CIS-1,4-DIACETOXY-2-BUTENE Chemical Properties

Boiling point:

120-121 °C/18 mmHg (lit.)

Density 

1.08 g/mL at 25 °C (lit.)

vapor pressure 

0.24-13.1Pa at 20-50℃

refractive index 

1.4416

Flash point:

>110°C

storage temp. 

2-8°C

form 

Liquid

color 

Clear colorless

Water Solubility 

Not miscible in water.

BRN 

1724379

LogP

-0.1-1.1 at 25℃ and pH3.3

CAS DataBase Reference

25260-60-0(CAS DataBase Reference)

Safety Information

Hazard Codes 

Xi

Risk Statements 

36/37/38

Safety Statements 

26-36/37/39-36

WGK Germany 

3

HS Code 

29161995

MSDS

• Language:English Provider:ALFA

CIS-1,4-DIACETOXY-2-BUTENE Usage And Synthesis

Uses

cis-1,4-Diacetoxy-2-butene is used as an organic chemical synthesis intermediate.

General Description

cis-1,4-Diacetoxy-2-butene is an ester. Ruthenium olefin metathesis catalysts having cyclic (alkyl)(amino)carbenes effectively catalyzes the cross-metathesis of cis-1,4-diacetoxy-2-butene with allylbenzene. cis-1,4-Diacetoxy-2-butene on pyrolysis affords 1-acetoxy-1,3-butadiene, a diacetate and an isomeric 1,2-diacetoxy-3-butene. Mechanism of pyrolysis has been investigated.

Synthesis

1. 20.5 mL (0.25 mol) of cis-1,2-dihydroxymethylene and 105 mL (0.75 mol) of triethylamine were dissolved in 400 mL of tetrahydrofuran at room temperature, and 60 mL (0.63 mol) of acetic anhydride was added slowly with stirring. The reaction mixture was stirred for 16 hours and then the reaction was terminated by adding 300 mL of saturated aqueous sodium chloride solution. Subsequently, sodium bicarbonate solution and 300 mL of diethyl ether were added for extraction. The aqueous phase was further extracted with 200 mL of diethyl ether and the organic phases were combined, washed with 300 mL of saturated saline, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by reduced pressure distillation (3 mbar, 80-82°C) to give 39.3 g cis-1,4-diacetoxy-2-butene in 91% yield (based on cis-1,2-dihydroxymethylene). 2. 17.2 g of cis-1,4-diacetoxy-2-butene (100 mmol) was dissolved in a solvent mixture of 150 mL of acetone and 50 mL of water, to which were added 26 g of N-methylmorpholine-N-oxide (NMO, 200 mmol) and 270 mg of osmium tetroxide (OsO4-H2O, 0.75 mmol), and the reaction was stirred for 3 hours at room temperature. After TLC monitoring showed that the reaction was complete, the reaction was terminated by adding 300 mL of saturated aqueous sodium bisulfite and 300 mL of ethyl acetate. The aqueous phase was extracted with 600 mL of ethyl acetate, and the organic phases were combined, washed with 400 mL of saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 18.5 g of diol as white crystals in 90% yield (based on cis-1,4-diacetoxy-2-butene). 3. 8.2 g of the diol (40 mmol) was dissolved in 150 mL of dichloromethane, 80 g of sodium periodate (NaIO4, 55 mmol) was added, and the reaction was stirred at room temperature for 1.4 h. After the reaction was complete as indicated by TLC, the silica was removed by filtration and the filter cake was washed with 100 mL of dichloromethane. The filtrates were combined, concentrated under reduced pressure and the residue was purified by fine distillation to give 4.1 g of the target aldehyde in 50% yield (based on diol). The structure of the product was confirmed by 1H NMR and 13C NMR spectroscopy.

References

[1] Synthesis, 1992, # 10, p. 1007 - 1012
[2] Tetrahedron, 1997, vol. 53, # 48, p. 16423 - 16434
[3] Tetrahedron Letters, 1997, vol. 38, # 20, p. 3595 - 3598
[4] Patent: WO2008/34598, 2008, A1. Location in patent: Page/Page column 17-18
[5] Tetrahedron Asymmetry, 2001, vol. 12, # 5, p. 691 - 693

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