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| | tert-Butyl 4-methylenepiperidine-1-carboxylate Basic information |
| | tert-Butyl 4-methylenepiperidine-1-carboxylate Chemical Properties |
| 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) |
| Hazard Codes | Xi | | Hazard Note | Irritant | | HS Code | 2933399990 |
| | tert-Butyl 4-methylenepiperidine-1-carboxylate Usage And Synthesis |
| 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 |
| | tert-Butyl 4-methylenepiperidine-1-carboxylate Preparation Products And Raw materials |
| Raw materials | 1-(tert-Butyl)-5-(methylsulfonyl)-1H-tetrazole-->1-methyl-2-(methylsulfonyl)-1H-benzo[d]imidazole-->TRIMETHYLSILYLMETHYLMAGNESIUM CHLORIDE-->N-(tert-Butoxycarbonyl)-4-piperidone-->Methyltriphenylphosphonium iodide-->Methyltriphenylphosphonium bromide-->Potassium tert-butoxide-->Diethyl ether | | Preparation Products | tert-butyl 2-oxo-7-azaspiro[3.5]nonane-7-carboxylate-->tert-Butyl 4-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methylene)piperidine-1-carboxylate-->4-METHYLENEPIPERIDINE-->7-Azaspiro[3.5]nonane-7-carboxylic acid, 2-amino-, 1,1-dimethylethyl ester-->7-Azaspiro[3.5]nonane-7-carboxylic acid, 2-hydroxy-, 1,1-dimethylethyl ester-->7-Aza-spiro[3.5]nonane-->Piperidine, 4-[(3,5-difluorophenyl)methyl]--->4-[(5-bromo-2-pyridinyl)methyl]-1-piperidinecarboxylic
acid 1,1-dimethylethyl ester-->4-methylenepiperidine trifluoroacetate |
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