Nitrosyl chloride
Names | |
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IUPAC name Nitrosyl chloride[citation needed] | |
Identifiers | |
CAS Number |
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3D model (JSmol) |
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ChemSpider |
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ECHA InfoCard | 100.018.430 |
EC Number |
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E number | E919 (glazing agents, ...) |
MeSH | nitrosyl+chloride |
PubChem CID |
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RTECS number |
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UNII |
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UN number | 1069 |
CompTox Dashboard (EPA) |
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InChI
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Properties | |
Chemical formula | NOCl |
Molar mass | 65.459 g mol−1 |
Appearance | yellow 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) |
Solubility in water | Reacts |
Structure | |
Molecular shape | Dihedral, digonal |
Hybridisation | sp2 at N |
1.90 D | |
Thermochemistry | |
Std molar entropy (S⦵298) | 261.68 J K−1 mol−1 |
Std enthalpy of formation (ΔfH⦵298) | 51.71 kJ mol−1 |
Hazards | |
NFPA 704 (fire diamond) | 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). Y verify (what is YN ?) Infobox references |
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]
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.
- Combining nitrosylsulfuric acid and HCl affords the compound. This method is used industrially.[3]
- HCl + NOHSO4 → H2SO4 + NOCl
- A more convenient laboratory method involves the (reversible) dehydration of nitrous acid by HCl[4]
- HNO2 + HCl → H2O + NOCl
- By the direct combination of chlorine and nitric oxide; This reaction reverses above 100 °C.
- Cl2 + 2 NO → 2 NOCl
- By reduction of nitrogen dioxide with hydrogen chloride:[5]
- 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, for example antimony pentachloride, converts to nitrosonium salts:
- NOCl + SbCl5 → [NO]+[SbCl6]−
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.[8]
Nitrosyl chloride is used to prepare metal nitrosyl complexes. With molybdenum hexacarbonyl, NOCl gives the dinitrosyldichloride complex:[9]
- Mo(CO)6 + 2 NOCl → MoCl2(NO)2 + 6 CO
It dissolves platinum:[10]
- 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.[11] The addition of NOCl follows the Markovnikov rule. Ketenes also add NOCl, giving nitrosyl derivatives:
- H2C=C=O + NOCl → ONCH2C(O)Cl
Epoxides react with NOCl to give an α-chloronitritoalkyl derivatives. In the case of propylene oxide, the addition proceeds with high regiochemistry:[12]
It converts amides to N-nitroso derivatives.[13] 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]
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.:[14]
Safety
Nitrosyl chloride is very toxic and irritating to the lungs, eyes, and skin.
References
- ^ Tilden, William A. (1874). "XXXII.—On aqua regia and the nitrosyl chlorides". J. Chem. Soc. 27: 630–636. doi:10.1039/JS8742700630.
- ^ Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN 0-12-352651-5.
- ^ a b 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.
- ^ 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.
- ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 456. ISBN 978-0-08-037941-8.
- ^ Beckham, L. J.; Fessler, W. A.; Kise, M. A. (1951). "Nitrosyl Chloride". Chemical Reviews. 48 (3): 319–396. doi:10.1021/cr60151a001. PMID 24541207.
- ^ 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.
- ^ Kirby, G. W. (1977). "Tilden Lecture. Electrophilic C-Nitroso Compounds". Chemical Society Reviews. 6: 1. doi:10.1039/CS9770600001.
- ^ 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}}
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ignored (help) - ^ Moravek, Richard T. (1986). "Nitrosyl Hexachloroplatinate(IV)". Inorganic Syntheses. Vol. 24. pp. 217–220. doi:10.1002/9780470132555.ch63. ISBN 9780470132555.
- ^ Ohno, M.; Naruse, N.; Terasawa, I. (1969). "7-Cyanoheptanal". Org. Synth. 49: 27. doi:10.15227/orgsyn.049.0027.
- ^ 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)
- ^ Van Leusen, A. M.; Strating, J. (1977). "p-Tolylsulfonyldiazomethane". Org. Synth. 57: 95. doi:10.15227/orgsyn.057.0095.
- ^ Hanson, J.S. (2001). "The development of strategies for terpenoid structure determination". Natural Product Reports. 18: 607–617. doi:10.1039/b103772m.
External links
- Media related to Nitrosyl chloride at Wikimedia Commons
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HCl | He | ||||||||||||||||||||
LiCl | BeCl2 | B4Cl4 B12Cl12 BCl3 B2Cl4 +BO3 | C2Cl2 C2Cl4 C2Cl6 CCl4 +C +CO3 | NCl3 ClN3 +N +NO3 | ClxOy Cl2O Cl2O2 ClO ClO2 Cl2O4 Cl2O6 Cl2O7 ClO4 +O | ClF ClF3 ClF5 | Ne | ||||||||||||||
NaCl | MgCl2 | AlCl AlCl3 | Si5Cl12 Si2Cl6 SiCl4 | P2Cl4 PCl3 PCl5 +P | S2Cl2 SCl2 SCl4 +SO4 | Cl2 | Ar | ||||||||||||||
KCl | CaCl CaCl2 | ScCl3 | TiCl2 TiCl3 TiCl4 | VCl2 VCl3 VCl4 VCl5 | CrCl2 CrCl3 CrCl4 | MnCl2 MnCl3 | FeCl2 FeCl3 | CoCl2 CoCl3 | NiCl2 | CuCl CuCl2 | ZnCl2 | GaCl GaCl3 | GeCl2 GeCl4 | AsCl3 AsCl5 +As | Se2Cl2 SeCl2 SeCl4 | BrCl | Kr | ||||
RbCl | SrCl2 | YCl3 | ZrCl3 ZrCl4 | NbCl3 NbCl4 NbCl5 | MoCl2 MoCl3 MoCl4 MoCl5 MoCl6 | TcCl3 TcCl4 | RuCl2 RuCl3 RuCl4 | RhCl3 | PdCl2 | AgCl | CdCl2 | InCl InCl2 InCl3 | SnCl2 SnCl4 | SbCl3 SbCl5 | Te3Cl2 TeCl2 TeCl4 | ICl ICl3 | XeCl XeCl2 XeCl4 | ||||
CsCl | BaCl2 | * | LuCl3 | HfCl4 | TaCl3 TaCl4 TaCl5 | WCl2 WCl3 WCl4 WCl5 WCl6 | ReCl3 ReCl4 ReCl5 ReCl6 | OsCl2 OsCl3 OsCl4 OsCl5 | IrCl2 IrCl3 IrCl4 | PtCl2 PtCl4 | AuCl (Au[AuCl4])2 AuCl3 | Hg2Cl2 HgCl2 | TlCl TlCl3 | PbCl2 PbCl4 | BiCl3 | PoCl2 PoCl4 | AtCl | Rn | |||
FrCl | RaCl2 | ** | LrCl3 | RfCl4 | DbCl5 | SgO2Cl2 | BhO3Cl | Hs | Mt | Ds | Rg | Cn | Nh | Fl | Mc | Lv | Ts | Og | |||
* | LaCl3 | CeCl3 | PrCl3 | NdCl2 NdCl3 | PmCl3 | SmCl2 SmCl3 | EuCl2 EuCl3 | GdCl3 | TbCl3 | DyCl2 DyCl3 | HoCl3 | ErCl3 | TmCl2 TmCl3 | YbCl2 YbCl3 | |||||||
** | AcCl3 | ThCl3 ThCl4 | PaCl4 PaCl5 | UCl3 UCl4 UCl5 UCl6 | NpCl3 | PuCl3 | AmCl2 AmCl3 | CmCl3 | BkCl3 | CfCl3 CfCl2 | EsCl2 EsCl3 | FmCl2 | MdCl2 | NoCl2 |