The Vespiary

The Hive => Methods Discourse => Topic started by: Aurelius on May 24, 2004, 11:44:00 PM

Title: Compilation of P2P Syntheses
Post by: Aurelius on May 24, 2004, 11:44:00 PM

This project will probably be slow in coming as Rhodium's site is already a compendium in itself.

P2P from :
Benzyl Cyanide, PAA, FC of Benzene w/ 2-nitropropane, Red. of P2NP, FC of Benzene w/ Chloroacetone, Hydrolysis of Ephedrine derivatives, Electrolysis of Benzyl Chloride and AA, Ni-med. Coupling of Benzyl Chloride and Acetyl Chloride, Semipinacol Rearrangement of Phenyl-2-Propanal, Acetone Enolate add'n to Bromobenzene, Mn⁺³-mediated radical add'n of Acetone to Benzene, Oxythallation of alpha-Me-Styrene, Wittig Rxn of Benzaldehyde, Cu⁺¹-catalyzed Arylation of K Acetylacetonate, Pd-cat. Arylation of Isoprenylacetate, Alkylation of Benzyl CN with TriMe-Al, Phenylacetaldehyde with DiMe-Cd, Phenacetylchloride with DiMe-Cd, Grignard Add'n to Benzyl CN or AA

https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenylacetone.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenylacetone.html)

From Reagent X:

PAA:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2p.phenylacetic.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2p.phenylacetic.html)

Via Heavy Metal Salts of PAA and Acetic Acid

Patent GB1591538 (http://l2.espacenet.com/dips/viewer?PN=GB1591538&CY=gb&LG=en&DB=EPD)

Via MeLi and CeCl₃

Post 507803 (https://www.thevespiary.org/talk/index.php?topic=11495.msg50780300#msg50780300)

(Rhodium: "PAA + 2 MeLi + 2 CeCl3 -> P2P (62%)", Novel Discourse)

Post 297386 (https://www.thevespiary.org/talk/index.php?topic=6582.msg29738600#msg29738600)

(Elementary: "P2P from Acetone and Phenylacetic Acid", Chemistry Discourse)

P2NP:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/meth.louisfreeh.html#4.0 (https://www.thevespiary.org/rhodium/Rhodium/chemistry/meth.louisfreeh.html#4.0)

Benzyl Chloride:
Via Grignard:
(add'n to acetoacetone)

Post 507580 (missing)

(Bandil: "P2P by grignard addition to acetylacetone trial", Novel Discourse) (must read next link also)

Post 508778 (missing)

(Bandil: "Improvement and proof of concept", Novel Discourse)

Post 482060 (https://www.thevespiary.org/talk/index.php?topic=12073.msg48206000#msg48206000)

(Rhodium: "P2P by grignard addition to acetylacetone", Novel Discourse)
Synth of Acetoacetone:

Post 482694 (https://www.thevespiary.org/talk/index.php?topic=12073.msg48269400#msg48269400)

(lugh: "Alternative Acetylacetone Syntheses", Novel Discourse)

Post 508778 (missing)

(Bandil: "Improvement and proof of concept", Novel Discourse)

https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenylacetone.html#benzylcyanide (https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenylacetone.html#benzylcyanide)

Via Sonochemical

Post 227076 (https://www.thevespiary.org/talk/index.php?topic=11495.msg22707600#msg22707600)

(Lilienthal: "P2P from benzylchloride / LiAc / Li", Novel Discourse)

Patent US4936966 (http://l2.espacenet.com/dips/viewer?PN=US4936966&CY=gb&LG=en&DB=EPD)

Patent US4629541 (http://l2.espacenet.com/dips/viewer?PN=US4629541&CY=gb&LG=en&DB=EPD)

Via Zn Metal

Patent US5146001 (http://l2.espacenet.com/dips/viewer?PN=US5146001&CY=gb&LG=en&DB=EPD)

: requires Pd catalyst

Via Ni-Mediated Coupling

https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenylacetone.html#phenylacetaldehyde (https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenylacetone.html#phenylacetaldehyde)

Post 409150 (https://www.thevespiary.org/talk/index.php?topic=11373.msg40915000#msg40915000)

(Rhodium: "Ni-catalyzed coupling of BnCl + AcCl -> P2P", Novel Discourse)

Via Electrosynthesis

https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenylacetone.html#benzylcyanide (https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenylacetone.html#benzylcyanide)

alpha-Phenylacetoacetonitrile

https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenylacetone.html#benzylcyanide (https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenylacetone.html#benzylcyanide)

Aniline:
(Meerwein Arylation)

https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2p.meerwein.aniline.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2p.meerwein.aniline.html)

Allylbenzene and Propenylbenzene:
(Starting from 1-Chloro-3-Phenylpropane)

https://www.thevespiary.org/rhodium/Rhodium/chemistry/allylbenzene.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/allylbenzene.html)

https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2p.phenylpropenes.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2p.phenylpropenes.html)

Via the Di-bromide

Post 227831 (https://www.thevespiary.org/talk/index.php?topic=11411.msg22783100#msg22783100)

(uemura: "Ketones from Propenylbenzenes via the di-bromides", Novel Discourse)

Via ThalliumNot suggested due to toxicity

Post 263173 (missing)

(Rhodium: "Thallium(III) oxidation of safrole to MDP2P", Novel Discourse)

Patent US4731482 (http://l2.espacenet.com/dips/viewer?PN=US4731482&CY=gb&LG=en&DB=EPD)

or see link below

https://www.thevespiary.org/rhodium/Rhodium/chemistry/peroxotungstate.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/peroxotungstate.html)

(Oxymercuration, Oxidation)

https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2p.oxymercuration.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2p.oxymercuration.html)

(Epoxidation of Alkenes)

https://www.thevespiary.org/rhodium/Rhodium/pdf/oxone.epoxidation-2.pdf (https://www.thevespiary.org/rhodium/Rhodium/pdf/oxone.epoxidation-2.pdf)

Chromic's Oxone Oxidation to P2P's

https://www.thevespiary.org/rhodium/Rhodium/chemistry/oxone.epoxidation.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/oxone.epoxidation.html)

Peracetic Acid Oxid. to P2P's

https://www.thevespiary.org/rhodium/Rhodium/chemistry/peracetic.chromic.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/peracetic.chromic.html)

An improved procedure for the KMnO4 oxidation of olefins to cis-1,2-glycols by use of phase transfer catalysis, William P. Weber and James Peter Shepherd. Tetrahedron Letters No. 48, pp 4907 - 4908, 1972.

Post 303460 (https://www.thevespiary.org/talk/index.php?topic=11443.msg30346000#msg30346000)

(Elementary: "Process for producing phenylacetones", Novel Discourse) (requires PdCl₂ (see also Pat. Below)

Patent US4638094 (http://l2.espacenet.com/dips/viewer?PN=US4638094&CY=gb&LG=en&DB=EPD)

Phenylpropyne:
(Hydroboration)

https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2p.phenylpropyne.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2p.phenylpropyne.html)

Phenylacetaldehyde:
(Grignard Add'n)

https://www.thevespiary.org/rhodium/Rhodium/chemistry/meth.phenylacetaldehyde.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/meth.phenylacetaldehyde.html)

(DiMeCd Add'n)

https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenylacetone.html#phenylacetaldehyde (https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenylacetone.html#phenylacetaldehyde)

(DiMeZn Add'n)

Phenyl-2-Propanal:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/2-phenylpropanal.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/2-phenylpropanal.html)

Synth of Phenyl-2-Propanal:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/2-phenylpropanal.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/2-phenylpropanal.html)

http://www.orgsyn.org/orgsyn/prep.asp?prep=cv3p0733 (http://www.orgsyn.org/orgsyn/prep.asp?prep=cv3p0733)

http://www.orgsyn.org/orgsyn/prep.asp?prep=cv3p0727 (http://www.orgsyn.org/orgsyn/prep.asp?prep=cv3p0727)

P2Pol

Post 367667 (https://www.thevespiary.org/talk/index.php?topic=6322.msg36766700#msg36766700)

(ChemisTris: "Oxidation of P2Pol - a literature search", Chemistry Discourse)

A mild and efficient oxidation of alcohols with N-tBu-Ph-Sulfinimidoylchloride in the Coexistence of ZnO₂
Chem. Lett. (2001) 2, 150-151

(PhCH₂PPh₃)₂S₂O₈: A Mild and Inexpensive Reagent for Effective Oxidation of Organic Compounds under Non-Aqueous and Aprotic Conditions
Bull. Chem. Soc. Jpn. (1998) 71, (17) 1649-1653

Oxidation of Alcohols by Silica-Gel Supported Bis-(TrimethylSilyl)-Chromate
Synth. Comm. (1992) 22, (19)

Oxidation of Secondary Alcohols to Ketones wih Trichloroisocyanuric  Acid
Synth. Comm. (1992) 22 (19)

Oxidation of Alcohols by Metallic Nitrates on Silica Gel
JOC 54 (7), 1531-1535, (1989)

Rhodium Catalyzed Oxidation of Organic Compounds with tBuOOH
J. Org-Met. Chem. (1988) 345, (1-2), 187-99

Oxidation of Aryl Alkanols by Peroxydisulfate-Copper (II)
JOC (1983) 48, (25) 4914-4917

Post 392005 (missing)

(Aurelius: "Oxidation of alcohols with (NH4)2Cr4O7 in solution", Methods Discourse)
Swern Oxid.

Patent US3901896 (http://l2.espacenet.com/dips/viewer?PN=US3901896&CY=gb&LG=en&DB=EPD)

Via Jones Reagent:

Post 319365 (https://www.thevespiary.org/talk/index.php?topic=12144.msg31936500#msg31936500)

(3base: "2,3-diMeO-P2Pol --> P2P", Novel Discourse)

(PCC, Other Chromates, H2O2, etc.)

Synth of P2Pol:

Post 310648 (missing)

(Chemikaze: "Translation", Russian HyperLab)

Post 367709 (https://www.thevespiary.org/talk/index.php?topic=6322.msg36770900#msg36770900)

(Rhodium: "Phenyl-2-propanol", Chemistry Discourse)

Ephedrine and Derivatives:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2p.ephedrine.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2p.ephedrine.html)

Post 173860 (missing)

(Bwiti: "P2P via German Patent", Methods Discourse)

Synthesis of Ephedrine and Many of its Derivates:

Post 422067 (missing)

(Aurelius: "Ephedrine Compilation", Stimulants)

Styrene:
takes place through many routes:

Post 490112 (https://www.thevespiary.org/talk/index.php?topic=7781.msg49011200#msg49011200)

(praeseodymium: "Styrene to P2P, Amphetamine, Meth & Ephedrine", Stimulants)

Via the Epoxide:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2pol.styrenepoxide.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/p2pol.styrenepoxide.html)

Benzene
Via FC'ing

Post 458895 (https://www.thevespiary.org/talk/index.php?topic=6945.msg45889500#msg45889500)

(ChemisTris: "P2P via 2-Nitropropene and Benzene", Chemistry Discourse)

Post 76334 (https://www.thevespiary.org/talk/index.php?topic=12258.msg7633400#msg7633400)

(Rhodium: "New synthesis of Phenyl-2-propanones", Novel Discourse)

Post 219742 (https://www.thevespiary.org/talk/index.php?topic=12258.msg21974200#msg21974200)

(Rhodium: "Re: Alternate 2-nitropropanol synthesis", Novel Discourse)
Specfically for MDP2P:

Post 210023 (https://www.thevespiary.org/talk/index.php?topic=12258.msg21002300#msg21002300)

(Scooby_Doo: "Re: New synthesis of Phenyl-2-propanones", Novel Discourse)

2-NitroPropene:

Post 184263 (https://www.thevespiary.org/talk/index.php?topic=12258.msg18426300#msg18426300)

(Scooby_Doo: "Re: New synthesis of Phenyl-2-propanones", Novel Discourse)
2-NitroPropanol:

Post 219572 (https://www.thevespiary.org/talk/index.php?topic=12258.msg21957200#msg21957200)

(foxy2: "Alternate 2-nitropropanol synthesis", Novel Discourse)

Via Radical Add'n
(Promoted by Mn (III) with acetone)

Post 205055 (https://www.thevespiary.org/talk/index.php?topic=11741.msg20505500#msg20505500)

(Antoncho: "P2Ps from benzene, acetone and Mn(AcO)3", Novel Discourse)
(The Proposed Mechanisms)

https://www.thevespiary.org/rhodium/Rhodium/archive/mechanism_beta.doc (https://www.thevespiary.org/rhodium/Rhodium/archive/mechanism_beta.doc)

Post 215706 (https://www.thevespiary.org/talk/index.php?topic=11741.msg21570600#msg21570600)

(Rhodium: "Re: Possible mechanism", Novel Discourse)

Mn (III) Acetate:

Post 220197 (https://www.thevespiary.org/talk/index.php?topic=11741.msg22019700#msg22019700)

(PEYOTE: "New preparation methods for Mn(OAc)3", Novel Discourse)

https://www.thevespiary.org/rhodium/Rhodium/chemistry/manganous.acetate.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/manganous.acetate.html)

Alkylboranes:

Post 453831 (https://www.thevespiary.org/talk/index.php?topic=11519.msg45383100#msg45383100)

(Rhodium: "Synthesis of ketones (P2P) via alkylboranes", Novel Discourse)

Weinreb Amides:
Via Grignard Add'n:

Post 29390 (https://www.thevespiary.org/talk/index.php?topic=11683.msg2939000#msg2939000)

(psyloxy: "Re: 3,4 dimethoxy phenethyl alcohol as precursor?", Novel Discourse) (read the whole thread) -comments appreciated

Benzaldehydes:
Via Nitropropenes: see above

Twodogs Procedure:
Via acidic condensation w/ MEK

Post 245942 (https://www.thevespiary.org/talk/index.php?topic=12139.msg24594200#msg24594200)

(twodogs: "New method for P2P", Novel Discourse)read the whole thread, works as described

Via Diazomethane in Methanolic Solution:

Post 509822 (https://www.thevespiary.org/talk/index.php?topic=11356.msg50982200#msg50982200)

(Rhodium: "Piperonal + CH2N2 -> MDP2P + Safrole Epoxide", Novel Discourse) (good route w/o nitroethane!)

Via Darzens Condensation:
information on the Darzens Condensation:

Post 488412 (https://www.thevespiary.org/talk/index.php?topic=11449.msg48841200#msg48841200)

(Rhodium: "OR5: The Darzens Glycidic Ester Condensation", Novel Discourse)

Post 333551 (https://www.thevespiary.org/talk/index.php?topic=11449.msg33355100#msg33355100)

(Barium: "benzaldehydes to phenylacetones", Novel Discourse) (or links below)

https://www.thevespiary.org/rhodium/Rhodium/chemistry/25dmp2p.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/25dmp2p.html)

https://www.thevespiary.org/rhodium/Rhodium/chemistry/2ch.darzen.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/2ch.darzen.html)

Post 345353 (https://www.thevespiary.org/talk/index.php?topic=12979.msg34535300#msg34535300)

(Barium: "Indole-3-acetone from indole-3-carboxaldehyde", Tryptamine Chemistry)

Post 333615 (https://www.thevespiary.org/talk/index.php?topic=11449.msg33361500#msg33361500)

(Barium: "Holy cow!!!", Novel Discourse)

Post 334617 (https://www.thevespiary.org/talk/index.php?topic=11449.msg33461700#msg33461700)

(Barium: "A 500mmol batch of 2,5-dimethoxybenzaldehyde was ...", Novel Discourse)

Post 336530 (https://www.thevespiary.org/talk/index.php?topic=11449.msg33653000#msg33653000)

(Barium: "2,5-DMMA", Novel Discourse)

Post 339354 (https://www.thevespiary.org/talk/index.php?topic=11449.msg33935400#msg33935400)

(Barium: "Check this out!!", Novel Discourse)

Post 379632 (https://www.thevespiary.org/talk/index.php?topic=11449.msg37963200#msg37963200)

(Barium: "Final touch", Novel Discourse)

Post 421443 (https://www.thevespiary.org/talk/index.php?topic=11449.msg42144300#msg42144300)

(GC_MS: "Darzens article", Novel Discourse)

Post 488433 (https://www.thevespiary.org/talk/index.php?topic=11449.msg48843300#msg48843300)

(dioulasso: "Drazens in DMF with K2CO3 + PTC", Novel Discourse)

Post 285765 (https://www.thevespiary.org/talk/index.php?topic=11334.msg28576500#msg28576500)

(foxy2: "Piperonal to MDP2P", Novel Discourse)

Synth of Propionates:

Post 220587 (https://www.thevespiary.org/talk/index.php?topic=9255.msg22058700#msg22058700)

(foxy2: "Preparation of alpha-Bromo Carboxylic Acids", Methods Discourse)

Post 462801 (https://www.thevespiary.org/talk/index.php?topic=11449.msg46280100#msg46280100)

(Rhodium: "Methyl 2-Chloropropionate from Methyl Lactate", Novel Discourse)

Post 461735 (https://www.thevespiary.org/talk/index.php?topic=6424.msg46173500#msg46173500)

(psyloxy: "ethyl chloropropionate from ethyl lactate / TsCl", Chemistry Discourse)

Post 285767 (https://www.thevespiary.org/talk/index.php?topic=11334.msg28576700#msg28576700)

(foxy2: "2-Chloropropionic acid methyl ester synthesis", Novel Discourse)

Post 285770 (https://www.thevespiary.org/talk/index.php?topic=11334.msg28577000#msg28577000)

(foxy2: "2-Chloropropionic acid synthesis", Novel Discourse)
(a lot of refs:)

Post 221276 (https://www.thevespiary.org/talk/index.php?topic=9255.msg22127600#msg22127600)

(megamole: "Re: Easy nitroethane in quantitative yield", Methods Discourse)

Post 221895 (https://www.thevespiary.org/talk/index.php?topic=9255.msg22189500#msg22189500)

(lugh: "(R)-2-Bromopropionic Acid from D-Alanine", Methods Discourse)

Post 227794 (https://www.thevespiary.org/talk/index.php?topic=9255.msg22779400#msg22779400)

(megamole: "Re: Easy nitroethane in quantitative yield", Methods Discourse)

Post 346512 (https://www.thevespiary.org/talk/index.php?topic=9255.msg34651200#msg34651200)

(moo: "alpha-bromopropionic acid from lactic acid", Methods Discourse) (could somebody please translate and send me the link)
Synth of Ethyl-2-chloropropionate:

Post 346417 (https://www.thevespiary.org/talk/index.php?topic=12979.msg34641700#msg34641700)

(Barium: "Cyrax: Ethyl 2-chloropropionate is cheaper and, ...", Tryptamine Chemistry)

Helpful additions to the Synthesis Links Provided:

Post 383426 (missing)

(Rhodium: "Grignard Reaction Initiation FAQ", Chemistry Discourse)

Does somebody have more information on this one?

Post 319326 (https://www.thevespiary.org/talk/index.php?topic=11933.msg31932600#msg31932600)

(3base: "Cl-benzene --> P2P", Novel Discourse)

misc

Post 358239 (https://www.thevespiary.org/talk/index.php?topic=11264.msg35823900#msg35823900)

(poix: "2,5-dimethoxy-phenylacetone from o-Allylphenol", Novel Discourse)