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Volumn 14, Issue 32, 2008, Pages 9830-9841

Electrophilic bromination of alkenes: Environmental, health and safety aspects of new alternative methods

Author keywords

Bromination; Mass balances oxidation; Oxone; Waste prevention

Indexed keywords

ALKENE; BROMINE;

EID: 55449113572     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200800462     Document Type: Article
Times cited : (97)

References (108)
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    • Translation of the literature (Organikum, 22nd edition, General protocol for the conversion of hex-l-en, oct-l-en, cyclohexene, styrene, fumaric acid: in a three-necked flask with stirrer, dropping funnel and inside thermometer, the unsaturated compound is cooled to 0°C in the two- to three-fold quantity of carbon tetrachloride or chloroform. At 0 to 5°C an equimolar amount of bromine solved in about the two-fold of the same solvent is added dropwise while stirring steadily in such a way that the temperature remains within the given limit. No large concentration of unconsumed bromine should appear (colour, The addition product precipitates and is suctioned. Otherwise, the solvent is distilled and the residue is purified by distillation or recrystallization. The yields for these examples are 90, 90, 95, 95% and 80, respectively. Additional remarks: 1) Fumaric acid is suspended in a two-fold of boiling water. Bromine is added dropwise at boiling heat. The add
    • Translation of the literature (Organikum, 22nd edition): General protocol for the conversion of hex-l-en, oct-l-en, cyclohexene, styrene, fumaric acid: in a three-necked flask with stirrer, dropping funnel and inside thermometer, the unsaturated compound is cooled to 0°C in the two- to three-fold quantity of carbon tetrachloride or chloroform. At 0 to 5°C an equimolar amount of bromine solved in about the two-fold volume of the same solvent is added dropwise while stirring steadily in such a way that the temperature remains within the given limit. No large concentration of unconsumed bromine should appear (colour!). The addition product precipitates and is suctioned. Otherwise, the solvent is distilled and the residue is purified by distillation or recrystallization. The yields for these examples are 90%, 90%, 95%, 95% and 80%, respectively. Additional remarks: 1) Fumaric acid is suspended in a two-fold volume of boiling water. Bromine is added dropwise at boiling heat. The addition product precipitates during cooling to 10 °C and the remaining bromine is washed out with water. 2) Converting cyclohexene, 10% less bromine should be applied because the yield is reduced due to substitution products in side reactions. Additional purification could be achieved by shaking the crude product with 1/3 of its volume with a 20% solution of potassium hydroxide in alcohol for five minutes, subsequent dilution with the same amount of water, alkali-free washing, drying with sodium sulphate and distillation. This procedure diminishes the yield by about 10%. 3) Styrene should be used freshly distilled.
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    • To clarify the full stoichiometric equations, it was necessary to contact several authors. We would like to recommend including the precise presentation of the full stoichiometric equations of a chemical synthesis including all coupled products (if possible). Additionally, we would like to suggest that chemists take a more thorough look at alternative methodologies in the introduction of an article. The consideration of the respective mass balances (see N. Winterton, Green Chem. 2001, 3, G73-G75.)
    • To clarify the full stoichiometric equations, it was necessary to contact several authors. We would like to recommend including the precise presentation of the full stoichiometric equations of a chemical synthesis including all coupled products (if possible). Additionally, we would like to suggest that chemists take a more thorough look at alternative methodologies in the introduction of an article. The consideration of the respective mass balances (see N. Winterton, Green Chem. 2001, 3, G73-G75.)
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    • and the characteristics of used substances could improve the value of a scientific work, see for example, S. Protti, D. Dondi, M. Fagnoni, A. Albini, Pure Appl. Chem. 2007, 79, 1929-1938;
    • and the characteristics of used substances could improve the value of a scientific work, see for example, S. Protti, D. Dondi, M. Fagnoni, A. Albini, Pure Appl. Chem. 2007, 79, 1929-1938;
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    • A. Kuzemko, S. D. Van Arnum, H. J. Niemcyk, Org. Process Res. Dev. 2007, 11, 470-476. There is a course for students to learn about mass balances given by NOP (Sustainability in the organic chemistry lab course), which is a laboratory course available via internet (www.oc-praktikum.de/en- entry). Two protocols (experiment no. 5004 and no. 2003) and their environmental performance metrics exist for the acetalisation of 3-nitrobenzaldehyde.
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    • We would like to mention a correction that B. K. Patel indicated to us relating to Ref. [28] page 4271. The weight of KBr corresponding to 225 mmol should be 26.7 mg and not 267 mg and the weight of Oxone® corresponding to 100 mmol should be 61.4mg and not 122.8 mg.
    • We would like to mention a correction that B. K. Patel indicated to us relating to Ref. [28] page 4271. The weight of KBr corresponding to 225 mmol should be 26.7 mg and not 267 mg and the weight of Oxone® corresponding to 100 mmol should be 61.4mg and not 122.8 mg.
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