| Revision as of 11:58, 7 August 2011 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Script assisted update of identifiers for the Chem/Drugbox validation project (updated: 'UNII', 'ChEBI').← Previous edit |
Latest revision as of 00:38, 20 December 2024 edit undoProject Osprey (talk | contribs)Extended confirmed users9,949 edits →Synthesis and production: Snia Viscosa process |
| (126 intermediate revisions by 67 users not shown) |
| Line 1: |
Line 1: |
|
{{chembox |
|
{{chembox |
|
|
|Watchedfields = changed |
|
| verifiedrevid = 409736389 |
|
|
|
|verifiedrevid = 443496556 |
|
| ImageFileL1 = Caprolactam-2D-skeletal.png |
|
|
|
|ImageFile = Pytel na Caprolactam.jpg |
|
| ImageSizeL1 = |
|
|
| ImageFileR1 = Caprolactam-3D-vdW.png |
|
|ImageFileL1 = Caprolactam-2D-skeletal.png |
|
|
|ImageFileR1 = Caprolactam-from-xtal-3D-sf.png |
|
| ImageSizeR1 = 120px |
|
|
|
|ImageSizeR1 = 130px |
|
| IUPACName = Azepan-2-one |
|
|
|
|PIN = Azepan-2-one |
|
| OtherNames = ε-Caprolactam, 1-Aza-2-cycloheptanone, 2-Azacycloheptanone, Capron PK4, Cyclohexanone iso-oxime, Extrom 6N, Hexahydro-2-azepinone, Hexahydro-2H-azepin-2-one (9CI), Hexanolactame |
|
|
|
|OtherNames = {{ubl|1-Aza-2-cycloheptanone|2-Azacycloheptanone|ε-Caprolactam|Capron PK4|Cyclohexanone iso-oxime|Extrom 6N|Hexahydro-2-azepinone|Hexahydro-2H-azepin-2-one (9CI)|Hexanolactam|Hexano-6-lactam|Aminocaproic lactam}} |
|
| Section1 = {{Chembox Identifiers |
|
|
|
|Section1 = {{Chembox Identifiers |
|
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
|
|
|
|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
|
| ChemSpiderID = 7480 |
|
|
|
|ChemSpiderID = 7480 |
|
| KEGG_Ref = {{keggcite|correct|kegg}} |
|
|
|
|KEGG_Ref = {{keggcite|correct|kegg}} |
|
| KEGG = C06593 |
|
|
|
|KEGG = C06593 |
|
| InChI = 1/C6H11NO/c8-6-4-2-1-3-5-7-6/h1-5H2,(H,7,8) |
|
|
|
|InChI = 1/C6H11NO/c8-6-4-2-1-3-5-7-6/h1-5H2,(H,7,8) |
|
| InChIKey = JBKVHLHDHHXQEQ-UHFFFAOYAF |
|
|
|
|InChIKey = JBKVHLHDHHXQEQ-UHFFFAOYAF |
|
| ChEMBL_Ref = {{ebicite|correct|EBI}} |
|
|
|
|ChEMBL_Ref = {{ebicite|correct|EBI}} |
|
| ChEMBL = 276218 |
|
|
|
|ChEMBL = 276218 |
|
| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
|
|
|
|StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
|
| StdInChI = 1S/C6H11NO/c8-6-4-2-1-3-5-7-6/h1-5H2,(H,7,8) |
|
|
|
|StdInChI = 1S/C6H11NO/c8-6-4-2-1-3-5-7-6/h1-5H2,(H,7,8) |
|
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
|
|
|
|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
|
| StdInChIKey = JBKVHLHDHHXQEQ-UHFFFAOYSA-N |
|
|
|
|StdInChIKey = JBKVHLHDHHXQEQ-UHFFFAOYSA-N |
|
| CASNo = 105-60-2 |
|
|
| CASNo_Ref = {{cascite|correct|CAS}} |
|
|CASNo = 105-60-2 |
|
|
|CASNo_Ref = {{cascite|correct|CAS}} |
|
| EINECS = 203-313-2 |
|
|EINECS = 203-313-2 |
|
| PubChem = 7768 |
|
|PubChem = 7768 |
|
|
|Beilstein = 106934 |
|
| UNII = 6879X594Z8 |
|
|
| ChEBI = 28579 |
|
|Gmelin = 101802 |
|
|
|UNII_Ref = {{fdacite|correct|FDA}} |
|
| SMILES = O=C1NCCCCC1 |
|
|
|
|UNII = 6879X594Z8 |
|
|
|ChEBI_Ref = {{ebicite|correct|EBI}} |
|
|
|ChEBI = 28579 |
|
|
|SMILES = O=C1NCCCCC1 |
|
|
}} |
|
|
|Section2 = {{Chembox Properties |
|
|
|C=6 | H=11 | N=1 | O=1 |
|
|
|Appearance = White solid |
|
|
|Density = 1.01 g/cm<sup>3</sup> |
|
|
|MeltingPtC = 69.2 |
|
|
|BoilingPtC = 270.8 |
|
|
|BoilingPt_notes = at 1013.25 hPa |
|
|
|Solubility = 866.89 g/l (22 °C)<!--Ullmann's--> |
|
|
|VaporPressure = 8.10<sup>−8</sup> mmHg (20°C)<ref name=NIOSH>{{PGCH|0097}}</ref> |
|
|
}} |
|
|
|Section3 = {{Chembox Hazards |
|
|
|GHSPictograms = {{GHS07}} |
|
|
|GHSSignalWord = Warning |
|
|
|HPhrases = {{H-phrases|302|315|319|332|335}} |
|
|
|PPhrases = {{P-phrases|261|264|270|271|280|301+312|302+352|304+312|304+340|305+351+338|312|321|330|332+313|337+313|362|403+233|405|501}} |
|
|
|FlashPtC = 125 |
|
|
|PEL = none<ref name=NIOSH/> |
|
|
|ExploLimits = 1.4%-8.0%<ref name=NIOSH/> |
|
}} |
|
}} |
|
| Section2 = {{Chembox Properties |
|
|
| Formula = C<sub>6</sub>H<sub>11</sub>NO |
|
|
| MolarMass = 113.16 g/mol |
|
|
| Appearance = white solid |
|
|
| Density = 1,01 g/cm<sup>3</sup> |
|
|
| MeltingPt = 68 °C |
|
|
| BoilingPt = 136-138 °C @ 10 mm Hg |
|
|
| Solubility = 820 g/L (20 °C)<!--Ullmann's--> |
|
|
}} |
|
|
| Section3 = {{Chembox Hazards |
|
|
| MainHazards = |
|
|
| RPhrases = {{R20}}, {{R22}}, {{R36/37/38}} |
|
|
| SPhrases = |
|
|
| FlashPt = 125 °C |
|
|
| Autoignition = |
|
|
}} |
|
|
}} |
|
}} |
|
|
|
|
|
'''Caprolactam''' is an ] with the ] (CH<sub>2</sub>)<sub>5</sub>C(O)NH. This colourless solid is a ] or a cyclic ] of ]. Approximately 2 billion kilograms are produced annually. Caprolactam is the precursor to ], a widely used synthetic ].<ref name=Ullmann>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}}</ref> |
|
'''Caprolactam''' ('''CPL''') is an ] with the ] (CH<sub>2</sub>)<sub>5</sub>C(O)NH. This colourless solid is a ] (a cyclic ]) of ]. Global demand for this compound is approximately five million tons per year, and the vast majority is used to make ] filament, fiber, and plastics.<ref name=Ullmann>{{Ullmann | author1 = Josef Ritz | author2 = Hugo Fuchs | author3 = Heinz Kieczka | author4 = William C. Moran | title = Caprolactam | doi = 10.1002/14356007.a05_031.pub2}}</ref> |
|
|
|
|
|
==Synthesis and production== |
|
==Synthesis and production== |
|
Caprolactam was first described in the late 1800s when it was prepared by the cyclization of ε-], the product of the hydrolysis of caprolactam. Given the commercial significance of nylon-6, many methods have been developed for the production of caprolactam. Most of the caprolactam is synthesised from ] ('''1'''), which is first converted to its ] ('''2'''). Treatment of this oxime with acid induces the ] to give caprolactam ('''3'''): |
|
Caprolactam was first described in the late 1800s when it was prepared by the cyclization of ε-], the product of the hydrolysis of caprolactam. World demand for caprolactam was estimated to reach five million tons per year for 2015. 90% of caprolactam produced is used to make filament and fiber, 10% for plastics, and a small amount is used as a chemical intermediate.<ref name = Ullmann/> Due to its commercial significance, many methods have been developed for the production of caprolactam. It was estimated that 90% of all caprolactam is synthesised from ] ('''1'''), which is first converted to its ] ('''2'''). Treatment of this oxime with acid induces the ] to give caprolactam ('''3'''):<ref name=Ullmann/> |
|
|
|
|
|
: ] |
|
: ] |
|
|
|
|
|
The immediate product of the acid-induced rearrangement is the bisulfate salt of caprolactam. This salt is neutralized with ] to release the free lactam and cogenerate ammonium sulfate. In optimizing the industrial practices, much attention is directed toward minimizing the production of ammonium salts. |
|
The immediate product of the acid-induced rearrangement is the bisulfate salt of caprolactam. This salt is neutralized with ] to release the free lactam and cogenerate ]. In optimizing the industrial practices, much attention is directed toward minimizing the production of ammonium salts.<ref name = Ullmann/> |
|
|
|
|
|
The other major industrial route involves formation of the oxime from ] using ]. The advantage of this method is that ] is less expensive than ]. In earlier times, caprolactam was prepared by treatment of ] with ammonia.<ref name=Ullmann/> |
|
The other major industrial route involves formation of the oxime from ] using ], and this method accounts for 10% of world production.<ref name = Ullmann/> The advantage of this method is that cyclohexane is less expensive than ]. |
|
|
|
|
|
A minor industrial route involves the treatment of ] with ] (the Snia Viscosa process). This is thought to proceed via a ]. |
|
|
|
|
|
:] |
|
|
|
|
|
Other paths to caprolactam include the depolymerization of waste Nylon 6, and the reaction of ] with ammonia.<ref name=Ullmann/> At bench scale, the reaction between cyclohexanone with ] to give caprolactam in the ] has been reported.<ref>{{cite journal | doi = 10.1016/S0040-4020(00)00218-0 | journal = Tetrahedron | title = Expansion to Seven-Membered Rings | author1 = Eric J. Kantorowski | author2 = Mark J. Kurth | volume = 56 | issue = 26 | pages = 4317–4353 | year = 2000}}</ref> |
|
|
|
|
|
:] |
|
|
|
|
|
==Uses== |
|
==Uses== |
|
Caprolactam is the precursor to Nylon-6. The conversion entails a ]: |
|
Almost all caprolactam produced goes into the manufacture of ]. The conversion entails a ]: |
|
|
|
|
:n (CH<sub>2</sub>)<sub>5</sub>C(O)NH → <sub>n</sub> |
|
|
|
:] |
|
Nylon-6 is widely used in ]s and ]s. |
|
|
|
|
|
|
Nylon 6 is widely used in ]s and ]s. |
|
|
|
|
|
In situ anionic polymerization is employed for cast nylon production where conversion from ε-caprolactam to Nylon 6 takes place inside a mold. In conjunction with endless fiber processing the term thermoplastic resin transfer molding (T-RTM) is often used. |
|
|
|
|
|
Caprolactam is also used in the synthesis of several pharmaceutical drugs including ], ], and ]. |
|
|
|
|
|
==Safety== |
|
==Safety== |
|
Caprolactam is an ] and is mildly ], with an {{LD50}} of 1.1 g/kg (rat, oral). In 1991, it was included on the list of hazardous air pollutants by the U.S. ]. It was subsequently removed from the list in 1993.<ref></ref> In water, caprolactam hydrolyzes to ], which is used medicinally. |
|
Caprolactam is an ] and is mildly ], with an {{LD50}} of 1.1 g/kg (rat, oral). In 1991, it was included on the list of hazardous air pollutants by the U.S. ]. It was subsequently removed from the list in 1996 at the request of the manufacturers.<ref></ref> In water, caprolactam hydrolyzes to ], which is used medicinally. |
|
|
|
|
|
As of 2011 caprolactam had the unusual status of being the only chemical in the ]'s lowest hazard category, Group 4 "probably not carcinogenic to humans".<ref>{{Citation |
|
As of 2016 caprolactam had the unusual status of being the only chemical in the ]'s lowest hazard category, Group 4: "probably not carcinogenic to humans".<ref>{{cite web | url=https://monographs.iarc.fr/ENG/Monographs/vol71/mono71-16.pdf | title=Agents Classified by the ''IARC Monographs'' |volume=71 |page=395 | accessdate=21 October 2016| publisher=]| date=February 22, 2016}}</ref> |
|
|
|
|
|date=May 31 2011 |
|
|
|
Currently, there is no official ] set for workers handling caprolactam in the United States. The ] is set at 1 mg/m<sup>3</sup> over an eight-hour work shift for caprolactam dusts and vapors. The ] is set at 3 mg/m<sup>3</sup> for caprolactam dusts and vapors.<ref>{{Citation|access-date=November 8, 2013|title = NIOSH Pocket Guide to Chemical Hazards|publisher = CDC | url =https://www.cdc.gov/niosh/npg/npgd0097.html}}</ref> |
|
|title=World Health Organisation verdict on mobile phones and cancer |
|
|
|
|
|
|publisher=Cancer Research UK |
|
|
|
==Climate impact== |
|
|url=http://scienceblog.cancerresearchuk.org/2011/05/31/who-verdict-on-mobile-phones-and-cancer/ |
|
|
|
|
|
| access-date=2011-06-01 |
|
|
|
The production of caprolactam can produce ] as a by-product, a highly potent greenhouse gas. Emissions differ significantly due to different production processes and inconsistent use of emission abatement technology. A study commissioned by the German ] estimates emissions between 9 kg of nitrous oxide per ton of caprolactam and almost zero. <ref>{{cite web | url=https://www.oeko.de/fileadmin/oekodoc/NACAG-N2O-mitigation-potentials.pdf|title=Mitigation potentials for emissions of nitrous oxide from chemical industry in industrialised countries world-wide|publisher=Öko-Institut|date=March 2023|access-date=2023-10-17}}</ref> |
|
}}</ref><ref>{{Citation |
|
|
|
|
|
| access-date=July 15 2011 |
|
|
|
Nitrous oxide emissions from caprolactam production are unregulated in most countries. Unlike other chemical production processes, nitrous oxide emissions from caprolactam production are not included in the ]. <ref>{{cite news |last=Böck |first=Hanno |date=2023-09-28 |title=The avoidable Super-Greenhouse-Gas from Fertilizer, Nylon, and Vitamin B3 production |url=https://industrydecarbonization.com/news/the-avoidable-super-greenhouse-gas-from-fertilizer-nylon-and-vitamin-b3-production.html |work=Industry Decarbonization Newsletter |access-date=2023-10-17}}</ref> |
|
|title=Agents Classified by the IARC Monographs, Volumes 1–102 |
|
|
|publisher=WHO |
|
|
|url=http://monographs.iarc.fr/ENG/Classification/ClassificationsGroupOrder.pdf |
|
|
}}</ref> |
|
|
|
|
|
|
==References== |
|
==References== |
|
{{Reflist}} |
|
{{Reflist}} |
|
|
|
|
|
|
{{Carcinogen|state=collapsed}} |
|
] |
|
|
] |
|
|
] |
|
|
|
|
|
|
|
] |
|
] |
|
|
] |
|
] |
|
|
] |
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|
|
] |
|