Glycin Synthesis/Production

Nikola Dulgiarov · May 19, 2013

So, I've had this idea in my head ever since I read about glycin and decided to try it as a developing agent. Originally, I tried to buy it from dealers in chemical reagents, only to discover prices in the range or $10-15 to the gram, shipping from Artcraft/Photoformulary is out of the question (I live in Bulgaria).
I do have p-aminophenol, which I mix Rodinal with; and from what I gather, hydroxyphenyl-glycine can be synthesized from it and monochloroacetic acid(MCA). My search did turn up one old thread there on APUG, but it had only references to science articles and no relevant experiences.
I have two of the articles outlined in the merck index, but they are somewhat vague as to procedure, focusing more on the structure and properties of the derivatives. What I have done, to no success, is to mix p-aminohenol and MCA in aqueous solution and reflux until dissolution and a color change.
However, instead of glycin, ongly slightly soluble in water, I get, upon cooling down to 0C, crystals that dissolve readily and respond to a test for paraamniophenol, suggesting presumably a conversion to the HCl salt.
Has anyone actually done this? I have no relevant experience in organic chemistry, besides very rudimentary reactions like nitrations, dehydrations, etc.
My chemistry teacher is also not too well acquainted (11-graders here learn nothing ). So anyone, who can chime in with some practical advice, I'd be deeply indebted . Also, if all goes well, I will post a detailed account and references, so that anyone else without access to glycin may try it out.
PS: I follow safety procedures, and I'm well aware of the toxicity of the compounds above, I have no intentions to harm myself in the process
Cheers,
Nick

Sal Santamaura · May 19, 2013

Nikola Dulgiarov said:
...11-graders here learn nothing ...

I have no knowledge about Glycin synthesis, but feel compelled to chime in. You clearly learned something, namely excellent English as well as the ability to think logically. Would that most US 11th graders possessed your skills in those areas!

Best wishes for success. The photography world needs a second source of Glycin; producing it could be a business for you.

Nikola Dulgiarov · May 19, 2013

Thanks Not to wander off-topic too much, but what I have noticed is that students worldwide are becoming more and more alike, mainly due to the spreading popularity of the internet as a means of communicating. But even with a sea of information at their fingertips, students would rather use the net for entertainment and socializing, but that is a whole 'nother story
Vis. my English... it's a necessity; knowing foreign languages empowers one so
I do mix developers and chemistry for friends who shoot film, but even at prices 1/2 of store ones, photochemistry is on the bottom of the shopping-priority-list of Bulgarians

Gerald C Koch · May 19, 2013

After a brief search on the net The only reference to a synthesis was that p-aminophenol and chloroacetic acid were allowed to react in a solvent. I assume that the solvent is not water. The solvent may have to be basic in nature to catalyse the reaction.

Since you have no experience in chemical synthesis I would strongly suggest that you do not attempt to make this chemical. If the solvent is the one I am thinking about then it is particularly nasty to work with.

So many photographers seem to be ignorant of the lesson of the marketplace. The reason why Glycin and other older developing agents are no longer used is that they did not provide an advantage to counter their increased cost.

Sal Santamaura · May 19, 2013

Nikola Dulgiarov said:
...I do mix developers and chemistry for friends who shoot film, but even at prices 1/2 of store ones, photochemistry is on the bottom of the shopping-priority-list of Bulgarians...

I was suggesting that, should you make Glycin available commercially, your market would be worldwide, not limited to Bulgaria. And you'd only have one competitor anywhere else on the globe!

Nikola Dulgiarov · May 19, 2013

The two solvents that I have seen referred to are water and diethyl ether, by Vater in 1888. Meldola in 1917 worked in aqueous solution with the addition of sodium acetate, although a particular reason was not disclosed. He claims precipitating glycin "after digesting a mixture of molar quantities of p-aminophenol and MCA in 20 parts water", but no times, temperatures or experimental setup beyond that are given.
Working in ether didn't yield a considerably different result, apart from a phase separation of the crystallization water of my chloroacetic acid. Upon evaporating the ether, needle-like crystals of pap.HCl still formed.
Just as I was speaking about language as empowering, I do have a request to make, a favor to ask anyone, who knows German, maybe also is aware of basic chemistry terminology. Vater's article is and old sca in pdf, OCR fails on it; I am unable to translate the full text, so I only have had a cursory idea of what it says. If anyone is willing to read through some pages that I need and interpret a passage or two, I would be grateful PM me if you you'd like to help, and I'll send you the pdf( I would upload it here, but since it's still copyrighted, I am unwilling to share it publicly; still, if you are interested in having the articles, feel free to contact me )
Sal, if my plan to enter a US institute of technology and study chemical engineering doesn't get derailed, I expect your suggestion to become more than viable

removed account4 · May 19, 2013

nikola

have you tried the people mentioned in this thread?
(there was a url link here which no longer exists)
or at fadu?
http://www.film-and-darkroom-user.org.uk/forum/showthread.php?t=5192

it might be easier to find a already made source rather than make it yourself,
from what i remember, it takes 2 weeks to manufacture from start to finish ...

good luck !
john

Nikola Dulgiarov · May 19, 2013

Thank you, John. I have seen the links and I have talked to suppliers and importers, who can offer me similar prices. The point of the whole endeavor, I am unwilling to admit, is to satisfy my own interest in chemistry, and to see if I can make a viable point. Purchasing it is the least worry I have, I stressed the price in my first point to kinda "justify" trying to do something that will eventually end up being more expensive and tiresome
You comment on the time it takes to make glycin makes me wonder if the conversion doesn't occur at a much slower rate than I had imagined (no more than 24hrs), much like Gainer's Metonal, or Rodinal itself, taking several weeks to reach stability. of course, the commercial process probably involves purification steps, such as recrystallization, sublimation, desiccating the final product (although that shouldn't take that long ). But there could be something to it.
I'll keep trying, keeping in mind safety and sanity

removed account4 · May 19, 2013

Nikola Dulgiarov said:
Thank you, John. I have seen the links and I have talked to suppliers and importers, who can offer me similar prices. The point of the whole endeavor, I am unwilling to admit, is to satisfy my own interest in chemistry, and to see if I can make a viable point. Purchasing it is the least worry I have, I stressed the price in my first point to kinda "justify" trying to do something that will eventually end up being more expensive and tiresome
You comment on the time it takes to make glycin makes me wonder if the conversion doesn't occur at a much slower rate than I had imagined (no more than 24hrs), much like Gainer's Metonal, or Rodinal itself, taking several weeks to reach stability. of course, the commercial process probably involves purification steps, such as recrystallization, sublimation, desiccating the final product (although that shouldn't take that long ). But there could be something to it.
I'll keep trying, keeping in mind safety and sanity

aaahhh, i geddit ..
totally understand the "i gotta try to make this stuff" point of view
i just wasn't sure if hadn't seen the other "pre made" alternatives.
i learned about the time period years ago when you could ask the good
folks at TPF to send you "the freshest - stuff" and they would say it takes 2 weeks
and at the end is when it is crushed .. i have no idea what it is, how it is made
or much else, it just seems to take its time ( drying out ? ) before it can be used.
and then it has to be used before it becomes use-less ..
have fun with your mad-science
john

Gerald C Koch · May 19, 2013

Some years ago a friend of mine was severely burned doing a routine synthesis that he had done many times before. On that particular day the reaction mixture decided to explode.

AS A TRAINED CHEMIST, I WILL SAY IT AGAIN -- UNLESS YOU HAVE A DEGREE IN CHEMISTRY AND ARE FAMILIAR WITH ORGANIC SYNTHESIS AND HAVE ALL THE NECESSARY EQUIPMENT INCLUDING AN EXHAUST HOOD DO NOT ATTEMPT TO MAKE THIS DEVELOPING AGENT OR ANY OTHER ONE.

I was suggesting that, should you make Glycin available commercially, your market would be worldwide, not limited to Bulgaria. And you'd only have one competitor anywhere else on the globe!

Encouraging someone to undertake a dangerous synthesis is really not being helpful.

Nikola Dulgiarov · May 20, 2013

Gerald, I am well-aware of the dangers in working with organic synthesis, Max Gergel's autobiography (Excuse Me Sir, Would You Like to Buy a Kilo of Isopropyl Bromide) has some vivid examples of reactions going awry and unexpected problems occurring. My interest in the aforementioned synthesis is theoretical, but I would like to see if it could be implemented in reality. I work in sub-gram quantities, under a fume hood, respirator and filters as per OSHA regulations (just that cost as much as the school's whole budget on chemicals last year ), so my safety shouldn't be your concern Whether I'll pursue the task any further is still vague

PhotoJim · May 20, 2013

Have you absolutely ruled out that Photographer's Formulary won't ship glycin to Bulgaria? It might be worth phoning them to see if there is any way to get it.

Alternatively if you investigated whether the chemical is legal to mail or fly with, perhaps if you know someone going to the United States or Canada soon, they could have the chemical shipped to them and then have it forwarded to Bulgaria (or bring it home on their flight).

Photographer's Formulary will ship glycin internationally, to Canada at least, so it's worth investigating. I buy 100 grams every few years to mix up nine litres of Ansco 130 stock solution. (And no, nothing else is like a glycin developer, so while the market has spoken, it has not spoken correctly from my perspective.)

Relayer · May 20, 2013

other thread about glycin: (there was a url link here which no longer exists)
and some info from last post maybe interesting for you:

I recieved the article over the computer network of the local univerity library. Her is the part, which relates to the synthesis of glycin:
... Vater CJ. pr. Chem., 1884 [ii], 29, 286) obtained this compound by digesting one molecular proportion of monochloro acetic acid with two molecular proportions of p-aminophenol and 20 parts of water. we found that a better yield was obtained by using molecular proportions of p-aminophenol (3g), monochloroacetic acid (2,6g), and sodium acetate (4g) in aqueous solution. The pink solid which separated was collected and crystallised from water, from which it separated only on stirring in a somewhat floculent form. (Found, N= 8,42. Calc., N= 8,39 per cent). ...

Nikola Dulgiarov · May 20, 2013

Yes, this is an excerpt from Meldola, et.al./1917. However, this is the only reference in the article as to procedure, and it's vague at best, as it only refers to "digesting" but no there is no further mention regarding temperature or time. A Kodak patent refers to a German one, in which it is outlined how to produce glycin, but I've had no luck finding it - it is German Patent 383,190, abstracted in Chemisches Zentralblatt, vol. 24, part I, page 1592. It refers also to an article by L. Galatis in Helvetica Chimica Acta 4, 574-9, (1921), which I don't have.
PhotoJim, I will in fact be purchasing glycin, regardless of whether I succeed or fail in its synth, which more or less a proof of concept I'm interested in. I was referenced to dealers in Europe who offer glycin at acceptable prices. I don't know yet....

Gerald C Koch · May 20, 2013

Nikola Dulgiarov said:
Gerald, I am well-aware of the dangers in working with organic synthesis, ... I work in sub-gram quantities, under a fume hood, respirator and filters as per OSHA regulations

Unfortunately there are others who are not as careful that may attempt a synthesis.

Nikola Dulgiarov · May 20, 2013

Yes, I was just reminded of the fact that I am not alone in such experiments. So, please do not view this as an encouragement to do things you're not fully acquainted with, as mr. Koch has so put it in a previous post. My primary concern is safety, success is far back in the list. If you want to use glycin, I recommend you buy it . After all, the price for the synth. reagents will get you enough glycin for the next decade . If in the end I am successful (a goal that seems distant so far), it will prove a concept, and nothing further. As a matter of fact, said concept has been proven, many times over, by the chemists at PF

eclarke · May 20, 2013

To take this on a moderate detour, I buy 3-4# a year from PF and store it in the freezer. It has lomg keeping qualities this way compared to keeping it on the shelf, stays white for a long time..

Photo Engineer · May 20, 2013

Nikola, Chloroacetic acid is extremely toxic even via what appears at the time to be mild skin contact: http://en.wikipedia.org/wiki/Chloroacetic_acid

The Formulary makes their own Glycin as the market is so small and the cost is so high. A trained lab worker can make it in a jiffy, but accidents do happen!

If you insist on going ahead, I suggest the 20+ volume set by Arnold Weissberger entitled "Synthetic Organic Chemistry" or something like that. It gives the exact method for making just about any common organic chemical. I studied those books for hours during my thesis work learning how to make some of the esoteric starting materials I needed for my research work.

Whatever you do, I strongly endorse what Jerry said, BE CAREFUL! You are playing out of the league of most everyone and are courting a serious problem. I wish you the best and remind you that if there is no market, then the chemical is not made, or if made it is very expensive.

PE

brianmquinn · May 20, 2013

Photo Engineer said:
Nikola, Chloroacetic acid is extremely toxic even via what appears at the time to be mild skin contact: http://en.wikipedia.org/wiki/Chloroacetic_acid

I work in a lab and have worked with Trichloracetic acid in the past often. Actually one time I had a co worker drop and break a 100 mL bottle of it outside of the hood and had to help clean it up. I am surprised that Chloroacetic acid is so much more toxic and am glad it was not that I had to clean up. The LD50 amounts to just a few mL absorbed through the skin.

Photo Engineer · May 20, 2013

Trichloroacetic Acid is used as an antiseptic by some dermatologists. It is not very toxic except it is good in promoting skin healing after minor surgery.

PE

Wayne · May 20, 2013

Nikola Dulgiarov said:
Has anyone actually done this? I have no relevant experience in organic chemistry, besides very rudimentary reactions like nitrations, dehydrations, etc.
My chemistry teacher is also not too well acquainted

Red flag red flag red flag. If you can't afford the shipping, can you afford the phone call to Montana? I know even less than you about organic chemistry (though I did somehow pull a "C" in college, and I gather you aren't there yet), but I've talked to Photographer's Formulary about the glycin manufacturing process a number of times and they impressed me on me what an unpleaseant, noxious and obnoxious process it is. They are the only ones who can really give you good advice about the process since they are the only ones doing it. Call them; all we can do is in the way of good advice is "uh...don't do it".

Alan Johnson · May 20, 2013

I have read "The Methylation of Para-Aminophenol by means of Formaldehyde" by Ernest Carl Wagner, available as a print on demand book, as one does.
My conclusion was that it would be difficult (and without a lab setup dangerous) even to make Metol from p-aminophenol.
Though Glycin from p-aminophenol is not discussed it's an interesting read.

Photo Engineer · May 20, 2013

Ok, I have had the privilege of watching them make Glycin at the Formulary. It is difficult and time consuming. And, it is a good thing that it sits on many acres of land and that there are no problems downwind!

This is NOT for the home chemist.

PE

Rudeofus · May 21, 2013

Photo Engineer said:
Trichloroacetic Acid is used as an antiseptic by some dermatologists. It is not very toxic except it is good in promoting skin healing after minor surgery.

A dermatologist knows a lot better how to apply this stuff safely than the bottle you accidently drop on your legs. According to Wikipedia, covering 6% of your skin in Chloroacetic Acid can kill you. Another thing that concerns me in these synthesis steps is the need for boiling Ether in sealed glass tubes. If one of these breaks for whatever reason, you might well have an uncontrolled fuel-air explosive going off right in your lab.

Nikola Dulgiarov · May 21, 2013

Yes, if the acid is 80% +, there is the risk of acute poisoning. However, a lab coat and gloves are sufficient to prevent problems with spillage, as you can easily take them off before the acid can seep through. Keeping some base to neutralize the acid and a first aid/poisoning kit is a must.
Boiling ether in a sealed glass tube sounds like the perfect mad-man suicide scenario , although small quantities and a water bath(heated by an induction heater) wouldn't be problematic.
The key, from what I have seen so far, is to find a salt to bind to the HCl produced during the reaction, yet something that would not react immediately with the monochloroacetic acid. I have found several suggestions, and recommended procedures, temperatures and times. This will remain in the theoretical stage until I am absolutely sure it is safe, and I won't be posting details, so as not to encourage pointless experimentation

Glycin Synthesis/Production

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