confirmation in March's text, on the reduction of Phenylalaninol to Amphetamine by using the RP\I method....I was able to find this study, once quoted as a needed reference Post 172334 (Rhodium: "HI/P reduction REFERENCES?", Stimulants) and never made available, in which an arene aliphatic alcohol is reduced to the hydrocarbon with this system.....java Synthesis of Desoxybenzoins . Deoxygenation with the Red Phosphorous /Iodine system Tse-Lok Ho, C.M. Wong Synthesis 161, 1975 It is better to die on your feet than to live on your knees...Emiliano Zapata |
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java (Hive Addict) 09-28-04 13:37 No 533626 |
Reducing Phenylalaninol.......articles | |||||||
Mining the web and following up leads in related articles , I came upon a couple of studies dealing with the reduction of arene aliphatic alcohols, checked the archives and found no listings on the HIve and so I present them here now for discussion.......java Chlorotrimethylsilane/SodiumIodide/Zinc as a Simple and Convenient Reducing System:One pot Deoxygenation of Alcohols and ethers Tsuoshi Morita, Yoshiki Okamoto, Hiroshi sakurai Synthesis 32, 1981 Note: with this method both primary and secondary alcohols are reduced to hydrocarbons
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nightshade (Newbee) 09-29-04 10:26 No 533768 |
Fermenting phenylalanine in a bio brew like... | |||||||
Fermenting phenylalanine in a bio brew like that producing L-Pac will will produce phenylalaniol, which can be extracted with a non polar solvent then reduced by electrochemical reaction to amphetamine is this correct? |
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java (Hive Addict) 09-29-04 14:21 No 533796 |
Biotransformation of Phenyalanine.........? | |||||||
nightshade.... do you have some references for that?..........I myself not familiar with the way you've outlioned the procedure.....java It is better to die on your feet than to live on your knees...Emiliano Zapata |
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indole_amine 09-29-04 17:09 |
I guess he meant some enzymatic conversion of...
(Rated as: insignificant) |
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nightshade (Newbee) 09-30-04 10:22 No 533923 |
Post 9775,Post 10417 | |||||||
Post 9775,Post 10417 |
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java (Hive Addict) 09-30-04 10:34 No 533926 |
Biotransformation References....to Phenylalaninol | |||||||
I just put brackets around the post number you volunteered as reference and this is what came up, hence it's easier to just click and go to it than having to go to the search engine looking for them. This will help your posting next time you want to reference a post number............java Post 9775 (in_outsider: "Tryptophol from Tryptophan via yeast", Tryptamine Chemistry) Post 10417 (psyloxy: "Re: Tryptophol from Tryptophan via yeast", Tryptamine Chemistry) P.S. Thank you for the reference as I will read it and comment if I have any questions or suggestions It is better to die on your feet than to live on your knees...Emiliano Zapata |
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java (Hive Addict) 09-30-04 17:05 No 533979 |
Missing one of two ref on RP/I reductions | |||||||
Thanks to gsus he has provided the referenced article Post 533954 (gsus: "Fieser and Fieser for java", Novel Discourse)....that was posted by Labrat...on the reduction of Phenylalaninol with the RP/I method ......java
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java (Hive Addict) 10-02-04 18:58 No 534221 |
RP/I Reduction of aminoalcohol....... | |||||||
Preparation of alpha ,alpha -Dimethyl- and N,alpha ,alpha -Trimethyl-beta -cyclohexylethylamine Bernard L. Zenitz, Elizabeth B. Macks, Maurice L. Moore J. Am. Chem. Soc. 70, 955-957 (1948) (../rhodium/pdf /hi-rp.aminoa Excerp...... A reduction of alpha-methyl-norephedrine to alpha-methyl-amphetamine (Phentermine) with HI/P (80-88% yield). They use 20g RP to 0.4 moles of the aminoalcohol (66g, it has the same molar weight as ephedrine) together with 170 mL 57% HI. The mixture is reacted for 25h at reflux and 12h at room temp before workup (filtration, thiosulfate addition, acid/base extraction, distillation, gassing w/ HCl). pdf is located at ...... Post 511694 (Rhodium: "HI/RP reduction of aminoalcohols", Stimulants) It is better to die on your feet than to live on your knees...Emiliano Zapata |
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