Aliye ALTUNDAŞ

Bromination of 1,2-Dimethylenecyclohexane: Temperature Effect on Product Distribution

In this study the electrophlic addition of bromine to an exocyclic diene, 1,2dimethylenecyclohexane, was investigated. The bromination of 1,2-dimethylenecyclohexaneyielded 1,2-bis(bromomethyl)cylohex-1-en at low temperature. Nevertheless, thebromination of 1,2-dimethylenecyclohexane at room temperature gave 1,4 addition product1,2-bis(bromomethyl)cylohex-1-en as a main product together with 1-bromo-1-(bromomethyl)-2-methylenecylohexane and 3-bromo-1,2-bis(bromomethyl)cyclohex-1-ene.Similarly, high temperature bromination of 1,2-bismethylenecyclohexane gave the radicalbromination products (3-bromo-1,2-bis(bromomethyl)cyclohex-1-ene and 3,6-dibromo-1,2-bis(bromomethyl)cyclohex-1-ene) in addition to the 1,4 addition product. While thebromination of exocylicdiene at room temperature with excess bromine gavetetrabrominated product 1,2-dibromo-1,2-bis(bromomethyl)cyclohexane as a sole product,the bromination of exocyclicdiene in high temperature with excess bromine resulted in atetra brominated product 1,2-dibromo-1,2-bis(bromomethyl)cyclohexane and the threebrominated product 3-bromo-1,2-bis(bromomethyl)cyclohex-1-ene together with theradicalic tetrabrominated product 3,6-dibromo-1,2-bis(bromomethyl)cyclohex-1-ene asmain products. However, the high temperature bromination of 1,4 brominated product withexcess bromine provided only the radicalic brominated product 3-bromo-1,2-bis(bromomethyl)cyclohex-1-ene and 3,6-dibromo-1,2-bis(bromomethyl)cyclohex-1-ene.Thus the functional agents which can be used as starting material in the synthesis ofmany compounds were synthesized, purified and characterized.

PDF

___

Ozer, M. S., Kilbas, B., Balci, M., “High temperature bromination Part XXIII: Bromination of octahydro-1H-indene and octahydro-1H-4,7-methanoindene”, ARKIVOC, 4: 388-404, (2013).
Wiclatz, J. E, Short, J. N., 1952, US 26010, 75: 19520617.
Bailey, J. W., Golden, R. H., “Cyclic Dienes. I. 1,2-Dimethlenecyclohexane”, J. Am. Chem. Soc., 75: 4780-4782, (1953).
Bailey, J. W., Sorenson, R. W., “Cyclic Dienes.VIII. 1,2-Dimethylenecyclopentane”, J.Am. Chem. Soc., 76: 5421-5423, (1954).
Groesbeek M., Van Galen J. J. A., Ippel J.H., Berden J. A., Lugtenburg J., “Three bacteriorhodopsins with ring‐didemethylated 6‐s‐locked chromophores and their properties” Rec. Trav. Chim. Pays-Bas, 112: 237-246, (1993).
Fujiwara, K., Kurahashi, T., Matsubara, S., “Cationic Iron (III) Porphyrin-Catalyzed [4 + 2] Cycloaddition of Unactivated Aldehydes with Simple Dienes”, J. Am. Chem. Soc., 134(12): 5512- 5515, (2012).
Liang, D., Zou, Y., Wang, Q., Goeke, A., “Sequential Diels–Alder Reaction/Rearrangement Sequence: Synthesis of Functionalized Bicyclo[2.2.1]heptane Derivatives and Revision of Their Relative Configuration”, J. Org. Chem., 79(14): 6726-6731, (2014).
De Lucchi, O., Daştan, A., Altundaş, A., Fabris, F., Balci, M., “Cyclotrimerization of Oxabenzonorbornadiene: Synthesis of syn- and anti-5,6,11,12,17,18-hexahydro-5,18:6,11:12,17- triepoxytrinaphthylene”, Helv. Chim. Acta, 87(9): 2364-2367, (2004).
Thakur, A., Facer, M. E., Louie, J., “Nickel-Catalyzed Cycloaddition of 1,3-Dienes with 3- Azetidinones and 3-Oxetanones”, Angew. Chem., Int. Ed., 52(46): 12161-12165, (2013).
Wittig, G., Knaus, E., “Dehydrobenzol und Cyclopentadien”, Chem Berr., 91: 895-907, (1958).
Wilt, J. W., Gutman, G., Raunus W. J. Jr.; Ziegman, A. R., “Studies of benzonorbornene and derivatives. I. Chloro- and bromobenzonorbornenes and related compounds”, J. Org. Chem., 32: 893-901, (1967).
Essiz, S., Sengul, M. E., Sahin, E., Dastan, A., “Bromination of 2,3-dihydrobenzobarrelene and synthesis of its mono- and dibromide derivatives: unexpected Wagner-Meerwein rearrangement on silica gel”, Turk. J. Chem., 35: 587-598, (2011).
Taskesenlioglu, S., Dastan, A., Dalkilic, E., Guney, M., Abbasoglu, R., “Low and high temperature bromination of 2,3-dicarbomethoxy and 2,3-dicyano benzobarrelene: unexpected substituent effect on bromination”, New J. Chem., 34: 141-150, (2010).
Harmandar, M.; Balcı, M., “The Bromination of 3-Bromo –6,7- Benzobicyclo [3.2.1] octa- 2,6- diene”, Tetrahedron Lett., 26: 5465-5468, (1985).
Daştan, A., Balcı, M., Hökelek, T., Ülkü, D., Büyükgüngör, O., “High temperature bromination VI: Bromination of benzobarrelene”, Tetrahedron, 50: 10555-10578, (1994).
Dastan, A., Tasgesenligil, Y., Tümer, F., Balci, M., “High temperature bromination VIII: Bromination of homobenzonorbornadiene”, Tetrahedron, 52: 14005-14020, (1996).
Altundaş, A., Daştan, A., McKee, M. M., Balci, M., “High Temperature Bromination. Part 12:1 Bromination of 7-Oxabenzonorbornadiene: Synthesis of 2,3-Dibromo-7-oxabenzonorbornadiene”, Tetrahedron, 56: 6115-6120, (2000).
March, J. Advanced Organic Chemistry; Wiley: New York, (1991).
Horasan, N.,Kara, Y., Azizoğlu, A., Balcı, M., “Low and high temperature bromination of exocyclic dienes: high temperature bromination. Part 16”, Tetrahedron, 59: 3691-3699, (2003).
Jahn, R., Schmidt, U., “Lichtreaktionen mit Carbonsäurederivaten, IX. Abfangversuche mit photochemisch erzeugtem monoatomarem und diatomarem Schwefel. Schwefeladdition an 1, 2‐ Dimethylencyclohexan. – Synthese von 1,4,5,6,7,8‐Hexahydrobenzo[d][1,2]dithiin und 1,3,4,5,6,7‐ Hexahydrobenzo[c]thiophen”, Chem.Ber., 108: 630-639, (1975).