947-04-6

Usage

Uses

Used in Chemical Industry:
CYCLODODECANONE ISOOXIME is used as a chemical intermediate for the synthesis of various compounds and materials. Its unique structure and properties make it a valuable component in the development of new chemical products and processes.
Used in Pharmaceutical Industry:
CYCLODODECANONE ISOOXIME is used as a building block in the synthesis of pharmaceutical compounds. Its reactivity and versatility allow for the creation of new drugs with potential therapeutic applications.
Used in Research and Development:
CYCLODODECANONE ISOOXIME is used as a research compound in academic and industrial laboratories. Its unique properties and reactivity make it an interesting subject for scientific investigations and the development of new technologies.

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

• 693-57-2 12-Aminododecanoic acid 
• 18934-81-1 N-(tert-butyloxycarbonyl)-12-aminododecanoic acid 
• 1502-06-3 cyclodecanone 
• 946-89-4 cyclododecanone oxime 
• 53005-24-6 methyl 12-aminododecanoate 
• 91083-88-4 N-nitroso-12-dodecanelactam 
• 118162-56-4 12-Azido-dodecanethioic acid S-pyridin-2-yl ester 
• 830-13-7 cyclododecanone 
• 1129-90-4 cyclododecyne 
• 80667-36-3 11-azidoundecane carboxylic acid 
• 6407-35-8 N-cyclohexylidenemethylamine 
• 1074-51-7 cyclooctanone oxime 
• 19878-42-3 N-benzoyl-12-dodecanelactam 
• 111-86-4 n-Octylamine 

Downstream Products

• 295-03-4 azacyclotridecane 
• 693-57-2 12-Aminododecanoic acid 
• 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 

Relevant academic research and scientific papers

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.

A process for preparing laurolactam

A novel process for the preparation of laurolactam (laurolactam) is disclosed. More specifically, cyclo dodecanone (C) as a starting material. 12 H22 O Is a process for the preparation of laurolactam with won -pot reactions (one-pot reaction) by adding a hydroxyl ammonium compound and an inorganic acid.

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.

Synthesis of macrocyclic and medium-sized ring thiolactonesviathe ring expansion of lactams

A side chain insertion method for the ring expansion of lactams into macrocyclic thiolactones is reported, that can also be incorporated into Successive Ring Expansion (SuRE) sequences. The reactions are less thermodynamically favourable than the analogous lactam- and lactone-forming ring expansion processes (with this notion supported by DFT data), but nonetheless, three complementary protecting group strategies have been developed to enable this challenging transformation to be achieved.

Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles

The Schmidt reaction has been an efficient and widely used synthetic approach to amides and nitriles since its discovery in 1923. However, its application often entails the use of volatile, potentially explosive, and highly toxic azide reagents. Here, we report a sequence whereby triflic anhydride and formic and acetic acids activate the bulk chemical nitromethane to serve as a nitrogen donor in place of azides in Schmidt-like reactions. This protocol further expands the substrate scope to alkynes and simple alkyl benzenes for the preparation of amides and nitriles.

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.

Water-dispersible polyamide powder

A powder of polyamide particles, in which: said polyamide includes more than 50 mol % of amine ends among the total number of amine and acid ends of the polyamide; said particles include, on the surface thereof, primary amine groups neutralized by a phosphorous Bronsted acid, such as phosphoric acid; and the D50 of the particles falls within the range of 100 nm to 50 μm, preferably 100 nm to 20 μm. A method for producing such a powder and to the production of aqueous dispersions including same.

The one-port process for laurolactam from cyclododecanone

The present invention relates to a method for manufacturing laurolactam. More specifically, the present invention relates to a method for manufacturing laurolactam by a one-pot reaction by adding a hydroxyl ammonium compound and a chlorine-based catalyst to a starting cyclododecanone. The method for manufacturing laurolactam according to the present invention does not produce byproducts resulting from the use of an acid catalyst, and does not produce gas by-products that can cause an explosion accident, thereby achieving economic efficiency and stability at the same time.COPYRIGHT KIPO 2019

Process for preparing polymers from monomers comprising laurolactam

Polymers can be prepared from monomers comprising laurolactam, by a process including a. Beckmann rearrangement of cyclododecanone oxime to give laurolactam in the presence of a Beckmann rearrangement catalyst, b. removal of impurities from the laurolactam to obtain purified laurolactam, and c. polymerization of monomers comprising purified laurolactam. For avoidance of discolouration or yellowing under ageing conditions, prior to the polymerization, polycyclic substances containing 24 carbon atoms and at least one heteroatom selected from oxygen and nitrogen and having a molar mass between 300 and 380 g/mol are limited to 500 ppm, based on laurolactam.

METHOD FOR MANUFACTURING CYCLODODECANONE AND APPARATUS FOR MANUFACTURING THE SAME

A method for manufacturing cyclododecanone according to the present invention has an effect of having a significantly high conversion rate of cyclododecene and selectivity of cyclododecanone, can minimize the cost used for equipment and processes, is practical, and has an advantageous effect on industrial mass production compared to the prior art by significantly reducing a reaction residence time and a required reaction volume of a reactor.COPYRIGHT KIPO 2019