Bromocyclobutane

Bromocyclobutane
Names
Other names
Cyclobutyl bromide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.022.302
EC Number
  • 224-530-9
UNII
  • InChI=1S/C4H7Br/c5-4-2-1-3-4/h4H,1-3H2
    Key: KXVUSQIDCZRUKF-UHFFFAOYSA-N
  • C1CC(C1)Br
Properties
C4H7Br
Molar mass 135.004 g·mol−1
Density 1.3719
Boiling point 103–104 °C (217–219 °F; 376–377 K)
Related compounds
Related compounds
 bromocyclopropane; Bromocyclopentane; Fluorocyclobutane; Chlorocyclobutane; Iodocyclobutane;
1,1-Dibromocyclobutane;
cis/trans 1,2-Dibromocyclobutane;
cis/trans 1,3-Dibromocyclobutane
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Cyclobutyl bromide or bromocyclobutane is an organic compound containing a cyclobutane ring with one hydrogen atom replaced by bromine. The formula is C4H7Br.

Production

Cyclobutyl bromide can be produced from cyclobutane carboxylic acid in a reaction with bromine in the presence of mercuric oxide.[1] It can be made from silver cyclobutane carboxylate and bromine.[2]

It can be made from cyclopropylmethanol, in a reaction with hydrogen bromide (HBr).[3]

Cyclobutanol can react with HBr to yield cyclobutyl bromide.[4]

Bromination of cyanocyclobutane produces a small amount of bromocyclobutane. In addition to the dominant product, 1-bromo-1-cyanocyclobutane.[5]

Properties

The lengths of the bonds in the bromocyclobutane molecule are as follows: Cα is carbon atom in position 1 adjacent to bromine. Cβ is the carbon in position 2 or 4 of the ring. Cγ is the carbon in position 3, opposite the bromine atom. Length Cα–Cβ = 1.540 Å. Length Cβ–Cγ = 1.548 Å. Length Cα–Br = 1.939 Å. The lengths of C–H = 1.096 Å, and C—D = 1.087 Å. The bond angles ∠ CβCγCβ = 88.1°, ∠ CβCαCβ = 88.7°, HCγH = 110.7°, HCβH = 108.7°, HCαBr = 111°. The angle of CβCαCβ plane with C–Br is 131.0°, and the dihedral angle (angle made by the normals of the CβCαCβ and CβCγCβ planes) is 29.35°.[6]

There are two conformers based on the orientation of the bromine atom. The axial conformer comprises 3% of molecules, and the equatorial conformer comprises 97%. However there is a very low barrier to interconversion.[7]

In the far-infrared spectrum there are Q-branch transitions at 143.0, 135.5, 129.2, and 124.0 cm-1.[8]

The LF Raman spectrum has lines at 149.0, 139.5, 134.8, 128.5, 124.0 cm−1.[9]

Refractive index N25D is 1.4768. Boiling point is 106-108°C.[10]

NMR spectrum

[4]
position cis-trans orientation shift Hz
α axial 4.441
β trans equatorial 2.597
β cis axial 2.465
γ cis equatorial 2.094
γ trans axial 1.873

Reactions

When heated to temperatures between 791–1,224 K (518–951 °C) at low pressure, hydrogen bromide is eliminated producing cyclobutene.[11]

When heated around 436°C, butadiene and hydrogen bromide are produced.[12]

Cyclobutyl bromide reacts with magnesium in ether solution to yield the Grignard reagent C4H7MgBr.[1]

234 nm UV light photodissociates cyclobutyl bromide to form a cyclobutyl radical and atomic bromine.[13][14]

Hydrogenation of bromocyclobutane yields cyclobutane.[15] Cyclobutyl bromide can be reduced by Bu3SnH (or Bu3SnD) to cyclobutane.[16]

Diphenylphosphide reacts in liquid ammonia to displace bromide to form cyclobutyldiphenylphosphine.[17]

Tributylstannyllithium reacts with cyclobutyl bromide to form tributyl(cyclobutyl)tin.[18]

Electro-oxidation of bromocyclobutane dissolved in acetonitrile yields N-cyclobutylacetamide.[19]

Sodium methanesulfinate reacts with cyclobutyl bromide to yield some methylsulfonylcyclobutane.[20]

In Lucas reagent (ZnCl2 + HCl), cyclobutyl bromide forms the cyclobutyl cation (c-C4H7+), which can rearrange or break the ring and then reform to yield cyclopropylcarbiny chloride (c-C3H5CH2Cl) and allylcarbinyl chloride (CH2=CHCH2CH2Cl).[2]

Cyclobutyl bromide can do a carbon-carbon coupling to form 1,1'-bicyclobutyl c-C4H7-C4H7.[21]

It is possible to substitute the bromine in bromocyclobutane with a trifluoromethyl, or trifluoroacetyl group under blue light.[22]

References

  1. 1 2 Dupont, Andrea C.; Audia, Vicki H.; Waid, Philip P.; Carter, J. Paul (April 1990). "A Convenient Large-Scale Synthesis of Cyclobutyl Halides". Synthetic Communications. 20 (7): 1011–1021. doi:10.1080/00397919008052804.
  2. 1 2 Roberts, John D.; Mazur, Robert H. (June 1951). "Small-Ring Compounds. IV. Interconversion Reactions of Cyclobutyl, Cyclopropylcarbinyl and Allylcarbinyl Derivatives". Journal of the American Chemical Society. 73 (6): 2509–2520. Bibcode:1951JAChS..73.2509R. doi:10.1021/ja01150a029.
  3. ↑ Dupont, Andrea C.; Audia, Vicki H.; Waid, Philip P.; Carter, J. Paul (April 1990). "A Convenient Large-Scale Synthesis of Cyclobutyl Halides". Synthetic Communications. 20 (7): 1011–1021. doi:10.1080/00397919008052804.
  4. 1 2 Wiberg, Kenneth B.; Barth, Donald E.; Pratt, William E. (June 1977). "Effect of carbon-halogen bonds on nuclear magnetic resonance chemical shifts. 2. Proton and carbon nuclear magnetic resonance spectra of cyclobutyl halides". Journal of the American Chemical Society. 99 (13): 4286–4289. Bibcode:1977JAChS..99.4286W. doi:10.1021/ja00455a013.
  5. ↑ Ashton, D. S.; Singh, H.; Tedder, J. M.; Walton, J. C.; Watt, E. A. (1973). "Free-radical substitution in aliphatic compounds. Part XXVII. Chlorination and bromination of 1-cyanobutane and cyanocyclobutane". Journal of the Chemical Society, Perkin Transactions 2 (2): 125. doi:10.1039/P29730000125.
  6. ↑ Rothschild, W. G.; Dailey, B. P. (1 June 1962). "Microwave Spectrum of Bromocyclobutane". The Journal of Chemical Physics. 36 (11): 2931–2940. Bibcode:1962JChPh..36.2931R. doi:10.1063/1.1732404.
  7. ↑ Gatial, A.; Klaeboe, P.; Nielsen, C. J.; Powell, D. L.; Sülzle, D.; Kondow, A. J. (April 1989). "Vibrational spectra and conformations of chloro- and bromo-cyclobutane". Journal of Raman Spectroscopy. 20 (4): 239–250. Bibcode:1989JRSp...20..239G. doi:10.1002/jrs.1250200408.
  8. ↑ Blackwell, C. S.; Carreira, L. A.; Durig, J. R.; Karriker, J. M.; Lord, R. C. (15 February 1972). "Far-Infrared Spectra of Ring Compounds. VII. The Ring-Puckering Vibration in Chlorocyclobutane, Bromocyclobutane, and Cyanocyclobutane". The Journal of Chemical Physics. 56 (4): 1706–1711. Bibcode:1972JChPh..56.1706B. doi:10.1063/1.1677428.
  9. ↑ Durig, J.R.; Shing, A.C.; Carreira, L.A. (August 1973). "Raman spectra of gases V. Bromocyclobutane". Journal of Molecular Structure. 17 (2): 423–425. Bibcode:1973JMoSt..17..423D. doi:10.1016/0022-2860(73)85186-5.
  10. ↑ Buchman, E. R.; Conly, J. C. (April 1953). "The Reaction of Silver Cyclobutanecarboxylate with Bromine 1". Journal of the American Chemical Society. 75 (8): 1990. Bibcode:1953JAChS..75Q1990B. doi:10.1021/ja01104a504.
  11. ↑ King, Keith D.; Gilbert, Robert G. (May 1980). "The thermal unimolecular decomposition of bromocyclobutane". International Journal of Chemical Kinetics. 12 (5): 339–346. doi:10.1002/kin.550120505.
  12. ↑ Bullivant, John Thomas (1971). Rearrangements of cyclic compounds in the gas phase (Thesis). UNSW Sydney. p. 102. doi:10.26190/unsworks/9732. hdl:1959.4/64762.
  13. ↑ Liu, Yi; Lau, Kai-Chung; Butler, Laurie J. (1 April 2006). "Photodissociation of Cyclobutyl Bromide at 234 nm Studied Using Velocity Map Imaging". The Journal of Physical Chemistry A. 110 (16): 5379–5385. doi:10.1021/jp056255m. PMID 16623465.
  14. ↑ Chan, Ya-Chu; Nesbitt, David J. (2024). "High-resolution infrared spectroscopy of jet cooled cyclobutyl in the α-CH stretch region: large-amplitude puckering dynamics in a 4-membered ring radical". Physical Chemistry Chemical Physics. 26 (4): 3081–3091. Bibcode:2024PCCP...26.3081C. doi:10.1039/D3CP04812H. PMID 38180446.
  15. ↑ Cason, James; Way, Richard L. (January 1949). "The Preparation of Cyclobutane". The Journal of Organic Chemistry. 14 (1): 31–36. doi:10.1021/jo01153a006. PMID 18123434.
  16. ↑ Rafilipomanana, C.; Cavagnat, D.; Cavagnat, R.; Lassegues, J.C.; Biran, C. (March 1985). "Infrared and Raman study of monodeuterated four and five membered rings". Journal of Molecular Structure. 127 (3–4): 283–296. doi:10.1016/0022-2860(85)80011-9.
  17. ↑ Nazareno, Mónica A.; Palacios, Sara M.; Rossi, Roberto A. (July 1993). "Reactions of cycloalkyl chlorides and bromides with diphenylphosphide ions in liquid ammonia". Journal of Physical Organic Chemistry. 6 (7): 421–426. doi:10.1002/poc.610060707.
  18. ↑ Newcomb, Martin; Smith, Michael G. (March 1982). "Reactions of Tributylstannyl Anionoids with Alkyl Bromides". Journal of Organometallic Chemistry. 228 (1): 61–70. doi:10.1016/S0022-328X(00)86774-1.
  19. ↑ Becker, James Y.; Zemach, Dvora (1979). "Anodic oxidation of alicyclic bromides in acetonitrile". Journal of the Chemical Society, Perkin Transactions 2 (7): 914. doi:10.1039/P29790000914.
  20. ↑ Truce, William E.; Milionis, Jerry P. (November 1952). "Preparation of Cycloalkyl Alkyl Sulfones". The Journal of Organic Chemistry. 17 (11): 1529–1533. doi:10.1021/jo50011a021.
  21. ↑ Tang, Wenbin; Yang, Hao; Tang, Lin; Wang, Jingbo (December 2025). "The kinetic model of 1,1′-bicyclobutyl at high temperatures". Computational and Theoretical Chemistry. 1254 115536. doi:10.1016/j.comptc.2025.115536.
  22. ↑ Yanai, Hikaru; Hoshikawa, Shoki; Kawai, Kentaro; Matsumoto, Takashi (December 2025). "Synthetic Methods for Four-Membered Carbocycles Bearing Emerging Fluorinated Motifs". Chemistry: An Asian Journal. 20 (23) e70414. doi:10.1002/asia.70414. PMC 12696810. PMID 41205187.

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