BENZYL 2,2,2-TRICHLOROACETIMIDATE CAS 81927-55-1
BENZYL 2,2,2-TRICHLOROACETIMIDATE Basic information
| Product Name: | BENZYL 2,2,2-TRICHLOROACETIMIDATE |
| Synonyms: | 2,2,2-TRICHLOROACETIMIDIC ACID BENZYL ESTER;Benzyl 2,2,2-trichloroacetimidate, 98+%;Ethanimidic acid, 2,2,2-trichloro-, phenylmethyl ester;Benzyl 2,2,2-trichloroacetimidate, GC 99%;BENZYLPHOSPONIC ACID;Benzyl 2,2,2-trichloroethanimidoate;Benzyl trichloroacetimidate;TRICHLOROACETIMIDIC ACID BENZYL ESTER |
| CAS: | 81927-55-1 |
| MF: | C9H8Cl3NO |
| MW: | 252.52 |
| EINECS: | |
| Product Categories: | Protection & Derivatization Reagents (for Synthesis);Synthetic Organic Chemistry;Amidates/Imidates;Building Blocks;Chemical Synthesis;Nitrogen Compounds;Benzene series;Organic Building Blocks |
| Mol File: | 81927-55-1.mol |
BENZYL 2,2,2-TRICHLOROACETIMIDATE Chemical Properties
| Melting point | 3 °C |
| Boiling point | 106-114 °C0.5 mm Hg(lit.) |
| density | 1.359 g/mL at 25 °C(lit.) |
| refractive index | n |
| Fp | >230 °F |
| storage temp. | 2-8°C |
| solubility | Miscible with cyclohexane/dichloromethane. |
| pka | 2.23±0.70(Predicted) |
| form | Liquid |
| color | Clear colorless to yellow |
| Sensitive | Moisture Sensitive |
| BRN | 2525375 |
| Stability: | Moisture Sensitive |
| InChI | InChI=1S/C9H8Cl3NO/c10-9(11,12)8(13)14-6-7-4-2-1-3-5-7/h1-5,13H,6H2 |
| InChIKey | HUZCTWYDQIQZPM-UHFFFAOYSA-N |
| SMILES | C(=N)(OCC1=CC=CC=C1)C(Cl)(Cl)Cl |
| CAS DataBase Reference | 81927-55-1(CAS DataBase Reference) |
Safety Information
| Hazard Codes | Xn |
| Risk Statements | 22-36/37/38 |
| Safety Statements | 26 |
| WGK Germany | 3 |
| F | 8-10-21 |
| HS Code | 29252900 |
| Storage Class | 10 - Combustible liquids |
| Hazard Classifications | Acute Tox. 4 Oral Eye Irrit. 2 Skin Irrit. 2 STOT SE 3 |
| Chemical Properties | clear colorless to yellow liquid |
| Uses | Benzyl 2,2,2-trichloroacetimidate is used for the acid-catalyzed benzylation of hydroxy groups. |
| Uses | Benzyl 2,2,2-trichloroacetimidate is used for the acid-catalyzed benzylation of hydroxy groups. It acts as reagent during the synthesis of funiculosin dimethyl ether and (S)-3-(benzyloxy)-2-methylpropanal. It can also be used for mild esterification of carboxylic acids in the presence of a catalytic amount of BF3 etherate. |
| Uses | Benzyl 2,2,2-trichloroacetimidate was used as reagent during the synthesis of funiculosin dimethyl ether and (S)-3-(benzyloxy)-2-methylpropanal. It was used in the acid-catalyzed benzylation of hydroxy groups. |
| Synthesis | 545-06-2 100-51-6 81927-55-1 DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) (1.24 mL, 8.31 mmol) was slowly added dropwise to a solution of dichloromethane (86 mL) containing benzyl alcohol (8.60 mL, 83.11 mmol) and trichloroacetonitrile (41.66 mL, 415.57 mmol), and the reaction mixture was cooled under ice bath conditions to 0 °C . Subsequently, the mixture was gradually warmed up to room temperature reaction. The progress of the reaction was monitored by thin layer chromatography (TLC) (petroleum ether/ethyl acetate, 95:5, V/V) until the formation of trichloroacetimide was observed. After 3 h of reaction, the solvent was removed by distillation under reduced pressure and the resulting residue was purified by silica gel column chromatography (eluent: petroleum ether/ethyl acetate, 95:5, V/V), followed by distillation at 80 °C/0.3 mbar to afford the target product 2,2,2-trichloroacetimidobenzyl ester as a colorless oil in 94% yield.TLC Rf value: 0.27 (petroleum ether/ethyl acetate. 95:5, V/V).1H NMR (400.13 MHz, CDCl3) δ (ppm): 5.26 (s, 2H, H1'); 7.24-7.36 (m, 5H, HPh); 8.31 (wide s, 1H, =NH).13C NMR (100.62 MHz, CDCl3) δ (ppm): 70.7 (Cl'); 91.3 (C2); 127.7, 128.3 and 128.5 (5C, CPh); 134.4 (C2'); 162.5 (C1). |
| Purification Methods | Purify the imidate by distillation to remove up to 1% of PhCH2OH as stabiliser. A solution in hexane can be stored for up to 2 months without decomposition. It is hygroscopic and has to be stored dry. [Wessel et al. J Chem Soc, Perkin Trans 1 2247 1985, Beilstein 6 IV 2265.] |
| References | [1] Tetrahedron Letters, 1996, vol. 37, # 9, p. 1481 - 1484 [2] Tetrahedron Letters, 2009, vol. 50, # 21, p. 2533 - 2535 [3] Bioorganic and Medicinal Chemistry Letters, 2016, vol. 26, # 2, p. 636 - 639 [4] Patent: US6348478, 2002, B1. Location in patent: Page column 32-33 [5] Journal of Organic Chemistry, 2003, vol. 68, # 19, p. 7234 - 7242 |
BENZYL 2,2,2-TRICHLOROACETIMIDATE Preparation Products And Raw materials
| Raw materials | Trichloroacetonitrile-->Dichloromethane-->Benzyl alcohol-->DBU |
| Preparation Products | H-THR(BZL)-OH-->1402393-56-9 |
