Nitrosyl chloride

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Nitrosyl chloride
Nitrosyl-chloride-2D-dimensions.png
Nitrosyl-chloride-3D-vdW.png
Names
IUPAC name
Nitrosyl chloride[ citation needed ]
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.018.430 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 220-273-1
E number E919 (glazing agents, ...)
MeSH nitrosyl+chloride
PubChem CID
RTECS number
  • QZ7883000
UNII
UN number 1069
  • InChI=1S/ClNO/c1-2-3 Yes check.svgY
    Key: VPCDQGACGWYTMC-UHFFFAOYSA-N Yes check.svgY
  • ClN=O
Properties
NOCl
Molar mass 65.459 g mol−1
Appearanceyellow gas
Density 2.872 mg mL−1
Melting point −59.4 °C (−74.9 °F; 213.8 K)
Boiling point −5.55 °C (22.01 °F; 267.60 K)
Reacts
Structure
Dihedral, digonal
Hybridisation sp2 at N
1.90 D
Thermochemistry
Std molar
entropy (S⦵298)
261.68 J K−1 mol−1
51.71 kJ mol−1
Hazards
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazard W+OX: Reacts with water in an unusual or dangerous manner AND is oxidizer
3
0
1
W
OX
Safety data sheet (SDS) inchem.org
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Nitrosyl chloride is the chemical compound with the formula NOCl. It is a yellow gas that is commonly encountered as a component of aqua regia, a mixture of 3 parts concentrated hydrochloric acid and 1 part of concentrated nitric acid. It is a strong electrophile and oxidizing agent. It is sometimes called Tilden's reagent, after William A. Tilden, who was the first to produce it as a pure compound. [1]

Contents

Structure and synthesis

The molecule is bent. A double bond exists between N and O (distance = 1.16 Å) and a single bond between N and Cl (distance = 1.96 Å). The O=N–Cl angle is 113°. [2]

Production

Nitrosyl chloride can be produced in many ways.

HCl + NOHSO4 → H2SO4 + NOCl
HNO2 + HCl → H2O + NOCl
Cl2 + 2 NO → 2 NOCl
2NO2 + 4 HCl → 2NOCl + 2H2O + Cl2

Occurrence in aqua regia

NOCl also arises from the combination of hydrochloric and nitric acids according to the following reaction: [6]

HNO3 + 3 HCl → 2[Cl] + 2 H2O + NOCl

In nitric acid, NOCl is readily oxidized into nitrogen dioxide. The presence of NOCl in aqua regia was described by Edmund Davy in 1831. [7]

Reactions

NOCl behaves as an electrophile and an oxidant in most of its reactions. With halide acceptors it gives nitrosonium salts, and synthesis of nitrosonium tetrachloroferrate is typically performed in liquid NOCl: [8]

NOCl + FeCl3 → [NO]+[FeCl4]−

In a related reaction, sulfuric acid gives nitrosylsulfuric acid, the mixed acid anhydride of nitrous and sulfuric acid:

ClNO + H2SO4 → ONHSO4 + HCl

NOCl reacts with silver thiocyanate to give silver chloride and the pseudohalogen nitrosyl thiocyanate:

ClNO + AgSCN → AgCl + ONSCN

Similarly, it reacts with silver cyanide to give nitrosyl cyanide. [9]

Nitrosyl chloride is used to prepare metal nitrosyl complexes. With molybdenum hexacarbonyl, NOCl gives the dinitrosyldichloride complex: [10]

Mo(CO)6 + 2 NOCl → MoCl2(NO)2 + 6 CO

It dissolves platinum: [11]

Pt + 6 NOCl → (NO+)2[PtCl6]2- + 4 NO

Applications in organic synthesis

Aside from its role in the production of caprolactam, NOCl finds some other uses in organic synthesis. It adds to alkenes to afford α-chloro oximes. [12] The addition of NOCl follows the Markovnikov rule. Ketenes also add NOCl, giving nitrosyl derivatives:

H2C=C=O + NOCl → ONCH2C(O)Cl

Carbonyl compounds enolize; and then NOCl attacks the nucleophilic end of the alkene to give a vicinal keto- or aldo-oxime. [13]

Epoxides react with NOCl to give an α-chloronitritoalkyl derivatives. In the case of propylene oxide, the addition proceeds with high regiochemistry: [14]

Electrophilic addition of NOCl to propylene oxide.png

It converts amides to N-nitroso derivatives. [15] NOCl converts some cyclic amines to the alkenes. For example, aziridine reacts with NOCl to give ethene, nitrous oxide and hydrogen chloride.

Industrial applications

NOCl and cyclohexane react photochemically to give cyclohexanone oxime hydrochloride. This process exploits the tendency of NOCl to undergo photodissociation into NO and Cl radicals. The cyclohexanone oxime is converted to caprolactam, a precursor to nylon-6. [3] [16]

Historical importance

Before the advent of modern spectroscopic methods for chemical analysis, informative chemical degradation and structure elucidation required the characterization of the individual components of various extracts. Notably, the aforementioned introduction of nitrosyl chloride by Tilden in 1875, as a reagent for producing crystalline derivatives of terpenes, e.g. α-pinene from oil of turpentine allowed investigators to readily distinguish one terpene from another.: [17]

Safety

Nitrosyl chloride is very toxic and irritating to the lungs, eyes, and skin.

Related Research Articles

<span class="mw-page-title-main">Aqua regia</span> Mixture of nitric acid and hydrochloric acid in a 1:3 molar ratio

Aqua regia is a mixture of nitric acid and hydrochloric acid, optimally in a molar ratio of 1:3. Aqua regia is a fuming liquid. Freshly prepared aqua regia is colorless, but it turns yellow, orange or red within seconds from the formation of nitrosyl chloride and nitrogen dioxide. It was so named by alchemists because it can dissolve noble metals like gold and platinum, though not all metals.

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

Nitrous acid is a weak and monoprotic acid known only in solution, in the gas phase, and in the form of nitrite salts. It was discovered by Carl Wilhelm Scheele, who called it "phlogisticated acid of niter". Nitrous acid is used to make diazonium salts from amines. The resulting diazonium salts are reagents in azo coupling reactions to give azo dyes.

Iron(III) chloride describes the inorganic compounds with the formula FeCl3(H2O)x. Also called ferric chloride, these compounds are some of the most important and commonplace compounds of iron. They are available both in anhydrous and in hydrated forms, which are both hygroscopic. They feature iron in its +3 oxidation state. The anhydrous derivative is a Lewis acid, while all forms are mild oxidizing agents. It is used as a water cleaner and as an etchant for metals.

<span class="mw-page-title-main">Chromium(III) chloride</span> Chemical compound

Chromium(III) chloride (also called chromic chloride) is an inorganic chemical compound with the chemical formula CrCl3. It forms several hydrates with the formula CrCl3·nH2O, among which are hydrates where n can be 5 (chromium(III) chloride pentahydrate CrCl3·5H2O) or 6 (chromium(III) chloride hexahydrate CrCl3·6H2O). The anhydrous compound with the formula CrCl3 are violet crystals, while the most common form of the chromium(III) chloride are the dark green crystals of hexahydrate, CrCl3·6H2O. Chromium chlorides find use as catalysts and as precursors to dyes for wool.

Iron(II) chloride, also known as ferrous chloride, is the chemical compound of formula FeCl2. It is a paramagnetic solid with a high melting point. The compound is white, but typical samples are often off-white. FeCl2 crystallizes from water as the greenish tetrahydrate, which is the form that is most commonly encountered in commerce and the laboratory. There is also a dihydrate. The compound is highly soluble in water, giving pale green solutions.

<span class="mw-page-title-main">Thionyl chloride</span> Inorganic compound (SOCl2)

Thionyl chloride is an inorganic compound with the chemical formula SOCl2. It is a moderately volatile, colourless liquid with an unpleasant acrid odour. Thionyl chloride is primarily used as a chlorinating reagent, with approximately 45,000 tonnes per year being produced during the early 1990s, but is occasionally also used as a solvent. It is toxic, reacts with water, and is also listed under the Chemical Weapons Convention as it may be used for the production of chemical weapons.

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

Phosphorus trichloride is an inorganic compound with the chemical formula PCl3. A colorless liquid when pure, it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus compounds. It is toxic and reacts readily with water to release hydrogen chloride.

<span class="mw-page-title-main">Rhodium(III) chloride</span> Chemical compound

Rhodium(III) chloride refers to inorganic compounds with the formula RhCl3(H2O)n, where n varies from 0 to 3. These are diamagnetic red-brown solids. The soluble trihydrated (n = 3) salt is the usual compound of commerce. It is widely used to prepare compounds used in homogeneous catalysis.

<span class="mw-page-title-main">Gold(III) chloride</span> Chemical compound

Gold(III) chloride, traditionally called auric chloride, is an inorganic compound of gold and chlorine with the molecular formula Au2Cl6. The "III" in the name indicates that the gold has an oxidation state of +3, typical for many gold compounds. It has two forms, the monohydrate (AuCl3·H2O) and the anhydrous form, which are both hygroscopic and light-sensitive solids. This compound is a dimer of AuCl3. This compound has a few uses, such as an oxidizing agent and for catalyzing various organic reactions.

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

Nitrosylsulfuric acid is the chemical compound with the formula HSO4NO. It is a colourless solid that is used industrially in the production of caprolactam, and was formerly part of the lead chamber process for producing sulfuric acid. The compound is the mixed anhydride of sulfuric acid and nitrous acid.

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

Sulfuryl chloride is an inorganic compound with the formula SO2Cl2. At room temperature, it is a colorless liquid with a pungent odor. Sulfuryl chloride is not found in nature, as can be inferred from its rapid hydrolysis.

<span class="mw-page-title-main">Ruthenium(III) chloride</span> Chemical compound

Ruthenium(III) chloride is the chemical compound with the formula RuCl3. "Ruthenium(III) chloride" more commonly refers to the hydrate RuCl3·xH2O. Both the anhydrous and hydrated species are dark brown or black solids. The hydrate, with a varying proportion of water of crystallization, often approximating to a trihydrate, is a commonly used starting material in ruthenium chemistry.

The nitrosonium ion is NO+, in which the nitrogen atom is bonded to an oxygen atom with a bond order of 3, and the overall diatomic species bears a positive charge. It can be viewed as nitric oxide with one electron removed. This ion is usually obtained as the following salts: NOClO4, NOSO4H (nitrosylsulfuric acid, more descriptively written ONSO3OH) and NOBF4. The ClO−4 and BF−4 salts are slightly soluble in acetonitrile CH3CN. NOBF4 can be purified by sublimation at 200–250 °C and 0.01 mmHg (1.3 Pa).

<span class="mw-page-title-main">Nitroso</span> Class of functional groups with a –N=O group attached

In organic chemistry, nitroso refers to a functional group in which the nitric oxide group is attached to an organic moiety. As such, various nitroso groups can be categorized as C-nitroso compounds, S-nitroso compounds, N-nitroso compounds, and O-nitroso compounds.

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

Chloroplatinic acid (also known as hexachloroplatinic acid) is an inorganic compound with the formula [H3O]2[PtCl6](H2O)x (0 ≤ x ≤ 6). A red solid, it is an important commercial source of platinum, usually as an aqueous solution. Although often written in shorthand as H2PtCl6, it is the hydronium (H3O+) salt of the hexachloroplatinate anion (PtCl2−
6). Hexachloroplatinic acid is highly hygroscopic.

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

Triflic acid, the short name for trifluoromethanesulfonic acid, TFMS, TFSA, HOTf or TfOH, is a sulfonic acid with the chemical formula CF3SO3H. It is one of the strongest known acids. Triflic acid is mainly used in research as a catalyst for esterification. It is a hygroscopic, colorless, slightly viscous liquid and is soluble in polar solvents.

The chemical element nitrogen is one of the most abundant elements in the universe and can form many compounds. It can take several oxidation states; but the most common oxidation states are -3 and +3. Nitrogen can form nitride and nitrate ions. It also forms a part of nitric acid and nitrate salts. Nitrogen compounds also have an important role in organic chemistry, as nitrogen is part of proteins, amino acids and adenosine triphosphate.

<span class="mw-page-title-main">Metal nitrosyl complex</span> Complex of a transition metal bonded to nitric oxide: Me–NO

Metal nitrosyl complexes are complexes that contain nitric oxide, NO, bonded to a transition metal. Many kinds of nitrosyl complexes are known, which vary both in structure and coligand.

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

Chloroauric acid is an inorganic compound with the chemical formula H[AuCl4]. It forms hydrates H[AuCl4]·nH2O. Both the trihydrate and tetrahydrate are known. Both are orange-yellow solids consisting of the planar [AuCl4]− anion. Often chloroauric acid is handled as a solution, such as those obtained by dissolution of gold in aqua regia. These solutions can be converted to other gold complexes or reduced to metallic gold or gold nanoparticles.

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

Nitrosyl perchlorate is the inorganic compound with the formula NO(ClO4). A hygroscopic white solid, it is the salt of the nitrosonium cation with the perchlorate anion. It is an oxidant and strong electrophile, but has fallen out of use with the availability of the closely related salt nitrosonium tetrafluoroborate NO(BF4).

References

  1. ↑ Tilden, William A. (1874). "XXXII.—On aqua regia and the nitrosyl chlorides". J. Chem. Soc. 27: 630–636. doi:10.1039/JS8742700630.
  2. ↑ Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN   0-12-352651-5.
  3. 1 2 Ritz, Josef; Fuchs, Hugo; Kieczka, Heinz; Moran, William C. (2002). "Caprolactam". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a05_031. ISBN   3527306730.
  4. ↑ Morton, J. R.; Wilcox, H. W.; Moellerf, Therald; Edwards, Delwin C. (1953). "Nitrosyl Chloride". In Bailar, John C. Jr (ed.). Inorganic Syntheses. Vol. 4. McGraw-Hill. p. 48. doi: 10.1002/9780470132357.ch16 . ISBN   9780470132357.
  5. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 456. ISBN   978-0-08-037941-8.
  6. ↑ Beckham, L. J.; Fessler, W. A.; Kise, M. A. (1951). "Nitrosyl Chloride". Chemical Reviews. 48 (3): 319–396. doi:10.1021/cr60151a001. PMID   24541207.
  7. ↑ Edmund Davy (1830–1837). "On a New Combination of Chlorine and Nitrous Gas". Abstracts of the Papers Printed in the Philosophical Transactions of the Royal Society of London. 3: 27–29. JSTOR   110250.
  8. ↑ Williams, D. L. H. (1988). Nitrosation . Cambridge, UK: Cambridge University. p. 11. ISBN   0-521-26796-X.
  9. ↑ Kirby, G. W. (1977). "Tilden Lecture. Electrophilic C-Nitroso Compounds". Chemical Society Reviews. 6: 1. doi:10.1039/CS9770600001.
  10. ↑ Johnson, B. F. G.; Al-Obadi, K. H. (1970). "Dihalogenodinitrosylmolybdenum and Dihalogenodinitrosyltungsten". Inorganic Syntheses. Vol. 12. pp. 264–266. doi:10.1002/9780470132432.ch47. ISBN   9780470132432.{{cite book}}: |journal= ignored (help)
  11. ↑ Moravek, Richard T. (1986). "Nitrosyl Hexachloroplatinate(IV)". Inorganic Syntheses. Vol. 24. pp. 217–220. doi:10.1002/9780470132555.ch63. ISBN   9780470132555.
  12. ↑ Ohno, M.; Naruse, N.; Terasawa, I. (1969). "7-Cyanoheptanal". Org. Synth. 49: 27. doi:10.15227/orgsyn.049.0027.
  13. ↑ Williams 1988, p. 11.
  14. ↑ Malinovskii, M. S.; Medyantseva, N. M. (1953). "Olefin Oxides. IX. Condensation of Olefin Oxides with Nitrosyl Chloride". Zhurnal Obshchei Khimii. 23: 84–6. (translated from Russian)
  15. ↑ Van Leusen, A. M.; Strating, J. (1977). "p-Tolylsulfonyldiazomethane". Org. Synth. 57: 95. doi:10.15227/orgsyn.057.0095.
  16. ↑ Williams 1988, p. 12.
  17. ↑ Hanson, J.S. (2001). "The development of strategies for terpenoid structure determination". Natural Product Reports. 18 (6): 607–617. doi:10.1039/b103772m.
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