Loptr
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Interest Check: Sodium Dithionite, Na2S2O4 (Sodium Hydrosulfite)
Hello everyone,
I have come across a source of Sodium Dithionite and wanted to gauge the amount of interest that would be found if it were to be offered up for sale
here on SM.
I can't figure out how to post this as a poll, so just reply in this thread with a statement towards your interests in this compound. I know this
compound is pretty easily prepared by the amateur, so I just need to figure out if purchasing it would be worth our while.
I look forward to your feedback!
| Quote: |
Sodium Dithionite
Na2S2O4
[7775-14-6] · Na2O4S2 · Sodium Dithionite · (MW 174.12)
(versatile reagent for reduction of aldehydes,2 ketones,2-6 unsaturated conjugated ketones,7,8 quinones,9-10 diunsaturated acids,11 azo,12 nitro,13
and nitroso compounds,14,15 imines,16 oximes,17 tropylium salts,18 pyridinium salts,19 pyrazine,20 and vinyl sulfones;21 intramolecular Marschalk
cyclizations,22,23 dehalogenation of vic dibromides24 and a-halo ketones,25 Claisen rearrangement of allyloxyanthraquinones26 and for the synthesis of
8-arylaminopurines27,28)
Alternate Name: sodium hydrosulfite.
Physical Data: mp 52 °C (dec).
Solubility: very sol water; sol alcohol.
Form Supplied in: white or gray-white crystalline powder.
Preparative Methods: by the action of Sulfur Dioxide on Sodium Amalgam in alcoholic solution.29,30
Handling, Storage, and Precautions: flammable; moisture sensitive.
Reduction of Aldehydes and Ketones.2
Sodium dithionite is an alternative and less expensive reducing agent than metal hydrides. The reactions are performed in water for soluble
substrates, otherwise a 50:50 mixture of water and dioxane or DMF can be used; sodium bicarbonate is added to keep the reaction mixture basic.
Examples are hexanal to 1-hexanol (67%), benzaldehyde to benzyl alcohol (84%), cyclohexanone to cyclohexanol (80%),3 and acetophenone to
a-hydroxyethylbenzene (94%).2 Reduction of methylcyclohexanones by Na2S2O4 in benzene-water using adogen (commercial mixture of methyl trialkyl C8-C10
ammonium chloride) as a phase-transfer agent afforded good yields of isomeric mixtures of the corresponding methylcyclohexanols.3 Reduction using
Na2S2O4 proceeds with stereoselectivity4-6 similar to that obtained with metal hydrides (Sodium Borohydride) and opposite to dissolving metals
reductions, e.g. the reductions of 3a-hydroxy-7-keto-5b-cholanic acid to diols (eq 1).
Regiospecific Reduction of Unsaturated Conjugated Ketones.7,8
Exclusive reduction of conjugated carbon-carbon double bonds is achieved with Na2S2O4 to afford the corresponding saturated carbonyl compound. A
two-phase (benzene-water) system using adogen as the phase-transfer catalyst is used. The isolated carbon-carbon double bond remains unaffected. No
alcohols are detectable (eqs 2-4).
Quinones to Hydroquinones.9
Most quinones are reduced by sodium dithionite to hydroquinones. Naphthacenequinone and higher linear benzologs are exceptional in that they are not
reduced by alkaline sodium dithionite.10 Sodium dithionite reduces anthraquinone to anthrone.
Conjugated Diunsaturated Acids (and Esters) to Monounsaturated Acids (and Esters).11
a,b;g,d-Unsaturated acids are reduced by Na2S2O4 in an alkaline medium (NaOH or NaHCO3) to a mixture of (Z)- and (E)-b,g-unsaturated acids (and
esters) (40-75% yield) (eq 5).
Azo to Amine.12
Azobenzene is reduced to aniline by sodium dithionite. This reaction is used to introduce an amino group into a phenolic compound by first coupling
with an aromatic diazonium salt and then reducing the resulting hydroxyazo derivatives with Na2S2O4, e.g. 2- and 4-amino-1-naphthols can be prepared
from 1-naphthol.
Nitro to Amine.13
Various aromatic nitro compounds are reduced conveniently to the corresponding aniline derivatives with sodium dithionite using dioctyl viologen as an
electron-transfer catalyst in a two-phase system (CH2Cl2-H2O), e.g. 1-nitronaphthalene to 1-naphthylamine.
Nitroso to Amine.
Nitroso compounds are reduced to amines by sodium dithionite, e.g. nitrosouracil to diaminouracil (eq 6).14 Reduction of N-nitrosodibenzylamine15 with
Na2S2O4 is accompanied by liberation of N2 and rearrangement to dibenzyl. Mixed benzylaryl or diaryl-N-nitrosoamines are reduced to hydrazines (eq 7).
Imines to Amines.
Sodium dithionite in DMF reduces imines16 to N-alkylamines at 110 °C with yields ranging from 40 to 73%. Heating N-cyclohexyldibenzylamine, sodium
dithionite, and NaHCO3 in DMF for 30 min at 110 °C gives 73% benzylcyclohexylamine.
Oximes to Amines.17
Oximes are readily reduced to amines by sodium dithionite. Substituted phenylethylamines are key intermediates required for the synthesis of
isoquinoline derivatives. They are readily obtained from aryl alkyl ketones by nitrosation of the alkyl group followed by the reduction of the
resulting oxime derivatives by sodium dithionite (eq 8).
Cleavage of Oximes.16
Both aldehydes and ketones are regenerated from their oxime derivatives with aqueous sodium dithionite either alone or in the presence of Na2CO3 at 25
°C, e.g. cyclohexanone oxime to cyclohexanone (95%) and benzaldehyde oxime to benzaldehyde (96%).
Reduction of Tropylium and Cyclopropenium Halides.18
Na2S2O4 in acetonitrile at 25 °C reduces the tropylium halides to ditropyl (eq 9) and triphenylcyclopropenium halides to bicyclopropenyl sulfones (eq
10).
Reduction of Pyridinium Salt.19
Sodium dithionite has been extensively used for the reduction of N-methylpyridinium-3-carboxamide to N-methyl-1,4-dihydropyridine-3-carboxamide (eq
11), which is a model of reduced dihydrophosphopyridine nucleotide (DPNH).
Reduction of Pyrazine Derivatives.20
2,3,5,6-Tetraethoxycarbonyl-1,4-dihydropyrazine is prepared from 2,3,5,6-tetraethoxycarbonylpyrazine using sodium dithionite as reducing agent (eq
12). It is a more convenient and simpler method than catalytic hydrogenation and no saponification of esters occurred during this reduction process.
Reduction of Vinyl Sulfone.
An insect phermone, (Z)-8-dodecenyl 1-acetate,21 is readily obtained by the reduction of corresponding vinyl sulfone in aqueous ethanol with retention
of configuration (eq 13). The mechanism involves the Michael addition of SO2- to the vinylic sulfone, accompanied by protonation and expulsion of SO2
and sulfinate ion to give the alkene.
Intramolecular Marschalk Cyclization.22,23
This cyclization reaction is a key step in the total synthesis of daunomycinone, the aglycon of an anthracycline antibiotic. Treatment of the
anthraquinone derivative with sodium dithionite and sodium hydroxide in dioxane at 25-90 °C gives the anticipated cyclized product in 52% yield (eq
14).
Dehalogenation of vic-Dibromides, a-Bromo and a-Chloro Ketones.
Vicinal dibromides are debrominated24 with Na2S2O4 in DMF (140-145 °C). The yields are moderate to high but the reaction is not stereospecific. Both
meso- and (±)-2,3-dibromobutane give 1:1 mixtures of cis- and trans-2-butene. The dehalogenation25 of a-bromo or a-chloro ketones can be effected
with Na2S2O4 in aqueous DMF at 25-90 °C in yields of 50-95%. The rate can be enhanced by addition of NaHCO3.25
Claisen Rearrangement of Allyloxyanthraquinone.26
1-Allyloxyanthraquinones rearrange to 1-hydroxy-2-allylanthraquinones in high yields when heated in DMF-H2O containing 1.3-1.8 equiv Na2S2O4.
1,4-Bis(allyloxy)anthraquinone rearranges slowly under these conditions, but more readily if 4 equiv NaOH is added (eq 15).
Synthesis of 8-Arylaminotheophyllines.27,28
Treatment of 5-arylazo-1,3-dimethyl-6-ethoxymethyleneaminouracil with Na2S2O4 in formic acid gives 8-arylaminotheophyllines (eq 16). The key
intermediates required for this reaction are prepared by reaction of the appropriate 6-amino-5-arylazo-1,3-dimethyluracils with a mixture of Triethyl
Orthoformate and DMF at 180 °C for 5 h.
1. (a) FF 1967, 1, 1081; 1980, 8, 456; 1981, 9, 426; 1982, 10, 363; 1988, 13, 277. (b) Louis-Andre, O.; Gelbard, G. BSF(2) 1986, 565. 2. de Vries, J.
G.; van Bergen, T. J.; Kellogg, R. M. S 1977, 246. 3. Camps, F.; Coll, J.; Riba, M. CC 1979, 1080. 4. House, H. O. Modern Synthetic Reactions, 2nd
ed.; Benjamin/Cummings: London, 1972; p 150. 5. Castaldi, G.; Perdoncin, G.; Giordano, C.; Minisci, F. TL 1983, 24, 2487. 6. Giordano, C.; Perdoncin,
G.; Castaldi, G. AG(E) 1985, 24, 499. 7. Camps, F.; Coll, J.; Guitart, J. T 1986, 42, 4603. 8. Louis-Andre, O.; Gelbard, G. TL 1985, 26, 831. 9.
Fieser, L. F. JACS 1931, 53, 2329. 10. Fieser, L. F.; Peters, M. A. JACS 1931, 53, 4080. 11. Camps, F.; Coll. J.; Guerrero, A.; Guitart, J.; Riba, M.
CL 1982, 715. 12. Fieser, L. F. OSC 1943, 2, 35, 430. 13. Park, K. K.; Oh, C. H.; Joung, W. K. TL 1993, 34, 7445. 14. Sherman, W. R.; Taylor, Jr., E.
C. OSC 1963, 4, 247. 15. Overberger, C. G.; Lombardino, J. G.; Hiskey, R. G. JACS 1958, 80, 3009. 16. Pojer, P. M. AJC 1979, 32, 201. 17. Pictet, A.;
Gams, A. CB 1909, 42, 2943. 18. Weiss, R.; Schlierf, C.; Koelbl, H. TL 1973, 4827. 19. Mauzerall, D.; Westheimer, F. H. JACS 1955, 70, 2261. 20.
Mager, H. I. X.; Berends, W. RTC 1960, 79, 282. 21. Julia, M.; Lauron, H.; Stacino, J.-P.; Verpeaux, J.-N.; Jeannin, Y.; Dromzee, Y. T 1986, 42, 2475.
22. Suzuki, F.; Trenbeath, S.; Gleim, R. D.; Sih, C. J. JACS 1978, 100, 2272. 23. Kende, A. S.; Tsay, Y.-G.; Mills, J. E. JACS 1976, 98, 1967. 24.
Kempe, T.; Norin, T.; Caputo, R. ACS 1976, B30, 366. 25. Chung, S.-K.; Hu, Q.-Y. SC 1982, 12, 261. 26. Boddy, I. K.; Boniface, P. J.; Cambie, R. C.;
Craw, P. A.; Larsen, D. S.; McDonald, H.; Rutledge, P. S.; Woodgate, P. D. TL 1982, 23, 4407. 27. Senga, K.; Ichiba, M.; Kanazawa, H.; Nishigaki, S.;
Higuchi, M.; Yoneda, F. S 1977, 4, 264. 28. Senga, K.; Ichiba, M.; Kanazawa, H.; Nishigaki, S.; Higuchi, M.; Yoneda, F. JHC 1978, 15, 641. 29. Chia,
K.-S; Wang, W.-P. Union Ind. Res. Inst. Report (Hsinchu, Taiwan), No. 40, 1959; p.1 (CA 1960, 54, 19 252g). 30. Chia, K.-S; Wang, W.-P. Chemistry
(Taipei) 1960, 29 (CA 1961, 55, 2327h).
Marudai Balasubramanian & James G. Keay
Reilly Industries, Indianapolis, IN, USA
Copyright � 1995-2000 by John Wiley & Sons, Ltd. All rights reserved.
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Quoted from: http://reag.paperplane.io/00002516.htm
[Edited on 21-7-2016 by Loptr]
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Praxichys
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I love buying things just to have them in stock. I'm assuming this is the dihydrate? I'd be interested in half a kilo if the price is right.
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Loptr
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Quote: Originally posted by Praxichys  | | I love buying things just to have them in stock. I'm assuming this is the dihydrate? I'd be interested in half a kilo if the price is right.
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You and I seem to be very similar in that regard. I was planning to go ahead and buy some to have on hand, but wanted to see if others were interested
first.
I have also enrolled in a couple of chemistry courses at a local college for this fall, which is exciting because all of my chemistry work was a good
~10 years ago in college. It will be nice to have a more immediate understanding and intuition of what can be used for something, and how so.
Cheers!
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Melgar
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My guess would be no. It's not super useful, and its main attraction is how cheaply it can be manufactured on an industrial scale. I can't really
think of any amateur syntheses where sodium dithionite would be the reagent of choice, as opposed to another partially oxidized sulfur salt of sodium,
like sodium metabisulfite or sodium thiosulfate.
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carrant
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I would be interested in at least 500g (or more depending on pricing).
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careysub
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| Quote: Originally posted by Melgar | | My guess would be no. It's not super useful, and its main attraction is how cheaply it can be manufactured on an industrial scale. I can't really
think of any amateur syntheses where sodium dithionite would be the reagent of choice, as opposed to another partially oxidized sulfur salt of sodium,
like sodium metabisulfite or sodium thiosulfate. |
Here is a document that recounts a range of chemical applications:
http://www.sciencemadness.org/talk/files.php?pid=109817&...
It is used for example in a high yield hydrolysis of melatonin to 5-Methoxytryptamine:
Neurochemical Research, 26 (2001) 1171-1176
US Pat 4,772,726
Presumably this would work equally well for tryptophan.
Also:
Attachment: 10.1021@jo01309a011.pdf (560kB)
This file has been downloaded 677 times
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Texium
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It can also be used in place of aluminum in the luminol synthesis for a much cleaner and easier to work up product. I already have some though, thanks
to careysub.
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Cryolite.
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The issue is of course price. Super iron out provides a reasonable source of sodium dithionite (~35% pure, with the contaminants all being various
soluble sodium salts which should not interact), and for very cheap (amazon lists it at 10.99 for 28 ounces).
If you are after purity, there is a seller on ebay selling 100g of dithionite for 13.80. And finally, it can be made easily at home by the reaction of
zinc powder and sodium bisulfite, followed by crashing out of the product with ethanol.
I might be interested in purchasing some (mostly to just have some around), but what price will you be selling at?
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Loptr
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That's the purpose of this interest check, which is to gauge interest to determine an amount for purchase. I have not worked the numbers yet, but I
could probably sell it for $35-45/kg. Again, that depends on interest.
This is from an actual chemical supply company.
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Fleaker
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Just be wary of DOT rules on shipping and consult the HMT.
Neither flask nor beaker.
"Kid, you don't even know just what you don't know. "
--The Dark Lord Sauron
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Loptr
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Thank you for the advice. It is appreciated.
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careysub
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Shannon & Sons Minerals has sodium dithionite (from Germany) at $9 for one kilogram. 10 kg for $67.
https://www.shannonsminerals.com/shop/index.php/shannonsmine...
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Loptr
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*** EDITED ***
It seems they are in the USA. It looks like that if you want Sodium Dithionite, then go to Shannon & Sons.
[Edited on 21-7-2016 by Loptr]
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careysub
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| Quote: Originally posted by Loptr | *** EDITED ***
It seems they are in the USA. It looks like that if you want Sodium Dithionite, then go to Shannon & Sons.
[Edited on 21-7-2016 by Loptr] |
If you are in Europe, try contacting them anyway.
They have a German connection I do not quite understand. Their chemicals are all of German origin, with German labelling. Much of their inventory is
in Germany and ships from there.
This has created a problem trying to buy some of the things the site advertises (fossils, and pitchblende from the Hartz Mountains) - I could not get
those things since they either could not ship (pitchblende) or was damaged in customs (!).
[Edited on 21-7-2016 by careysub]
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Loptr
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They also have cheap calcium carbide. The cheapest I had found it was some site called Cheap Carbide, and I do believe these guys are cheaper.
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careysub
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| Quote: Originally posted by Loptr | | They also have cheap calcium carbide. The cheapest I had found it was some site called Cheap Carbide, and I do believe these guys are cheaper.
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One of the things I found I could not actually buy since it is in Germany, and shipping issues were a problem.
They do distribute from Gilbert, Arizona where Michael Shannon lives. But for some things I had to wait for a mineral shipment from Germany for a
major Arizona mineral show. I didn't mind waiting.
But yes, there prices are good. I suggest contacting them and seeing what you work out whereever you are, Europe or U.S.
I got U.S. pitchblende from them, which is otherwise extremely hard to source.
[Edited on 22-7-2016 by careysub]
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UC235
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| Quote: Originally posted by zts16 | | It can also be used in place of aluminum in the luminol synthesis for a much cleaner and easier to work up product. I already have some though, thanks
to careysub. |
I'm pretty sure Nurdrage was just making shit up when he chose to reduce luminol using aluminum. Sodium Dithionite is the literature reagent of
choice. See: http://www.orgsyn.org/Content/pdfs/procedures/CV3P0069.pdf
I've found that Thiourea dioxide (Thiox/Spectralite) is a quick, efficient, and reliable reducing agent for this transformation as well. Thiox is DOT
packing group III while dithionite is considered group II.
[Edited on 22-7-2016 by UC235]
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