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Organikum
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Tired of wasting Nitromethane for making Hydroxylamine I got myself a big bag of Sodium Nitrite and had an astonishing hard time to find the related
simple method for making the Amine from Nitrite and Bisulfite.
Everybody mentions it but nobody just links or quotes it.
Here we go:
From Brauers in the SCM library page 503
| Quote: | Potassium Hydroxylamine Disulfonate
HON(SO3K)2
NaNO2 + 2NaHSO3 = HON(SO3Na)2 + NaOH
69.0 208.1 237.1 40.0
A solution of 69 g. of NaNO3 in the minimal quantity of water
is prepared and mixed with 200 g. of ice. A cooled solution of NaHSO3, prepared either by dissolving 208 g. in the minimal quantity of water or by
dissolving the same quantity in 600 ml. of technical (35%) bisulfite solution, is added in portions with agitation.
Ice should still be present at the end of the addition. A cold, saturated solution of 150 g. of KCl is then added and the reaction mixture is left to
stand for 24 hours. Half of the theoretical yield of disulfonate separates as compact crystals together with fine needles of trisulfonate. The
nitrilotrisulfonate can be easily removed by washing and decantation. The HON(SO3K)3 is then recrystallized from a small amount of hot water to which
some KOH or ammonia is added (a few seed crystals are retained for this purpose from the first crystallization because the salt tends to form
supersaturated solutions).
In another procedure, one mole of KNO2 and 1.1-1.2 moles of
potassium acetate are dissolved in 200 ml. of ice water; 1500 g. of
finely shaved ice is added and SO3 is bubbled through the agitated
reaction mixture until the solution gives the characteristic odor of the gas. The temperature may not exceed 0°C. The disulfonate formed may be
washed with a small amount of water and recrystallized as above.
PROPERTIES:
Formula weight 269.35. Hard, shiny crystals, which readily decompose to K2SO4 and hydroxylamine on boiling with water.
REFERENCES:
F. Raschig, Lieb. Ann. Chem. 241^, 183 (1887).
G. K. Rollefson and C. F. Oldershaw, J. Amer. Chem. Soc. 54, 977
81932). |
The second attached article contains the IMHO best way to prepare Hydroxylamine as it uses only the more common Sodium Nitrite, the abundant Sodium
Meta Bisulfite, HCl and Alcohol to yield the HCl salt of Hydroxylamine.
regards
/ORG
Attachment: phpKGYzJS (197kB)
This file has been downloaded 210 times
Attachment: hydroxylamine_nitrit sulfit.djvu (135kB)
This file has been downloaded 243 times
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clearly_not_atara
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| Quote: | and SO3 is bubbled through the agitated
reaction mixture |
Surely he means to say "and SO2 is bubbled..."
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Organikum
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You are right, SO2, the OCR on the document is horrible, I fixed most before posting it but I must have overlooked this one. Thx. for pointing it out.
regards
/ORG
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Dr.Bob
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And Hydroxylamine HCl is quite stable to store, used it for a few reactions, easy to free base when needed or just react along with one eq of TEA or
Hunig's base. Or it can react with carbonyls as the salt, then reduce with NaCNBH3 to make alkyl hydroylamines. Used in many metal chelators.
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Fery
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Hi Organikum, the cheapest way is to buy the hydroxylamine hydrochloride or sulfate.
https://chemcraft.su/search/node/hydroxylamine
How much do you need? I have few very old jars (few decades old), it reacted well.
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Lionel Spanner
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I recently tried the first method in Brauer, and found it reliably reproducable. The only difference is that I went via sodium hydroxylamine
disulphonate (didn't have any potassium chloride), and ended up with a lower yield - 36% as opposed to 50%.
The sulphonate salt can then be converted to hydroxylamine sulphate in near-quantitative yields simply by refluxing for 4 hours (Brauer p. 499).
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