dormouse (Member)
04-19-00 06:50
No 122782
      visciously beating a dead horse: MDP2-Pol, back from the dead -drone 342  Bookmark   


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Author  Topic:   visciously beating a dead horse: MDP2-Pol, back from the dead 
drone 342
Member   posted 12-30-98 01:00 PM          
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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          
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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          
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I really hope this thread heats up again. To minimize the horse beating I offer a neophite's synopsis of the discussion thus far:
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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.


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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          
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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          
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Chemhack, you said:

quote:
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"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.
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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          
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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          
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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          
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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          
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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          
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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          
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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          
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Shall I post a selection of ref's detailing variuous allyl hydrations?
 
ChemHack
Member   posted 01-05-99 05:08 PM          
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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          
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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 ÝC
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;


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-the good reverend drone


rev drone
Member   posted 01-05-99 06:28 PM          
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Here's a few more ref's on acid-catalyzed (and base-catalyzed!) hydration of allyls:
Reaction

Reaction 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 ÝC
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 ÝC
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 ÝC
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 ÝC
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;
-------------------------


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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;
-------------------------


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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;
-------------------------


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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          
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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          
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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          
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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          
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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.


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-the good reverend drone


ChemHack
Member   posted 01-14-99 08:35 PM          
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Drone: I know that there are a gazillion RELATED refs but none that are completely topical. I sure do wonder why that is the case ?!?
Anyway, in THE RIGHT WAY you said that you had experimentally tried a few oxidizers and came up with a winner. If you just tell me what that SuperSecret bad-boy is then I can avoid a lot of wasted oil. Even if you can tell me what WON'T work I'd be starting from a much better spot.

The problem for me is not finding references to things that are KINDA the same, it is having the O.Chem acumen to know that such-and-such won't work because the Beta-Pi-Orbital is in the House-Of-Jupitar until the third lunar eclipse of the acidic proton of Leo. Know what I mean?

I'm just a HACK for ChristSake! Everything looks good on paper through my eyes! But I am willing to spend some time and reagents on some kitchen chemistry. I waste stuff all the time "just to see what will happen" so I'm not saying that I have to have a full theoretical synth just to procede. I just need a little guidence. Thats all.

Enough of that...

I am partial to chrome, permanganate, and hypochlorite. Not only because they are generally available to bees but also because they are specifically available to me without additional aquisiton  So anyway, I could try my #1-3 and #6 suggestions above this weekend even...

Email me: chemhack@hotmail.com


 
The Cook
Member   posted 01-14-99 11:20 PM          
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Here's the reason I'd dump a PTC & pool shock into my p2pol.. US Patent #3996259. And here's the quote of the week, for all y'all who feel pretty quick in your separation skills.. (12h to the 1-ol, right?)
"For Example, a secondary alcohol is quantitatively oxidized by this invention to a ketone BEFORE the ketone itself is oxidized via the haloform reaction to a carboxylic acid." And that ain't bad...
->Drone, HOW LONG have you been playing with PTC's?
 
ChemHack
Member   posted 01-15-99 12:55 AM          
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Cook: Maybe if I look at the patent I'll see what you mean but as written, that sentence sounds like:
"I have to get in my car and start the engine BEFORE I drive my car to the store to get beer."


ChemHack
Member   posted 01-25-99 09:54 PM          
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I found this in the stuff section:

quote:
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Posted by Laborat on December 09, 1997 at 04:23:29:
This worked perfect in my dream(realy). I had 72 gram mdp2pol(distilled) coled to about 5 Celsius. I made a solution of 25,3 gram KMnO4 in 5 liter of distilled water, also cooled to 5 Celsius. Stirred and put the Alc. in it, stirred for an additional 5 minutes and put the flask in the refrigerator. Let stand 12 Hrs. On the bottem there was brown MnO2, in the middle almost clear water and on top al layer of Piperonylacetone. Sucked it up with a pipet and store it for next (final) step. Contents about 54 gram. Not bad is it? Oh yeh, i made the aquas solution acidic with some H2SO4 (pH 4-5). Oxidation ratio is 1:2.5 in this medium. By the way the mdp2pol dissolved without problems in the big(5L) portion of water. Hope this is what you want to know. Please let me know the results, o.k.?

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The Cook
Member   posted 02-10-99 03:57 AM          
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I hope people see that the # of posts changed from 23->24. Ok. Here's how it is. I got into it a bit before Strike's P2Pol text, so when it I saw it, it was my new bible. Liters of sassy died that year, to no avail. I honestly believe the addition is fine, but I had nightmares about the oxidation to the ketone. KMnO4, ala Laborat, failed 30/30. I'm not saying it don' work, I'm saying It don' work in MY wildest dreams..
But is the 2-ol worth the trouble. Muratic & a PTC (In an SRV) are your dream date. A quick hypochlorite oxidation to some Wal-Mart ketone...
Oh, about the hypochlorite oxidation (ChemHack) - What that sentence meant was that bleach oxidizes ALL the -ol to ketone Long Before it thinks about breaking that propene. Where Permanganate will overoxidize anything it can, in ANY slight concentration gradient. (Not good for an oil, eh?)
So what do y'all think about the chlorosafrole thing. - look at the mechanism of the hypochlorite oxidation before you flame, though.
Love,
-cook
 
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