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All 8 posts Subject: One-pot Reductive Nitromethylation of Aldehydes Please login to post Down

Rhodium
(Chief Bee)
06-27-03 10:02
No 442875
User Picture       One-pot Reductive Nitromethylation of Aldehydes
(Rated as: excellent)

One-pot Reductive Nitromethylation of Aldehydes

R-CHO -> R-CH₂CH₂NO₂ (One Pot, 70-90% yield)

Fluoride ion catalyzed condensation of aldehydes with nitromethane to form the beta-nitroalcohol, followed by acetylation and reduction of the beta-nitroacetate with sodium borohydride to form the nitroalkane in 70-90% overall yield.

Tet. Lett. 3219-3222 (1978) (https://www.rhodium.ws/pdf/aldehyde.reductive.nitromethylation.pdf)

(The reference originally found here: Post 371253 (Barium: "Hey Ritter old chap!", Novel Discourse))

Kinetic
(Hive Bee)
06-28-03 00:37
No 443022
      Very nice

This will make a welcome addition to Post 367468 (Regis: "The most interesting CTH reaction ever documented?", Novel Discourse); in fact, I've just noticed Barium refers to it in that same thread: Post 371253 (Barium: "Hey Ritter old chap!", Novel Discourse). This route seems very promising indeed. I wonder if it'll work on acetophenones? smile

It may also be worth trying CsF as the catalyst - from the Synthesis article cited by GC_MS in the above thread, both CsF and RbF are more active than KF as catalysts - RbF slightly more so, but it's cost probably outweighs the increase in yield.

Aurelius
(Active Asperger Archivist)
07-02-03 15:02
No 443995
      Your page

Hey Rhodium, don't you already have a pretty impressive list of references regarding this reaction? If so, please include this one in that list.

Act quickly or not at all.

Rhodium
(Chief Bee)
07-02-03 15:31
No 444001
User Picture       Nitromethylation

Yup. I will - and I must say that I totally missed the connection betwen this article and the excerpt in Barium's post as I found this independent of that. I must have been tired when reading Barium's post.

hest
(Hive Adickt)
07-02-03 17:52
No 444028
      Mescaline

Made an eksp. with 3,4,5-trimethoxy-benzaldehyde, 2 mole nitromethane, in 2-propanol and some KF. Yeald under 50%, the rest was starting material.

Rhodium
(Chief Bee)
07-02-03 18:18
No 444041
User Picture       3,4,5-TMB is a notoriously bad substrate

Nice that you tried it out! As you got the remaining 50% back as unreacted starting material, then at least it is selective for the nitroalcohol and does not give the alkene under these conditions. By avoiding the nitrostyrene, the borohydride reduction will not cause the formation of any dimers through michael addition.

3,4,5-TMB is a notoriously bad substrate in the Henry reaction with many catalysts, EDDA gives 15-30% yield if I remember correctly. If you try another substrate I'm sure it will go much better.

hest
(Hive Adickt)
07-03-03 14:30
No 444229
      I'm sure you right Rhodium, but as you ...

I'm sure you right Rhodium, but as you know3,4,5-TMBA is one of the reaction's I would love to gain betteher yeald from. I'll give 2,5-dimethoxybensaldehyde a shot tomorrow.

hest
(Hive Adickt)
07-10-03 11:03
No 446151
      Result's

And the resul't was the same as last time. Approx. 50% of the 2,5-DMBA reacted with the nitromethane after 12 houers.

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	All 8 posts		Subject: One-pot Reductive Nitromethylation of Aldehydes		Please login to post		Down


		Rhodium (Chief Bee) 06-27-03 10:02 No 442875				One-pot Reductive Nitromethylation of Aldehydes (Rated as: excellent)
						One-pot Reductive Nitromethylation of Aldehydes R-CHO -> R-CH₂CH₂NO₂ (One Pot, 70-90% yield) Fluoride ion catalyzed condensation of aldehydes with nitromethane to form the beta-nitroalcohol, followed by acetylation and reduction of the beta-nitroacetate with sodium borohydride to form the nitroalkane in 70-90% overall yield. Tet. Lett. 3219-3222 (1978) (https://www.rhodium.ws/pdf/aldehyde.reductive.nitromethylation.pdf) (The reference originally found here: Post 371253 (Barium: "Hey Ritter old chap!", Novel Discourse))



		Kinetic (Hive Bee) 06-28-03 00:37 No 443022				Very nice
						This will make a welcome addition to Post 367468 (Regis: "The most interesting CTH reaction ever documented?", Novel Discourse); in fact, I've just noticed Barium refers to it in that same thread: Post 371253 (Barium: "Hey Ritter old chap!", Novel Discourse). This route seems very promising indeed. I wonder if it'll work on acetophenones? It may also be worth trying CsF as the catalyst - from the Synthesis article cited by GC_MS in the above thread, both CsF and RbF are more active than KF as catalysts - RbF slightly more so, but it's cost probably outweighs the increase in yield.



		Aurelius (Active Asperger Archivist) 07-02-03 15:02 No 443995				Your page
						Hey Rhodium, don't you already have a pretty impressive list of references regarding this reaction? If so, please include this one in that list. Act quickly or not at all.



		Rhodium (Chief Bee) 07-02-03 15:31 No 444001				Nitromethylation
						Yup. I will - and I must say that I totally missed the connection betwen this article and the excerpt in Barium's post as I found this independent of that. I must have been tired when reading Barium's post.



		hest (Hive Adickt) 07-02-03 17:52 No 444028				Mescaline
						Made an eksp. with 3,4,5-trimethoxy-benzaldehyde, 2 mole nitromethane, in 2-propanol and some KF. Yeald under 50%, the rest was starting material.



		Rhodium (Chief Bee) 07-02-03 18:18 No 444041				3,4,5-TMB is a notoriously bad substrate
						Nice that you tried it out! As you got the remaining 50% back as unreacted starting material, then at least it is selective for the nitroalcohol and does not give the alkene under these conditions. By avoiding the nitrostyrene, the borohydride reduction will not cause the formation of any dimers through michael addition. 3,4,5-TMB is a notoriously bad substrate in the Henry reaction with many catalysts, EDDA gives 15-30% yield if I remember correctly. If you try another substrate I'm sure it will go much better.



		hest (Hive Adickt) 07-03-03 14:30 No 444229				I'm sure you right Rhodium, but as you ...
						I'm sure you right Rhodium, but as you know3,4,5-TMBA is one of the reaction's I would love to gain betteher yeald from. I'll give 2,5-dimethoxybensaldehyde a shot tomorrow.



		hest (Hive Adickt) 07-10-03 11:03 No 446151				Result's
						And the resul't was the same as last time. Approx. 50% of the 2,5-DMBA reacted with the nitromethane after 12 houers.

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