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| NOCl reacts with silver thiocyanate to give ] and the ] nitrosyl thiocyanate: | NOCl reacts with silver thiocyanate to give ] and the ] nitrosyl thiocyanate: | ||
| : ClNO + AgSCN → AgCl + ONSCN | : ClNO + AgSCN → AgCl + ONSCN | ||
| Nitrosyl chloride is used to prepare ]es. With ], NOCl gives the dinitrosyldichloride complex:<ref>B. F. G. Johnson, K. H. Al-Obadi "Dihalogenodinitrosylmolybdenum and Dihalogenodinitrosyltungsten" Inorg. Synth. 1970, vol. 12, pp. 264–266. {{DOI|10.1002/9780470132432.ch47}}</ref> | |||
| :Mo(CO)<sub>6</sub> + 2 NOCl → MoCl<sub>2</sub>(NO)<sub>2</sub> + 6 CO | |||
| ===Applications in organic synthesis=== | ===Applications in organic synthesis=== | ||
| Aside from its role in the production of caprolactam, NOCl finds some other uses In ]. It adds to ]s to afford α-chloro ]s.<ref>{{OrgSynth | author = Ohno, M,; Naruse, N.; Terasawa, I. | title =7-cyanoheptanal | collvol = 5 | collvolpages = 266 | year = 1973 | prep = cv5p0266}}</ref> The initial addition of NOCl follows the ]. ]s also add NOCl, giving nitrosyl derivatives: | Aside from its role in the production of caprolactam, NOCl finds some other uses In ]. It adds to ]s to afford α-chloro ]s.<ref>{{OrgSynth | author = Ohno, M,; Naruse, N.; Terasawa, I. | title =7-cyanoheptanal | collvol = 5 | collvolpages = 266 | year = 1973 | prep = cv5p0266}}</ref> The initial addition of NOCl follows the ]. ]s also add NOCl, giving nitrosyl derivatives: | ||
| : |
: H<sub>2</sub>C=C=O + NOCl → ONCH<sub>2</sub>C(O)Cl | ||
| ] also undergoes electrophilic addition with NOCl to give an α-chloro-nitritoakyl derivative: | ] also undergoes electrophilic addition with NOCl to give an α-chloro-nitritoakyl derivative: | ||
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| ] | ] | ||
| It converts amides to N-nitroso derivatives.<ref>A. M. van Leusen and J. Strating "p-Tolylsulfonyldiazomethane" Org. Synth. 1977, vol. 57, 95. {{DOI|10.15227/orgsyn.057.0095}}}</ref> NOCl converts some cyclic amines to the alkenes. For example, ] reacts with NOCl to give ], ] and ]. | |||
| ==Industrial applications== | ==Industrial applications== | ||
Revision as of 00:23, 29 August 2014
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| Names | |
|---|---|
| Preferred IUPAC name Nitrosyl chloride | |
| Systematic IUPAC name Nitrooyl chloride | |
Other names
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| Identifiers | |
| CAS Number | |
| 3D model (JSmol) | |
| ChemSpider | |
| ECHA InfoCard | 100.018.430 
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| EC Number |
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| E number | E919 (glazing agents, ...) |
| MeSH | nitrosyl+chloride |
| PubChem CID | |
| RTECS number |
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| UN number | 1069 |
| CompTox Dashboard (EPA) | |
InChI
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SMILES
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| Properties | |
| Chemical formula | NOCl |
| Molar mass | 65.459 g mol |
| Appearance | Yellow gas |
| Density | 2.872 mg mL |
| 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 | sp at N |
| Dipole moment | 1.90 D |
| Thermochemistry | |
| Std molar entropy (S298) |
261.68 J K mol |
| Std enthalpy of formation (ΔfH298) |
51.71 kJ mol |
| Hazards | |
| NFPA 704 (fire diamond) |
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| Related compounds | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa).
 Y verify (what is ?)
Infobox references
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Nitrosyl chloride is the chemical compound with the formula NOCl. It is a yellow gas that is most commonly encountered as a decomposition product of aqua regia, a mixture of hydrochloric acid and nitric acid. It is a strong electrophile and oxidizing agent.
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 = 1.69 Å). The O-N-Cl angle is 113°.
Production
Since nitrosyl chloride is chemically simple and stable at room temperature and below, it can be produced in many ways.
- Combining nitrosylsulfuric acid and HCl affords the compound. This method is used industrially.
- HCl + NOHSO4 → H2SO4 + NOCl
- A more convenient laboratory method involves the (reversible) dehydration of nitrous acid by HCl
- HNO2 + 2HCl → H2O + NOCl
- Michael Faraday prepared nitrosyl chloride by reacting palladium with aqua regia:
- Pd + HNO3 + 3 HCl → PdCl2 + 2 H2O + NOCl
- NOCl forms by the direct combination of chlorine and nitric oxide; This reaction reverses above 100 °C.
- Cl2 + 2NO → 2NOCl
- Another method of producing nitrosyl chloride is by direct union of the elements at 400 °C, although there is some regression as above.
- N2 + O2 + Cl2 → 2 NOCl ↔ 2NO + Cl2
Occurrence in aqua regia
NOCl also arises from the combination of hydrochloric and nitric acids according to the following reaction:
- HNO3 + 3 HCl → Cl2 + 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.
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 →
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
Nitrosyl chloride is used to prepare metal nitrosyl complexes. With molybdenum hexacarbonyl, NOCl gives the dinitrosyldichloride complex:
- Mo(CO)6 + 2 NOCl → MoCl2(NO)2 + 6 CO
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. The initial addition of NOCl follows the Markovnikov rule. Ketenes also add NOCl, giving nitrosyl derivatives:
- H2C=C=O + NOCl → ONCH2C(O)Cl
Propylene oxide also undergoes electrophilic addition with NOCl to give an α-chloro-nitritoakyl derivative:
It converts amides to N-nitroso derivatives. 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 oxide is converted to caprolactam, a precursor to Nylon-6.
Safety
Nitrosyl chloride is very toxic and irritating to the lungs, eyes, and skin.
References
- Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
- ^ Josef Ritz, Hugo Fuchs, Heinz Kieczka, William C. Moran "Caprolactam" Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2002. doi:10.1002/14356007.a05_031
- J. R. Morton, H. W. Wilcox "Nitrosyl Chloride" Inorganic Syntheses 1953, vol. 48-52. doi:10.1002/9780470132357.ch16
- L. J. Beckham, W. A. Fessler, M. A. Kise (1951). "Nitrosyl Chloride". Chemical Reviews. 48 (3): 319–396. doi:10.1021/cr60151a001.
{{cite journal}}: CS1 maint: multiple names: authors list (link) - 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, Vol. 3. JSTOR: 27–29. JSTOR 110250.
- B. F. G. Johnson, K. H. Al-Obadi "Dihalogenodinitrosylmolybdenum and Dihalogenodinitrosyltungsten" Inorg. Synth. 1970, vol. 12, pp. 264–266. doi:10.1002/9780470132432.ch47
- Ohno, M,; Naruse, N.; Terasawa, I. (1973). "7-cyanoheptanal". Organic Syntheses
{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 5, p. 266. - A. M. van Leusen and J. Strating "p-Tolylsulfonyldiazomethane" Org. Synth. 1977, vol. 57, 95. doi:10.15227/orgsyn.057.0095}