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;