Cyrax (Hive Bee)
11-17-02 15:44
No 380467
      o-nitromethoxybenzene synthesis, procedure needed  Bookmark   

I am looking quite a while for a lab procedure involving the synthesis of o-methoxyanisole.

The benzene ring for anisole is activated, so from a theoretical point of view, I think it would be best to protect the para position by a sulphonate and then do the nitration.  If one doesn't do this, I fear that a considerable amount of anisole would be nitrated in the para position ...

However, if some bee could give me a ref. or a clear cut lab procedure for the synthesis of o-nitro-anisole, I would be gratefull.
 
 
 
 
    lugh
(Moderator)
11-17-02 17:06
No 380485
      Purification  Bookmark   

One reference that may bee helpful is Ber 39 1084 (1906); it covers the purification of o nitro anisole by means of repeated vacuum distillation smile It's probably prepared like any other aromatic nitro compound, using nitric and possibly sulfuric acid for the nitration smile
 
 
 
 
    Cyrax
(Hive Bee)
11-17-02 17:13
No 380487
      Thx for that ref., I 'm going to check it out.  Bookmark   

Thx for that ref., I 'm going to check it out.  Since they give the purification, the article will probably include the preparation too smile.
 
 
 
 
    Rhodium
(Chief Bee)
11-17-02 21:27
No 380543
      Anisole -> 2-Nitroanisole  Bookmark   

Copyright 1988-2001 Beilstein Institut zur Foerderung der
Chemischen Wissenschaften. All rights reserved.
Reaction (BS0203AE:Reactions:Q02 hit 9, RX.ID 657713)
Reaction ID 657713
Reactant BRN 506892 methoxybenzene
Product BRN 1868032 1-methoxy-2-nitro- benzene 1865361 1-methoxy-4-nitro- benzene
No. of Reaction 29
Details

Field Availability List (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Code Field Name Occ.
RX Reaction 29 Details

Reaction Details 1 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classification
Reagent NH4NO3 TFAA [HNEtPri2][CF3COO]
Temperature 20 C
Note 1 Title compound not separated from byproducts
Ref. 1 6262670;LitLink; Journal; Laali, Kenneth K.; Gettwert, Volker J.; JOCEAH; J.Org.Chem.; EN; 66; 1; 2001; 35 - 40.

Reaction Details 2 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classification
Reagent isoamyl nitrate TfOH [emim][OTf]
Temperature 0 C
Note 1 Title compound not separated from byproducts
Ref. 1 6262670;LitLink; Journal; Laali, Kenneth K.; Gettwert, Volker J.; JOCEAH; J.Org.Chem.; EN; 66; 1; 2001; 35 - 40.

Reaction Details 3 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classificati
on
Reagent HNO3
Catalyst zeolite beta-I
Reaction Nitration
Type
Ref. 1 6217685;LitLink; Journal; Choudary, B. M.; Sateesh, M.; Kantam, M. Lakshmi; Rao, K. Koteswara; Prasad, K. V. Ram; Raghavan, K. V.; Sarma, J. A. R. P.; CHCOFS; Chem.Commun.; EN; 1; 2000; 25 - 26.

Reaction Details 4 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classificatio
n
Yield 70 percent (BRN=1868032) 30 percent (BRN=1865361)
Reagent acetyl nitrate silica
Solvent CHCl3
Temperature -20 - 20 C
Reaction Type Nitration
Ref. 1 6184050;LitLink; Journal; Rodrigues, J. Augusto R.; Filho, Antonio Pedro de Oliveira; Moran, Paulo J. S.; Custodio, Rogerio; TETRAB; Tetrahedron; EN; 55; 22; 1999; 6733 - 6738.

Reaction Details 5 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classificatio
n
Yield 23 percent (BRN=1865361) 38 percent (BRN=1868032)
Reagent NO, air
Solvent acetonitrile
Time 60 hour(s)
Other Ambient temperature
Conditions
Ref. 1 6065420;LitLink; Journal; Mizuno, Kazuhiko; Tamai, Toshiyuki; Hashida, Isao; Otsuji, Yoshio; Inoue, Hiroo; JRPSDC; J.Chem.Res.Synop.; EN; 7; 1995; 284-285.

Reaction Details 6 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classificatio
n
Yield 38 percent (BRN=1868032) 23 percent (BRN=1865361)
Reagent NO, air
Solvent acetonitrile
Time 60 hour(s)
Other Ambient temperature
Conditions
Ref. 1 6065420;LitLink; Journal; Mizuno, Kazuhiko; Tamai, Toshiyuki; Hashida, Isao; Otsuji, Yoshio; Inoue, Hiroo; JRPSDC; J.Chem.Res.Synop.; EN; 7; 1995; 284-285.

Reaction Details 7 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classificatio
n
Reagent cupric nitrate trihydrate supported on K 10 montmorillonite clay, 100percent HNO3, Ac2O
Solvent CCl4
Time 15 min
Other Ambient temperature
Conditions
Note 1 Yield given. Yields of byproduct given
Ref. 1 5963484;LitLink; Journal; Gigante, Barbara; Prazeres, Angela O.; Marcelo-Curto, Maria J.; Cornelis, Andre; Laszlo, Pierre; JOCEAH; J.Org.Chem.; EN; 60; 11; 1995; 3445-3447.

Reaction Details 8 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classificatio
n
Reagent cupric nitrate trihydrate supported on K 10 montmorillonite clay, 100percent HNO3, Ac2O
Solvent CCl4
Time 15 min
Other Ambient temperature
Conditions
Note 1 Yield given. Yields of byproduct given
Ref. 1 5963484;LitLink; Journal; Gigante, Barbara; Prazeres, Angela O.; Marcelo-Curto, Maria J.; Cornelis, Andre; Laszlo, Pierre; JOCEAH; J.Org.Chem.; EN; 60; 11; 1995; 3445-3447.

Reaction Details 9 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classification
Reagent 12N HNO3
Solvent diethyl ether H2O
Time 12 hour(s)
Other Ambient temperature
Conditions
Note 1 Yield given
Ref. 1 5800162;LitLink; Journal; Gaude, D.; Goaller, R. Le; Pierre, J. L.; SYNCAV; Synth.Commun.; EN; 16; 1; 1986; 63-68.

Reaction Details 10 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classification
Reagent 12N HNO3
Solvent diethyl ether H2O
Time 12 hour(s)
Other Ambient temperature
Conditions
Note 1 Yield given
Ref. 1 5800162;LitLink; Journal; Gaude, D.; Goaller, R. Le; Pierre, J. L.; SYNCAV; Synth.Commun.; EN; 16; 1; 1986; 63-68.

Reaction Details 11 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classificatio
n
Reagent MeNO3H(1-)/methane, O2, SF6
Temperature 37.5 C
Pressure 720.0002 Torr
Other Irradiation
Conditions
Note 1 Yield given. Yields of byproduct given
Ref. 1 5687943;LitLink; Journal; Attina, Marina; Cacace, Fulvio; Petris, Giulia de; ANCEAD; Angew.Chem.; GE; 99; 11; 1987; 1174-1175.

Reaction Details 12 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classificatio
n
Reagent MeNO3H(1-)/methane, O2, SF6
Temperature 37.5 C
Pressure 720.0002 Torr
Other Irradiation
Conditions
Note 1 Yield given. Yields of byproduct given
Ref. 1 5687943;LitLink; Journal; Attina, Marina; Cacace, Fulvio; Petris, Giulia de; ANCEAD; Angew.Chem.; GE; 99; 11; 1987; 1174-1175.

Reaction Details 13 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classification
Yield 65.0 percent Chromat. (BRN=1868032) 35.0 percent Chromat (BRN=1865361)
Reagent Bu4NNO3, TFAA
Solvent nitromethane
Temperature 25 C
Ref. 1 5608860;LitLink; Journal; Masci, Bernardo; TETRAB; Tetrahedron; EN; 45; 9; 1989; 2719- 2730.

Reaction Details 14 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classification
Yield 18.1 percent Chromat. (BRN=1865361) 81.9 percent Chromat (BRN=1868032)
Reagent Bu4NNO3, TFAA
Solvent various solvent(s)
Temperature 25 C
Ref. 1 5608860;LitLink; Journal; Masci, Bernardo; TETRAB; Tetrahedron; EN; 45; 9; 1989; 2719- 2730.

Reaction Details 15 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classification
Yield 22 percent (BRN=1865361) 55 percent (BRN=1868032)
Reagent NH4NO3, Trifluoroacetic Anhydride
Solvent CHCl3
Time 2 hour(s)
Temperature 25 C
Ref. 1 5572557;LitLink; Journal; Crivello, J.V.; JOCEAH; J.Org.Chem.; EN; 46; 15; 1981; 3056- 3060.

Reaction Details 16 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classification
Yield 55 percent (BRN=1868032) 22 percent (BRN=1865361)
Reagent NH4NO3, Trifluoroacetic Anhydride
Solvent CHCl3
Time 2 hour(s)
Temperature 25 C
Ref. 1 5572557;LitLink; Journal; Crivello, J.V.; JOCEAH; J.Org.Chem.; EN; 46; 15; 1981; 3056- 3060.

Reaction Details 17 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classificati
on
Reagent concentrated nitric acid
Ref. 1 1512420;LitLink; Journal; Brunck; Zeitschrift fuer Chemie; 1867; 205; JCVWAE; Jahresber.Fortschr.Chem.Verw.Theile Anderer Wiss.; 1867; 619.
Ref. 2 1512510;LitLink; Journal; Cahours; ANCPAC; Ann.Chim.(Paris); <3> 27; 1849; 465; JLACBF; Justus Liebigs Ann. Chem.; 74; 1850; 315.

Reaction Details 18 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classificati
on
Reagent concentrated nitric acid
Ref. 1 1512420;LitLink; Journal; Brunck; Zeitschrift fuer Chemie; 1867; 205; JCVWAE; Jahresber.Fortschr.Chem.Verw.Theile Anderer Wiss.; 1867; 619.
Ref. 2 1512510;LitLink; Journal; Cahours; ANCPAC; Ann.Chim.(Paris); <3> 27; 1849; 465; JLACBF; Justus Liebigs Ann. Chem.; 74; 1850; 315.

Reaction Details 19 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classification
Reagent bismuth nitrate
Ref. 1 1536816;LitLink; Journal; Spiegel; Haymann; CHBEAM; Chem.Ber.; 59; 1926; 203.

Reaction Details 20 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Preparation
Classification
Reagent bismuth nitrate
Ref. 1 1536816;LitLink; Journal; Spiegel; Haymann; CHBEAM; Chem.Ber.; 59; 1926; 203.

Reaction Details 21 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Chemical behaviour
Classificatio
n
Reagent NO2, O3
Solvent CH2Cl2
Temperature 0 C
Other relative rates (competition with benzene),
Conditions partial rate factors
Subject Rate constant
Studied
Ref. 1 5817405;LitLink; Journal; Suzuki, Hitomi; Murashima, Takashi; Kozai, Iku; Mori, Tadashi; JCPRB4; J.Chem.Soc.Perkin Trans.1; EN; 14; 1993; 1591-1598.

Reaction Details 22 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Chemical behaviour
Classificatio
n
Yield 44 percent (BRN=1865361) 16 percent (BRN=1868032)
Reagent Al2O3, N2O4
Solvent CCl4
Time 1 hour(s)
Other Ambient temperature
Conditions also in the presence of SiO2 or Al2O3; other solvents and reagents; other nitrating agents
Subject Product distribution
Studied Mechanism
Ref. 1 5751781;LitLink; Journal; Nagy, S. M.; Zubkov, E. A.; Shubin, V. G.; Pelmenschikov, A. G.; Paukshtis, E. A.; Razdobarova, Natalia L.; ACHUDC; Acta Chim.Hung.; EN; 129; 5; 1992; 579-586.

Reaction Details 23 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Chemical behaviour
Classificatio
n
Reagent 2,6-Me2PyNO2+BF4-
Solvent acetonitrile
Time 35 hour(s)
Temperature -40 C
Other Irradiation
Conditions other aromatic hydrocarbons, other substituted N-nitropyridinium derivatives; other temp. and time
Subject Product distribution
Studied Mechanism
Ref. 1 5751309;LitLink; Journal; Kim, E. K.; Bockman, T. M.; Kochi, J. K.; JACSAT; J.Amer.Chem.Soc.; EN; 115; 8; 1993; 3091- 3104.

Reaction Details 24 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Chemical behaviour
Classification
Reagent CH4, MeNO3
Temperature 37.6 C
Other Irradiation
Conditions gas-phase nitration by radiolytically formed MeO(1+)(H)NO2
Subject Product distribution
Studied
Ref. 1 5727699;LitLink; Journal; Attina, Marina; Cacace, Fulvio; JACSAT; J.Amer.Chem.Soc.; EN; 108; 2; 1986; 318-319.

Reaction Details 25 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Chemical behaviour
Classificatio
n
Reagent MeNO3H(1-), methane, O2, SF6
Temperature 37.5 C
Pressure 720.0002 Torr
Other Irradiation
Conditions relative reactivity
Ref. 1 5687943;LitLink; Journal; Attina, Marina; Cacace, Fulvio; Petris, Giulia de; ANCEAD; Angew.Chem.; GE; 99; 11; 1987; 1174-1175.

Reaction Details 26 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Chemical behaviour
Classification
Reagent cerium (IV) ammonium nitrate
Solvent acetonitrile
Temperature 84 C
Other other reagent
Conditions
Subject Product distribution
Studied
Ref. 1 5620658;LitLink; Journal; Dinctuerk, Suphi; Ridd, John H.; JCPKBH; J.Chem.Soc.Perkin Trans.2; EN; 1982; 965-970.

Reaction Details 27 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Chemical behaviour
Classification
Yield 54 percent (BRN=1868032) 46 percent (BRN=1865361)
Reagent aq. nitric acid, hydrazine
Temperature 25 C
Other other concetrations of acid, other
Conditions temperatures
Subject Rate constant
Studied
Ref. 1 5611257;LitLink; Journal; Draper, Mark R.; Ridd, John H. A.; JCPKBH; J.Chem.Soc.Perkin Trans.2; EN; 1981; 94-99.

Reaction Details 28 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Chemical behaviour
Classificatio
n
Reagent 65percent nitric acid, sodium nitrite
Solvent CCl4
Time 10 min
Temperature 25 C
Other var. solvents
Conditions
Subject Product distribution
Studied
Ref. 1 5528428;LitLink; Journal; Germain, Alain; JCCCAT; J.Chem.Soc.Chem.Commun.; EN; 23; 1990; 1697-1698.

Reaction Details 29 of 29 (BS0203AE:Reactions:Q02 hit 9,
RX.ID 657713)
Reaction Chemical behaviour
Classificati
on
Reagent N2O4
Solvent acetonitrile
Temperature 25 C
Other electrochemical nitration (1.6 V), anode: Pt,
Conditions cathode: Ni, electrolyte: Et4NBF4; same reaction in the system anisole-benzene or anisole-toluene (relative molar yield); polarization curves
Subject Product distribution
Studied Kinetics
Ref. 1 5521176;LitLink; Journal; Evtyugin, G. A.; Semanov, D. A.; Rydvanskii, Yu. V.; Iskanderov, R. R.; Latypova, V. Z.; Kargin, Yu. M.; JGCHA4; J.Gen.Chem.USSR (Engl.Transl.); EN; 59; 10; 1989; 2089-2093; ZOKHA4; Zh.Obshch.Khim.; RU; 59; 10; 1989; 2331-2336.
 
 
 
 
    moo
(Hive Bee)
11-17-02 22:13
No 380546
      Purification  Bookmark   

o- and p-nitrotoluenes can be separated by crystallization of the p-isomer as it is a solid at room temperature. Melting points for o- and p-nitroanisoles are 9.5C and 54C, according to chemfinder. But I think someone would have used that trick already.
 
 
 
 
    lugh
(Moderator)
11-17-02 22:23
No 380548
      More References  Bookmark   

Some more references are Ann 327 114 (1903), Journal of Scientific and Industrial Research(India) 4 369 (1945) and Patent US1578943, Patent US1875916 & Patent US2370524 smile
 
 
 
 
    Cyrax
(Hive Bee)
11-18-02 01:35
No 380568
      This really helped alot  Bookmark   

Wow, really I mean this: thank you VERY much.
Good old Cyrax is going to make a little trip to the library this week smilesmilesmile.

You 've all made my day.  Thanks smile: damn, I love this place smile
 
 
 
 
    Cyrax
(Hive Bee)
12-03-02 22:31
No 385885
      Phenol --> o- and p-nitrophenol --> o-nitro ...  Bookmark   

Phenol  -->  o- and p-nitrophenol  --> o-nitro anisole

Cautiously add 250 g (136 ml, ca. 2.5 mol) of concentrated sulphuric acid in a thin stream and with stirring to 400 ml of water contained in a 1-litre three necked flask, and then dissolve 150 g (1.75 mol) of sodium nitrate in the diluted acid.  Cool in a bath of ice water.  Melt 94 g (1 mol) of phenol with 20 ml of water, and add this dropwise from a separatory funnel to the vigorously stirred mixture in the flask; maintain the temperature at about 20 C.  Continue the stirring for a further 2 hours after all the phenol has been added.  Pour of the mother-liquor from the resinous mixture of nitro compounds.  Melt the residue with 500 ml of water, shake and allow the contents of the flask to settle.  Pour off the wash liquor and repeat the washing at least 2 or 3 times to ensure the complete removal of any residual acid.  Steam distill the mixture until no more o-nitrophenol passes over; if the latter tends to solidify in the condenser, turn of the cooling water temporarily.  Collect the distillate in cold water, filter at the pump and drain thoroughly.  Dry upon filter-paper in the air.  The yield of o-nitrophenol is 50 g (36 %), m.p.: 46 C.

If the m.p. is not quite satisfactory, dissolve the o-nitrophenol in hot ethanol under reflux, add hot water drop by drop until cloudiness just appears and allow to cool spontaneously.  Filter off the bright yellow crystals and dry between filter-paper.


Now, I just need a procedure to make the methyl and ethyl ethers.  Guess a weak base such as K2CO3 with methyl and ethyl iodide will do the trick.  Just looking for a clear cut cooking recipe now.

Note: o-nitrophenol is deadly toxic
 
 
 
 
    cattleprodder
(Stranger)
12-03-02 23:30
No 385900
      Then what?  Bookmark   

Since this is a drug forum, I have made the presumption that you have a PEA in mind.

So let's say you find yourself with approximately two ounces of o-nitro-anisole, then what?
Formylation will lead to 4-methoxy-3-nitrobenzaldehyde, unless the Ar-NO2 group interferes somehow in a way that I haven't imagined. 

If you are looking for a more active amphetamine, 3-methoxy-4-nitroamphetamine would be a better bet, but for all I know, the sugar plums dancing in your head may have more to do with nitrating hexamine.

Is this a rude question to be asking?
 
 
 
 
    Cyrax
(Hive Bee)
12-04-02 00:43
No 385938
      But for all I know, the sugar plums dancing in ...  Bookmark   

But for all I know, the sugar plums dancing in your head may have more to do with nitrating hexamine.

Nitrating hexamethylenetetramine huh?  For that, you have to fetch JACS (1925) vol 47 p 2754 - 2763

Actually, the sugar plums dancing in my head tell me that the target compound is o-aniside.  What does the synthesis of this compound in a Drug forum?  Well, I let the narcs figure this out smile.
 
 
 
 
    cattleprodder
(Stranger)
12-04-02 00:54
No 385943
      Netiquette.  Bookmark   

When posting a common name such as o-aniside, please also try to approximate an IUPAC name for it as well so that some of us can rely less on ChemFinder.com.  

Thank you.
 
 
 
 
    Cyrax
(Hive Bee)
12-04-02 12:23
No 386147
      2-Methoxy-1-aminobenzene o-aminophenol methyl ...  Bookmark   

2-Methoxy-1-aminobenzene
o-aminophenol methyl ether
o-methoxyaniline
o-methoxyphenylamine
o-Aminoanisole

Are you happy now?  By the way, I resent IUPAC nomenclature.  It is good for simple molecules, but it is rather messed up when things get a little complex in heterocyclic chemistry. 
 
 
 
 
    cattleprodder
(Newbee)
12-06-02 02:38
No 386662
      Yes, thank you.  Bookmark   

I found the list of names that you gave to be decipherable, but I still don't know what I would want to do with any of them.  Luckily, however, that is not my business or pet project at this time either. 

As for the International Union of Pure and Applied Chemistry (IUPAC) nomenclature system, let me just say that, while I too am no fan of it at all for certain things, learning certain IUPAC rules for PEA's and even heterocyclic compounds has, in the past, made reading higher level organic chemical procedures more visualizable and thus more understandable for me personally.