| Identification | More | [Name]
BENZYL 2,2,2-TRICHLOROACETIMIDATE | [CAS]
81927-55-1 | [Synonyms]
2,2,2-TRICHLOROACETIMIDIC ACID BENZYL ESTER
BENZYL 2,2,2-TRICHLOROACETIMIDATE
LABOTEST-BB LT00455324
TRICHLOROACETIMIDIC ACID BENZYL ESTER
Benzyl 2,2,2-trichloroethanimidoate
Benzyl trichloroacetimidate
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-trichloroacetimidate, 99 % | [Molecular Formula]
C9H8Cl3NO | [MDL Number]
MFCD00000805 | [Molecular Weight]
252.52 | [MOL File]
81927-55-1.mol |
| Chemical Properties | Back Directory | [Appearance]
clear colorless to yellow liquid | [Melting point ]
3 °C | [Boiling point ]
106-114 °C0.5 mm Hg(lit.) | [density ]
1.359 g/mL at 25 °C(lit.)
| [refractive index ]
n20/D 1.545(lit.)
| [Fp ]
>230 °F
| [storage temp. ]
2-8°C
| [solubility ]
Miscible with cyclohexane/dichloromethane. | [form ]
Liquid | [pka]
2.23±0.70(Predicted) | [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 Data | Back Directory | [Hazard Codes ]
Xn | [Risk Statements ]
R22:Harmful if swallowed.
R36/37/38:Irritating to eyes, respiratory system and skin . | [Safety Statements ]
S26:In case of contact with eyes, rinse immediately with plenty of water and seek medical advice . | [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 |
| Hazard Information | Back Directory | [Chemical Properties]
clear colorless to yellow liquid | [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. | [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 is used for the acid-catalyzed benzylation of hydroxy groups.
| [Synthesis]
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 |
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