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Chemical Structure| 50893-53-3 Chemical Structure| 50893-53-3

Structure of 1-Chloroethyl chloroformate
CAS No.: 50893-53-3

Chemical Structure| 50893-53-3

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Product Details of [ 50893-53-3 ]

CAS No. :50893-53-3
Formula : C3H4Cl2O2
M.W : 142.97
SMILES Code : O=C(Cl)OC(Cl)C
MDL No. :MFCD00000647
InChI Key :QOPVNWQGBQYBBP-UHFFFAOYSA-N
Pubchem ID :521305

Safety of [ 50893-53-3 ]

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H226-H302-H314-H330
Precautionary Statements:P210-P233-P240-P241-P242-P243-P260-P264-P270-P271-P280-P284-P301+P312+P330-P301+P330+P331-P303+P361+P353-P304+P340+P310-P305+P351+P338+P310-P363-P370+P378-P403+P233-P403+P235-P405-P501
Class:6.1(3,8)
UN#:2742
Packing Group:

Application In Synthesis of [ 50893-53-3 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Upstream synthesis route of [ 50893-53-3 ]
  • Downstream synthetic route of [ 50893-53-3 ]

[ 50893-53-3 ] Synthesis Path-Upstream   1~2

  • 1
  • [ 100-02-7 ]
  • [ 50893-53-3 ]
  • [ 101623-69-2 ]
YieldReaction ConditionsOperation in experiment
97% With pyridine In dichloromethane at 0 - 20℃; for 1.5 h; To an ice cold reaction mixture containing p-nitrophenol (1.39 g, 10 mmol) and pyridine (0.81 g, 10 mmol) in dichloromethane (60 mL) was added 1-chloroethyl chloroformate (1.2 mL, 11 mmol). The mixture was stirred at 0° C. for 30 min and then at room temperature for 1 hour. After removing the solvent under reduced pressure, the residue was dissolved in ether, washed with water, 10percent citric acid and water. The ether layer was dried over Na2SO4 and evaporated under reduced pressure to give 2.4 g (97percent) of the title compound (57) as an off-white solid. 1H NMR (CDCl3): 1.93 (d, 3H), 6.55 (q, 1H), 7.42 (d, 2H), 8.28 (d, 2H).
92% With pyridine In dichloromethane at 0 - 20℃; for 6 h; Example 3: 1-iodoethyl 4-nitrophenyl carbonateSTEP A: 1-chloroethyl 4-nitrophenyl carbonate.To a solution of 4-nitrophenol (3.0 g, 21.6 mmol) and pyridine (1.9 mL, 24 mmol) in CH2C12 (48 mL) cooled to 0°C, 1-chloroethyl chloroformate (2.3 mL, 21.6 mmol) was added. The reaction was stirred at room temperature for 5-6 hours, then washed with NaH2PC>4 (5percent) and brine, dried over Na2SC>4 and concentrated affording the title compound (4.88 g, 92percent) as a pale yellow solid.
92% at 0 - 20℃; STEP A: 1-chloroethyl 4-nitrophenyl carbonateTo a solution of 4-nitrophenol (3.0 g, 21.6 mmol) and pyridine (1.9 mL, 24 mmol) cooled to 0°C, 1-chloroethyl chloroformate (2.3 mL, 21.6 mmol) was added. The reaction was stirred at room temperature for 5-6 hours, then washed with Na3/4P04 (5percent) and brine, dried over Na2 S C>4 and concentrated affording the title compound (4.88 g, 92percent) as a pale yellow solid.1H-NMR (CDC13) : 8.32 (2H,m); 7.44 (2H,m); 6.52 ( 1H, q, J=5.8 Hz); 1.94 (3H, d, J=5.5Hz) .
88% With pyridine In chloroform at 0 - 20℃; Step 1:
1-Chloroethylchloroformate (7.8 ml, 72 mmol, 1 eq.) was added to an ice-cold solution of p-nitrophenol (10 g, 72 mmol) in chloroform (100 mL), followed by drop wise addition of pyridine (8.8 ml, 108 mmol, 1.5 eq.) over a period of 20 min.
The mixture was stirred in the ice-cold bath for 15 min, and then at room temperature overnight.
The reaction mixture was sequentially washed with water, 1 N hydrochloric acid, water, 1 N sodium hydroxide, water, and brine.
The organic phase was dried over Na2SO4, and concentrated to give yellow oil which, upon standing, crystallized to afford the corresponding chloroethyl carbonate (15.5 g, 88percent).
85% With triethylamine In dichloromethane at 0 - 20℃; To an ice-cold solution of 4-nitrophenol (2.0 g, 15 mmol) and triethylamine (1.6 g, 16 mmol) in dichloromethane (20 ml) was added a solution of 1-chloroethyl chloroformate (2.1 g, 19 mmol) in dichloromethane, and the mixture was stirred for 15 min at 0 °C and then overnight at room temperature. The mixture was extracted with dichloromethane (50 ml), washed successively with water (50 ml), 0.5 N sodium hydroxide (50 ml), saturated aqueous sodium chloride solution (50 ml), and water (3 x 50 ml), and dried over Na2SO4. The dichloromethane solution was filtered and evaporated under reduced pressure, and the residue was purified by silica gel column chromatography with chloroform (100percent) as eluent to furnish pure 1-chloroethyl 4- nitrophenyl carbonate, as a white solid in 85percent yield.

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[14] Patent: US2002/19437, 2002, A1, .
[15] Patent: US5602118, 1997, A, .
[16] Patent: US2004/138108, 2004, A1, .
[17] Patent: WO2008/79839, 2008, A1, . Location in patent: Page/Page column 40.
[18] Patent: WO2010/63002, 2010, A2, . Location in patent: Page/Page column 26.
  • 2
  • [ 50893-53-3 ]
  • [ 161357-89-7 ]
References: [1] Patent: US2012/196824, 2012, A1, .
 

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