tert-Butyl 4-methylenepiperidine-1-carboxylate

tert-Butyl 4-methylenepiperidine-1-carboxylate Property

Boiling point:

80°C/1mmHg(lit.)

Density 

1g/ml

refractive index 

1.4630 to 1.4670

storage temp. 

under inert gas (nitrogen or Argon) at 2-8°C

form 

liquid

pka

-1.41±0.20(Predicted)

color 

Clear, colourless

InChI

InChI=1S/C11H19NO2/c1-9-5-7-12(8-6-9)10(13)14-11(2,3)4/h1,5-8H2,2-4H3

InChIKey

PDTZMULNKGUIEJ-UHFFFAOYSA-N

SMILES

N1(C(OC(C)(C)C)=O)CCC(=C)CC1

CAS DataBase Reference

159635-49-1(CAS DataBase Reference)

Safety

Hazard Codes 

Xi

Hazard Note 

Irritant

HS Code 

2933399990

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Warning

Hazard statements

H315Causes skin irritation

H319Causes serious eye irritation

Precautionary statements

P261Avoid breathing dust/fume/gas/mist/vapours/spray.

P264Wash hands thoroughly after handling.

P264Wash skin thouroughly after handling.

P270Do not eat, drink or smoke when using this product.

P271Use only outdoors or in a well-ventilated area.

P280Wear protective gloves/protective clothing/eye protection/face protection.

P305+P351+P338IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continuerinsing.

P332+P313IF SKIN irritation occurs: Get medical advice/attention.

P337+P313IF eye irritation persists: Get medical advice/attention.

P501Dispose of contents/container to..…

tert-Butyl 4-methylenepiperidine-1-carboxylate Chemical Properties,Usage,Production

Uses

tert-Butyl 4-Methylenepiperidine-1-carboxylate is a useful reagent for the design of anion exchange membranes (AEMs) and ionomers for use in storage devices such as fuel cells and batteries.

Synthesis

Generalized method: Step 1: Synthesis of tert-butyl 4-methylene piperidine-1-carboxylate To a suspension of methyltriphenylphosphonium bromide (36.3 g, 101.6 mmol, 1.35 eq.) in dry ether (300 mL) was added potassium tert-butoxide (1 g, 98 mmol, 1.3 eq.) in a single addition at 0°C under nitrogen protection. The mixture was heated to reflux and stirred for 2 hours. Subsequently, the reaction mixture was cooled to 0 °C using an external ice bath and a solution of N-tert-butoxycarbonyl-4-piperidone (15 g, 75.3 mmol, 1.0 equiv) in ether (60 mL) was added dropwise. The mixture was slowly warmed to room temperature and stirring was continued at this temperature for 1 hour. After that, the mixture was heated to reflux again and stirred overnight (16 hours). Upon completion of the reaction, the mixture was cooled to room temperature, hexane (300 mL) was added, stirred for 10 minutes, filtered, and eluted with a solvent mixture of hexane/EtOAc (100/100 mL). The organic phases were combined and concentrated to give the crude product, which was finally purified by a CombiFlash system (100 g silica gel column, EtOAc/Hexane gradient elution, 0-30%) to give 14 g (94% yield) of tert-butyl 4-methylene piperidine-1-carboxylate as a colorless oil. 1H NMR (400 MHz, CDCl3): δ 4.74 (s, 2H), 3.42 (t, 4H), 2.18 (t, 4H), 1.47 (s, 9H).

References

[1] Patent: CN103635456, 2016, B. Location in patent: Paragraph 0270-0272; 0381-0383
[2] Patent: CN106674112, 2017, A. Location in patent: Paragraph 0035-0036
[3] Patent: WO2013/13308, 2013, A1. Location in patent: Paragraph 00196-00198
[4] Patent: US2010/222324, 2010, A1. Location in patent: Page/Page column 55
[5] Patent: US2010/234340, 2010, A1. Location in patent: Page/Page column 42