Sciencemadness Discussion Board - Simple Ideas in Organic

Simple Ideas in Organic

mewrox99 - 25-5-2011 at 02:49

Hello.

I am curious about some simple (and relatively) simple organic experiments to try. I do not have any distill apparatus. I also do not want to use anything too toxic.

Not anything super simple like making ethyl acetate in a test-tube or oxidizing ethanol with dilute H+/Cr2O7{-}

I've thought of isopropyl nitrite as a simple synthesis but its vasodilator propitiates I'm not interested in and sound unpleasent (headache)

What other simple ideas are they? I don't have anything too exotic but I have:

Simple inorganic chems (conc, H2SO4, HCl, HNO3, NaOH, NaHCO3, Na2CO3, NaNO3)

Ethanol

Ethanoic Acid 100%

Citric Acid

Urea

Acetone

And I can probably buy methanol on trademe
and on eBay they are some organic solids like sodium benozate, benzoic acid, phatlic acid I can get

Nicodem - 25-5-2011 at 12:44

If you have no equipment, then you can only do preparative reactions that give solid products which can be purified by recrystallization. This narrows down mostly to heterocyclic chemistry as the field most rich in solid products that don't require chromatographic separation.

Nicodem - 28-5-2011 at 02:04

Given that you have nitric acid, you could do the oxidation of toluene with dilute aq. HNO3 (UTFSE for the references, there is a dedicated thread and experiments on the related xylenes oxidation). You did not list to have toluene available, but you can just buy it in a hardware store (unless things are different in your location). You only need a reflux setup which can be improvised and you can use an air cooled condenser for aq. reflux. Benzoic acid is a solid product, so you can purify it and characterize it easily without any special technique other than recrystallization and m.p. measurement. It is also an acid forming water soluble salts, so it can be first purified from non-acid impurities by extraction techniques (if required).

From this, you can prepare m-nitrobenzoic acid: "m-Nitrobenzoic acid can be prepared by the nitration of benzoic acid by means of nitric acid,1 a mixture of nitric and sulfuric acids,2 or mixtures of nitrates and sulfuric acid;3 all these methods lead to the production of a mixture containing principally the m-nitrobenzoic acid with a smaller proportion of the ortho and 1–2 per cent of the para isomer. " (from Org. Synth.) There references 1, 2 and 3 given are:
1. Mulder, Ann. 34, 297 (1840); Hübner, Ann. 222, 72 (1884).
2. Gerland, Ann. 91, 186 (1854); Varma and Kulkarni, J. Am. Chem. Soc. 47, 143 (1925).
3. Gerland, Ann. 91, 185 (1854); Liebermann, Ber. 10, 862 (1877).
(This way you will also learn how to read scientific literature - use our References section if you have no access to any scientific library or access to the publisher's site. You will also experience some german literature - a very important skill for organic chemists. Consider also that there must be more recent examples described in the literature - thus you can learn the literature searching skills, which are probably the most important skills for any scientist.)

According to Org. Synth., the nitration of benzoic acid is not as clean and good yielding as the nitration of its ester, but for your use it is more convenient.

m-Nitrobenzoic acid can be used for a plethora of further reactions so that you can actually build upon a multi-step synthesis of an end target as you go, gaining a lot of knowledge and experience for further work. Of course, this is just an example of a plan. You can do whatever else, but you listed just five organic compounds from which you can barely prepare anything solid. Acetamide and some citric acid derived products are solid (there is a dedicated thread, so UTFSE), but all but citrazinic acid and its amide require a vacuum distillation setup. If you don't like this plan, you can use other organic starting material available OTC (paracetamol or eugenol for the chemistry of phenols, vanillin for aldehydes, aspirin, naproxen or ibuprophen as carboxylic acids, pinenes as alkene, etc., etc.).

Nonpreparative experiments in organic chemistry are rarely a possibility for the amateurs, because they generally require access to GC, HPLC or spectroscopic equipment (and often the use of authentic standards). This is because there are rarely any interesting and characteristic visual changes to be observed. Some reactions give products of characteristic smell (like various esters), colors (like reactions of phenols with various reagents), gas evolution (CO2, N2), phase separation (precipitation, crystallization or oiling out) but in general, for non-preparative chemistry, the inorganic experiments are much more fun.

Nonobligatory advices:

If you want people to think you are at least somewhat experienced in chemistry, you should not call acetic acid as "ethanoic acid". Only total beginners do that. It is disrespectful for the history of chemistry (it is an "standing on the shoulders of giants" issue). It is as improper as calling toluene "methylbenzene". You just don't do that if you are respectful of chemistry as a science (it also shows that you have sovereignty over IUPAC rules - which do allow trivial names based on arbitrary decision).

Read Vogel's or Organicum before you start practicing organic chemistry. I see many beginners don't do that (as it is so bloody obvious), but you simply have to or else you remain totally ignorant of the most basic org. lab techniques needed to do anything properly.

Always read on the theory and mechanism involved of any reaction you are planing. This way you not only learn, but also understand what can go wrong and why something went differently from what you expected. This way you also learn how to improvise, for example, if which solvent, catalyst or reagent can be changed with what you have (an issue very important for amateurs!). It is also important for safety reasons (runaway reactions, scale up behaviour, (geno)toxic intermediates, etc.).

Always test the reactions on <10 mmol scale first and observe the exotherm, gas evolution and phase behavior. Scale up based on what you learned.

Never neglect the power of stirring, especially in multiphasic reactions. Build yourself a good magnetic stirrer for small scale experiments.

Buy or make some TLC plates if you are seriously getting into organic chemistry experiments.

peach - 28-5-2011 at 05:24

I think you are seeing a generation gap difference here Nicodem.

The younger people are hammered into not using 'slang' but the IUPAC name. Conversely, they'll see acetic as beginner terminology. Personally, I'm well stuck in the middle of the metric to imperial swap and find it annoying when people spell it sulfur or aluminum, as I find it disrespectful to the English language.

In terms of organic chemistry, you are really going to benefit from being able to at least reflux something. Add a few bends so you can distil it and you've got lots more options. There are some seriously cheap kits available on eBay from China. Glass can cost an fortune for the really specific things (there are standard items that cost a few thousand dollars each), but refluxing and distilling are easily the most common. Filtration is also useful, but coffee filters work remarkably well - I still use them rather than the sintered glass if the thing I'm filtering isn't critical. Saves doing the washing up.

Have you tried acid base extraction and recrystallisation of organics? That's a fairly important skill and using a natural source for the organic material makes it harder than it would be for the results of a glass reaction. The natural product will inevitably contains a lot of 'junk' that's going to try following your product round. So getting a pure white, crystalline solid is an achievement. With all the waxes, fats and oils in natural products, they also form persistent emulsions quite easily, meaning you have to get used to gauging when it's about to turn into milk rather than going straight to shaking the ass out of a funnel.

Even doing this simple operation, you will probably have to resort to letting your solvent boil off into the atmosphere, never to return, because it'll be difficult catching it again without some form of still.

And if you think it's too simple, I can assure you I've spoken to someone doing a degree in chemistry who couldn't manage it, even when given precise instructions.

Never underestimate the power of small scale reactions. It's quite possible to overtake people using bigger glassware because they're so busy messing around with setting it up and trying to stop things bumping or splashing around. It is without any doubt easier to vastly overtake them, and for a lot less money, in terms of actual experimentation, as the volumes are smaller, less is needed to get the answer.

This kit is about $160.

I have something very similar and use it far more regularly than the 2l flasks.

Me checking an organic actually works and how it behaves with a tiny flask. Does it foam up? Get too hot? Fume too much to be left open?

Yes to the latter. It'd have been crazy on a litre scale. I now have the answer and enough of the product to test it's own properties or use it for something else. This experiment is also answering another question related to the ethanol I used, which I cleaned up using Squirrel Science's method. The question being whether or not it's usable in organic reactions as a reagent.

I had already tried this reaction using a different method, and it went horribly. None of what made it horrible was mentioned in the texts describing it; it got extremely hot, thermally ran away, boiled it's self and then foamed out of the flask. Meaning it was well worth my while trying it with smaller amounts first.

This is the end of a weeks worth of week, with 3l of benzene going through some bigger glass. There's no point me making the product above on this scale, because it'd cost about hundred pounds just to fill the flask up and I have no use for a litre of the result. I made so much of the benzene because it's so toxic and messy I didn't want to have to repeat the process by which it was made.

[Edited on 28-5-2011 by peach]

mewrox99 - 31-5-2011 at 04:24

Distillation wise in NZ I would see ordering glass from china as risky because here we need a EUL to have it and the importation will be another great "intercept" for the NZ customs force.

But I might just bite the bullet and go through with the End User License all the NZ glassware sites use (I'd rather choke than order from Labwarehouse though). Like seriously what's the worst which could happen. A cop ringing.

Back on topic. If I do get some distallation equipment then they would be plenty to do.

I'll start with a good fischer esterification like making CH3COOEt. And since I love the smell so much Methyl Salicylate.

The WiZard is In - 31-5-2011 at 06:18

Quote: Originally posted by peach

I think you are seeing a generation gap difference here Nicodem.

The younger people are hammered into not using 'slang' but the IUPAC name. Conversely, they'll see acetic as beginner terminology. Personally, I'm well stuck in the middle of the metric to imperial swap and find it annoying when people spell it sulfur or aluminum, as I find it disrespectful to the English language.

I think — He doth protest too much.

Cribbed from the OED
-------sulphur (_________), n. Forms: 47 sulphre, 57 sulphure, 5, 7, 9 (now U.S.)
sulfur, 67 sulpher, (4 sou(l)fre, soulphre, 5 solfre, 6 sulfure, sulfre, sulphyr, 7 sulfer),
5 sulphur. [a. AF. sulf(e)re (12th c.), OF. (mod.F.) soufre (from 13th c.) = Pr. solfre solpre,
sulpre, It. solfo, zolfo, OSp. çufre, Pg. xofre (also, with Arabic article prefixed, OSp. açufre,
Sp. azufre, Pg. enxofre):–L. sulfur(em), sulphur(em), whence also Du. sulfer, solfer.]

Sulfur is da' American spelling. You know the people who use the Non-IUPAC
spelling of aluminium. Then some leave the "a" out of archaeology.

Hackh's Chemical Dictionary 2nd ed. 1937 notes:—sulfur is the spelling adopted by the
American Chemical Society, and the Pharmacoæia of the United States XI.

In the 4th ed of the Merck Index [1930] it's sulphur. In the 5th ed. [1940] it's sulfur.

Aluminum without the I is the current American spelling.
And why were have stumbled here - what happened to the I in
platinum and another metal or two I cannot bring upon my mind at
the moment.

I would start the Society to have all metal names end with
ium . However, I am up against history and the IUPAC
which reapologizes older usage, e.g., Bi vs Di.

"The only generallity to be made about names for the elements
is that the ending -ium (-um in three instances) usually indicates
a metal. Helium, selenium, and tellurium are exceptions and a
number of metals do not have names ending in -ium or -um,
even in alternate forms (examples: bismuth, nickel, and zinc.)"

Block, Powell, Fernelius
Inorganic Chemical Nomenclature : Principles and Practice
ACS 1990

--
donald j haarmann — colophon

[Edited on 31-5-2011 by The WiZard is In]

Nicodem - 31-5-2011 at 07:49

Quote: Originally posted by mewrox99

I'll start with a good fischer esterification like making CH3COOEt. And since I love the smell so much Methyl Salicylate.

Didn't you say you can only do syntheses that don't require the use of a distillation setup?

peach - 31-5-2011 at 08:15

Quote:

But I might just bite the bullet and go through with the End User License all the NZ glassware sites use (I'd rather choke than order from Labwarehouse though). Like seriously what's the worst which could happen. A cop ringing.

Back on topic. If I do get some distallation equipment then they would be plenty to do.

He's putting his life out on the line and ordering some glassware.

Some sites in the UK use EUL's. Others, like Sigma and Cole Parmer, won't discuss public accounts (it's VAT code or nothing). Others still don't bother with any of it, but sell more mundane things. It's not against the law to sell things here without the EUL or VAT codes, but it's the easiest way to demonstrate that you vet customers in some way other another.

Are you sure EUL's are a mandatory requirement in NZ? I'd post you the stuff myself but you'd get destroyed on the postage and UK VAT / Exchange / Duty charges (they are extremely high).

So long as you're not running a mega drug / bomb lab, order it up! If you're worried, call customs first and say you'll be importing a chemistry set and ask if it'll get stopped or what you need to sort out. It's always a good idea to record these kind of calls, or at least note down roughly what was said, the date and who you spoke to. It's far more suspicious when you try to sneak things past companies and customs than just outright saying what you want to do and asking what needs to happen.

[Edited on 31-5-2011 by peach]

mewrox99 - 31-5-2011 at 17:09

@Nicodem

I meant if I got distill stuff I'd try CH3COOEt. Afaik It isn't too risky to distill except it's rather flammable.

@Peach
How am I putting my life out on the line? Are you referring to that Iodoform scare. Because I heated the chloroform contaminated iodoform directly pretty much zero phosgene is produced. I've decided to be a lot more careful after that and only try synthesises at test tube scale, unless it's something I've checked out. I've made a few really stupid mistakes but I would disagree I'm putting my life on the line. Then again one stupid mistake is all it takes

DJF90 - 31-5-2011 at 19:45

He was being sarcastic (to a degree), and referring to your intended purchase of glassware.

Ozone - 31-5-2011 at 20:18

I would have tried to keep it to the "birds and the bees", but as it stands, IUPAC is horse-shit* for conversation, or most discourse between practitioners (yes! Trade Language!)...A structure will be unambiguous. For a computer model...It is the bee's-knees. While IUPAC allows us to enter a name and have a program produce a structure with reasonable fidelity, it's regular use with colleagues is probably bull-shit.

YMMV.

The issue of scale is a serious issue, however. It really sucks to take a product that took a week to prepare and blow it all over the inside of a hood on the next step...

Cheers,

O3

* could you imagine a conversation involving the IUPAC name for sucrose?

mewrox99 - 1-6-2011 at 00:49

Dave: John, this coffee is awfully sweet; what did you put in it.
John: About 5.00g of (2R,3R,4S,5S,6R)-2-[(2S,3S,4S,5R)-3,4-dihydroxy-2,5-bis(hydroxymethyl)oxolan-2-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol
Dave: What!?
John: Hmm, prehaps I should have used (2R,3S,4R,5R)-2,3,4,5,6-Pentahydroxyhexanal
Dave:

peach - 1-6-2011 at 05:24

It's a good point that, whilst they'll try to enforce IUPAC names for more basic things, the teacher would probably get all annoyed if I'd used the full IUPAC names for everything at school. I got told off for using phase angle and degrees when describing how two waves in a question were out of sync in GCSE physics.

"Got to stop reading ahead of yourself!"

What a splendid inspiration to continue my education.

The answer was correct.