(Active Asperger Archivist)
05-19-04 19:29
No 508238
(Rated as: excellent)
Synthesis of Benzaldehyde and it Substituted Analogues
Benzaldehyde Derived:
Benzaldehyde:
Post 511939 (Kinetic: "Cinnamic acid to benzaldehyde", Newbee Forum)
Post 208719 (Osmium: "Re: The easiest synth of benzaldehyde from toluene", Chemistry Discourse)
Patents Related To Link Above:
Post 208782 (PolytheneSam: "Re: The easiest synth of benzaldehyde from toluene", Chemistry Discourse)
Post 377691 (moo: "Aldehydes from Grignard reagents with formic acid", Methods Discourse)
Post 241349 (foxy2: "benzaldehyde from toluene - Additions", Chemistry Discourse)
Post 244957 (Chemikaze: "Benzaldehyde via MnO2 oxidation of toluene", Novel Discourse)
Related: Post 296395 (hest: "You need 'activated' MnO2.", Newbee Forum)
or
../rhodium /oxycodo
Post 354314 (Rhodium: "General Method for the Preparation of ...", Chemistry Discourse) (from benzyl alcohol)
Post 479722 (lugh: "Reference Uploaded", Chemistry Discourse) (Deox. of Benzoic acid)
Post 493837 (moo: "Benzoic acid to benzaldehyde or benzene", Chemistry Discourse) (second part of deox.)
Refs for Various Methods:
Post 354361 (GC_MS: "Meyer", Chemistry Discourse)
Post 444540 (Lego: "Solventless oxidation with KMnO4/montmorillonite", Chemistry Discourse) (tol. to benz.)
Post 459026 (hermanroempp: "Just another oxidiser - Manganese-(III)-sulfate", Chemistry Discourse) (tol. to benz.)
Post 468094 (moo: "I've thought about the possibility of ...", Chemistry Discourse) (tol. to benz.)
Post 498021 (Organikum: "H2O2 toluene oxidation (vanadium catalyzed)", Chemistry Discourse) (tol. to benz.)
Post 473147 (Rhodium: "Toluene to Benzaldehyde using Co(II)-Peroxygen", Chemistry Discourse)
Post 457354 (LaBTop: "Crossposting, Hah!", Chemistry Discourse) (tol. to benz. by air ox.)
Post 471369 (halfkast: "Chomic", Chemistry Discourse) (tol. to benz. by air ox.)
http://www.sciencemadness.org/papers/tol
http://www.sciencemadness.org/papers/tol
Post 479888 (Rhodium: "More on Toluene -> Benzaldehyde", Chemistry Discourse)
Post 458012 (Tdurden969: "References", Chemistry Discourse) (electro. to benz.)
Post 493948 (Organikum: "Benzoic acid to benzaldehyde by electrolysis", Chemistry Discourse) (benz. acid. electro.)
Post 437235 (Organikum: "B-dehyde", Stimulants) (patents)
Mono-Substituted Benzaldehydes:
Salicylaldehyde: 2-OH-
Post 474077 (Rhodium: "Substituted Vanillins are Resistant to Oxidation", Methods Discourse) (see Ref # 11)
Post 422019 (Vitus_Verdegast: "found an interesting article", Methods Discourse)
Anisaldeyde: 4-MeO
Post 382264 (Antoncho: "Zealot: azomethinic (Haack) formylation", Novel Discourse)
Post 475637 (Rhodium: "Synthesis of 2C-B from Anise Oil (Anethole)", Novel Discourse)
../rhodium /me3po4.
Post 504013 (starlight: "some interesting mandelic acid patents", Chemistry Discourse)
Post 474077 (Rhodium: "Substituted Vanillins are Resistant to Oxidation", Methods Discourse) (see ref #11)
Di-Substituted Benzaldehydes:
2-OH-3-BuO-
Post 355308 (foxy2: "More Duff Reaction", Novel Discourse)
2-OH-3-t-Amyl-
Post 355308 (foxy2: "More Duff Reaction", Novel Discourse)
2-OH-4-Me-
Post 234191 (megamole: "Re: Magnesium Alkoxides", Chemistry Discourse)
2-OH-5-Br: (5-BromoSalicylaldehyde)
Post 511284 (lugh: "5-bromosalicylaldehyde", Chemistry Discourse)
2-OH-5-Me-
Post 355308 (foxy2: "More Duff Reaction", Novel Discourse)
2-OH-5-MeO-
Post 214710 (Karl: "2-Hydroxy-5-methoxybenzaldehyde", Chemistry Discourse)
Post 511008 (demorol: "Methoxylation of various aryl bromides", Chemistry Discourse)
2,5-DiEtO-
Post 239307 (Rhodium: "Re: Syringaldehyde via Duff formylation", Novel Discourse)
2-OH-5-MeO-
Post 290438 (Lilienthal: "2-hydroxy-5-MeO-BA: The easy way", Chemistry Discourse)
Post 234191 (megamole: "Re: Magnesium Alkoxides", Chemistry Discourse)
Post 475637 (Rhodium: "Synthesis of 2C-B from Anise Oil (Anethole)", Novel Discourse)
Post 330714 (Antoncho: "A patented improvement", Chemistry Discourse)
2-OH-6-Me-
Post 234191 (megamole: "Re: Magnesium Alkoxides", Chemistry Discourse)
2,5-DiMeO-
Post 510729 (not existing)
Post 493429 (Nicodem: "HCHO/Mg(II) formylation + methylation patent", Methods Discourse)
Post 348592 (Antoncho: "Methyl iodide methylation of 2-OH-5-MeO-BA.", Chemistry Discourse)
Post 423268 (foxy2: "Synthesis of 2,5-dimethoxybenzaldehyde", Chemistry Discourse)
Post 473079 (Rhodium: "Gattermann 2,5-Dimethoxybenzaldehyde", Novel Discourse)
Post 454518 (Rhodium: "Two Syntheses of 2,5-Dimethoxybenzaldehyde", Chemistry Discourse)
Post 475637 (Rhodium: "Synthesis of 2C-B from Anise Oil (Anethole)", Novel Discourse)
Post 214710 (Karl: "2-Hydroxy-5-methoxybenzaldehyde", Chemistry Discourse)
../rhodium /me3po4.
The following procedure is NOT valid:
Post 70528 (karel: "Synth of 2,5-dimethoxybenzaldehyde", Serious Chemistry) (must also read Post 299121 (karel: "Revision of post 70528", Chemistry Discourse))
Veratraldehyde: 3,4-DiMeO-
http://www.orgsyn.org/orgsyn/orgsyn/prep
Protocatechualdehyde: 3,4-DiOH-
Post 477628 (Rhodium: "Vanillin to Protocatechualdehyde (AlCl3/Py)", Methods Discourse)
../rhodium /methyle
Bourbonal: 3-EtO-4-OH-
3,5-DiMeO-
Post 473076 (Rhodium: "Benzoic Acids to Benzaldehydes", Chemistry Discourse)
Vanillin: 4-OH-3-MeO-
Post 275285 (foxy2: "5-Br-Vanillin Methoxylation (CuBr/EtOAc/NaOMe)", Chemistry Discourse) (or the direct link below)
http://valhalla.chem.udel.edu/vanillin.h
Post 286983 (foxy2: "Hmmm, CO2????", Chemistry Discourse)
Post 504013 (starlight: "some interesting mandelic acid patents", Chemistry Discourse)
Post 474077 (Rhodium: "Substituted Vanillins are Resistant to Oxidation", Methods Discourse) (see ref # 11)
Post 211048 (Rhodium: "Re: Vanillin from OTC Vanilla Extract", Chemistry Discourse)
Post 511008 (demorol: "Methoxylation of various aryl bromides", Chemistry Discourse)
3-Alkoxy-4-OH-
Post 504013 (starlight: "some interesting mandelic acid patents", Chemistry Discourse)
4-EtO-3-MeO-
../rhodium /me3po4.
Tri-Substituted Benzaldehydes:
2-Bromo-3,4-DiMeO-
Post 474077 (Rhodium: "Substituted Vanillins are Resistant to Oxidation", Methods Discourse)
Post 214376 (foxy2: "Re: 2 Bromination of 3,4-dimethoxybenzaldehyde", Chemistry Discourse)
2-OH-3,5-DiBr
Post 355308 (foxy2: "More Duff Reaction", Novel Discourse)
2-OH-3,5-Di-t-Bu- (also: 3,5-Di-t-Bu-Salicylaldehyde)
Post 355308 (foxy2: "More Duff Reaction", Novel Discourse)
2-OH-3-Cl-5-t-Bu
Post 355308 (foxy2: "More Duff Reaction", Novel Discourse)
2-OH-3-Me-5-t-Amyl
Post 355308 (foxy2: "More Duff Reaction", Novel Discourse)
2,3,5-TriMeO-
Post 494386 (Rhodium: "Synthesis of TMA-2 Precursors from Vanillin", Novel Discourse)
../rhodium /me3po4.
2-OH-3-MeO-5-Me-
Post 486611 (Rhodium: "Reference #5: C-Methylation of Vanillin", Novel Discourse)
2-BromoVanillin: 2-Br-3-MeO-4-OH-
Post 474077 (Rhodium: "Substituted Vanillins are Resistant to Oxidation", Methods Discourse)
2-Br-4,5-DiMeO-
Post 214369 (foxy2: "2 Bromination of 3,4-dimethoxybenzaldehyde", Chemistry Discourse)
Asarylaldehyde: 2,4,5-TriMeO-
../rhodium /me3po4.
Post 471601 (Rhodium: "Indirect 6-Methoxylation of Veratraldehyde", Methods Discourse)
2,4,6-TriMeO-
Post 480958 (hest: "Synt of 2,4,6-trimethoxybenzaldehyde", Chemistry Discourse)
Post 481038 (Rhodium: "Synthesis of 2,4,6-Trimethoxybenzaldehyde", Chemistry Discourse)
2,5-DiMeO-3-Me-
Post 300201 (Antoncho: "3-methyl-2,5-diMeO-benzaldehyde", Novel Discourse)
../rhodium /methyld
2,5-DiMeO-4-Me-
../rhodium /methyld
3,4-DiMeO-5-OH-
Post 506221 (Mephisto: "Synthesis of 3,4-dimethoxy-5-hydroxybenzaldehyde", Chemistry Discourse)
3,4,5-TriMeO-
Post 501059 (ning: "TRANSLATED: Chinese 3,4,5 TMB article", Methods Discourse)
Post 507150 (Rhodium: "3,4,5-Trimethoxybenzaldehyde from Gallic Acid", Methods Discourse)
../rhodium /345-tmb
../rhodium /me3po4.
3,4,6-TriMeO-
Post 464340 (imp: "Synthesis of MMDA-3a and MMDA-3b Benzaldehydes", Novel Discourse)
6-BromoVanillin: 3-MeO-4-OH-6-Br-
Post 474077 (Rhodium: "Substituted Vanillins are Resistant to Oxidation", Methods Discourse)
3-DiMe-2-OH-
Post 486611 (Rhodium: "Reference #5: C-Methylation of Vanillin", Novel Discourse)
3,5-Bis(DiMeAminoMe)-2-OH-
Post 486611 (Rhodium: "Reference #5: C-Methylation of Vanillin", Novel Discourse)
3,5-DiBr-4-OH-
Post 275643 (Antoncho: "Syringaldehyde from p-cresol in two steps", Chemistry Discourse)
3,5-DiMe-4-OH-
Post 486611 (Rhodium: "Reference #5: C-Methylation of Vanillin", Novel Discourse)
3,5-DiMeO-4-OH-
Post 275269 (Antoncho: "Re: Vanillin", Chemistry Discourse)
3,5-Bis(DiMeAminoMe)-4-OH-
Post 486611 (Rhodium: "Reference #5: C-Methylation of Vanillin", Novel Discourse)
3,5-Di-t-Bu-4-OH-
Post 208298 (Antoncho: "Duff formylation in aq. AcOH - 90% yield :))", Chemistry Discourse)
4-I-2,5-DiMeO-
Post 422838 (GC_MS: "1-(4-iodo-2,5-dimethoxyphenyl)-2-propan
Post 469528 (Chimimanie: "halogenation of 2,5-DMB & benzonitrile + DOI ?", Methods Discourse)
4-Cl-2,5-DiMeO-
Post 106232 (rev drone: "Re: Iodination via NIS -- various conditions", Chemistry Discourse)
Post 482940 (Lego: "Duff formylation of 2-chloro-1,4-dimethoxybenzene", Chemistry Discourse)
4-Br-2,5-DiMeO-
Post 106232 (rev drone: "Re: Iodination via NIS -- various conditions", Chemistry Discourse)
Post 469528 (Chimimanie: "halogenation of 2,5-DMB & benzonitrile + DOI ?", Methods Discourse)
Post 468077 (moo: "Oxidations and brominations w/ H2O2/Br2/HBr", Methods Discourse)
Post 468078 (moo: "Oxidations and brominations w/ H2O2/Br2/HBr", Methods Discourse)
5-NO2-2,3-DiMeO-
Post 425432 (Vitus_Verdegast: "J. Chem. Soc. (1923) 123, page 1587 and 1588", Methods Discourse)
5-NO2-2-MeO-3-EtO-
Post 425432 (Vitus_Verdegast: "J. Chem. Soc. (1923) 123, page 1587 and 1588", Methods Discourse)
Syringaldehyde: 4-OH-3,5-DiMeO-
Post 355336 (Antoncho: "Another EXCELLENT formylation!", Novel Discourse)
Post 275285 (foxy2: "5-Br-Vanillin Methoxylation (CuBr/EtOAc/NaOMe)", Chemistry Discourse)
../rhodium /345-tmb
Post 275643 (Antoncho: "Syringaldehyde from p-cresol in two steps", Chemistry Discourse)
Post 286983 (foxy2: "Hmmm, CO2????", Chemistry Discourse)
Post 235806 (Osmium: "Re: Magnesium Alkoxides", Chemistry Discourse) (as seen in ../rhodium /mmda.me
Post 239082 (Antoncho: "Syringaldehyde via Duff formylation", Novel Discourse)
Post 511008 (demorol: "Methoxylation of various aryl bromides", Chemistry Discourse)
4-OH-5-MeO-3-Me- (aka: 5-Me-Vanillin)
Post 253386 (slothrop: "5-Methyl-MDA", Novel Discourse)
4-OH-5-Me-3-MeO-
Post 486611 (Rhodium: "Reference #5: C-Methylation of Vanillin", Novel Discourse)
4,5-DiOH-3-Me-
Post 253386 (slothrop: "5-Methyl-MDA", Novel Discourse)
5-DiMeAminoMe-2-OH-3-MeO-
Post 486611 (Rhodium: "Reference #5: C-Methylation of Vanillin", Novel Discourse)
5-Bromo-3-DiMeo-
Post 474077 (Rhodium: "Substituted Vanillins are Resistant to Oxidation", Methods Discourse)
5-DiMeAminoMe-4-OH-3-MeO-
Post 253386 (slothrop: "5-Methyl-MDA", Novel Discourse)
Post 486611 (Rhodium: "Reference #5: C-Methylation of Vanillin", Novel Discourse)
Higher-Poly-Substituted Benzaldehydes:
2-OH-3-i-Pro-5-Cl-6-Me-
Post 355308 (foxy2: "More Duff Reaction", Novel Discourse)
2,5-DiMeO-3,6-DiMe-
Post 472752 (Manichi: "Methylated PEA benzaldehyde precursors", Novel Discourse)
2,3,4-TriMeO-3,6-DiMe-
Post 472752 (Manichi: "Methylated PEA benzaldehyde precursors", Novel Discourse)
2,4,5-TriMeO-3,6-DiMe-
Post 472752 (Manichi: "Methylated PEA benzaldehyde precursors", Novel Discourse)
4-OH-2,5-DiMeo-3,6-DiMe-
Post 472752 (Manichi: "Methylated PEA benzaldehyde precursors", Novel Discourse)
Piperonal Derived:
Piperonal (Heliotropine): 3,4-MD-Benz.
Post 463350 (Antoncho: "A great piperonal patent", Novel Discourse)
Post 391475 (pHarmacist: "One More piperonal patent, High-yielding", Novel Discourse)
Post 328397 (demorol: "Piperonal synthesis", Novel Discourse)
Post 329015 (demorol: "More patents", Novel Discourse)
Post 382264 (Antoncho: "Zealot: azomethinic (Haack) formylation", Novel Discourse)
5-OH-
Post 504409 (Rhodium: "5-Hydroxypiperonal and Myristicinaldehyde", Novel Discourse)
Also: ../rhodium /5-hydro
5-Br-
Post 507151 (Rhodium: "Synthesis of 5-Bromopiperonal", Methods Discourse)
5-Me-
Post 253386 (slothrop: "5-Methyl-MDA", Novel Discourse)
6-OH-
Post 464339 (imp: "2-Alkoxy-4,5-methylenedioxybenzaldehyde
6-NH2-
Post 464339 (imp: "2-Alkoxy-4,5-methylenedioxybenzaldehyde
6-NO2-
Post 464339 (imp: "2-Alkoxy-4,5-methylenedioxybenzaldehyde
2-Br-6-MeO-
Post 507151 (Rhodium: "Synthesis of 5-Bromopiperonal", Methods Discourse)
1-MeO-2,3-MD-
Post 484717 (Rhodium: "Croweacinaldehyde & Isomers", Novel Discourse)
2,3-MD-4-MeO-
Post 464340 (imp: "Synthesis of MMDA-3a and MMDA-3b Benzaldehydes", Novel Discourse)
Post 484717 (Rhodium: "Croweacinaldehyde & Isomers", Novel Discourse)
Croweacinaldehyde: 2-MeO-3,4-MD-
Post 484271 (Rhodium: "Croweacinaldehyde from Pyrogallol (55%)", Novel Discourse)
Post 484720 (Rhodium: "Croweacinaldehyde", Novel Discourse)
Post 464340 (imp: "Synthesis of MMDA-3a and MMDA-3b Benzaldehydes", Novel Discourse)
Post 245205 (Rhodium: "Re: Benzaldehyde Of Croweacin?", Chemistry Discourse)
Post 484717 (Rhodium: "Croweacinaldehyde & Isomers", Novel Discourse)
2-Alkoxy-4,5-MD-
Post 464339 (imp: "2-Alkoxy-4,5-methylenedioxybenzaldehyde
Carpacinaldehyde: 2-MeO-4,5-MD-
Post 247833 (Rhodium: "Carpacin isolation & Physical Data", Chemistry Discourse)
Post 464339 (imp: "2-Alkoxy-4,5-methylenedioxybenzaldehyde
Apiolaldehyde: 2,5-DiMeO-3,4-MD-
Post 489559 (Rhodium: "Synthesis of Myristicinaldehyde/Apiolealdehyde", Novel Discourse)
../rhodium /myristi
Myristicinaldehyde: 3-MeO-3,4-MD-
Post 509800 (Rhodium: "Myristicin Derivatives", Novel Discourse)
Post 508799 (Wraith: "Methylenation without KF or PTC", Novel Discourse)
Post 504409 (Rhodium: "5-Hydroxypiperonal and Myristicinaldehyde", Novel Discourse)
Also: ../rhodium /5-hydro
Post 489659 (Rhodium: "Myristicin & Myristicinaldehyde", Novel Discourse)
IR of Myristicin
Post 494937 (Islamybad: "Here's the IR spectrum of myristicin from two...", Serious Chemistry)
Post 452949 (GC_MS: "myristicinaldehyde", Chemistry Discourse)(see warning below before attempting this synthesis:)
Warning about TetraNitroMethane and Relatives:
Post 355957 (GC_MS: "How dangerous is tetranitromethane?", Chemistry Discourse)
3,4-MD-6-OH-
Post 464339 (imp: "2-Alkoxy-4,5-methylenedioxybenzaldehyde
6-OH-2-MeO-3,4-MD-
Post 484717 (Rhodium: "Croweacinaldehyde & Isomers", Novel Discourse)
General Aldehyde Synthesis or those containing large numbers of aldehyde products:
../rhodium /formyla
Post 355321 (foxy2: "formylation by the "nitroso" method", Novel Discourse)
Post 355336 (Antoncho: "Another EXCELLENT formylation!", Novel Discourse)
Post 235460 (Antoncho: "Re: Formylations", Chemistry Discourse)
Post 422033 (Vitus_Verdegast: "R-T articles that might be interesting", Methods Discourse)
../rhodium/pdf /bromo2hydroxy
Side Notes:
Formylation Mechanism:
Post 481046 (Rhodium: "Magnesium ortho-Formylation Mechanism", Methods Discourse)
Several Naturally Occuring Aldehydes:
../rhodium /me3po4.
Act quickly or not at all.
