ADOX MCC in Ansco 130

gerich · 2014-03-20T11:02:30+00:00

Hallo, ich hätte das MCC gerne in den hellen Tönen leicht wärmer. Hat jemand schon das Ansco 130 Rezept (Metol, Hydrochinon, Glycin) Rezept mit diesem Entwi...

gerich

Hello, I’d like the MCC to be slightly warmer in the highlights. Has anyone tried the Ansco 130 formula (Metol, hydroquinone, glycine) with this developer? Formula: Water (125°F) . . . . . . . . . . . . . 750 ml Metol . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2 g Sodium sulphite (anhydrous) . . . . . . . . . 50 g Hydroquinone . . . . . . . . . . . . . . . . . . . . . 11 g Sodium Carbonate (Monohydrate) . . . . . 78 g Potassium Bromide . . . . . . . . . . . . . . . . 5.5 g Glycine . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 g Cold water to make . . . . . . . . . . . . . . . . 1 litre Use undiluted for high contrast. Dilute 1:1 for normal work. Produces neutral tones on bromide papers. As I don’t have any glycine and can hardly find it in Germany—or rather, it is very expensive in small quantities—I have found the following synthesis method: mix 3 g p-aminophenol + 2.6 g monochloroacetic acid + 4 g sodium acetate in an aqueous solution, decant the precipitate and allow it to crystallise. This is supposed to be glycine. I haven’t worked out the molar ratios yet, but I assume they are equimolar. Does anyone know where one can buy p-aminophenol and monochloroacetic acid cheaply (quantities of approx. 500g)?

jochen53

Hello, In the VWR (Merck) catalogue, 1 kg of chloracetic acid for synthesis (item no. 800412.1000) costs €25.70. 1 kg of 4-aminophenol for synthesis (item no. 800421.1000) costs €73.20, and 250 g (800421.0250) costs €22.30. 1 kg anhydrous sodium acetate, for analysis (item no. 106268.1000) costs €60.50, 250 g €23 (106268.0250). € However, if you are not a commercial customer with specialist knowledge but a private individual, you will not be able to obtain the chemicals. You would need to know someone in the chemical industry or a pharmacist who could order it for you. For example, the medicine paracetamol is produced from 4-aminophenol. May I ask where the synthesis procedure comes from? It seems very rudimentary to me.

gerich

Thanks, I’ve since discovered VWR; they have a minimum order value of €100. Fisher Scientific is a bit cheaper, but I need to wait for the registration confirmation email to see if they have a minimum order quantity as well. I’ve registered a company and have already placed orders with chemical suppliers from time to time. ? I found the synthesis a while ago in an older book. The copy is in the lab; I’ll post the title and the full procedure when I get home. Is there a more up-to-date synthesis procedure?

Gast

http://www.moersch-photochemie.de/content/rohchemie € I’ve ordered from Suvatlar many times before, and it’s always been hassle-free. They stock Glycin-Photo in 25g packs. € Best regards, Wolfgang

gerich

Thanks for the tip, but that’s what I meant by ‘very expensive in small quantities’ – €31.54 for 25g. A litre of Ansco 130 working solution contains 5.5g of glycine, which works out at €6.69 for the glycine alone; the residue is negligible in terms of cost. In America, a pound costs about $79. If the synthesis were really as simple as described in the old text, it would be even much cheaper to produce yourself. Here is the text. Unfortunately, I didn’t note down the exact source details on the copy: ? Title: Asymmetric Quinquevalent Nitrogen Compounds III. p. 551 ff. ? Experiments on the preparation of asymmetric quinquevalent nitrogen compounds. Part III. Hydroxyphenylglycine. By (the late) Raphael Meldola, Henry Stennett Foster and Rainald Brightman. ? p. 552, para. 2 Experimental ? p-Hydroxyphenylglycine ? Vater (J. pr. Chem., 1884, (ii), 29, 286) obtained the compound by digesting one mole of monochloroacetic acid with two moles of p-aminophenol and 20 parts of water. We found that a better yield was obtained by using molar proportions of p-aminophenol (3 g), monochloroacetic acid (2.6 g) and sodium acetate (4 g) in aqueous solution. The pink solid that precipitated was collected and crystallised from water, from which it precipitated only when stirred, in a somewhat flocculent form. (Found, N=8.42. Calc., N=8.39 per cent.) .... ? At the end of the paragraph it says: Finbury Technical College (Received, 25 April 1917.) ? I am not yet clear what N=8.42 or N=8.39 per cent means. ? Have a lovely evening

jochen53

Hello, Thank you very much for the synthesis procedure. Precisely because it dates from 1884, we can assume that it works; chemists back then were still ‘skilled craftsmen’. The reason for the N=8.42... is as follows: back then, it was not yet possible to characterise a synthesised compound or test its purity using the spectroscopic and chromatographic methods common today. A so-called elemental analysis was therefore carried out; in this case, most likely a Kjeldahl nitrogen determination. The first value is the theoretical nitrogen content calculated from the molecular formula, the second is that determined from the synthesised substance. The deviation of just 0.03% shows that the identity of the substance is confirmed, it corresponds to the molecular formula, and the purity is very good.

gerich

Based on the molecular ratio and the use of anhydrous sodium acetate, the mass ratio should, according to my calculations, be as follows: p-Aminophenol C6H7NO 3g + chloroacetic acid C2H2ClO2 anhydrous 2.6g + sodium acetate C2H3NaO2 anhydrous 2.255g Molecular weights: p-Aminophenol: 109.125 Chloroacetic acid: 94.50 Sodium acetate anhydrous: 82.03, trihydrate: 136.08 I haven’t quite worked out the reaction equation yet. A hydrogen atom is lost from the NH₂ radical of the p-aminophenol, the chlorine from the chloroacetic acid, the residue binds to the nitrogen, and a Cl⁻ and H₃O⁺ ion each float in the water, i.e. hydrochloric acid. As the solubility of glycine in neutral and acidic water is low, it precipitates. So far, I seem to have understood it. But I don’t understand why Father reacts 2 parts p-aminophenol with one part chloroacetic acid. I also haven’t understood the reaction with the additional sodium acetate, except that, amongst other things, dissociated NaCl is then present in the solution. Here is the reference for the volume; however, it can only be downloaded from the internet with access authorisation. It may be that I logged in at the time using the authorisation from the local university library. Volume 111, 1917. The Journal of the Chemical Society, Transactions was published from 1878 to 1925.

jochen53

Hello, I have another recipe for a warm-tone developer without photo-glycine: € [size=-1][color=#000000]In 1996, *Foto & Labor* published the following recipe for Neutol WA [/colo [/size] [color=#000000][size=medium]Neutol WA F&L [/colo [/size] [size=-1][color=#000000]Please note: Recipe for 1000 ml of concentrate! Water (50 °C) ??????????????????????????????????????????????? 300 cc EDTANa4 ???????????????????????????????????????????????????????? 10 g Potassium sulphite solution (45%) ?? ?????????????? ?????????????? 50 cc Hydroquinone ??????????????????????????????????????????????????? 45 g Phenidone ????????????????????????????????????????????????????????? 1.5 g Potassium sulphite solution (45%) ????????????????? ?????????????? 450 ml Potassium carbonate ????????????????? ?????????????? ?????????????? 45 g Potassium hydroxide ????????????????? ?????????????? ?????????????? 15 g Potassium bromide ????????????????????????????????????????????????? 10 g Water to: ???????????????????????????????????????????????????? 1000 ml [/colo [/size] € [size=-1][color=#000000]pH value (at 1+9) 10.70–10.90, dilution for use: 1+7 to 1+14. The potassium sulphite solution (45% w/w) is added in two stages to protect the developing agents and ensure they dissolve rapidly. The concentration in vol. % (m/V) is 65%. Development time 1–1.5 min. The concentrate is packaged in glass bottles and has a shelf life of several years. Source: Foto & Labor, 3/1996, page 17[/colo [/size]

gerich

Thank you very much for the developer recipe! However, I can’t try it out straight away because I don’t have any potassium carbonate, potassium sulphite or KOH. My experience with developer concentrates that also contain potassium cyanide (Eukobrom) has so far been that they initially achieve high final densities in the tray and, in the case of Eukobrom with warm-tone papers, almost neutral image tones were achievable; however, this changed rapidly as the developer was used up: the image tone became warmer again, and the density and contrast diminished. Carbonate developers are much more consistent and long-lasting, which is why I only use them as sodium salts. This is how the reaction appears to proceed: C6H7NO (p-aminophenol) + C2H3ClO2 (chloroacetic acid) + C2H3NaO2 (sodium acetate) = C8H9NO3 (glycine) + CH3COOH (acetic acid) + NaCl I’m not sure whether the synthesis route starts with anhydrous sodium acetate or the trihydrate. Could it be that in 1917 the trihydrate is more likely, and do I need to convert this to anhydrous, as in my previous post? With an excess of sodium acetate, a buffer would form with the acetic acid produced – could that be the intention in the recipe?

Gast

I vaguely remember reading somewhere online that Moersch Sepia developer contains glycine and is a variation of Ansco 130. Why not have a go at asking Mr Moersch? He usually replies to emails. € <A>wolfgang@moersch-photochemie.de</A> € Best regards, Wolfgang

sputnik

Hello, I have another recipe for a warm-tone developer without photoglycine: € [size=-1][color=#000000]In 1996, *Foto & Labor* published the following recipe for Neutol WA [/colo [/size] [color=#000000][size=medium]Neutol WA F&L [/colo [/size] [size=-1][color=#000000]Please note: Recipe for 1000 ml of concentrate! Water (50 °C) – 300 ml EDTANa4 – 10 g Potassium sulphite solution (45%) – 50 ml Hydroquinone – 45 g Phenidone – 1.5 g Potassium sulphite solution (45%) – 450 ml Potassium carbonate – 45 g Potassium hydroxide – 15 g Potassium bromide – 10 g Water to: – 1000 ml [/colo [/size] € [size=-1][color=#000000]pH value (at 1+9) 10.70–10.90, dilution for use: 1+7 to 1+14. The potassium sulphite solution (45% w/w) is added in two stages to protect the developing agents and ensure they dissolve rapidly. The concentration in vol.% (m/V) is 65%. Development time 1–1.5 min. The concentrate can be stored in glass bottles for several years. Source: Foto & Labor, 3/1996, page 17[/colo [/size]

€ Erm, why go to all that trouble to concoct something when it’s been available ready-made everywhere for ages? You can’t really get the MCC to develop a proper warm tone anyway. Just use Fomatone. It’s the better choice for true warm-tone fans.

gerich

Here I have found a method for converting p-aminophenol and acetic anhydride (glacial acetic acid) into paracetamol (4-acetylaminophenol). Since the photo shows that glycine is similar to paracetamol and is also produced from p-aminophenol (albeit using monochloroacetic acid and sodium acetate), the procedure could be similar to that described below, particularly with regard to heating, pouring, filtering and recrystallisation. ? 10.9 g of p-aminophenol (0.1 mol) are suspended in 15 ml of water. Under vigorous stirring, 12 ml (13 g, 0.125 mol) of acetic anhydride are added, causing the p-aminophenol to dissolve. The mixture is then heated to 80–90°C for 10 minutes. As the mixture cools in an ice bath, the reaction product crystallises out. The crystalline mass is scraped off and washed with 50 ml of ice-cold water. It is then decolourised with activated carbon and recrystallised. To do this, dissolve the product in 80 ml of boiling water, add 1 teaspoon of activated carbon and stir for about one minute. The suspension is then filtered whilst hot and the filtrate cooled in ice water. Once cooled, the crystals obtained can be scraped off and weighed after drying.

jochen53

Hello, The synthesis of paracetamol is the main use of p-aminophenol (not the production of Rodinal). We have carried this out on several occasions as part of our trainee training. Apparently, there are even people who produce a Rodinal-like developer by performing hydrolysis on paracetamol tablets. The sodium acetate used in glycine synthesis may not actually need to be used in stoichiometric quantities; it may serve as a buffer to prevent the pH from becoming too acidic and to suppress the formation of p-aminophenol hydrochloride by the resulting HCl. If you carry out the synthesis, please take care with the monochloroacetic acid; it is toxic and highly corrosive (in concentrated solution, it is also used to remove warts).

gerich

I have found another source on glycine synthesis here: Heinrich Vater: On the effect of monochloroacetic acid on ortho- and para-amidophenol and the resulting oxyphenylglycines; in: Journal für praktische Chemie Vol. 29 1884, pp. 286–299 p. 289: O-Oxyphenylglycine 1 mole of monochloroacetic acid and 2 moles of O-amidophenol are heated to boiling with twenty times the volume of water until hydrochloric acid ceases to be released, which takes about half an hour. After cooling, the solution is freed from resinous products by filtration and shaking with ether, and then the O-oxyphenylglycine, which is sparingly soluble in water, is separated from the hydrochloric acid O-amidophenol, which is readily soluble in water, by recrystallisation. This is followed by the calculated and experimental values of the elemental analysis and a few sentences on the water of crystallisation and the preparation of the anhydride. p. 291: P-Oxyphenylglycine P-Oxyphenylglycine is prepared from P-amidophenol in a manner analogous to the ortho compound; however, this process proceeds almost without resin formation. This glycine is sparingly soluble in water and crystallises without water of crystallisation; on rapid cooling, it forms spherical aggregates, whilst on slow cooling it forms mica-like lamellae. Solubility in alcohol is low; the substance is insoluble in ether. When heated to 200 °C, p-oxyphenylglycine, unlike the ortho compound, undergoes no changes whatsoever. The hydrochloric acid solution turns dark violet, then yellowish, upon the addition of a drop-by-drop solution of calcium hypochlorite. My understanding of the reaction is as follows: In Vater’s method, the monochloroacetic acid loses the Cl and substitutes an H from the NH₂ group of the p-aminophenol; glycine precipitates out and the resulting HCl is driven out of the solution by heat; however, p-aminophenol hydrochloride also forms, which reduces the yield. In Meldola et al., NaCl forms and the substituted hydrogen forms acetic acid with the acetate group of the sodium acetate. The excess sodium acetate forms an acetic acid–acetate buffer (pH 4.75). After cooling, the glycine precipitates; acetate, acetic acid and NaCl remain in solution. As with the paracetamol synthesis, the filter cake is washed with ice water (to ensure that as little of the substance as possible dissolves). The question now is whether glycine dissolves in hot water, making recrystallisation possible, and whether it is necessary at all. A small residue of acetate and table salt should not harm the developer. A word on the amount of water. The 20-fold amount, as in Vater’s method, seems rather excessive to me, whilst 15 ml of water for 10.9 g of p-aminophenol, as in the paracetamol recipe, seems rather too little. I would proceed as follows: dissolve the acetate and monochloroacetic acid in water in separate vessels; add the p-aminophenol to the acetate solution; prepare a suspension whilst stirring continuously; add the monochloroacetic acid solution (does the p-aminophenol now dissolve, as it did when acetic anhydride was added?); and, whilst continuing to stir, slowly raise the temperature and observe whether a reaction product precipitates; if so, maintain this temperature for 10 minutes. If not, continue heating to approx. 85 °C and maintain this temperature for 10 minutes. Then allow to cool and filter off. Discard the filtrate and wash the cake with ice water. Once dry, use it to prepare the Ansco 130. Any suggestions on this? Regarding the hazards of monochloroacetic acid: I have a fume cupboard and will be working behind a Plexiglas safety screen, wearing thick nitrile gloves with long cuffs, a rubber apron and eye protection. I will also wear a dust mask whilst weighing. Thank you very much for your interest and your tips!

jochen53

Hello, As far as I can recall from Udo Raffay’s description of glycine in the chemicals appendix of his collection of recipes, it is relatively poorly soluble in water, but highly soluble in alkaline solutions—including sodium sulphite solution—due to the formation of a salt at the carboxyl group. I’m not sure how soluble it is in hot water, but you’ll find that out quickly once you’ve got the substance to hand; perhaps there’s something on that in Eder too. The synthesis strategy looks quite good.

gerich

Speaking of chemical descriptions, I can’t access the Meck Index online database via the local university library. Could anyone who has access tell me about the glycine entry? How can I determine whether p-aminophenol hydrochloride might also have formed? With Meldola’s nitrogen analysis, the same values come out regardless of whether it’s glycine, p-aminophenol or p-aminophenol hydrochloride, if I’m not mistaken. Not all the chemicals have arrived yet; if I’m lucky, they’ll be here tomorrow. I’ll report back on my first attempt as soon as I know more.