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All 20 posts Subject: New Electrosynthesis of P2P Please login to post Down

foxy2
(Distinctive Doe)
11-28-01 19:32
No 241695
      New Electrosynthesis of P2P
(Rated as: excellent)

Check this patent out! This synthesis seems pretty easy, if you have acetic anhydride. The yeilds for substituted benzyl chlorides are not stellar, however they were able to get an 80% conversion of BzCl to P2P.

Synthesis of benzyl methyl ketone (phenylacetone) from benzyl chloride and acetic anhydride.
Patent US4629541

In these examples, the anode is made of magnesium or aluminium, the cathode of nickel the solvent is DMF (110 g) and the supporting electrolyte is tetrabutylammonium fluoroborate (2 g, i.e. 6 mmol).

After the electrolysis (2.2 faradays per mole of benzyl chloride), the remaining benzyl chloride, the toluene which is a byproduct of the reduction of benzyl chloride, and benzyl methyl ketone, both in free form and in the form of its enol acetate, are determined by GC in an aliquot portion.

After the DMF has been evaporated off and the residue has been hydrolysed with hot dilute HCl, benzyl methyl ketone is isolated by extraction with ether. Pure benzyl methyl ketone has been identified from its IR and NMR spectra, and its purity has been verified by GC.

Do Your Part To Win The War

Rhodium
(Chief Bee)
11-28-01 22:10
No 241752
User Picture       Re: New P2P/MDP2P Synthesis

And now also in HTML. Nice find! https://www.rhodium.ws/chemistry/p2p.electro.html

Goodtimes
(Hive Bee)
11-28-01 23:46
No 241804
      Re: New P2P/MDP2P Synthesis

It's always great to have another option. But I think electrolysis might bee over somebee's heads.. But something to think about! smile
It is impossible to make anything foolproof because fools are so ingenious. Murphy's Law

foxy2
(Distinctive Doe)
11-29-01 00:10
No 241815
      Re: New P2P/MDP2P Synthesis

Did you read the patent?
Its actually very simple electrlysis.

Do Your Part To Win The War

PolytheneSam
(Master Searcher)
11-29-01 03:24
No 241897
User Picture       Re: New P2P/MDP2P Synthesis

Post 174633 (PolytheneSam: "Re: a SERIOUS discussion of Tolulene ---> Meth", Stimulants)
Post 227898 (PolytheneSam: "Re: P2P from benzylchloride / LiAc / Li", Novel Discourse)

uemura
(Hive Bee)
11-29-01 08:41
No 241986
      Re: New P2P/MDP2P Synthesis

Goodtimes!
It is impossible to make anything foolproof because fools are so ingenious. Murphy's Law

Uemura has another one:

A fool with a tool is still a fool...

Carpe Diem

foxy2
(Distinctive Doe)
11-29-01 17:11
No 242103
      Re: New P2P/MDP2P Synthesis

Sam
I could probably have guessed that you had posed this before. At least my post convinced Rhodium to put it on his site.
smile
Do Your Part To Win The War

Rhodium
(Chief Bee)
11-29-01 21:59
No 242223
User Picture       how to make things an interesting read

If you guys would bother to include an abstract together with your posted references to make it interesting enough, there is a much greater chance people will read it, and me reading it is a prerequisite for the article to end up on my page.

PoohBear4Ever
(Junior Service Representative)
12-03-01 02:29
No 243415
      Re: New P2P/MDP2P Synthesis

Team-work, people smile !

PB

Scooby_Doo
(Hive Bee)
12-05-01 07:09
No 244388
      Re: New P2P/MDP2P Synthesis

Here's another ref on P2P production, but this time no acetic anhydride which is kinda handy.

"Ketones are obtained by the acylation of cathodically generated carbanions. The carbanions can be formed by the reduction of halogenoalkanes."

Chem Lett 1021 (1977)

Basically zapping (technical ehh) Benzyl chloride in MeCN with something called Et4NOTs

Elementary
(Hive Bee)
03-25-02 02:12
No 287462
User Picture       Confirmation

From reading the patent would I be correct in thinking,
that the solvent could be acetonitrile instead of DMF ?
The anode could also be zinc, cathode could be graphite and that other chemicals such as alkali chlorides could be used as the supporting electrolyte ?

I know an everyday cell like that !!! A typical zinc chloride battery (dry cell), remove the electrolyte from the new battery and you have a ready made ketone cell complete with graphite cathode !

Umm, how interesting !!

Prdy2GO
(Hive Bee)
03-25-02 21:28
No 287752
      "typical zinc chloride battery (dry cell)" Ok now ...

"typical zinc chloride battery (dry cell)"
Ok now are you talking a 6vlantern bTTERY what and where might one be had? What is it used for?
Thanks
Don't look at me I didn't do it!

Rhodium
(Chief Bee)
03-26-02 08:47
No 288016
User Picture       battery

Buy the cheapest 1.5 volt non-alkaline battery you can find, and it will be the correct one - a D cell preferably, the largest available. Open it, and the rod in the biddle is graphite, while the inner casing is zinc. The "filling" is MnO2/NH4Cl and the outer case is most likely steel/iron. Discard the outer case and the filling.

Prdy2GO
(Hive Bee)
03-29-02 05:25
No 289346
      Rhodium, Ahh ok that is making more sense.

Rhodium,
Ahh ok that is making more sense. I thought they were talking about some kind of dry cell like the empty lead acid cycle barrerys you see at the auto parts store.
Thanks laugh
Don't look at me I didn't do it!

quantum
(Hive Bee)
12-05-02 06:31
No 386442
      alkali chloride

ok I have posted this before but I belive it was none to descriptive.
this synth looks amazing only prob is the electrolyt
so would any alkali chloride do the trick maby even
common table salt :)
hmm tolulene pool shock acetone salt and some charge what
a otc way to p2p

e3500 console login: root
bash-2.05#

Rhodium
(Chief Bee)
05-04-04 21:06
No 504852
User Picture       P2P by Electroreductive Acylation
(Rated as: excellent)

(Note: The major product, (E)-1-phenyl-2-acetoxypropene (P2P enol acetate), is quantitatively hydrolyzed to P2P by shaking with 5% aqueous NaOH)

Electroreductive Acylation of Benzyl Chlorides with Acid Anhydrides. Stereoselective Formation of (E)-Enol Esters from Benzyl Alkyl Ketones.
Ikuzo Nishiguchi, Tsuneo Oki, Tsuneaki Hirashima, and Jiro Shiokawa
Chemistry Letters 2005-2008 (1991) (https://www.rhodium.ws/chemistry/p2p.electroreductive.acylation.html)

Abstract
Electroreduction of benzyl chlorides in the presence of acid anhydrides brought about stereoselective formation of (E)-enol esters of the corresponding benzyl alkyl ketones, the initial acylated products, in good to moderate yields.

In this study, we report a unique electroreductive acylation of benzyl chlorides (1) with aliphatic acid anhydrides (2) to give the (E)-enol esters (3) of the corresponding benzyl alkyl ketones (4) as the main product in satisfactory yields. The corresponding benzyl alkyl ketones (4) and benzyl esters (5) were obtained as the by-products in small amounts.

A typical procedure is as follows:

A solution of 20 g (0.067 mol) of tetraethylammonium p-toluenesulfonate in 80 ml of anhydrous N,N-dimethylformamide was placed in cathodic (64 ml) and anodic (16 ml) chambers of a divided cell separated with a cylindrical ceramic diaphragm, to which a lead-plate cathode and a carbon-rod anode were attached. To a catholyte was added 2.53 g (0.02 mol) of benzyl chloride (1a) and 20.4 g (0.20 mol) of acetic anhydride (2a). The mixture was electrolyzed with stirring at room temperature under constant current condition (current density: 15-10 mA/cm² ) until 4.0 F/mol of electricity has been charged. The usual work-up of the catholyte and the distillation of the product mixture gave 2.50 g of (E)-1-phenyl-2-acetoxypropene (3a) (yield 71%), along with benzyl methyl ketone (4a) and benzyl acetate (5a) in 2% and 5% yields, respectively.

Other Electroreductive Acylations of Benzyl Chloride with Acetic Anhydride:

Post 458776 (ning: "Electrosynth of Ketones From Halides/Anhydrides", Methods Discourse)
Post 241695 (foxy2: "New Electrosynthesis of P2P", Methods Discourse)

^{The Hive - Clandestine Chemists Without Borders}

DrLucifer
(Hive Bee)
05-10-04 13:20
No 506201
User Picture       Great news.

Im surprised this thread hasnt received more attention!
These findings are absolutely fuckin marvellous, thanks for spurring a little discussion foxy2, swim is grinning uncontrollably. This venture into foreign territory has certainly paid for itself, thanks again guys.
Foxy i could kiss ya smile

I'm a diamond that is tired, of all the faces i've aquired.

Rhodium
(Chief Bee)
06-03-04 22:33
No 511294
User Picture       Electro-arylation of Chloroacetone -> P2P
(Rated as: excellent)

Synthesis of 1-Aryl-2-propanones by Electrochemical Arylation of α-chloro Ketones
M. Durandetti, S. Sibille, J.-Y. Nédélec and J. Périchon
Synthetic Communications 24(2), 145-151 (1994) (https://www.rhodium.ws/chemistry/p2p.electroarylation.haloketones.html)

Abstract
α-Arylated ketones were obtained in moderate to good yields by one-step electroreductive coupling of α-chloroketones
and arylhalides in DMF and in the presence of a Al- or Zn-sacrificial anode and a catalytic amount of a nickel complex.

^{The Hive - Clandestine Chemists Without Borders}

Organikum
(Wonderful Personality)
06-04-04 12:01
No 511430
      But sadly on second sight.....

But sadly on second sight.....
The experimental part shows the drawbacks:
the aromatic halides (10 mmol) were introduced into a one-compartment cell fitted with Al rod/nickel-sponge or Zn rod/carbon fiber as the anode/cathode set of electrodes (cathode area ~20 cm2). The ?-chloroketone was added constantly to the solution via a syringe pump at a rate of 0.5 ml/h

20cmxcm cathode on 10mmol substrate and additition od 0,5ml chloroketone per hour....
I doubt the practical worth of the procedure (not to talk about iodobenzene for best yields). But its nevertheless a highly interesting approach as all the Ni-couplings are.

Schnabufugl!

armageddon
06-20-04 18:12
      P2P via chloroacetone
(Rated as: insignificant)

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	All 20 posts		Subject: New Electrosynthesis of P2P		Please login to post		Down


		foxy2 (Distinctive Doe) 11-28-01 19:32 No 241695				New Electrosynthesis of P2P (Rated as: excellent)
						Check this patent out! This synthesis seems pretty easy, if you have acetic anhydride. The yeilds for substituted benzyl chlorides are not stellar, however they were able to get an 80% conversion of BzCl to P2P. Synthesis of benzyl methyl ketone (phenylacetone) from benzyl chloride and acetic anhydride. Patent US4629541 In these examples, the anode is made of magnesium or aluminium, the cathode of nickel the solvent is DMF (110 g) and the supporting electrolyte is tetrabutylammonium fluoroborate (2 g, i.e. 6 mmol). After the electrolysis (2.2 faradays per mole of benzyl chloride), the remaining benzyl chloride, the toluene which is a byproduct of the reduction of benzyl chloride, and benzyl methyl ketone, both in free form and in the form of its enol acetate, are determined by GC in an aliquot portion. After the DMF has been evaporated off and the residue has been hydrolysed with hot dilute HCl, benzyl methyl ketone is isolated by extraction with ether. Pure benzyl methyl ketone has been identified from its IR and NMR spectra, and its purity has been verified by GC. Do Your Part To Win The War



		Rhodium (Chief Bee) 11-28-01 22:10 No 241752				Re: New P2P/MDP2P Synthesis
						And now also in HTML. Nice find! https://www.rhodium.ws/chemistry/p2p.electro.html



		Goodtimes (Hive Bee) 11-28-01 23:46 No 241804				Re: New P2P/MDP2P Synthesis
						It's always great to have another option. But I think electrolysis might bee over somebee's heads.. But something to think about! It is impossible to make anything foolproof because fools are so ingenious. Murphy's Law



		foxy2 (Distinctive Doe) 11-29-01 00:10 No 241815				Re: New P2P/MDP2P Synthesis
						Did you read the patent? Its actually very simple electrlysis. Do Your Part To Win The War



		PolytheneSam (Master Searcher) 11-29-01 03:24 No 241897				Re: New P2P/MDP2P Synthesis
						Post 174633 (PolytheneSam: "Re: a SERIOUS discussion of Tolulene ---> Meth", Stimulants) Post 227898 (PolytheneSam: "Re: P2P from benzylchloride / LiAc / Li", Novel Discourse)



		uemura (Hive Bee) 11-29-01 08:41 No 241986				Re: New P2P/MDP2P Synthesis
						Goodtimes! It is impossible to make anything foolproof because fools are so ingenious. Murphy's Law Uemura has another one: A fool with a tool is still a fool... Carpe Diem



		foxy2 (Distinctive Doe) 11-29-01 17:11 No 242103				Re: New P2P/MDP2P Synthesis
						Sam I could probably have guessed that you had posed this before. At least my post convinced Rhodium to put it on his site. Do Your Part To Win The War



		Rhodium (Chief Bee) 11-29-01 21:59 No 242223				how to make things an interesting read
						If you guys would bother to include an abstract together with your posted references to make it interesting enough, there is a much greater chance people will read it, and me reading it is a prerequisite for the article to end up on my page.



		PoohBear4Ever (Junior Service Representative) 12-03-01 02:29 No 243415				Re: New P2P/MDP2P Synthesis
						Team-work, people ! PB



		Scooby_Doo (Hive Bee) 12-05-01 07:09 No 244388				Re: New P2P/MDP2P Synthesis
						Here's another ref on P2P production, but this time no acetic anhydride which is kinda handy. "Ketones are obtained by the acylation of cathodically generated carbanions. The carbanions can be formed by the reduction of halogenoalkanes." Chem Lett 1021 (1977) Basically zapping (technical ehh) Benzyl chloride in MeCN with something called Et4NOTs



		Elementary (Hive Bee) 03-25-02 02:12 No 287462				Confirmation
						From reading the patent would I be correct in thinking, that the solvent could be acetonitrile instead of DMF ? The anode could also be zinc, cathode could be graphite and that other chemicals such as alkali chlorides could be used as the supporting electrolyte ? I know an everyday cell like that !!! A typical zinc chloride battery (dry cell), remove the electrolyte from the new battery and you have a ready made ketone cell complete with graphite cathode ! Umm, how interesting !!



		Prdy2GO (Hive Bee) 03-25-02 21:28 No 287752				"typical zinc chloride battery (dry cell)" Ok now ...
						"typical zinc chloride battery (dry cell)" Ok now are you talking a 6vlantern bTTERY what and where might one be had? What is it used for? Thanks Don't look at me I didn't do it!



		Rhodium (Chief Bee) 03-26-02 08:47 No 288016				battery
						Buy the cheapest 1.5 volt non-alkaline battery you can find, and it will be the correct one - a D cell preferably, the largest available. Open it, and the rod in the biddle is graphite, while the inner casing is zinc. The "filling" is MnO2/NH4Cl and the outer case is most likely steel/iron. Discard the outer case and the filling.



		Prdy2GO (Hive Bee) 03-29-02 05:25 No 289346				Rhodium, Ahh ok that is making more sense.
						Rhodium, Ahh ok that is making more sense. I thought they were talking about some kind of dry cell like the empty lead acid cycle barrerys you see at the auto parts store. Thanks Don't look at me I didn't do it!



		quantum (Hive Bee) 12-05-02 06:31 No 386442				alkali chloride
						ok I have posted this before but I belive it was none to descriptive. this synth looks amazing only prob is the electrolyt so would any alkali chloride do the trick maby even common table salt :) hmm tolulene pool shock acetone salt and some charge what a otc way to p2p e3500 console login: root bash-2.05#



		Rhodium (Chief Bee) 05-04-04 21:06 No 504852				P2P by Electroreductive Acylation (Rated as: excellent)
						(Note: The major product, (E)-1-phenyl-2-acetoxypropene (P2P enol acetate), is quantitatively hydrolyzed to P2P by shaking with 5% aqueous NaOH) Electroreductive Acylation of Benzyl Chlorides with Acid Anhydrides. Stereoselective Formation of (E)-Enol Esters from Benzyl Alkyl Ketones. Ikuzo Nishiguchi, Tsuneo Oki, Tsuneaki Hirashima, and Jiro Shiokawa Chemistry Letters 2005-2008 (1991) (https://www.rhodium.ws/chemistry/p2p.electroreductive.acylation.html) Abstract Electroreduction of benzyl chlorides in the presence of acid anhydrides brought about stereoselective formation of (E)-enol esters of the corresponding benzyl alkyl ketones, the initial acylated products, in good to moderate yields. In this study, we report a unique electroreductive acylation of benzyl chlorides (1) with aliphatic acid anhydrides (2) to give the (E)-enol esters (3) of the corresponding benzyl alkyl ketones (4) as the main product in satisfactory yields. The corresponding benzyl alkyl ketones (4) and benzyl esters (5) were obtained as the by-products in small amounts. A typical procedure is as follows: A solution of 20 g (0.067 mol) of tetraethylammonium p-toluenesulfonate in 80 ml of anhydrous N,N-dimethylformamide was placed in cathodic (64 ml) and anodic (16 ml) chambers of a divided cell separated with a cylindrical ceramic diaphragm, to which a lead-plate cathode and a carbon-rod anode were attached. To a catholyte was added 2.53 g (0.02 mol) of benzyl chloride (1a) and 20.4 g (0.20 mol) of acetic anhydride (2a). The mixture was electrolyzed with stirring at room temperature under constant current condition (current density: 15-10 mA/cm² ) until 4.0 F/mol of electricity has been charged. The usual work-up of the catholyte and the distillation of the product mixture gave 2.50 g of (E)-1-phenyl-2-acetoxypropene (3a) (yield 71%), along with benzyl methyl ketone (4a) and benzyl acetate (5a) in 2% and 5% yields, respectively. Other Electroreductive Acylations of Benzyl Chloride with Acetic Anhydride: Post 458776 (ning: "Electrosynth of Ketones From Halides/Anhydrides", Methods Discourse) Post 241695 (foxy2: "New Electrosynthesis of P2P", Methods Discourse) ^{The Hive - Clandestine Chemists Without Borders}



		DrLucifer (Hive Bee) 05-10-04 13:20 No 506201				Great news.
						Im surprised this thread hasnt received more attention! These findings are absolutely fuckin marvellous, thanks for spurring a little discussion foxy2, swim is grinning uncontrollably. This venture into foreign territory has certainly paid for itself, thanks again guys. Foxy i could kiss ya I'm a diamond that is tired, of all the faces i've aquired.



		Rhodium (Chief Bee) 06-03-04 22:33 No 511294				Electro-arylation of Chloroacetone -> P2P (Rated as: excellent)
						Synthesis of 1-Aryl-2-propanones by Electrochemical Arylation of α-chloro Ketones M. Durandetti, S. Sibille, J.-Y. Nédélec and J. Périchon Synthetic Communications 24(2), 145-151 (1994) (https://www.rhodium.ws/chemistry/p2p.electroarylation.haloketones.html) Abstract α-Arylated ketones were obtained in moderate to good yields by one-step electroreductive coupling of α-chloroketones and arylhalides in DMF and in the presence of a Al- or Zn-sacrificial anode and a catalytic amount of a nickel complex. ^{The Hive - Clandestine Chemists Without Borders}



		Organikum (Wonderful Personality) 06-04-04 12:01 No 511430				But sadly on second sight.....
						But sadly on second sight..... The experimental part shows the drawbacks: the aromatic halides (10 mmol) were introduced into a one-compartment cell fitted with Al rod/nickel-sponge or Zn rod/carbon fiber as the anode/cathode set of electrodes (cathode area ~20 cm2). The ?-chloroketone was added constantly to the solution via a syringe pump at a rate of 0.5 ml/h 20cmxcm cathode on 10mmol substrate and additition od 0,5ml chloroketone per hour.... I doubt the practical worth of the procedure (not to talk about iodobenzene for best yields). But its nevertheless a highly interesting approach as all the Ni-couplings are. Schnabufugl!



		armageddon 06-20-04 18:12				P2P via chloroacetone (Rated as: insignificant)

All 20 posts	End of thread	Top