Author Topic: Safrole -> MDP2Pol -> MDP2P (Read 7266 times)

Bandil · « **on:** September 26, 2001, 04:37:00 AM »

Hi!

I have read a lot of posts on the Safrole -> MDP2Pol -> MDP2P synth using sulfuric acid hydration followed by ammonium nitrate and some cuprous catalyst. None of them seem to agree. Does anyone have a definite answer on the reaction? Does it work at all or is it BS?

Thanks!

Regards
Peter

Rhodium · « **Reply #1 on:** September 26, 2001, 05:06:00 AM »

There are no theoretical obstacles to the method in question, but I don't know of anyone who have succeeded in practice with it.

Antoncho · « **Reply #2 on:** September 26, 2001, 08:19:00 AM »

There are no theoretical obstacles to the method in question, but I don't know of anyone who have succeeded in practice with it.

But what of tBOC's write-up on your page - it seems to bee very practical... Was it a fake? Did he fail eventually? How did you know?

Please, elaborate - sad news for me, i used to put much hope into that method...

Antoncho

sunlight · « **Reply #3 on:** September 26, 2001, 08:35:00 AM »

I'll believe in it when some reliable bee post he did it, and worked, and the ketone was aminated and the product had at least the correct melting point. May be it works and we are so silly, but I've not seen a good reason to try it, specially after seeing all the fiascos in mdp2pol with dichromates, dual phase etc... it supposedly worked for some bees, but...

Semtexium · « **Reply #4 on:** September 26, 2001, 10:33:00 AM »

I have to agree, if we've all been fucking around using up expensive PdCl2, etc if this method proves viable then perhaps we should all be sitting in the corner with a dunce cap on our heads. The fact remains however that if this method is ever GOING to work it's going to require some research and a bunch of trial and error. Now luckily we have access thru the hive to a LOT of notes on the subject, if we can wade thru them and pick out the really relivent bits then perhaps this method will in the future lead to un-Godly amounts of honey being produced easily and safely and without alot of eviromental impact...

I think the cold H2SO4 route has been proven to produce the MDP2Pol, as long as the temp is kept down and one doesn't try to distill it(thanks Brightstar). Have any of the MDP2Pol --> MDP2P routes been proven...? I've seen examples with AA and cupric salts as well as a purposed route with Permaganate, but I've seen nothing conclusive as to the outcomes, sure Tboc said it worked as did a couple others, but when asked questions about it they quickly disapeared...

Mean People Suck

Rhodium · « **Reply #5 on:** September 26, 2001, 11:43:00 AM »

The problem is that some bees have reported success, but that the success wasn't measured with any analytical equipment, and only one or two unknown bees said the produced ketone aminated fine to a working amine. But then again, several who have tried it have failed.

Bandil · « **Reply #6 on:** September 26, 2001, 01:14:00 PM »

I think my cat might give the synth a whirl this forthcoming week. Any suggestions on how to test the products? Is it not the common practise to check for sec ketones using 2,4-Dinitrophenylhydrazine and the primary using fehlings? I have no access to nmr, MS etc. Perhaps some TLC will be possible.

Ideas anyone?

Thanks!

Regards
Peter

PEYOTE · « **Reply #7 on:** September 27, 2001, 12:58:00 AM »

If you make an hydratation using only conc. H2SO4, your product cannot be only MDP2Pol. The best way is oxymercuriation/demercuriation using first HgSO4/H2SO4, then NaBH4.

The reason is: there will be appreciable rearrangement of the secondary carbocation that safrole will form when a H+ attack the double bond.

Ar-CH2-CH=CH2 + H⁺ ==> Ar-CH2-CH⁺-CH3 ==> Ar-C⁺(CH3)2 =(H2O)=> Ar-CHOH(CH3)2 + H⁺

This is a bad stuff.

Just a Touch Of Mojo Hand

Bandil · « **Reply #8 on:** September 27, 2001, 01:54:00 AM »

Im aware that the final MDPxPol intermediate is a mixture of MDP1Pol/everything else and MDP2Pol. I will just have to live with this. If i carefully keep the temerature of the mixture around zero degrees celcius, do you have any idea of the ratio of the two compounds? 80:20 i can live with.

How about the final oxidation using ammonium nitrate, do you have any comments on this one?

Thanks, my cat really appereciates your feedback before he gets going!

Regards
Peter

PEYOTE · « **Reply #9 on:** September 27, 2001, 01:59:00 AM »

If i carefully keep the temperature of the mixture
around zero degrees celcius, do you have any idea of the
ratio of the two compounds? 80:20 i can live with.
Maybe, I dunno the exact thermodynamic data for this reaction.

final oxidation using ammonium
nitrate
I dunno, do you have the rxn?

Bandil · « **Reply #10 on:** September 27, 2001, 03:48:00 AM »

Got this ref from rhodiums page:

R-C(OH)-R' + 2 Cu(OAc)2 ==> R-CO-R' + 2 CuOAc + 2 AcOH

2 CuOAc + NH4NO3 + 2 AcOH ==> 2 Cu(OAc)2 + NH4NO2 + H2O

NH4NO2 == H+ ==> N2 + 2 H2O

And abbreviated to one line:

R-C(OH)-R' + NH4NO3 == Cu(OAc)2/AcOH ==> R-CO-R' + 3 H2O + N2

https://www.thevespiary.org/rhodium/Rhodium/chemistry/mdp2pol.txt

Thanks!

PEYOTE · « **Reply #11 on:** September 27, 2001, 04:28:00 AM »

Well, N2 is formed, and this is a VERY stable compound, so the equilibrium will be totally moved to right, and I think this rxn will work very well. Le Chatelier docet

Bandil · « **Reply #12 on:** September 27, 2001, 04:53:00 AM »

OK, i need a verdict on what my cat should do, as it is not sure here.

a) Be a post-pioneer and try out the Safrole->MDP2Pol->MDP2P using the H2SO4 and ammonium nitrate oxidizer and post results?

b) Be boring and go with the safrol->isosafrol->MDP2P using the peracetic acid method and a lot of vacuum?

By the way, if the cat choose to go the b way... Any commenst on the safrole + CaO + KOH -> isosafrole reaction? Can KOH be substituted with NaOH??

Either way, the cat will post what it finds out!

THANKS!

Regards
Peter + cat

PEYOTE · « **Reply #13 on:** September 27, 2001, 05:04:00 AM »

I'd choose A

Just A Touch Of Mojo Hand

Bandil · « **Reply #14 on:** September 27, 2001, 05:22:00 AM »

I think the cat will choose A for starters... But if/when it fails it sure will go for B.

There are just a few unanswered questions for this method. When refluxing the glycol(made from peracetic actid and isosafrole) in methanol and sulfuric acid(to obtain the ketone), is it possible to substitute the methanol with ethanol, as methanol is quite impossible to obtain?

Thanks!

Regards
Peter and Cat

PEYOTE · « **Reply #15 on:** September 27, 2001, 05:27:00 AM »

On

https://www.thevespiary.org/rhodium/Rhodium/chemistry/peracid.html

there is written MeOH, because, I suppose, the glycol is much better soluble in MeOH than in EtOH, or using MeOH reflux is at a lower temperature, but I dunno. Try to ask to Rhodium, the Chief...

Rhodium · « **Reply #16 on:** September 27, 2001, 08:47:00 AM »

I believe ethanol would work just as well.

Bandil · « **Reply #17 on:** September 27, 2001, 09:01:00 AM »

@Rhodium> Would you belive it is worth the effort to try out the safrole -> MDP2Pol -> MDP2P using method A?

Thanks!

Regards
Peter

Rhodium · « **Reply #18 on:** September 27, 2001, 09:03:00 AM »

Yes, we need someone to work out the right reaction parameters for the above to work.

terbium · « **Reply #19 on:** September 27, 2001, 07:32:00 PM »

a) Be a post-pioneer and try out the Safrole->MDP2Pol->MDP2P using the H2SO4 and ammonium nitrate oxidizer and post results?

b) Be boring and go with the safrol->isosafrol->MDP2P using the peracetic acid method and a lot of vacuum?

Or do both! If you do (B) first, a known good procedure, then you will have a reference sample of MDP2P. Then when you try (A) you will be able to compare.

Can you get TLC plates? Even if you can't get TLC plates you could probably use paper chromatography instead to compare your products from the two procedures. With the MDP2P from procedure (B) you could even prepare some MDP2P-ol by reduction to check the first step of procedure (A) again via paper chromatography.

Bandil · « **Reply #20 on:** September 28, 2001, 02:59:00 AM »

OK, i can see that would be a smart move! Now what is the best euluent for the TLC? For the amine salt, i would use EtOH/AcOH 80:20 perhaps? What about the ketone, what should be used in that case?

Thanks!

Regards
Peter and cat

zooligan · « **Reply #21 on:** September 28, 2001, 07:25:00 AM »

If I'm not mistaken, the trouble comes in when folks try to do the oxidation step. Any temp increase seems to fuck the yield by rearranging the p2pol to p1pol.

What are some good cold oxidation techniques? We have the am.nitrate, pot.permanganate, and ca.hypochlorite. What others exist that will operate at even lower temps, perhaps using H2O2 or something like that?

z

"And if we don't get some cool rules ourselves, pronto, then we'll just be bogus too!"

terbium · « **Reply #22 on:** September 28, 2001, 09:53:00 AM »

Pyridinium chlorochromate/methylene chloride at room temperature oxidizes MDP2P-ol to MDP2P in good yield.

I am skeptical about this 2-ol to 1-ol rearrangement bugaboo. I did not notice a problem with MDP2P-ol produced via oxymercuration/NaBH4 reduction. If there was going to be a problem with rearrangement of the 2-ol to 1-ol then it would seem to me that it would occur during the hydration with sulfuric acid not later. ... Actually, perhaps this explains a different version of the 2-ol to 1-ol story that I have heard here - that pure 2-ol is unstable and spontaneously converts, in a few hours, to 1-ol
A different explanation for the observation that 2-ol is highly unstable would be that 2-ol was never produced.

I must confess to not being familar with using sulfuric acid to hydrate an olefin. Are there any known examples where this is used commercially? How about a published example of this procedure in say Vogel or Organic Syntheses?

Acme · « **Reply #23 on:** September 29, 2001, 02:55:00 PM »

In an acidic environment the alcohol will rearrange to the most stable carbocation, therefore, any acidic method that gets you to MDP2Pol is going to go like a shot to MDP1Pol. However this alcohol, when oxidized to give the ketone, (at the carbon next to the benzene ring) can be reductively aminated, one would think to give, MALPHA (found in PIHKAL), which is active. So maybe tBoc made MALPHA

Rhodium · « **Reply #24 on:** September 29, 2001, 03:31:00 PM »

But there is a large number of other allylbenzenes that has been hydroxylated in the 2-position using this method in the literature. I wonder why the same trick does not work readily on safrole?

Here is a list of allyl compounds being hydrated, originally posted by Rev Drone:

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:
   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 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;

Rhodium · « **Reply #25 on:** September 29, 2001, 03:49:00 PM »

BTW, I found rev Drones list of hydrated allylic compounds:

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:
   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 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;

Vibrating_Lights · « **Reply #26 on:** September 30, 2001, 11:15:00 AM »

The Problem with using the ammonium nitrate to oxidise the alcohol is that the heat required to propogate the reaction and causes the rearrangement to the p1p.the p2p is still produced but unless you are able to seperate the p1p\p2p it will not be acceptable for animation. on the other hand you could prepare a jones regent of sodium dicromate/sulfuric acid and do the oxidation procedure at 0.c to obtain a high yeild of ketone.

amalgum · « **Reply #27 on:** September 30, 2001, 09:42:00 PM »

What about electrolytic oxidation?

Bandil · « **Reply #28 on:** October 01, 2001, 07:44:00 AM »

What about KMnO4 oxidation using acid or base as catalyst? I know from the Cat synth, that it does not require heat...

Regards
Peter

Rhodium · « **Reply #29 on:** October 01, 2001, 08:09:00 AM »

Neutral or basic KMnO4 would be needed, acid KMnO4 would overoxidize the side chain.

Vibrating_Lights · « **Reply #30 on:** October 03, 2001, 12:39:00 AM »

Does any one have any idea how far the saforle to mdp2pol can be scaled up. Swijm thinks that it could be scaled up to industrial sizes with internal cooling duirng. the acid addition. Swim has gotten ketone before from the from the amonium nitrate but it did not animate. he suspects it was the p1p ketone caused when acetone was used for the solvent in the oxidation. it had to evaporate all of the acetone out before the reaction would start and the temp was held to high for too long and rearrangement occoured..does any one know of the proper syenthesis of a jones regent with acetone, and the condition needed for the oxiditation to occour. i have a organic chem textbook that says that that is the best way to go to oxidise a secondary alcohol to a ketone. i have been studying this method for over a year and i believe that it will one day produce a high yeild of crystals. The theoretical yeild of the reaction is very high. I see no reason that a 0. oxidation, with a jones regent would produce high yeilding ketone. hte suspected P1P ketone had a distinctive cardemon smell and it caused a temp increse to the point of reflux in an AL?HG nitro reduction. I think he could have failed with the A/B but he also did not remove the d\DCM with vacume this temp increase could have caused enough rearrangment that it was not suitable for reduction....

Rhodium · « **Reply #31 on:** October 03, 2001, 12:43:00 AM »

Before attempting to scale it up, we must first devise a fool-proof way of performing the procedure on a small scale.

Semtexium · « **Reply #32 on:** October 03, 2001, 09:35:00 AM »

What was causing your reflux temperature was prob the nitromethane, remember it's getting reduced at the same time...

Mean People Suck

Vibrating_Lights · « **Reply #33 on:** October 03, 2001, 03:03:00 PM »

Swim has reduced nitromethane by it's self and it did not produce as much heat. i was under the impression that way back, Eulisis well documented the procedure with proper product analysis. and even promoted synths to various other compounds. Does any one remember this. How bout the jones regent preperation, just need a procedure chems known.

improv_chem · « **Reply #34 on:** October 03, 2001, 11:14:00 PM »

Oh no, not this bad memory! SWIM played with this method too much and got absolutely no product. I really can't be bothered to say it again so just click on my username and view my posts on the subject. When i think of all the wasted sassafras oil it makes me want to cry!
SWIM could not figure out exactly why it didn't work out but I can say that as stated by tBOC it doesn't work. Even with many modifications SWIM couldn't get it to work. The first real product that SWIM got was after using the oxone method (Chromic's write-up, totally otc). Don't expect to get a bunch of MDMA from this. For research however, I would be very interested in getting to the bottom of this.
This research might mean wasting a bunch of safrole in the process so be warned.
Please don't make my mistakes. If you are going to play with this don't simply follow the recipies, do some real investigation.
good luck!
-improv

Let's play with nature a little, I'm sure we can make her a little higher....

News:

Author Topic: Safrole -> MDP2Pol -> MDP2P (Read 7266 times)

Bandil

Rhodium

Antoncho

sunlight

Semtexium

Rhodium

Bandil

PEYOTE

Bandil

PEYOTE

Bandil

PEYOTE

Bandil

PEYOTE

Bandil

PEYOTE

Rhodium

Bandil

Rhodium

terbium

Bandil

zooligan

terbium

Acme

Rhodium

Rhodium

Vibrating_Lights

amalgum

Bandil

Rhodium

Vibrating_Lights

Rhodium

Semtexium

Vibrating_Lights

improv_chem