947-04-6

Basic information

• Product Name: CYCLODODECANONE ISOOXIME
• Synonyms: 12-amino-dodecanoicacilactam;1-Aza-2-cyclotridecanone;2-Oxo-dodecamethylenimine;Aza-cyclotridecan-2-on;Azacyclotridecan-2-one;Cyclododecalactam;Dodecalactam;Dodecanoic acid, 12-amino-, lactam
• CAS NO: 947-04-6
• Molecular Formula: C12H23NO
• Molecular Weight: 197.32
• EINECS: 213-424-8
• Product Categories: Organics;Building Blocks;Carbonyl Compounds;Chemical Synthesis;Lactams;Organic Building Blocks
• Mol File: 947-04-6.mol
• Article Data: 80

Chemical Properties

• Melting Point: 150-153 °C(lit.)
• Boiling Point: 334.44°C (rough estimate)
• Flash Point: 195 °C
• Appearance: /
• Density: 0.9415 (rough estimate)
• Vapor Pressure: 0.000453mmHg at 25°C
• Refractive Index: 1.4400 (estimate)
• PKA: 16.91±0.20(Predicted)
• Water Solubility: 223mg/L at 20℃
• BRN: 122031
• CAS DataBase Reference: CYCLODODECANONE ISOOXIME(CAS DataBase Reference)
• NIST Chemistry Reference: CYCLODODECANONE ISOOXIME(947-04-6)
• EPA Substance Registry System: CYCLODODECANONE ISOOXIME(947-04-6)

Safety Data

• RIDADR: 3257
• WGK Germany: 1
• RTECS: CL6940000
• HazardClass: IRRITANT
• Hazardous Substances Data: 947-04-6(Hazardous Substances Data)

Usage

Chemical Properties

Dry PowderSolid; very faintly beige crystalline lumps. Virtually insol in water.

Preparation

One route to dodecyllactam is from butadiene as follows: Butadiene is trimerized with a Ziegler-Natta catalyst to give 1,5,9-cyclododecatriene which is then hydrogenated to cyclododecane. Dodecyllactam is then obtained by a series of reactions similar to those used to prepare caprolactam from cyclohexane.

Health Hazard

The acute oral LD50 was 2,330 mg/kg bw (rat) with central nervous system stimulation (trembling, convulsive twitches, ataxia) as the main clinical sign appearing at about 1,580 mg/kg bw. The dermal LD50 was greater than 2,000 mg/kg bw (rat). Decreased food consumption and stagnation of body weight development were noted. Validacute inhalation studies are not available. Azacyclotridecan-2-one was not irritating to the rabbit skin or eye (OECD TG 404, 405). It was not sensitizing in aguinea pig maximization test (OECD TG 406; 1981).

Purification Methods

Azacyclotridecan-2-one crystallises from CHCl3 and is stored over P2O5 in a vacuum desiccator. [Beilstein 26/1 V 566.]

InChI:InChI=1/C12H23NO/c14-12-10-8-6-4-2-1-3-5-7-9-11-13-12/h1-11H2,(H,13,14)

Synthetic route

cyclododecanone oxime (946-89-4) → 2-azacyclotridecanone (947-04-6)

Conditions	Yield
With 1,3,5-trichloro-2,4,6-triazine In acetonitrile for 1h; Product distribution / selectivity; Heating / reflux;	100%
With 1,3,5-trichloro-2,4,6-triazine In Isopropylbenzene; Cyclooctan at 113℃; for 0.5h; Product distribution / selectivity;	100%
With 1,3,5-trichloro-2,4,6-triazine In octane at 113℃; for 1h; Product distribution / selectivity;	100%

cyclooctanone oxime (1074-51-7) + cyclododecanone oxime (946-89-4) → 2-azacyclononanone (935-30-8) + 2-azacyclotridecanone (947-04-6)

Conditions	Yield
With 1,3,5-trichloro-2,4,6-triazine In Cyclooctan at 113℃; for 0.5h; Product distribution / selectivity;	A 50% B 100%

cyclododecanone oxime (946-89-4) + 2,4-dichloro-6-cyclododecylidene'aminooxy-1,3,5-triazine → 2-azacyclotridecanone (947-04-6)

Conditions	Yield
In acetonitrile	100%

cyclododecanone oxime (946-89-4) + 2-chloro-4,6-bis(cyclododecylidene-aminooxy)-1,3,5-triazine (1178530-68-1) → 2-azacyclotridecanone (947-04-6)

Conditions	Yield
With hydrogenchloride In acetonitrile	100%

azacyclotridec-10-en-2-one → 2-azacyclotridecanone (947-04-6)

Conditions	Yield
With palladium 10% on activated carbon; hydrogen In methanol at 20℃; under 760.051 Torr;	99%

cyclododecanone (830-13-7) → 2-azacyclotridecanone (947-04-6)

Conditions	Yield
With sodium azide; sulfuric acid In ethyl acetate at 60 - 77℃; for 2h; Reagent/catalyst; Solvent; Temperature;	98%
With sodium azide; sulfuric acid; silica gel at 60℃; for 0.5h; Schmidt reaction;	95%
With hydroxylamine hydrochloride In benzonitrile at 90℃; for 12h; Beckmann Rearrangement; Inert atmosphere;	95%

cyclododecanone oxime hydrochloride (3046-04-6) → 2-azacyclotridecanone (947-04-6)

Conditions	Yield
With sulfuric acid for 0.416667h; Product distribution / selectivity;	95.1%

C15H31NOSi (136848-31-2) → 2-azacyclotridecanone (947-04-6)

Conditions	Yield
silver hexafluoroantimonate; antimonypentachloride In dichloromethane; acetonitrile for 3h; Heating;	77%
With silver hexafluoroantimonate; antimonypentachloride In acetonitrile for 3h; Heating;	77%

1-[3-(tritylthio)propanoyl]-1-azacyclotridecan-2-one → 2-azacyclotridecanone (947-04-6) + 1-thia-5-azacycloheptadecane-4,17-dione

Conditions	Yield
Stage #1: 1-[3-(tritylthio)propanoyl]-1-azacyclotridecan-2-one With trifluoroacetic acid In dichloromethane for 0.05h; Inert atmosphere; Stage #2: With chlorotriisopropylsilane In dichloromethane for 0.5h; Inert atmosphere; Stage #3: With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 20℃; for 18h; Reagent/catalyst;	A 4% B 56%

12-Aminododecanoic acid (693-57-2) → 2-azacyclotridecanone (947-04-6)

Conditions	Yield
With triethylamine; N-Hexadecyl-2-chloropyridinium iodide In 1,2-dichloro-ethane at 70℃; for 24h;	50%
With di(n-butyl)tin oxide In 1,3,5-trimethyl-benzene for 24h; Heating;	25%
With triethylamine; N-Hexadecyl-2-chloropyridinium iodide In 1,2-dichloro-ethane at 70℃; for 24h; Mechanism; also with N-methyl-2-chloropyridinium iodide, effect of micelles;

cyclododecanone oxime (946-89-4) + N-cyclohexylidenemethylamine (6407-35-8) → caprolactam (105-60-2) + 2-azacyclotridecanone (947-04-6)

Conditions	Yield
With 1,3,5-trichloro-2,4,6-triazine In Isopropylbenzene at 113℃; for 1.58333h; Product distribution / selectivity;	A 20% B 50%

cyclotridecyne (5601-68-3) → 2-azacyclotridecanone (947-04-6)

Conditions	Yield
With nitromethane; trifluoromethylsulfonic anhydride; acetic acid In formic acid at 80 - 120℃;	42%

(Z)-4,5,6,7,8,9,10,11,12,13-decahydro-1-oxa-3a-azacyclopentacyclotridecene-2,3-dione → 3-allylazacyclotridecan-2-one + 2-azacyclotridecanone (947-04-6) + (E)-azacyclotridec-3-en-2-one + 14-allyl-4,5,6,7,8,9,10,11,12,13-decahydro-1-oxa-3a-azacyclopentacyclotridecene-2,3-dione (831227-11-3)

Conditions	Yield
Stage #1: (Z)-4,5,6,7,8,9,10,11,12,13-decahydro-1-oxa-3a-azacyclopentacyclotridecene-2,3-dione With allyl methyl carbonate; tris(dibenzylideneacetone)dipalladium(0) chloroform complex In chloroform; acetonitrile for 48h; Heating / reflux; Stage #2: With sodium methylate In methanol at 0℃; for 1h; Stage #3: With hydrogenchloride In water; ethyl acetate	A 11% B 6% C 5% D 25%

methyl 12-aminododecanoate (53005-24-6) → 2-azacyclotridecanone (947-04-6) + 12-Aminododecanoic acid (693-57-2)

Conditions	Yield
With whole-cells or crude cell extract of recombinant E.coli BL21 (DE3) (pCom10_T31) In ethanol for 0.5h; pH=10; aq. buffer; Enzymatic reaction;	A 13% B n/a

Upstream product

• 19878-42-3 N-benzoyl-12-dodecanelactam 
• 111-86-4 n-Octylamine 
• 693-57-2 12-Aminododecanoic acid 
• 294-62-2 cyclododecane 
• 1129-90-4 cyclododecyne 
• 5601-68-3 cyclotridecyne 
• 1501-82-2 cyclododecene 
• 112-80-1 cis-Octadecenoic acid 
• 112-77-6 (Z)-9-octadecenoyl chloride 
• 943-93-1 1,2-epoxy-5,9-cyclododecadiene 
• 286-99-7 1,2-epoxycyclododecane 
• 4904-61-4 cyclododeca-1,5,9-triene 
• 53005-24-6 methyl 12-aminododecanoate 
• 3046-04-6 cyclododecanone oxime hydrochloride 

Downstream Products

• 131043-43-1 N-(o-azidobenzoyl)-2-azacyclotridecanone 
• 64414-61-5 N-(Aminopropyl)-12-dodecanlactam 
• 5498-70-4 1-methyl-1-azacyclotrideca-2-one 
• 1561902-50-8 C₃₁H₄₂N₂O₂ 
• 1561903-38-5 C₃₁H₄₂N₂O₂*ClH 
• 1561903-12-5 C₃₂H₄₂N₂O₄ 
• 1561903-43-2 C₃₂H₄₂N₂O₄*ClH 
• 1561903-17-0 C₃₃H₄₆N₂O₄ 
• 1561903-45-4 C₃₃H₄₆N₂O₄*ClH 
• 1561903-20-5 C₃₁H₄₂N₂ 
• 1561903-48-7 C₃₁H₄₂N₂*ClH 
• 1561903-22-7 C₃₂H₄₄N₂O 
• 1561903-50-1 C₃₂H₄₄N₂O*ClH 
• 1561903-24-9 C₃₃H₄₄N₂O₃ 

Relevant articles and documents

Dehydrative Beckmann rearrangement and the following cascade reactions

The Beckmann rearrangement has been predominantly studied for the synthesis of amide and lactam. By strategically using the in situ generated Appel's salt or Mitsunobu's zwitterionic adduct as the dehydrating agent, a series of Beckmann rearrangement and following cascade reactions have been developed herein. The protocol allows the conversion of various ketoximes into amide, thioamide, tetrazole and imide products in modular procedures. The generality and tolerance of functionalities of this method have been demonstrated.

Efficient nitriding reagent and application thereof

The invention discloses an efficient nitriding reagent and application thereof, wherein the nitriding reagent comprises nitrogen oxide, an active agent, a reducing agent and an organic solvent. By applying the nitriding reagent, nitrogen-containing compounds such as amide, nitrile and the like can be produced, and the method is simple in condition, low in waste discharge amount and simple in reaction equipment.

Chlorotropylium Promoted Conversions of Oximes to Amides and Nitriles

Chlorotropylium chloride as a catalyst for the transformations of oximes, ketones, and aldehydes to their corresponding amides and nitriles in excellent yields (up to 99 %) and in short reaction times (mostly 10–15 min). Oximes were electrophilically attacked on the hydroxyl oxygen by chlorotropylium. The produced tropylium oxime ethers were the key intermediates, of which the ketoxime ether led to amide through Beckmann rearrangement, and the aldoxime ether led to nitrile by nitrogen base DBU assisted formal dehydration. This chlorotropylium activation protocol offered general, mild, and efficient avenues bifurcately from oximes to both amides and nitriles by one organocatalyst.