[Fluorine]

I was wondering if this was possible whether by ozonolysis, potassium permanganate, or other. Is there any reaction that will split C=N bond to yield carboxylic group and some type of nitrogen on the other?

[sjb]

I was wondering if this was possible whether by ozonolysis, potassium permanganate, or other. Is there any reaction that will split C=N bond to yield carboxylic group and some type of nitrogen on the other?

Well, presumably you can reverse the imine formation and trap the amino aldehyde somehow. Then I think you can oxidise the amino group to the nitro group and the aldehyde to the acid..?

[Fluorine]

Sorry I didn't understand what's happening in your first sentence.

How about ozonolysis with oxidative work up? Is there any obvious/immediate reason why it wouldn't work? I found only one article discussing anything similar my inquiry and even then it's quite unrelated. Here's an excerpt;

Ozonolysis of 1a,b in the Presence of an Imine. Ozonolysis of 1a in the presence of diphenylmethyleneaniline (13a) is representative. A mixture of 1a (232 mg, 2mmol) and 13a (mg, 1mmol) in CH₂Cl₂ (15 mL) was treated with 2 mmol of ozone at -70 ºC. After evaporation of the solvent, the crude products  were triturated with methanol to give methyl 3,3,4-triphenyl-dioxazolidine-5-carboxylate (14a): mp 125-129 ºC (from ethyl acetate-hexane); 1H NMR 6 3.87 (s,  3 H), 5.88 (s,  1 H), 7.2-7.8 (m, 15 H); IR (KBr) 3060, 1755, 1602, 1502, 1450, 1358,1205, 1175,1042, 955, 748, 692 cm-1. Anal.  Calcd for C₂₂H₁₉NO₄: C, 73.12; H, 5.30;  N, 3.88. Found: C, 72.77; H, 5.38; N, 3.89.

Source: J. Org. Chem., 1993, 58 (16), pp 4212–4218

If I understood correctly;


Any help or direction is appreciated. The main purpose is to split the cyclic imine whether forming an amine, N-hydroxyl, or nitro with aldehyde or carboxylic acid. It can be worked with from there, though nitro/carboxylic is preferred.

[Honclbrif]

I think you'd probably get a nitroso out of it. Don't know much at all about nitroso chemistry myself though. Presumably they can be oxidized to a nitro, but I don't know how easily or safely.

If I needed a nitro there I'd be thinking about some sort of nitroaldol-like chemistry.

[Fluorine]

Thanks I'll read into your discussed topics/reaction.

[Fluorine]

A friend suggested imine hydrolysis which seems to be the 'gentler' approach than my initial suggestions. If anyone sees a fault in this please let me know otherwise thanks for the feedback given.


Hydrolysis of imines and related compounds

[orgopete]

I was going to second Honclbrif's suggestion, but the suggestion of hydrolyzing the imine to an amine makes me wonder what it is you are trying to do. An amine and a nitro compound are quite different, but I don't know whether either are what is wanted. How about an aminoacid as the ammonium salt or the aminooxime?

[Fluorine]

The reaction wouldn't end here which might be why there is confusion.

The nitro group should prevent the unwanted reactions an amine would have interfered with and an amine could be protected or if necessary converted to nitro. The purpose was to find a convenient way of breaking an imine (or cyclic imine). If hydrolysis of imine is a plausible choice I'm glad though if other methods of cleaving C=N in similar fashion are known they are also welcomed.

[sjb]

As I see it, the imine formation is reversible, so I don't know if you can get this to go backward and trap the amino aldehdehyde? I think you may be better going for reductive cleavage to the amino alcohol, as both aldehyde and acid will react with the amine, then perhaps oxidising both amino group and C-O group at once? Seems to be perhaps some useful material in the preview I'm getting from Google books for "The nitro group in organic synthesis" by Noboru Ono..

[orgopete]

The reaction wouldn't end here which might be why there is confusion.

The nitro group should prevent the unwanted reactions an amine would have interfered with and an amine could be protected or if necessary converted to nitro. The purpose was to find a convenient way of breaking an imine (or cyclic imine). If hydrolysis of imine is a plausible choice I'm glad though if other methods of cleaving C=N in similar fashion are known they are also welcomed.

Helpful, but not by a lot. I was already guessing that was the case. I would have suggested to just do your next step, but I don't know what it is. I don't know if you are trying to derivatize the amine or the aldehyde. I really kind of liked the oxime (if it can be formed and isolated?) as it can be converted to a carboxylic acid (without oxidation) or back to an aldehyde if needed.

[Fluorine]

orgopete: I've been taught almost nothing about oximes in general which is why I can't jump to the idea yet. Imines we learned in organic a bit, oximes we barely brushed over. I'm open to any reading material regarding these topics or organic synthesis in general. I feel like OChem. just barely gave me tools for synthesis which disappoints me. This is the only unfamiliar part of the synthesis route, the rest is applying concepts I've learned in most effective manner.

sjb: This is a bit beyond my current knowledge of chemistry so unfortunately I cannot bounce ideas back. I'll need to read into the topics mentioned so far but I do appreciate it - thanks!

[Honclbrif]

Fluorine: you keep switching things around and I'm unclear on what your goal is. Are you just trying to open this ring at any cost? Do you want an amine, a nitro, an aldehyde, a carboxylate? Are you just interested in immine hydrolysis? What bonds are you trying to break, and what type of functionality would you like to get out of this?

[Fluorine]

Honclbrif: I apologies for any lack in clarity from my end. This is the first step in a synthesis route I thought of so depending on what is yielded depends on how I would adjust what follows. I'm mostly concerned with cleaving the C=N and if it yields anything between alcohol and amine to carboxylic and nitro these could be worked with as they are 'synthetic equivalents'. The reason I chose carboxylic and nitro is because carboxylic could be selectively reduce and the nitro would remain until it was 'safe' to be reduced as well.

As for the imine hydrolysis I didn't mean to sneak this in, it was brought to my attention after I asked the question. From what I understood it cleaves the C=N into an aldehyde and amine respectively and with the simplicity/cost effectiveness so it seemed like a great alternative approach to what I initially suggested. I'm not necessarily looking for imine cleavage at any cost but I would interested in other methods.