The Vespiary

The Hive => Methods Discourse => Topic started by: Aurelius on June 06, 2004, 02:33:00 AM

Title: O-Alkylation Agents: Synthesis and Use
Post by: Aurelius on June 06, 2004, 02:33:00 AM: O-Alkylation Agents: Synthesis and Use:

This digest will cover Methylating agents as the sole alkylating agent, unless a particular agent or reagent is novel enough to include it.

Methyl Halides:
MeI:
Examples of use:
Post 486065 (https://www.thevespiary.org/talk/index.php?topic=7263.msg48606500#msg48606500)
(Wraith: "Selective methylation of 5-OH-Vanillin with CH3I", Chemistry Discourse)(whole thread)
Post 484676 (https://www.thevespiary.org/talk/index.php?topic=11869.msg48467600#msg48467600)
(Rhodium: "Phenol Alkylation using Cs2CO3 as base", Novel Discourse)
Post 498502 (missing)
(demorol: "Alkylation of Phenols in Water w/PTC", Novel Discourse)

Note that only MeI is used in the reactions here as a result of the gas phase conditions that the other halides adopt at standard conditions. This makes handling too hard for non-industrial preparations.

Methyl Tosylate
Post 417550 (https://www.thevespiary.org/talk/index.php?topic=11342.msg41755000#msg41755000)
(Antoncho: "Methyl tosylate: _finally_ , OTC!!!", Novel Discourse)
Post 466982 (missing)
(psyloxy: "practical alkyl tosylate synth - new approaches", Novel Discourse)
Post 505605 (missing)
(psyloxy: "the important parts", Chemistry Discourse)
Post 461039 (https://www.thevespiary.org/talk/index.php?topic=6333.msg46103900#msg46103900)
(psyloxy: "Ethyl toluenesulfonate from TsOH/ CH2(COOEt)2, 50%", Chemistry Discourse)

Dimethylsulfate: DMS
Examples of use:
Post 507716 (https://www.thevespiary.org/talk/index.php?topic=9924.msg50771600#msg50771600)
(GC_MS: "Permethylation of pyrogallol with DMS", Methods Discourse)
Post 508168 (https://www.thevespiary.org/talk/index.php?topic=9924.msg50816800#msg50816800)
(GC_MS: "Methylation of p-methoxyphenol with DMS", Methods Discourse)

Dimethylcarbonate: DMC
Post 426189 (https://www.thevespiary.org/talk/index.php?topic=11514.msg42618900#msg42618900)
(Vitus_Verdegast: "Methylation of phenols using DMC and a PTC", Novel Discourse)
Post 432395 (https://www.thevespiary.org/talk/index.php?topic=11514.msg43239500#msg43239500)
(Lego: "Methylation of phenol w/ DMC-derivates w/o PTC Pt1", Novel Discourse)( read next post in thread for rest)

Methyl ethers of N-trifluoroacetyl- and N-(m-trifluoromethyl) phenylsulfonyl-6-nitro-tyrosine t-butyl ester
Post 506741 (https://www.thevespiary.org/talk/index.php?topic=6574.msg50674100#msg50674100)
(Rhodium: "O-Methylation of Phenolic Phenethylamine", Chemistry Discourse)

Diazomethane:
Prep and Use:
Warning: Diazomethane is a very dangerous substance (explosive) and must be properly researched before use.
Post 288566 (https://www.thevespiary.org/talk/index.php?topic=11545.msg28856600#msg28856600)
(Antoncho: "Diazomethane. Methylations with diazomethane.", Novel Discourse)
Post 484470 (https://www.thevespiary.org/talk/index.php?topic=11545.msg48447000#msg48447000)
(Vitus_Verdegast: "Preparation of diazomethane solutions", Novel Discourse)
Post 484552 (https://www.thevespiary.org/talk/index.php?topic=11545.msg48455200#msg48455200)
(Rhodium: "Diazald Diazomethane", Novel Discourse)

Dimethyloxalate:DMO
Mentioned only:
Post 503306 (https://www.thevespiary.org/talk/index.php?topic=11514.msg50330600#msg50330600)
(ning: "Try dimethyl oxalate", Novel Discourse)

Betaine
Post 412790 (https://www.thevespiary.org/talk/index.php?topic=11997.msg41279000#msg41279000)
(Lego: "Betaine for O-methylation of Phenols", Novel Discourse)

Trimethylphosphate:TMP
https://www.thevespiary.org/rhodium/Rhodium/chemistry/me3po4.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/me3po4.html)

Post 478120 (https://www.thevespiary.org/talk/index.php?topic=9741.msg47812000#msg47812000)
(Vitus_Verdegast: "To avoid having to make DMS", Methods Discourse) (multiple links on this post)

MeOH: (yes, Methanol)
Post 421068 (https://www.thevespiary.org/talk/index.php?topic=8836.msg42106800#msg42106800)
(Mountain_Girl: "P-MeO Phenol abstracts 1980-1999 #1", Methods Discourse) (one example is at reflux)

NaMeSO₄: Sodium Methylsulfate
Post 256342 (https://www.thevespiary.org/talk/index.php?topic=12158.msg25634200#msg25634200)
(Antoncho: "Methylation of hydroquinone w/NaMeSO4: good news!", Novel Discourse)
Post 218431 (https://www.thevespiary.org/talk/index.php?topic=11362.msg21843100#msg21843100)
(PolytheneSam: "Re: ArOR, Alternatives to dimethyl sulfate", Novel Discourse)

KMeSO₄:Potassium Methylsulfate
Post 229389 (https://www.thevespiary.org/talk/index.php?topic=11362.msg22938900#msg22938900)
(PolytheneSam: "Re: ArOR, Alternatives to dimethyl sulfate", Novel Discourse)

Phenyltrimethylammonium Chloride
Post 443586 (missing)
(Lego: "O-Methylation with Phenyltrimethylammonium chlorid", Novel Discourse)

Random patents about O-Alkylation:
Post 221040 (https://www.thevespiary.org/talk/index.php?topic=11362.msg22104000#msg22104000)
(PolytheneSam: "Re: ArOR, Alternatives to dimethyl sulfate", Novel Discourse)

Trimethyloxonium Fluoroborate
Post 467042 (https://www.thevespiary.org/talk/index.php?topic=11900.msg46704200#msg46704200)
(zealot: "TRIETHYLOXONIUM FLUOBORATE", Novel Discourse) (exotic, but interesting)

Gramine
(not for the usual phenolic alkylation, this is for tryptamine chemistry)
Post 495965 (https://www.thevespiary.org/talk/index.php?topic=12882.msg49596500#msg49596500)
(Nicodem: "The papers mentioned in the above post", Tryptamine Chemistry)

Special thanks to Lego for offering help and showing interest in this project.