Hydroxylamine

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Hydroxylamine
Stereo, skeletal formula of hydroxylamine with all explicit hydrogens added Spacefill model of hydroxylamine
Stereo, skeletal formula of hydroxylamine with all explicit hydrogens added and assorted dimensions
Identifiers
CAS number 7803-49-8 YesY
PubChem 787
ChemSpider 766 YesY
UNII 2FP81O2L9Z YesY
EC number 232-259-2
KEGG C00192 YesY
MeSH Hydroxylamine
ChEBI CHEBI:15429 YesY
ChEMBL CHEMBL1191361 N
RTECS number NC2975000
Gmelin Reference 478
3DMet B01184
Jmol-3D images Image 1
Image 2
Properties
Molecular formula H3NO
Molar mass 33.03 g mol−1
Appearance Vivid white, opaque crystals
Density 1.21 g cm−3 (at 20 °C)[2]
Melting point 33 °C (91 °F; 306 K)
Boiling point 58 °C (136 °F; 331 K) (decomposes)
log P −0.758
Acidity (pKa) 5.95
Basicity (pKb) 8.05
Structure
Coordination
geometry
Trigonal at N
Molecular shape Tetrahedral at N
Dipole moment 0.67553 D
Thermochemistry
Specific
heat capacity
C
46.47 J K−1 mol−1
Std molar
entropy
So298
236.18 J K−1 mol−1
Std enthalpy of
formation
ΔfHo298
−39.9 kJ mol−1
Hazards
MSDS ICSC 0661
EU Index 612-122-00-7
EU classification E Harmful Xn Irritant Xi Dangerous for the Environment (Nature) N
R-phrases R2, R21/22, R37/38, R40, R41, R43, R48/22, R50
S-phrases (S2), S26, S36/37/39, S61
NFPA 704
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g., canola oil Health code 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g., chloroform Reactivity code 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g., fluorine Special hazards (white): no codeNFPA 704 four-colored diamond
Flash point 129 °C (264 °F; 402 K)
Autoignition temperature 265 °C (509 °F; 538 K)
LD50 408 mg/kg (oral, mouse); 59–70 mg/kg (intraperitoneal mouse, rat); 29 mg/kg (subcutaneous, rat)[3]
Related compounds
Related hydroxylammonium salts Hydroxylammonium chloride
Hydroxylammonium nitrate
Hydroxylammonium sulfate
Related compounds Ammonia

Hydrazine

Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 N (verify) (what is: YesY/N?)
Infobox references

Hydroxylamine is an inorganic compound with the formula NH2OH. The pure material is a white, unstable crystalline, hygroscopic compound.[4] However, hydroxylamine is almost always provided and used as an aqueous solution. It is used to prepare oximes, an important functional group. It is also an intermediate in biological nitrification. The oxidation of NH3 is mediated by the enzyme hydroxylamine oxidoreductase (HAO).

History[edit]

Hydroxylamine was first prepared as hydroxylamine hydrochloride in 1865 by the German chemist Wilhelm Clemens Lossen (1838-1906); he reacted tin and hydrochloric acid in the presence of ethyl nitrate.[5] It was first prepared in pure form in 1891 by the Dutch chemist Lobry de Bruyn and by the French chemist Léon Maurice Crismer (1858-1944).[6][7]

Production[edit]

NH2OH can be produced via several routes. The main route is via the Raschig process: aqueous ammonium nitrite is reduced by HSO3 and SO2 at 0 °C to yield a hydroxylamido-N,N-disulfonate anion:

NH4NO2 + 2 SO2 + NH3 + H2O → 2 NH4+ + N(OH)(OSO2)22−

This anion is then hydrolyzed to give (NH3OH)2SO4:

N(OH)(OSO2)22− + H2O → NH(OH)(OSO2) + HSO4
2 NH(OH)(OSO2) + 2 H2O → (NH
3
OH)
2
SO
4
+ SO2−
4

Solid NH2OH can be collected by treatment with liquid ammonia. Ammonium sulfate, (NH
4
)
2
SO
4
, a side-product insoluble in liquid ammonia, is removed by filtration; the liquid ammonia is evaporated to give the desired product.[4]

The net reaction is:

2NO
2
+ 4SO
2
+ 6H
2
O
+ 6NH
3
→ 4SO2−
4
+ 6NH+
4
+ 2NH
2
OH

Hydroxylammonium salts can then be converted to hydroxylamine by neutralization:

(NH3OH)Cl + NaOBu → NH2OH + NaCl + BuOH[4]

Julius Tafel discovered that hydroxylamine hydrochloride or sulfate salts can be produced by electrolytic reduction of nitric acid with HCl or H2SO4 respectively:[8][9]

HNO3 + 3H2 → NH2OH + 2H2O

Hydroxylamine can also be produced by the reduction of nitrous acid or potassium nitrite with bisulfite:

HNO2 + 2 HSO3 → N(OH)(OSO2)22− + H2O → NH(OH)(OSO2) + HSO4
NH(OH)(OSO2) + H3O+ (100 °C/1 h) → NH3(OH)+ + HSO4

Reactions[edit]

Hydroxylamine reacts with electrophiles, such as alkylating agents, which can attach to either the oxygen or the nitrogen:

R-X + NH2OH → R-ONH2 + HX
R-X + NH2OH → R-NHOH + HX

The reaction of NH2OH with an aldehyde or ketone produces an oxime.

R2C=O + NH2OH∙HCl , NaOH → R2C=NOH + NaCl + H2O

This reaction is useful in the purification of ketones and aldehydes: if hydroxylamine is added to an aldehyde or ketone in solution, an oxime forms, which generally precipitates from solution; heating the precipitate with an inorganic acid then restores the original aldehyde or ketone.[10]

Oximes, e.g., dimethylglyoxime, are also employed as ligands.

NH2OH reacts with chlorosulfonic acid to give hydroxylamine-O-sulfonic acid, a useful reagent for the synthesis of caprolactam.

HOSO2Cl + NH2OH → NH2OSO2OH + HCl

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

Hydroxylamine (NH2OH), or hydroxylamines (R-NHOH) can be reduced to amines.[11]

NH2OH (Zn/HCl) → NH3
R-NHOH (Zn/HCl) → R-NH2

Hydroxylamine explodes with heat:

4 NH2OH + O2 → 2 N2 + 6 H2O

The high reactivity comes in part from the partial isomerisation of the NH2OH structure to ammonia oxide (also known as azane oxide), with structure NH3+O-. [12]

Uses[edit]

Hydroxylamine and its salts are commonly used as reducing agents in myriad organic and inorganic reactions. They can also act as antioxidants for fatty acids. Some non-chemical uses include removal of hair from animal hides and photography developing solutions.[2]

The nitrate salt, hydroxylammonium nitrate, is being researched as a rocket propellant, both in water solution as a monopropellant and in its solid form as a solid propellant.

This has also been used in the past by biologists to introduce random mutations by switching base pairs from G to A, or from C to T. This is to probe functional areas of genes to elucidate what happens if their functions are broken. Nowadays other mutagens are used. Hydroxylamine can also be used to highly selectively cleave asparaginyl-glycine peptide bonds in peptides and proteins. It also bonds to and permanently disables (poisons) heme-containing enzymes. It is used as an irreversible inhibitor of the oxygen-evolving complex of photosynthesis on account of its similar structure to water.

In the semiconductor industry, hydroxylamine is often a component in the "resist stripper", which removes photoresist after lithography.

Safety[edit]

Hydroxylamine may explode on heating. The nature of the explosive hazard is not well understood. At least two factories dealing in hydroxylamine have been destroyed since 1999 with loss of life.[13] It is known, however, that ferrous and ferric iron salts accelerate the decomposition of 50% NH2OH solutions.[14] Hydroxylamine and its derivatives are more safely handled in the form of salts.

It is an irritant to the respiratory tract, skin, eyes, and other mucous membranes. It may be absorbed through the skin, is harmful if swallowed, and is a possible mutagen.[15]

Functional group[edit]

Substituted derivatives of hydroxylamine are known. If the hydroxyl hydrogen is substituted, this is called an O-hydroxylamine, if one of the amine hydrogens is substituted, this is called an N-hydroxylamine. Similarly to ordinary amines, one can distinguish primary, secondary and tertiary hydroxylamines, the latter two referring to compounds where two or three hydrogens are substituted, respectively. Examples of compounds containing a hydroxylamine functional group are N-tert-butyl-hydroxylamine or the glycosidic bond in calicheamicin. N,O-Dimethylhydroxylamine is a coupling agent, used to synthesize Weinreb amides.

Possible Deep-Space "Origin of Life"[edit]

In 2013, astrophysicists reported that the signature of hydroxylamine may have been detected in a star-forming field 1000 light years from earth. The scientists speculate that rocky bodies passing through such fields and later impacting distant planets may provide the basic building-blocks of life.[16]

See also[edit]

References[edit]

  1. ^ "Hydroxylamine - PubChem Public Chemical Database". The PubChem Project. USA: National Center for Biotechnology Information. 
  2. ^ a b Lide, David R., ed. (2006). CRC Handbook of Chemistry and Physics (87th ed.). Boca Raton, FL: CRC Press. ISBN 0-8493-0487-3. 
  3. ^ Martel, B.; Cassidy, K. (2004). Chemical Risk Analysis: A Practical Handbook. Butterworth–Heinemann. p. 362. ISBN 1-903996-65-1. 
  4. ^ a b c Greenwood and Earnshaw. Chemistry of the Elements. 2nd Edition. Reed Educational and Professional Publishing Ltd. pp. 431–432. 1997.
  5. ^ W. C. Lossen (1865) "Ueber das Hydroxylamine" (On hydroxylamine), Zeitschrift für Chemie, 8 : 551-553. From p. 551: "Ich schlage vor, dieselbe Hydroxylamin oder Oxyammoniak zu nennen." (I propose to call it hydroxylamine or oxyammonia.)
  6. ^ C. A. Lobry de Bruyn (1891) "Sur l'hydroxylamine libre" (On free hydroxylamine), Recueil des travaux chimiques des Pays-Bas, 10 : 100-112.
  7. ^ L. Crismer (1891) "Préparation de l'hydroxylamine cristallisée" (Preparation of crystalized hydroxylamine), Bulletin de la Société chimique de Paris, series 3, 6 : 793-795.
  8. ^ James Hale, Arthur (1919). The Manufacture of Chemicals by Electrolysis (1st ed.). New York: D. Van Nostrand Co. p. 32. Retrieved 5 June 2014. 
  9. ^ Osswald, Philipp; & Geisler, Walter; (1941). Process of preparing hydroxylamine hydrochloride (US2242477). U.S. Patent Office. 
  10. ^ Ralph Lloyd Shriner, Reynold C. Fuson, and Daniel Y. Curtin, The Systematic Identification of Organic Compounds: A Laboratory Manual, 5th ed. (New York: Wiley, 1964), chapter 6.
  11. ^ Smith, Michael and Jerry March. March's advanced organic chemistry : reactions, mechanisms, and structure. New York. Wiley. p. 1554. 2001.
  12. ^ "Ammonia oxide makes up some 20% of an aqueous solution of hydroxylamine.". National Center for Biotechnology Information. Chemical Communications (Cambridge, England). 28 February 2010. Retrieved 2 December 2014. 
  13. ^ Japan Science and Technology Agency Failure Knowledge Database.
  14. ^ Cisneros, L. O.; Rogers, W. J.; Mannan, M. S.; Li, X.; Koseki, H. (2003). "Effect of Iron Ion in the Thermal Decomposition of 50 mass% Hydroxylamine/Water Solutions". J. Chem. Eng Data 48 (5): 1164–1169. doi:10.1021/je030121p. 
  15. ^ MSDS Sigma-Aldrich
  16. ^ "Have Astronomers Found Chemical Precursor to Life In Gas Clouds?". www.livescience.com. 11 January 2013. 

Further reading[edit]

  • Hydroxylamine
  • Walters, Michael A. and Andrew B. Hoem. "Hydroxylamine." e-Encyclopedia of Reagents for Organic Synthesis. 2001.
  • Schupf Computational Chemistry Lab
  • M. W. Rathke A. A. Millard "Boranes in Functionalization of Olefins to Amines: 3-Pinanamine" Organic Syntheses, Coll. Vol. 6, p. 943; Vol. 58, p. 32. (preparation of hydroxylamine-O-sulfonic acid).

External links[edit]