The Periodic Table

9-BBN

12:30 AM

My last think, thanks to @orthocresol and some search about how to make methanal

In the industry Formox process is used

What do you think @jerepierre ?

jerepierre

Sure there are tons of ways to go from an alcohol to an aldehyde. That would work.

Do you need to methylate urea from the beginning though? Perhaps urea can be reduced directly to methanol.

9-BBN

I don't know

I found somewhere this reaction

I'm not that good to make reaction drawing

jerepierre

This synthetic challenge is very unusual, and I think reducing urea (either directly or after derivitization) to methanol and then oxidation is a believeable answer.

I think the more interesting idea raised by the question is whether there is a way to replace NH2 (from a urea or from a primary amide, for example) with a hydrogen. I doubt that reaction has received much attention. I don't think it is a reaction that synthetic chemists (like myself) need very much.

9-BBN

I will edit my answer with that for the moment saying this is impossible to do E-C reaction with amide (good to know by the way)

This is really awkward to do this reaction just to make formaldehyde

jerepierre

Formally, it's a reduction. LAH is just about the most reactive reducing agent around, so that's not suitable. However, maybe someone is doing research on this type of transformation by some new catalytic method. I think that would be very interesting. And maybe very useful. I just can't think of a time I would need to do that.

9-BBN

12:39 AM

The good question like you said is is it possible to cut C-N bond to replace it by C-H. (I bet in one step in your mind?)

jerepierre

It may have been studied, but I don't know.

Good on you for trying to come up with an approach to this unusual question and improving your answer. Gotta run. Good chatting with you.

9-BBN

I will ask my last teacher of organic chemistry, he has a tremondous culture, if he gas idea.

Well I'm very curious in general of particular things

I have a good culture but unfortunately it works only in particular things haha

Also maybe protect the ketone with a diol might help ? don't know

I have a lot of idea on head. To bad that it looks to be impossible tomake ozonolysis with terminal alkene

Jan

The most important thing you have to remember about urea is that it is damn unreactive per se. It’s not only an amide, it’s a double amide. So that ketone is not going to do very many things.

9-BBN

I keep it in mind. Would it be possible to make E-C reaction on the urea with protected ketone or because of four heteroatoms on the C something else happends ?

orthocresol

if you can actually get to the acetal, I don't see why it wouldn't work. I'm just skeptical of whether you can actually get to the acetal. You're really insistent on Eschweiler-Clarke, eh?

9-BBN

12:50 AM

Yes I like to use methanal to synthesize itself next

:D

orthocresol

well... if you insist

lol

the thing is that if you want to put all four methyl groups on to make N,N,N',N'-tetramethylurea, you need 4 eq. of formaldehyde

and you're producing 1 eq. from the central carbon

9-BBN

But I want to propose something which will may work

@orthocresol yes I know :D that's why I wrote "awfully awkward" :P

orthocresol

so you have a net loss of 3 eq of formaldehyde lol

i guess, it could be useful if you have 13C- labelled urea or something like that..

i still think deprotonate - MeI is straightforward and pretty likely to work

Jan

It’s all a secret scheme to sell the synthesis to <insert evil regime of choice> hoping they will fall for it!

orthocresol

Monsanto

9-BBN

12:53 AM

Because this question is typically unusual maybe I can take in a second part of the answer all idea I had. For example use urea as catalyst if we say that ozonolysis was possible for terminal alkene

orthocresol

It's not a catalyst if it doesn't come out regenerated

9-BBN

Depend look

orthocresol

Jan did say the ozonolysis of a terminal alkene would make formaldehyde, so...

so I don't think you have an issue there

9-BBN

urea --> (Wittig with ethylene) ---> urea with C=CH2 instead of C=O then ozonolysis and you get urea again etc

orthocresol

I doubt that double enamine is going to survive.

Jan

12:56 AM

Urea won’t participate in a Wittig.

9-BBN

What i say is that I can tell about some idea I had and then said this is not possible

orthocresol

Idk, it's up to you.. it just feels like you're trying really hard to fit in E-C somewhere

9-BBN

To make a complete answer explaining why a lot of idea even if they looked to be great wouldn't have work

orthocresol

Which is fine, given that you have a paper on E-C alkylation of amides

So you don't need to find a workaround, if anything the N on urea is more nucleophilic than the N on a normal amide

Jan

However, Organic-chemistry.org suggests that Tebbe would work.

orthocresol

12:57 AM

Oh yeah! Tebbe works with amides.

Jan

I like Tebbe because of the metal complex it uses =D

9-BBN

Wouuuuhouuuu :P

orthocresol

Is it the one after activation with AlMe3?

Or just the Cp2TiCH2 :D

9-BBN

My favourite reactions are E-C, H-V-Z, and M-P-V reduction

orthocresol

Well, there was one time where I (for whatever reason) fell in love with the Morita-Baylis-Hillman.

9-BBN

1:00 AM

Also CH2N2 to make methylation without other product than nitrogen

orthocresol

For a month or so, I was desperate to devise some synthetic pathway involving it.

9-BBN

Haha

Jan

What distinguishes Morita-BH from BH?

orthocresol

Is there a difference? I don't know..

Jan

My PI suggested to use a Baylis-Hillman without electrophile to isomerise an enone xD

orthocresol

1:03 AM

As in cis to trans?

Jan

Another reaction I like is the Passerini. I’m kinda sad that using a Buchwald-Hartwig instead is so much better in my molecule =C

Yes.

Also, it’s more the binuclear Ti/Al complex.

9-BBN

I like Mitsonobu too

orthocresol

yup, that's the one :D

Never seen the Passerini before.

Jan

I’m trying to deduce what HVZ and MPV are o.o'

9-BBN

Meerwein–Ponndorf–Verley reduction

The Meerwein–Ponndorf–Verley (MPV) reduction in organic chemistry is the reduction of ketones and aldehydes to their corresponding alcohols utilizing aluminium alkoxide catalysis in the presence of a sacrificial alcohol. The beauty of the MPV reduction lies in its high chemoselectivity, and its use of a cheap environmentally friendly metal catalyst. Figure 1, Exchange of carbonyl oxidation states in the presence of aluminium isopropoxide. The MPV reduction was discovered by Meerwein and Schmidt, and separately by Verley in 1925. They found that a mixture of aluminium ethoxide and ethanol could...

orthocresol

1:05 AM

Hell-Volhard-Zelinski and Meerwein-Ponndorf-Verley

Jan

Aaaah, that makes sense xD

orthocresol

I hope I got those right

9-BBN

Yep

Jan

I thought he was Werley but obviously I was wrong …

orthocresol

Ah, Germans.

Jan

1:06 AM

Yeah, and by using the name Passerini I have given away that my target molecule contains an Amide O:)

orthocresol

I actually gave away my target molecules to Loong

Jan

Another one I like for its name is Nozaki-Hiyama-Kishi. It keeps reminding me of an anime:

anidb.net/perl-bin/animedb.pl?show=anime&aid=4121

9-BBN

And Yamaguchi

Jan

@orthocresol That’s okay. I’m sure @Loong knows everything about my lab work, too, by now.

orthocresol

;D

Jan

1:08 AM

Damnit, why are AniDB links not inline-expanded? =C

orthocresol

I've watched a total of... 3 or something series of anime.

Jan

The thing is, I attempted obfuscation O:)

orthocresol

Did it not work

Jan

The lab work or the link expansion?

9-BBN

What is this ?

orthocresol

1:09 AM

The obfuscation

Loong

@Jan …

Jan

@orthocresol Dunno, ask him xD

I mean … many of my questions are clues, obfuscation or not. My institute is a double clue …

I was just thinking of linking my thesis as soon as it’s accepted and everything … until I realised that only the g-block elements will be able to read it. And Aaron in a few years’ time.

orthocresol

starts learning German on Duolingo

Ich bin ein junge?

Jan

> Ich bin eine junge Robbe.

9-BBN

@Jan why do you speak of that anidb.net/perl-bin/animedb.pl?show=anime&aid=4121 and also about chemistry and your work? I don't see the relationship

orthocresol

1:16 AM

What's that o.o

I'm not cut out for languages :D

Jan

@9-BBN The anime connects to the Nozaki-Hiyama-Kishi coupling by also being named NHK (ni youkoso) ;)

@orthocresol I’m a young seal ;)

9-BBN

Oh ok

Chemists joke ^^

orthocresol

Ah :D

Jan

(For boy, you want to capitalise the J.)

@9-BBN Like the way I keep naming iodomethane Misty Mei after a character in a ~~hentai~~ anime.

orthocresol

Ah... goes back to Duolingo

9-BBN

1:19 AM

@Jan which one ? (no it's OK)

Jan

@9-BBN Why don’t you try to find out yourself? ;p

9-BBN

Because those things are not my cup of tea too. I prefer practice than watch. It may depends on people :P

Jan

Fun fact: enter it on AniDB, it only gives you a single hit xD

orthocresol

wtf

Jan

?

orthocresol

1:24 AM

> I prefer practice than watch. It may depends on people :P

time to sleep

Goodnight \o

9-BBN

@orthocresol don't you ? HA :)

Good night !

Think about Eschweiler-Clarke in your dreams

Jan

What a way to say ‘I don’t like where this conversation is going’ =D

orthocresol

I'm a seal. I'm not supposed to be exposed to this sort of thing..

:<

Jan

Reminds me of a video including penguins I heard of …

(Also, seals reproduce, too!)

orthocresol

Need to find another seal before that happens ^^

Jan

1:35 AM

And with that the seal disappered before any undesired further comments were uttered.

9-BBN

Well I'll continue later to update my answer. See you soon ! :-)

user228700

2:24 AM

Hey everyone :-)

user228700

I've a quick question. I'm trying to find the solubility (in terms of molarity) of a gas dissolved in water, using Henry's law. The number of moles of water hasn't been specified. Is it OK to use the arbitrary value of 1 L? That's what my textbook seems to have done, despite not mentioning anything and I'm not even blind, I've read the question multiple times!

Martin - マーチン

6:53 AM

@Kaumudi seems like you might probably want to ask a question on main about that

@Jan tbh though... you never finish the introduction :/ At one point you just need to stop. I also made the mistake of writing that first, while all my colleagues said: do that last so you don't spend too much time on it... But congratz on the progress! Don't forget to have some fun inbetween...

user228700

7:19 AM

@Martin-マーチン Oh, really? Sounded a tad bit homework-tsy...no?

Martin - マーチン

well homework doesn't mean bad...

just make sure you include your research, the original question and what your issue with the concept is

it's a plus if its nicely formatted

I like well researched hw questions, and this one seems to have merit for future visitors

user228700

Erm, what can I include as my "research"?

Martin - マーチン

7:50 AM