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All 8 posts Subject: Butanediol or THF to GBL using KMnO4/CuSO4 Please login to post Down

Rhodium
(Chief Bee)
07-04-02 18:20
No 328762
User Picture       Butanediol or THF to GBL using KMnO4/CuSO4
(Rated as: good read)

Solvent-free Permanganate Oxidations
Tet Lett 42(34), 5833-5836 (2001) (https://www.rhodium.ws/pdf/solventfree.kmno4.oxidation.pdf)

The oxidant is prepared by grinding equal amounts of potassium permanganate and copper sulfate pentahydrate in a mortar until homogeneous, or preferably by adding a concentrated aqueous solution of potassium permanganate to alumina, giving a paste which is then ground with an equal amount of copper sulfate pentahydrate. The substrate (2 mmol) is added to a portion of the oxidant (~4 g) in a 25 mL round bottomed flask and stirred magnetically until TLC analysis indicates a completed reaction. The residue is then washed with a minimum amount of solvent (methylene chloride, hexane and/or ether). Evaporation of the solvent gives a product that is of acceptable purity for most purposes. If greater purity is required, the product can be distilled.

Tetrahydrofuran -> GBL (6h, 70% yield)
1,4-Butanediol -> GBL (14h, 95% yield)

Entropy just isn't what it used to be.

SPISSHAK
(Hive Bee)
07-04-02 18:45
No 328769
      Role of reagents in oxidation reaction?

I was wondering what the role of copper sulfate and alumina served in this oxidation reaction?
Inhibitors, accelerants, etc.?
It's a given that the permanganate is the oxidizer.

Antibody2
(Bee without a Title)
07-04-02 19:05
No 328776
      the alumina is a solid support for the ...

the alumina is a solid support for the permangnate, i've seen it employed in other KMnO4 oxidations.

the copper i suspect is the catalyst

all in all very OTC synth smile nice find Rhodium

SPISSHAK
(Hive Bee)
07-04-02 19:09
No 328778
      Thanks antibody

Thanks for straightening that all out in my feable little brain crazy
Anyway, do you know what direction the copper sulfate might take the oxidant(i.e. inhibitor, accelerant?).
Thanks again.

Trypstar
(Stranger)
07-04-02 21:23
No 328817
      Huh?

Isn't this just

https://www.rhodium.ws/pdf/solventfree.kmno4.oxidation.pdf

which has been on your site for quite a while?
I had the paper myself, but since it was on your site, I never posted it.

Rhodium
(Chief Bee)
07-05-02 03:13
No 328896
User Picture       Oops, you're right...

Oops, you're right... blush I had forgotten seeing that article before, as noone followed that reaction up after I put that PDF on my page...

Entropy just isn't what it used to be.

weedar
(Hive Bee)
07-05-02 08:37
No 328978
      But then...

Yuo really should rate your post redundant? laugh shocked

Weedar
Weedar contains 2,4-D dimethylamine salt,apparently

Rhodium
(Chief Bee)
09-29-04 13:21
No 533747
User Picture       THF --Mn2O7--> GBL (86%)
(Rated as: good read)

[Selective oxidation of organic compounds with Mn(VII) Oxide]
Martin Trömel & Manuel Russ
Angewandte Chemie 99(10), 1037-1038 (1987) (https://www.rhodium.ws/pdf/thf2gbl.mn2o7.pdf)

2 KMnO₄ + 2 H₂SO₄ -> Mn₂O₇ + 2 KHSO₄ + H₂O

3 THF + 2 Mn₂O₇ -> 3 GBL + 4 MnO₂ + 3 H₂O

Mn(VII) Oxide
To a stirred and cooled mixture of 24 mL H₂SO₄ and 100 mL anhydrous CCl₄, 16.3g finely ground KMnO₄ is added while keeping the temperature between 20-25°C. After stirring the solution for several hours, and the deep red red solution is decanted from the formed sediment and stored at 4°C. It is possible to prepare batches up to three times this size.

Titration
To determine the exact concentration, 0.3 mL of the above solution is mixed with 30 mL water and with stirring, 1.5g KI and 4 mL glacial acetic acid is added thereto. The resulting solution is then titrated with 0.100 M thiosulfate, each mL corresponding to 2.2 mg Mn₂O₇.

Oxidation
The [THF] is dissolved in an 1:1 mixture of acetone/CCl₄ (MeOAc & EtOAc also works), and after cooling to -45°C the Mn₂O₇ is added with stirring (0.7 molar equivalents as a 2.5% solution in CCl₄) at such a rate that the temperature does not increase above -40°C. After the addition, the solution is stirred for 5 min at -45°C and excess Mn₂O₇ is destroyed by the dropwise addition of IPA. The solution is allowed to warm to room temperature, the precipitated MnO₂ is filtered off and the solvent evaporated. The product is then isolated by vacuum distillation. Yield of GBL 86%.

^{The Hive - Clandestine Chemists Without Borders}

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	All 8 posts		Subject: Butanediol or THF to GBL using KMnO4/CuSO4		Please login to post		Down


		Rhodium (Chief Bee) 07-04-02 18:20 No 328762				Butanediol or THF to GBL using KMnO4/CuSO4 (Rated as: good read)
						Solvent-free Permanganate Oxidations Tet Lett 42(34), 5833-5836 (2001) (https://www.rhodium.ws/pdf/solventfree.kmno4.oxidation.pdf) The oxidant is prepared by grinding equal amounts of potassium permanganate and copper sulfate pentahydrate in a mortar until homogeneous, or preferably by adding a concentrated aqueous solution of potassium permanganate to alumina, giving a paste which is then ground with an equal amount of copper sulfate pentahydrate. The substrate (2 mmol) is added to a portion of the oxidant (~4 g) in a 25 mL round bottomed flask and stirred magnetically until TLC analysis indicates a completed reaction. The residue is then washed with a minimum amount of solvent (methylene chloride, hexane and/or ether). Evaporation of the solvent gives a product that is of acceptable purity for most purposes. If greater purity is required, the product can be distilled. Tetrahydrofuran -> GBL (6h, 70% yield) 1,4-Butanediol -> GBL (14h, 95% yield) Entropy just isn't what it used to be.



		SPISSHAK (Hive Bee) 07-04-02 18:45 No 328769				Role of reagents in oxidation reaction?
						I was wondering what the role of copper sulfate and alumina served in this oxidation reaction? Inhibitors, accelerants, etc.? It's a given that the permanganate is the oxidizer.



		Antibody2 (Bee without a Title) 07-04-02 19:05 No 328776				the alumina is a solid support for the ...
						the alumina is a solid support for the permangnate, i've seen it employed in other KMnO4 oxidations. the copper i suspect is the catalyst all in all very OTC synth nice find Rhodium



		SPISSHAK (Hive Bee) 07-04-02 19:09 No 328778				Thanks antibody
						Thanks for straightening that all out in my feable little brain Anyway, do you know what direction the copper sulfate might take the oxidant(i.e. inhibitor, accelerant?). Thanks again.



		Trypstar (Stranger) 07-04-02 21:23 No 328817				Huh?
						Isn't this just https://www.rhodium.ws/pdf/solventfree.kmno4.oxidation.pdf which has been on your site for quite a while? I had the paper myself, but since it was on your site, I never posted it.



		Rhodium (Chief Bee) 07-05-02 03:13 No 328896				Oops, you're right...
						Oops, you're right... I had forgotten seeing that article before, as noone followed that reaction up after I put that PDF on my page... Entropy just isn't what it used to be.



		weedar (Hive Bee) 07-05-02 08:37 No 328978				But then...
						Yuo really should rate your post redundant? Weedar Weedar contains 2,4-D dimethylamine salt,apparently



		Rhodium (Chief Bee) 09-29-04 13:21 No 533747				THF --Mn2O7--> GBL (86%) (Rated as: good read)
						[Selective oxidation of organic compounds with Mn(VII) Oxide] Martin Trömel & Manuel Russ Angewandte Chemie 99(10), 1037-1038 (1987) (https://www.rhodium.ws/pdf/thf2gbl.mn2o7.pdf) 2 KMnO₄ + 2 H₂SO₄ -> Mn₂O₇ + 2 KHSO₄ + H₂O 3 THF + 2 Mn₂O₇ -> 3 GBL + 4 MnO₂ + 3 H₂O Mn(VII) Oxide To a stirred and cooled mixture of 24 mL H₂SO₄ and 100 mL anhydrous CCl₄, 16.3g finely ground KMnO₄ is added while keeping the temperature between 20-25°C. After stirring the solution for several hours, and the deep red red solution is decanted from the formed sediment and stored at 4°C. It is possible to prepare batches up to three times this size. Titration To determine the exact concentration, 0.3 mL of the above solution is mixed with 30 mL water and with stirring, 1.5g KI and 4 mL glacial acetic acid is added thereto. The resulting solution is then titrated with 0.100 M thiosulfate, each mL corresponding to 2.2 mg Mn₂O₇. Oxidation The [THF] is dissolved in an 1:1 mixture of acetone/CCl₄ (MeOAc & EtOAc also works), and after cooling to -45°C the Mn₂O₇ is added with stirring (0.7 molar equivalents as a 2.5% solution in CCl₄) at such a rate that the temperature does not increase above -40°C. After the addition, the solution is stirred for 5 min at -45°C and excess Mn₂O₇ is destroyed by the dropwise addition of IPA. The solution is allowed to warm to room temperature, the precipitated MnO₂ is filtered off and the solvent evaporated. The product is then isolated by vacuum distillation. Yield of GBL 86%. ^{The Hive - Clandestine Chemists Without Borders}

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