the Hive BB Serious Chemistry Forum visciously beating a dead horse: MDP2-Pol, back from the dead profile | register | preferences | faq | search next newest topic | next oldest topic Author Topic: visciously beating a dead horse: MDP2-Pol, back from the dead drone 342 Member posted 12-30-98 01:00 PM -------------------------------------------------------------------------------- Making a fascile MDP-2-Pol synthesis using only OTC materials would be a coup, and while the conditions previously given seemed to only offer mixed results, I think there's plenty of hope for something simple, effective and OTC. There are hundreds of examples in the literature of alcohols being made from allyls in the fasion we're interested in, and only a few ref's have ever been evaluated here. Anybody else care to dig a little deeper? -drone #342 ChemHack Member posted 12-31-98 07:19 PM -------------------------------------------------------------------------------- Making wine out of water would also be a "serious coup" but... There ARE lots of refs about this sort of thing but, for this Hack at least, the subtlties of intra-molecular attraction and repulsion are completely outside of the realm of comprehension.What I am saying is that just because someone is interested and goes deep into the refs doesn't mean that they would be able to predict problems such as 2Pol to 1Pol migration and the like. I guess that I missed the lab report that Strike was planning to post about the migration, can anyone point me in that direction? psychokitty gave pretty straightforward looking ref for converting MDP1P to the 2P. Perhaps the existing techniques for converting safrole to the 1Pol (via the 2Pol THE RIGHT WAY) could be be utilized and the the 1Pol oxidized to the 1P! You wouldn't even have to wait for the 2Pol to 1Pol "degradation" to complete to do the oxidation...There would be two pathways to the 2P, one via the 1P and another via the 2Pol. The other option that I can see is to somehow do the 2Pol -> 2P oxidation selectively in situ while the alcohol is being formed. And Rain Makes Applesauce. C.Hack PS: Although I may not be able to make reasonable good evaluations of potential alcohol formation schemes, I am will to do the Hack work and do a full write-up of the procedure. If this really is the holy grail then it will have to be idiot proof. I am that idiot! ChemHack Member posted 01-01-99 05:04 AM -------------------------------------------------------------------------------- I really hope this thread heats up again. To minimize the horse beating I offer a neophite's synopsis of the discussion thus far: --------------------------------------------------------------------------------1. Drone 342 treated chilled safrole with chilled concentrated Sulfuric and then added water and refluxed to yield an alcohol. The alcohol was oxidized to ketone and aminated to yield an "active" product. Drone refused to disclose his oxidation technique but it was widely rumored to be household bleach. To his credit he did give the refs which, if I had bothered to look up, probably would have revealed the oxidising agent. So sue me! 2. Bright Star tested fresh alcohol with IR/NMR and found the 2Pol. The next day he discover that the 2Pol changed into 1Pol. This jives with the theoritical musings of RatHead and Osmium amoung others. 3. Strike paid some "real scientists" to confirm this discovery. A key element is apparantly the acid concentration but a detailed lab report was NOT given. Hint. Hint... 4. Rhodium pointed out that PiKAL lists "Alpha-M" as the product of aminating MDP1P, this substance is active but apparantly much weaker than MDMA. --------------------------------------------------------------------------------I hope I didn't leave anything important out of this review. The success of the SRV really took the wind out of this method's sails. Progress WAS being made here and it would be a shame to let this knowledge slip from our collective consciousness. If the 2Pol can be oxidized fast enough, or if PsychoKitty's 1P -> 2P conversion actually works, then this method can be considered viable. Rhodium Administrator posted 01-01-99 09:46 AM -------------------------------------------------------------------------------- I'd like to add a few things: Using 65% aqueous HNO3 or 70% H2SO4 in glacial acetic acid has resulted in explosively exothermic polymerizations. In runs using 70% aqueous H2SO4, various researchers have reported recoveries of only starting material, as confirmed by TLC or IR. drone 342 Member posted 01-01-99 12:59 PM -------------------------------------------------------------------------------- Chemhack, you said:quote: -------------------------------------------------------------------------------- "What I am saying is that just because someone is interested and goes deep into the refs doesn't mean that they would be able to predict problems such as 2Pol to 1Pol migration and the like. --------------------------------------------------------------------------------This is not true. What we're doing here is science. The whole point is that it be predictive. True, we may not KNOW with absolute certainty, but this isn't an unusual reaction -- scores of very similar reactions exist in the literature. Hydrating aryl allyl compounds is nothing new, highly theoretical, or complicated. Its been done. Lots of times. Additionally, I have to admit I'm skeptical about the immigration issues. If letting it sit around gives it time to migrate, as might be indicated from Bright Star's investiagtions, it would seem the reaction were catalyzed by an impurity of some sort -- P2Pol's are isolatable. It would seem then the big contrandication is that the material be oxidized into the ketone as fast as possible is the solution. drone 342 Member posted 01-01-99 02:14 PM -------------------------------------------------------------------------------- Whoops! AS a traveler, I am skeptical of "immigration" issues, but as a chemist, I'm also skeptical of "migration issues" when it comes to hydrations of allyl benzenes, and tha't what I was trying to express. ChemHack, What I was trying to say was, after reviewing the literature, I think it is thoroughly reasonable to make some predictions about this compound, and how to hydrate it the way we want to. ChemHack Member posted 01-01-99 02:19 PM -------------------------------------------------------------------------------- Let me try to put it another way: Certain bees,with more O.Chem talent than I'll ever have, looked at "tons of refs" and still failed to predict the migration.One could spend weeks dig through the "scores of very similar reactions" but, without a firm grasp of theromodinamic bond stability, delocalized charges, and the like, still be unable to formulate a reliable Hacker's technique. ChemHack Member posted 01-01-99 02:29 PM -------------------------------------------------------------------------------- Woah, we must be posting at the same time. You beat me to the reply of your own note! Anyway, I don't understand your skepticism of the migration. A good scientist is always skeptical I suppose but it is hard to argue with Bright Star's test. It doesn't even really matter if the migration is due to some "impurity" because if it happened to Bright Star and Strike's team of "chemists for hire" then it will certainly happen in the MasonJarLabs of middle America. Our best bet may well be to accept that it happens and come up with a method for dealing with it. Our options so far are speedy conversion to ketone and making the 2P from the 1P. ChemHack Member posted 01-01-99 02:35 PM -------------------------------------------------------------------------------- OK, now that we got that out of the way I have a real question about the rxn itself: Assuming a speedy isolation of the 2Pol before it has a chance to "migrate", would it not be MORE difficult to oxidize the 2Pol than the 1Pol ? Drone, do you think your SuperSecret oxidizer can handle the 2Pol? What is that oxidizer? You gonna make me go look it up just to prove that I care? ChemHack Member posted 01-02-99 05:40 PM -------------------------------------------------------------------------------- Also, what is the bp of MDP2Pol ? My guess is that it would be higher than MDP2P because Benzyl alcohol's bp is 25 degrees higher than benzalhyde. The alcohol's mw is a tad higher but I dunno if that is really matters.Come on Drone or anybody, don't leave me talking to myself on this thread! ChemHack Member posted 01-02-99 07:04 PM -------------------------------------------------------------------------------- OK how about I propose an oxidation scheme: Solution of 16g K2CrO4, 10ml conc. sulfuric, and Acetone at 0C is dripped over 10 minutes into a 0C stirring solution of 22g MDP2Pol in 20ml Acetone. Allowed to react for ? minutes. Or what about using Acetic Acid and water instead of sulfuric acid and acetone at an elevated temperature?
Come on guys, chime in! rev drone Member posted 01-05-99 03:07 PM -------------------------------------------------------------------------------- Shall I post a selection of ref's detailing variuous allyl hydrations? ChemHack Member posted 01-05-99 05:08 PM -------------------------------------------------------------------------------- That would be a good start. If have a chance to read any of the articles please post your comments as well. rev drone Member posted 01-05-99 06:12 PM -------------------------------------------------------------------------------- Reaction Reaction ID 66758 Reactant BRN 1100186 2-allyl-anisole Product BRN 3155657 1-(2-methoxy-5-<1-(2-methoxy-phenyl)-propyl>-phenyl)-propan-2-ol -------------------------Reaction Details Reaction Classification Preparation Reagent aqueous H2SO4 Ref. 1 1647843; Journal; van der Zanden; de Vries; RTCPA3; Recl.Trav.Chim.Pays-Bas; 74; 1955; 876, 882; Reaction Reaction ID 283003 Reactant BRN 1910871 4-allyl-1,2-dimethoxy-benzene Product BRN 2049658 (+-)-3.4-dimethoxy-1-<2-hydroxy-propyl>-benzene -------------------------Reaction Details 1 of 2 Reaction Classification Preparation Reagent aqueous sulfuric acid Temperature 5 øC Ref. 1 1595592; Journal; Clemo; Turnbull; JCSOA9; J.Chem.Soc.; 1947; 124, 127; ------------------------- Reaction Details 2 of 2 Reaction Classification Preparation Other conditions (i) aq. Hg(OAc)2, (ii) aq. NaOH, NaBH4 Note 1 Multistep reaction Ref. 1 156820; Journal; Manitto,P. et al.; JCPRB4; J.Chem.Soc.Perkin Trans.1; EN; 1975; 1548-1551; Reaction Reaction ID 1767861 Reactant BRN 136380 5-allyl-benzo<1,3>dioxole Product BRN 150198 1-benzo<1,3>dioxol-5-yl-propan-2-ol 150253 3-benzo<1,3>dioxol-5-yl-propan-1-ol -------------------------Reaction Details Reaction Classification Preparation Reagent 1.) BH3, 2.) sodium perborate Other conditions 1.) THF, from 0 deg C to RT, 2 h, 2.) H2O, 25 deg C, 2 h Note 1 Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Ref. 1 5568961; Journal; Kabalka, George W.; Shoup, Timothy M.; Goudgaon, Naganna M.; JOCEAH; J.Org.Chem.; EN; 54; 25; 1989; 5930-5933; Reaction Reaction ID 1770373 Reactant BRN 1366759 4-allyl-2-methoxy-phenol Product BRN 2048960 3-<4-hydroxy-3-methoxy-phenyl>-propan-1-ol 2577699 1-<4-hydroxy-3-methoxy-phenyl>-propan-2-ol -------------------------Reaction Details Reaction Classification Preparation Reagent 1.) tetrabutylammonium boranate, methyl iodide, 2.) aq. H2O2, aq. sodium hydroxide Other conditions 1.) CH2Cl2, reflux, 30 min, 2.) 1.5 h Note 1 Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts Ref. 1 5738171; Journal; Lindeberg, Otto; ACBOCV; Acta Chem.Scand.Ser.B; EN; 34; 1; 1980; 15-20; Reaction Reaction ID 3160087 Reactant BRN 5635571 C21H32O7 Product BRN 4574458 C21H34O8 ------------------------- Reaction Details Reaction Classification Preparation Note 1 Yield given. Multistep reaction Ref. 1 5691662; Journal; Dishong, Dennis M.; Diamond, Craig J.; Cinoman, Michael I.; Gokel, Geoge W.; JACSAT; J.Amer.Chem.Soc.; EN; 105; 3; 1983; 586-593; Reaction Reaction ID 3579096 Reactant BRN 6410096 7-(1-ethoxyethoxy)-2,2-dimethyl-6-(prop-2-enyl)-2,3-dihydrobenzofuran Product BRN 6409116 C17H26O4 -------------------------Reaction Details Reaction Classification Preparation Reagent 1.) mercuric acetate, 2.) 3 M NaOH, 0.5 M NaBH4 Other conditions 1.) water, THF, RT, 10 min, 2.) water, THF, RT, 10 min Note 1 Yield given. Multistep reaction Ref. 1 5805136; Journal; Brown, Roger F.C.; Edwards, Gavin L.; Jones, Christopher M.; Rae, Ian D.; Teo, Peter Y. T.; AJCHAS; Aust.J.Chem.; EN; 36; 6; 1983; 1263-1273; Reaction Reaction ID 3584775 Reactant BRN 6426701 2,4-diamino-5-(3-allyl-4-hydroxy-5-methoxybenzyl)pyrimidine Product BRN 6431601 2,4-diamino-5-<4-hydroxy-3-methoxy-5-(2-hydroxypropyl)benzyl>pyrimidine -------------------------Reaction Details Reaction Classification Preparation Reagent TFA Other conditions 1) 90 deg C, 1 h, 2) RT, 72 h Ref. 1 5808018; Journal; Roth, Barbara; Tidwell, Mary Y.; Ferone, Robert; Baccanari, David P.; Sigel, Carl W.; et al.; JMCMAR; J.Med.Chem.; EN; 32; 8; 1989; 1949-1958; Reaction Reaction ID 3676491 Reactant BRN 6803404 1,4-dimethoxy-2,3,5-trimethyl-6-(prop-2-enyl)benzene Product BRN 5813237 1,4-dimethoxy-2-(3-hydroxypropyl)-3,5,6-trimethylbenzene 6804945 1-(2-hydroxypropyl)-2,5-dimethoxy-3,4,6-trimethylbenzene -------------------------Reaction Details Reaction Classification Preparation Reagent 1.) 1M (BH3)2, 2.) 30percent H2O2, dil. NaOH Other conditions 1.) Et2O, THF, 0 deg C, overnight, 2.) Et2O, THF Note 1 Yield given. Multistep reaction. Yields of byproduct given Ref. 1 5894686; Journal; Riering, Helmut; Schaefer, Hans J.; CHBEAM; Chem.Ber.; EN; 127; 5; 1994; 859-874; Reaction Reaction ID 3951298 Reactant BRN 136380 5-allyl-benzo<1,3>dioxole Product BRN 150198 1-benzo<1,3>dioxol-5-yl-propan-2-ol -------------------------Reaction Details Reaction Classification Preparation Reagent 1.) Hg(OAc)2; 2.) NaBH4, 3M NaOH Other conditions 1.) THF/H2O, room temp., 1 h; 2.) THF/H2O, 1 h Note 1 Yield given. Multistep reaction Ref. 1 5940347; Journal; Barreiro, Eliezer J.; Costa, Paulo R. R.; Barros, Perola Regina V. R.; Queiroz, Waldemir M.; JRMPDM; J.Chem.Res.Miniprint; EN; 4; 1982; 1142-1165; Reaction Reaction ID 4742228 Reactant BRN 7759101 1,3-dimethoxy-2-methyl-5-(2-propenyl)benzene Product BRN 7760166 1-(3,5-dimethoxy-4-methylphenyl)propan-2-ol -------------------------Reaction Details Reaction Classification Preparation Reagent 1.) Hg(OAc)2, 2.) NaBH4 Other conditions 1.) THF, H2O, 20 min, 2.) THF, H2O, 20 min Note 1 Yield given. Multistep reaction Ref. 1 6064707; Journal; Cutler, Horace G.; Majetich, George; Tian, Xinrong; Spearing, Paul; JAFCAU; J.Agric.Food Chem.; EN; 45; 4; 1997; 1422-1429; ------------------ -the good reverend drone
rev drone Member posted 01-05-99 06:28 PM -------------------------------------------------------------------------------- Here's a few more ref's on acid-catalyzed (and base-catalyzed!) hydration of allyls: ReactionReaction ID 49375 Reactant BRN 109059 allyl-<1,4>dioxane Product BRN 104690 1-<1,4>dioxanyl-propan-2-ol ------------------------- Reaction Details Reaction Classification Preparation Reagent aqueous sulfuric acid Temperature -15 øC Ref. 1 514278; Journal; Meltzer et al.; JOCEAH; J.Org.Chem.; 24; 1959; 1763, 1764; Reaction Reaction ID 66758 Reactant BRN 1100186 2-allyl-anisole Product BRN 3155657 1-(2-methoxy-5-<1-(2-methoxy-phenyl)-propyl>-phenyl)-propan-2-ol -------------------------Reaction Details Reaction Classification Preparation Reagent aqueous H2SO4 Ref. 1 1647843; Journal; van der Zanden; de Vries; RTCPA3; Recl.Trav.Chim.Pays-Bas; 74; 1955; 876, 882; Reaction Reaction ID 99307 Reactant BRN 1209240 hex-1-ene Product BRN 1718996 hexan-2-ol ------------------------- Reaction Details 1 of 4 Reaction Classification Preparation Reagent formic acid aqueous perchloric acid Other conditions und Behandeln des Reaktionsprodukts mit aethanol.Kalilauge Ref. 1 1418123; Journal; Knight et al.; JACSAT; J.Amer.Chem.Soc.; 75; 1953; 6212,6215; ------------------------- Reaction Details 2 of 4 Reaction Classification Preparation Reagent sulfuric acid Temperature 15 øC Note 1 hexanol-(2);inactive form Ref. 1 1307342; Journal; Brooks; Humphrey; JACSAT; J.Amer.Chem.Soc.; 40; 1918; 834; ------------------------- Reaction Details 3 of 4 Reaction Classification Preparation Reagent 1.) Hg(OAc)2, 2.) aq. NaOH, NaBH4 Other conditions 1.) THF/H2O, 15 min, room temp. Note 1 Yield given. Multistep reaction Ref. 1 5573590; Journal; Brown, Herbert C.; Geoghegan, Philip J.; Kurek, Joseph T.; JOCEAH; J.Org.Chem.; EN; 46; 19; 1981; 3810-3812; ------------------------- Reaction Details 4 of 4 Reaction Classification Chemical behaviour Reagent Hg(OAc)2 Solvent tetrahydrofuran H2O Time 15 min Yield 94% Chromat. (BRN=1718996) Other conditions Ambient temperature other mercuri salts, other reaction time Subject studied Product distribution Ref. 1 5573590; Journal; Brown, Herbert C.; Geoghegan, Philip J.; Kurek, Joseph T.; JOCEAH; J.Org.Chem.; EN; 46; 19; 1981; 3810-3812; Reaction Reaction ID 169596 Reactant BRN 169139 5,5-diallyl-pyrimidine-2,4,6-trione Product BRN 219840 5-allyl-5-(2-hydroxy-propyl)-pyrimidine-2,4,6-trione -------------------------Reaction Details Reaction Classification Preparation Reagent aqueous H2SO4 Ref. 1 662219; Journal; Bobranski et al.; ROCHAC; Rocz.Chem.; 30; 1956; 175,181; Chem.Abstr.; 1957; 438; Reaction Reaction ID 218031 Reactant BRN 1734497 oct-1-ene Product BRN 1719325 inactive octanol-(2) ------------------------- Reaction Details Reaction Classification Preparation Reagent sulfuric acid Other conditions anschliessende Hydrolyse Ref. 1 1419020; Journal; Smolin; JOCEAH; J.Org.Chem.; 20; 1955; 295,296; Reaction Reaction ID 259179 Reactant BRN 180858 5-allyl-5-isopropyl-pyrimidine-2,4,6-trione Product BRN 218533 5-(2-hydroxy-propyl)-5-isopropyl-pyrimidine-2,4,6-trione -------------------------Reaction Details Reaction Classification Preparation Reagent H2O concentrated H2SO4 Ref. 1 662181; Journal; Loubriel; JACSAT; J.Amer.Chem.Soc.; 56; 1934; 1968; Reaction Reaction ID 282401 Reactant BRN 1909845 1-methyl-4-(prop-2-ene-1-sulfonyl)-benzene Product BRN 2526567 1--propan-2-ol -------------------------Reaction Details 1 of 2 Reaction Classification Preparation Reagent aqueous NaOH Ref. 1 1618301; Journal; Backer et al.; RTCPA3; Recl.Trav.Chim.Pays-Bas; 70; 1951; 365, 370, 371; ------------------------- Reaction Details 2 of 2 Reaction Classification Preparation Reagent aqueous Na2CO3 Ref. 1 1618301; Journal; Backer et al.; RTCPA3; Recl.Trav.Chim.Pays-Bas; 70; 1951; 365, 370, 371; Reaction Reaction ID 283003 Reactant BRN 1910871 4-allyl-1,2-dimethoxy-benzene Product BRN 2049658 (+-)-3.4-dimethoxy-1-<2-hydroxy-propyl>-benzene -------------------------Reaction Details 1 of 2 Reaction Classification Preparation Reagent aqueous sulfuric acid Temperature 5 øC Ref. 1 1595592; Journal; Clemo; Turnbull; JCSOA9; J.Chem.Soc.; 1947; 124, 127; Reaction Reaction ID 301290 Reactant BRN 202119 5-allyl-5-isobutyl-pyrimidine-2,4,6-trione Product BRN 234252 5-<2-hydroxy-propyl>-5-isobutyl-barbituric acid -------------------------Reaction Details 1 of 2 Reaction Classification Preparation Reagent concentrated H2SO4 H2O Ref. 1 662181; Journal; Loubriel; JACSAT; J.Amer.Chem.Soc.; 56; 1934; 1968; ------------------------- Reaction Details 2 of 2 Reaction Classification Preparation Reagent H2SO4 (d=1.83) Solvent H2O Time 1 hour(s) Yield 65. (BRN=234252) Other conditions Heating Ref. 1 5608281; Journal; Lafont, Olivier; Cave, Christian; Lambrey, Bernard; Briffaux, Jean-Paul; Jacquot, Christian; EJMCA5; Eur.J.Med.Chem.Chim.Ther.; FR; 18; 2; 1983; 163-168; Reaction Reaction ID 310316 Reactant BRN 2049 6-pent-4-enyl-2,3,4,5-tetrahydro-pyridine Product BRN 105334 5-<2>piperidyl-pentan-2-ol 108391 2-pent-4-enyl-piperidine -------------------------Reaction Details Reaction Classification Preparation Reagent water formic acid potassium formate Temperature 155 - 160 øC Other conditions und Erhitzen des Reaktionsgemisches mit wss.Schwefelsaeure Ref. 1 1019586; Journal; Lukes; Cervinka; CCCCAK; Collect.Czech.Chem.Commun.; 24; 1959; 1846,1848; ------------------------- Reaction Reaction ID 341606 Reactant BRN 225330 5-allyl-5-(1-methyl-butyl)-pyrimidine-2,4,6-trione Product BRN 249252 5-(2-hydroxy-propyl)-5-(1-methyl-butyl)-pyrimidine-2,4,6-trione -------------------------Reaction Details 1 of 3 Reaction Classification Preparation Reagent concentrated H2SO4 H2O Ref. 1 662204; Journal; Bobranski et al.; ROCHAC; Rocz.Chem.; 31; 1957; 559,564; Chem.Abstr.; 1959; 9906; Ref. 2 662205; Journal; Maynert; Washburn; JACSAT; J.Amer.Chem.Soc.; 75; 1953; 700,701,704; ------------------------- Reaction Details 2 of 3 Reaction Classification Preparation Reagent aq. H2SO4 Time 20 min Yield 60. (BRN=249252) Other conditions Ambient temperature Ref. 1 5642876; Journal; Polevaya, O. Yu.; Danilova, N. P.; Kovalev, I. E.; PCJOAU; Pharm.Chem.J.(Engl.Transl.); EN; 17; 3; 1983; 165-170; KHFZAN; Khim.Farm.Zh.; RU; 17; 3; 1983; 273-277; ------------------------- Reaction Details 3 of 3 Reaction Classification Preparation Reagent water, H(1+) Yield 72. (BRN=249252) Ref. 1 5724442; Journal; Lafont, Olivier; Chastang, Jean; Cave, Christian; Miocque, Marcel; EJMCA5; Eur.J.Med.Chem.Chim.Ther.; EN; 23; 1988; 283-290; Reaction Reaction ID 342489 Reactant BRN 226010 1-allyl-3,7-dimethyl-3,7-dihydro-purine-2,6-dione Product BRN 263332 1-(2-hydroxy-propyl)-3,7-dimethyl-3,7-dihydro-purine-2,6-dione -------------------------Reaction Details Reaction Classification Preparation Reagent concentrated H2SO4 Other conditions und anschliessenden Erhitzen mit wss.H2SO4 Ref. 1 826391; Journal; Eckstein; Gorczyca; DIPHAH; Diss.Pharm.; 14; 1962; 393,395,396; ------------------------- -------------------------
Reaction Reaction ID 344330 Reactant BRN 227510 5-allyl-5-phenyl-pyrimidine-2,4,6-trione Product BRN 283795 5-(2-hydroxy-propyl)-5-phenyl-pyrimidine-2,4,6-trione -------------------------Reaction Details 1 of 2 Reaction Classification Preparation Reagent concentrated H2SO4 H2O Ref. 1 662355; Journal; Bobranski et al.; ROCHAC; Rocz.Chem.; 31; 1957; 559,565; CHZEA6; Chem.Zentralbl.; GE; 130; 1959; 9906; ------------------------- Reaction Details 2 of 2 Reaction Classification Preparation Reagent H2O, cc. H2SO4 Yield 59.8 (BRN=283795) Ref. 1 5603743; Journal; Toth, Gy.; Makleit, S.; ACASA2; Acta Chim.Acad.Sci.Hung.; GE; 107; 1981; 147-154; ------------------------- Reaction Reaction ID 694419 Reactant BRN 605308 3-bromo-propene Product BRN 1718876 (+-)-1-bromo-propan-2-ol ------------------------- Reaction Details Reaction Classification Preparation Reagent sulfuric acid copper (II)-sulfate Other conditions Eintragen des Reaktionsgemisches in Wasser Ref. 1 1414458; Journal; de la Mare; Galandauer; JCSOA9; J.Chem.Soc.; 1958; 36,38; ------------------------- ------------------------- Reaction
Reaction ID 4445087 Reactant BRN 7430644 C12H18N2O2S Product BRN 7432599 C12H20N2O3S ------------------------- Reaction Details Reaction Classification Preparation Reagent 1.) AcOH, H2SO4, 2.) H2O Other conditions 1.) 100 deg C, 30 min, 2.) 1 h Note 1 Yield given. Multistep reaction Ref. 1 6005587; Journal; Yebga, A.; Menager, S.; Verite, P.; Farnoux, C. Combet; Lafont, O.; EJMCA5; Eur.J.Med.Chem.Chim.Ther.; EN; 30; 10; 1995; 769-778; ------------------------- -------------------------
Reaction Reaction ID 4703525 Reactant BRN 7724449 C20H28N2O3S Product BRN 7720600 C16H23NO5S ------------------------- Reaction Details Reaction Classification Preparation Reagent 3N aq. HCl Time 3.5 hour(s) Yield 77. (BRN=7720600) Other conditions Heating Ref. 1 6057007; Journal; Rottmann, Antje; Bartoczek, M.; Liebscher, Juergen; SYNTBF; Synthesis; EN; 3; 1997; 313-327; Reaction Reaction ID 4703684 Reactant BRN 7724908 C20H30N2O3S Product BRN 7720672 C16H25NO5S ------------------------- Reaction Details Reaction Classification Preparation Reagent 6N aq. H2SO4 Time 7 hour(s) Yield 61. (BRN=7720672) Other conditions Heating Ref. 1 6057007; Journal; Rottmann, Antje; Bartoczek, M.; Liebscher, Juergen; SYNTBF; Synthesis; EN; 3; 1997; 313-327; ------------------ -the good reverend drone
ChemHack Member posted 01-05-99 06:43 PM -------------------------------------------------------------------------------- You rule drone dude! Now lets talk oxidization!If a Jones-esqe oxidation would do it then this could be another OnePotWonder ! Safrole + H2SO4 --> Alcohol Add cold acetone and chrome to pot. God does not love me enough for this to be true. rev drone Member posted 01-06-99 11:29 AM -------------------------------------------------------------------------------- I have some amazing ref's using NaOCl and a PTC to oxidize olefins to epoxides and diols -- since both of these compounds are readily isomerizable into the methyl ketone, this is effectively a one-pot-shot. PTC's are the stuff of dreams, and with enough research, I think they could be used to quantitatively catalyze water into wine. One ref for this procedure is: JACS 107 (1985) 2000 I have a dozen more, but they're not with me.Still, this is off-top. You want alcohol oxidations, and alcohol oxidations is what you shall recieve. I'll be back... ------------------ -the good reverend drone ChemHack Member posted 01-06-99 08:58 PM -------------------------------------------------------------------------------- Hmmm, How about this terrible way to the alcohol: Mercuric acetate + Water + PTC + Safrole to yield the organomercury intermediate that is reduced with sodium borohydride to give the alcohol. heh, this is fun! ChemHack Member posted 01-13-99 04:53 AM -------------------------------------------------------------------------------- Yo Drone! Lets see those Oxidations! And while your at it, comment on these:1. Permangenate in Sulfuric (Fire ?) 2. Permangenate ala "Cold Cat" (too strong?) 3. Jones or Cold Jones ? 4. Pyridinium Chlorochromate in dichloromethane (PCC/DCM) 5. Ozone/Zinc (haha, prolly fuck it all up!) 6. Dichromate in acetic acid? Or maybe the way to go would be to forget the ketone completely and use either PBr3 or SOCl2 to go for bromosaf or chlorosaf! Yikes! rev drone Member posted 01-14-99 10:37 AM -------------------------------------------------------------------------------- Chemhack, There are literally thousands of oxidation conditions to choose from for this, and if you want, I can send you a few hundred to sift through. Maybe it can be your responsibility to review them and come up with a list of favorites (yeesh, I don't want to do it.) Just tell me how to send them to you. Oh yes, I can give you a list using only certain reagetns as well. ------------------ -the good reverend drone
ChemHack Member posted 01-14-99 08:35 PM ------------------------------------------------------------------------
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