Cyclopropyl bromide Chemical Properties

Boiling point:

69 °C (lit.)

Density 

1.51 g/mL at 25 °C (lit.)

refractive index 

n20/D 1.458(lit.)

Flash point:

20 °F

storage temp. 

2-8°C

solubility 

Chloroform (Sparingly), Methanol (Slightly)

form 

Liquid

Specific Gravity

1.510

color 

Clear colorless

Water Solubility 

immiscible

BRN 

1900287

InChI

InChI=1S/C3H5Br/c4-3-1-2-3/h3H,1-2H2

InChIKey

LKXYJYDRLBPHRS-UHFFFAOYSA-N

SMILES

C1(Br)CC1

CAS DataBase Reference

4333-56-6(CAS DataBase Reference)

NIST Chemistry Reference

Cyclopropyl bromide(4333-56-6)

EPA Substance Registry System

Cyclopropane, bromo- (4333-56-6)

Safety Information

Hazard Codes 

F,Xi

Risk Statements 

11-36/37/38

Safety Statements 

16-26-36-37/39

RIDADR 

UN 1993 3/PG 2

WGK Germany 

3

F 

8-19

Hazard Note 

Irritant

TSCA 

T

HazardClass 

3

PackingGroup 

II

HS Code 

29035990

MSDS

• Language:English Provider:Bromocyclopropane
• Language:English Provider:SigmaAldrich
• Language:English Provider:ACROS
• Language:English Provider:ALFA

Cyclopropyl bromide Usage And Synthesis

Description

Cyclopropyl bromide is also named as Bromocyclopropane. It is used in organic synthesis, for instance, for the formation of a Grignard Reagent, cyclopropyllithium. It is also used as an intermediate in the manufacture of pharmaceutical and agrochemical products.

Chemical Properties

Light yellow to clear colourless liquid, boiling point 67-69°C, refractive index (nD20) 1.4605, density (d420) 1.5120, flash point -6°C.

Uses

Bromocyclopropane is primarily used an intermediate in the manufacture of pharmaceutical and agrochemical products. It is also used in the production of cyclopropyl boric acid. It is used as an intermediate in organic synethesis.

Preparation

Bromocyclopropane has been prepared by the Hunsdiecker reaction by adding silver cyclopropanecarboxylate to bromine in dichlorodifluoromethane at ?29° (53% yield) or in tetrachloroethane at ?20° to ?25° (15–20% yield). Decomposition of the peroxide of cyclopropanecarboxylic acid in the presence of carbon tetrabromide gave bromocyclopropane in 43% yield. An attempt to prepare the bromide via the von Braun reaction was unsuccessful. Ten percent yields are reported for the photobromination of cyclopropane and the photochemical rearrangement of allyl bromide. Treatment of 1,1,3-tribromopropane with methyllithium prepared from methyl bromide furnishes a 60–65% yield of bromocyclopropane.

Application

Bromocyclopropane have anti-angiogenic effects that inhibits the growth of new blood vessels by interfering with the production of prostaglandins and nitric oxide, which are important for the formation of new blood vessels. Bromocyclopropane binds to cyclopropyl and hydrochloric acid, forming a hydrogen bond. It also forms a hydrogen bond with fatty acids and an a-type hydroxyl group.

Synthesis

(1) 179 g of 1,3-bromochloropropane was added to a three-necked flask, 29 g of potassium cyanide and 50 ml of water were added and heated and stirred until completely dissolved. Subsequently, 70 ml of ethanol solution was added and the mixture was stirred and refluxed for 2 hours. After completion of the reaction, it was cooled to room temperature and diluted with 300 ml of water to separate the oil and aqueous phases. The aqueous phase was extracted with 40 ml of chloroform, the organic phases were combined and dried with anhydrous calcium chloride. 316.9 g of hydrogen chloride was obtained. Chlorobutanenitrile 241.6 g was prepared by adding 100 ml of sodium hydroxide solution and stirring the reaction for 2 hours. Then 200 ml of water was added, cooled to about 10°C, 44 ml of concentrated sulfuric acid was added to acidify the reaction mixture, extracted with petroleum ether as an extractant, the organic phases were combined and dried with anhydrous sodium sulfate to obtain 330.1 g of cyclopropionic acid. (2) 324.8 g of cyclopropionic acid was added dropwise to a reaction flask with 48 g of mercuric oxide, 160 ml of a mixture of 1,1,2,2-tetrachloroethane and 64.4 g of liquid bromine, and stirred for 2 hours. After completion of the reaction, the mixture was cooled to 5°C, washed with tetrachloroethane and then dried with calcium chloride to give 419.15 g of bromocyclopropane.

References

Science of Synthesis: Houben-Weyl Methods of Molecular Transformation Vol. 7: Compounds of Group 13 and 2 (Al, Ga, In, Tl, Be…Ba), 2007, ISBN: 9783131484819
D. Seyferth, H. M. Cohen, The Stability of Cyclopropyllithium in diethyl ether and in tetrahydrofuran, Journal of Organometallic Chemistry, 1963, vol. 1, pp. 15-21
“Formal Nucleophilic Substitution of Bromocyclopropanes with Azoles”, Ryabchuk, P.; Rubina, M.; Xu, J.; Rubin, M. Org. Lett. 2012, 14, 1752.
“Formal Substitution of Bromocyclopropanes with Nitrogen Nucleophiles”, Banning, J. E.; Gentillon, J.; Ryabchuk, P. G.; Prosser, A. R.; Rogers, A.; Edwards, A.; Holtzen, A.; Babkov, I.; Rubina, M.; Rubin, M. J. Org. Chem., 2013, 78, 7601.

Cyclopropyl bromide(4333-56-6)Related Product Information

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