Hydroxylamine-O-sulfonic acid

Last updated
Hydroxylamine-O-sulfonic acid
H3NOSO3.png
HOSAimproved.jpg
   Oxygen, O
   Nitrogen, N
   Sulfur, S
   Hydrogen, H
Names
Other names
Aminosulfuric acid
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.019.065 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 220-971-6
PubChem CID
  • InChI=1S/H3NO4S/c1-5-6(2,3)4/h1H2,(H,2,3,4)
    Key: DQPBABKTKYNPMH-UHFFFAOYSA-N
  • NOS(=O)(=O)O
Properties
H3NO4S
Molar mass 113.09
Appearancewhite solid
Melting point 210 °C
cold water
Acidity (pKa)1.48 [1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Hydroxylamine-O-sulfonic acid (HOSA) or aminosulfuric acid is the inorganic compound with molecular formula H3NO4S that is formed by the sulfonation of hydroxylamine with oleum. [2] It is a white, water-soluble and hygroscopic, solid, commonly represented by the condensed structural formula H2NOSO3H, though it actually exists as a zwitterion [3] and thus is more accurately represented as +H3NOSO3. It is used as a reagent for the introduction of amine groups (NH2), for the conversion of aldehydes into nitriles and alicyclic ketones into lactams (cyclic amides), and for the synthesis of variety of nitrogen-containing heterocycles. [3] [4] [5]

Contents

Preparation

According to a laboratory procedure [2] hydroxylamine-O-sulfonic acid can be prepared by treating hydroxylamine sulfate with fuming sulfuric acid (oleum). The industrial process is similar. [6]

(NH3OH)2SO4 + 2SO3 → 2H2NOSO3H + H2SO4

The sulfonation of hydroxylamine can also be effected with chlorosulfonic acid [3] by a method first published in 1925 [7] and refined for Organic Syntheses . [8]

The hydroxylamine-O-sulfonic acid, which should be stored at 0 °C to prevent decomposition, can be checked by iodometric titration. [9]

Structure

Analogous to sulfamic acid (H3N+SO3) and as is the case generally for amino acids, HOSA exists in the solid state as a zwitterion: H3N+OSO3. It resembles an ammonia molecule coordinate covalently bonded to a sulfate group. [10]

Reactions

HOSA reacts under basic conditions as an electrophile and under neutral and acid conditions as a nucleophile. [4] [11]

Reaktivitat of Hydroxylamine-O-sulfonsaure als Elektrophil und als Nukleophil Hydroxylamine-O-sulfonsaure Reaktivitat.svg
Reaktivität of Hydroxylamine-O-sulfonsäure als Elektrophil und als Nukleophil

Aminations

Synthesis of N-Aminopiperidin with HOSA N-Aminopiperidin-Synthese.svg
Synthesis of N-Aminopiperidin with HOSA

It reacts with tertiary amines to trisubstituted hydrazinium salts and with pyridine to the 1-amino pyridinium salt. [12]

Synthesis of 1-Aminopyridin with HOSA 1-Aminopyridin-Synthese.svg
Synthesis of 1-Aminopyridin with HOSA

From 1-aminopyridinium salts the photochemically active 1-N-iminopyridinium ylides are accessible by acylation. [13] The photochemical rearrangement of the obtained 1-N-iminipyridinium ylides leads in high yields to 1H-1,2-diazepines [14]

Synthesis of 1,2-Diazepinen aus Iminopyridiniumyliden 1,2-Diazepine aus Iminopyridiniumyliden.svg
Synthesis of 1,2-Diazepinen aus Iminopyridiniumyliden

N-amination of 1H-benzotriazole with hydroxylamine-O-sulfonic acid yields a mixture of 1-aminobenzotriazole (major product) and 2-aminobenzotriazole (minor product). From 1-aminotriazole, benzyne is formed in an almost quantitative yield by oxidation with lead(IV) acetate, which rapidly dimerizes to biphenylene in good yields. [15]

Synthesis of Benzyne and Biphenylene from 1-Aminobenzotriazole Dehydrobenzol aus Aminobenztriazol.svg
Synthesis of Benzyne and Biphenylene from 1-Aminobenzotriazole

Electron deficient heterocycles, such as tetrazole, can be N-aminated with hydroxylamine-O-sulfonic acid, while even more electron-deficient compounds, such as 5-nitrotetrazole, react only with stronger aminating agents such as O-tosylhydroxylamine or O- mesitylene sulfonylhydroxylamine to amino compounds, which were investigated as explosives. [16]

1-Aminotetrazol und 2-Aminotetrazol durch Aminierung of Tetrazol with HOSA Aminierung von Tetrazol.svg
1-Aminotetrazol und 2-Aminotetrazol durch Aminierung of Tetrazol with HOSA

In the N-amination of the unsubstituted tetrazole, a mixture of 1-amino- and 2-aminotetrazole is obtained.

Synthesis of Sulfiminen with HOSA Sulfimine.svg
Synthesis of Sulfiminen with HOSA

Also sulfur compounds (such as thioethers) can be aminated with hydroxylamine-O-sulfonic acid to sulfinimines (isosteric with sulfoxides but far more unstable) or phosphorus compounds (such as triphenylphosphine) can be aminated to phosphine imides via the intermediate aminotriphenylphosphonium hydrogen sulfate. [17]

Phosphinimine.svg

The reaction of hydroxylamine-O-sulfonic acid with metal salts of sulfinic acids in sodium acetate solution produces primary sulfonamides in very good yields. [18]

Synthesis of primaren Sulfonamiden aus Sulfinaten Sulfonamide aus Sulfinaten.svg
Synthesis of primären Sulfonamiden aus Sulfinaten

Diimine can formed in situ from hydroxylamine-O-sulfonic acid respectively hydroxylamine-O-sulfonic acid hydroxylamine sulfate mixtures, which hydrogenates selectively conjugated multiple bonds.[20]

With carbonyl compounds

At room temperature and below, hydroxylamine-O-sulfonic acid reacts with ketones and aldehydes as a nucleophile to the corresponding oxime-O-sulfonic acids or their salts. [19] The oxime-O-sulfonic acids of aldehydes react above room temperature upon elimination of sulfuric acid in high yields to nitriles. [20]

Reaktion of HOSA with Carbonylverbindungen Reaktion von HOSA mit Carbonylverbindungen.svg
Reaktion of HOSA with Carbonylverbindungen

Aliphatic ketones provide under similar conditions in very high yields oximes, arylalkyl ketones react in a Beckmann rearrangement to amides. When heated to reflux for several hours under acidic conditions (e.g., in the presence of concentrated formic acid) alicyclic ketones react to provide lactams in high yields. [21]

2-Azacyclooctanon durch Reaktion of Cycloheptanon with HOSA 2-Azacyclooctanon aus Cycloheptanon.svg
2-Azacyclooctanon durch Reaktion of Cycloheptanon with HOSA

Under basic conditions in the presence of primary amines, hydroxylamine-O-sulfonic acid forms with aldehydes and ketones (e.g. cyclohexanone [22] ) diaziridines, which can easily be oxidized to the more stable diazirines.

3,3-Pentamethylendiaziridin durch Reaktion of Cyclohexanon mit HOSA 3,3-Pentamethylendiaziridin.svg
3,3-Pentamethylendiaziridin durch Reaktion of Cyclohexanon mit HOSA

The reaction also provides substituted aziridines from simple aldehydes and ketones with high yield and diastereoselectivity. [23]

Synthesis of Diaziridinen with HOSA Diaziridine.svg
Synthesis of Diaziridinen with HOSA

1,2-Benzisoxazole is efficiently produced by nucleophilic attack of hydroxylamine-O-sulfonic acid to the carbonyl group of 2-hydroxybenzaldehyde followed by cyclization. [24]

Synthesis of 1,2-Benzisoxazol aus Salicylaldehyd und HOSA 1,2-Benzisoxazol.svg
Synthesis of 1,2-Benzisoxazol aus Salicylaldehyd und HOSA

1,2-Benzisoxazole is a structural element in the antipsychotic risperidone and paliperidone, as well as the anticonvulsant zonisamide.

In a one-pot reaction, N-aryl[3,4-d]pyrazolopyrimidines are obtained in good yields from simple 4,6-dichloropyrimidine-5-carboxaldehyde, [25]

N-Aryl-Pyrazolopyrimidine N-Aryl-Pyrazolopyrimidine.svg
N-Aryl-Pyrazolopyrimidine

which can be used as purine analogs for a wide range of diagnostic and therapeutic applications. [26]

Further reactions

The chemiluminescence of the system luminol/cobalt(II) chloride is dramatically enhanced by the addition of hydroxylamine-O-sulfonic acid. [27]

Related Research Articles

<span class="mw-page-title-main">Ketone</span> Organic compounds of the form >C=O

In organic chemistry, a ketone is an organic compound with the structure R−C(=O)−R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group −C(=O)−. The simplest ketone is acetone, with the formula (CH3)2CO. Many ketones are of great importance in biology and in industry. Examples include many sugars (ketoses), many steroids, and the solvent acetone.

<span class="mw-page-title-main">Oxime</span> Organic compounds of the form >C=N–OH

In organic chemistry, an oxime is an organic compound belonging to the imines, with the general formula RR’C=N−OH, where R is an organic side-chain and R' may be hydrogen, forming an aldoxime, or another organic group, forming a ketoxime. O-substituted oximes form a closely related family of compounds. Amidoximes are oximes of amides with general structure R1C(=NOH)NR2R3.

<span class="mw-page-title-main">Hydroxylamine</span> Inorganic compound

Hydroxylamine is an inorganic compound with the chemical formula NH2OH. The compound is in a form of a white hygroscopic crystals. Hydroxylamine is almost always provided and used as an aqueous solution. It is consumed almost exclusively to produce Nylon-6. The oxidation of NH3 to hydroxylamine is a step in biological nitrification.

<span class="mw-page-title-main">Hydrazone</span> Organic compounds - Hydrazones

Hydrazones are a class of organic compounds with the structure R1R2C=N−NH2. They are related to ketones and aldehydes by the replacement of the oxygen =O with the =N−NH2 functional group. They are formed usually by the action of hydrazine on ketones or aldehydes.

<span class="mw-page-title-main">Imine</span> Organic compound or functional group containing a C=N bond

In organic chemistry, an imine is a functional group or organic compound containing a carbon–nitrogen double bond. The nitrogen atom can be attached to a hydrogen or an organic group (R). The carbon atom has two additional single bonds. Imines are common in synthetic and naturally occurring compounds and they participate in many reactions.

In organic chemistry, a nitrile is any organic compound that has a −C≡N functional group. The name of the compound is composed of a base, which includes the carbon of the −C≡N, suffixed with "nitrile", so for example CH3CH2C≡N is called "propionitrile". The prefix cyano- is used interchangeably with the term nitrile in industrial literature. Nitriles are found in many useful compounds, including methyl cyanoacrylate, used in super glue, and nitrile rubber, a nitrile-containing polymer used in latex-free laboratory and medical gloves. Nitrile rubber is also widely used as automotive and other seals since it is resistant to fuels and oils. Organic compounds containing multiple nitrile groups are known as cyanocarbons.

Reductive amination is a form of amination that involves the conversion of a carbonyl group to an amine via an intermediate imine. The carbonyl group is most commonly a ketone or an aldehyde. It is a common method to make amines and is widely used in green chemistry since it can be done catalytically in one-pot under mild conditions. In biochemistry, dehydrogenase enzymes use reductive amination to produce the amino acid, glutamate. Additionally, there is ongoing research on alternative synthesis mechanisms with various metal catalysts which allow the reaction to be less energy taxing, and require milder reaction conditions. Investigation into biocatalysts, such as imine reductases, have allowed for higher selectivity in the reduction of chiral amines which is an important factor in pharmaceutical synthesis.

<span class="mw-page-title-main">Iminium</span> Polyatomic ion of the form >C=N< and charge +1

In organic chemistry, an iminium cation is a polyatomic ion with the general structure [R1R2C=NR3R4]+. They are common in synthetic chemistry and biology.

<span class="mw-page-title-main">Carbonyl condensation</span> Organic reaction of carbonyl compounds with amines to imines

In organic chemistry, alkylimino-de-oxo-bisubstitution is the organic reaction of carbonyl compounds with amines to imines. The reaction name is based on the IUPAC Nomenclature for Transformations. The reaction is acid catalyzed and the reaction type is nucleophilic addition of the amine to the carbonyl compound followed by transfer of a proton from nitrogen to oxygen to a stable hemiaminal or carbinolamine. With primary amines water is lost in an elimination reaction to an imine. With aryl amines especially stable Schiff bases are formed.

The Leuckart reaction is the chemical reaction that converts aldehydes or ketones to amines by reductive amination in the presence of heat. The reaction, named after Rudolf Leuckart, uses either ammonium formate or formamide as the nitrogen donor and reducing agent. It requires high temperatures, usually between 120 and 130 °C; for the formamide variant, the temperature can be greater than 165 °C.

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<span class="mw-page-title-main">Hydroxylammonium sulfate</span> Chemical compound

Hydroxylammonium sulfate [NH3OH]2SO4, is the sulfuric acid salt of hydroxylamine. It is primarily used as an easily handled form of hydroxylamine, which is explosive when pure.

<span class="mw-page-title-main">Diisopinocampheylborane</span> Chemical compound

Diisopinocampheylborane is an organoborane that is useful for asymmetric synthesis. This colourless solid is the precursor to a range of related reagents. The compound was reported in 1961 by Zweifel and Brown in a pioneering demonstration of asymmetric synthesis using boranes. The reagent is mainly used for the synthesis of chiral secondary alcohols. The reagent is often depicted as a monomer but like most hydroboranes, it is dimeric with B-H-B bridges.

Electrophilic amination is a chemical process involving the formation of a carbon–nitrogen bond through the reaction of a nucleophilic carbanion with an electrophilic source of nitrogen.

Fluorination by sulfur tetrafluoride produces organofluorine compounds from oxygen-containing organic functional groups using sulfur tetrafluoride. The reaction has broad scope, and SF4 is an inexpensive reagent. It is however hazardous gas whose handling requires specialized apparatus. Thus, for many laboratory scale fluorinations diethylaminosulfur trifluoride ("DAST") is used instead.

Oxidation with chromium(VI) complexes involves the conversion of alcohols to carbonyl compounds or more highly oxidized products through the action of molecular chromium(VI) oxides and salts. The principal reagents are Collins reagent, PDC, and PCC. These reagents represent improvements over inorganic chromium(VI) reagents such as Jones reagent.

<span class="mw-page-title-main">Jones oxidation</span> Oxidation of alcohol

The Jones oxidation is an organic reaction for the oxidation of primary and secondary alcohols to carboxylic acids and ketones, respectively. It is named after its discoverer, Sir Ewart Jones. The reaction was an early method for the oxidation of alcohols. Its use has subsided because milder, more selective reagents have been developed, e.g. Collins reagent.

<span class="mw-page-title-main">Sodium triacetoxyborohydride</span> Chemical compound

Sodium triacetoxyborohydride, also known as sodium triacetoxyhydroborate, commonly abbreviated STAB, is a chemical compound with the formula Na[(CH3COO)3BH]. Like other borohydrides, it is used as a reducing agent in organic synthesis. This colourless salt is prepared by protonolysis of sodium borohydride with acetic acid:

<span class="mw-page-title-main">1-Tetralone</span> Chemical compound

1-Tetralone is a bicyclic aromatic hydrocarbon and a ketone. In terms of its structure, it can also be regarded as benzo-fused cyclohexanone. It is a colorless oil with a faint odor. It is used as starting material for agricultural and pharmaceutical agents. The carbon skeleton of 1-tetralone is found in natural products such as Aristelegone A (4,7-dimethyl-6-methoxy-1-tetralone) from the family of Aristolochiaceae used in traditional Chinese medicine.

<span class="mw-page-title-main">Formaldoxime</span> Chemical compound

Formaldoxime is the organic compound with the formula H2C=N−OH. It is the oxime of formaldehyde. A colorless liquid, the pure compound tends to polymerize into a cyclic trimer. Aqueous solutions are stable as is the formaldoxime hydrochloride. It is a reagent in organic synthesis for the conversion of aryl diazonium salts to aryl aldehydes.

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