4,4'-Biphenol

4,4′-Biphenol
Displayed structure of a 4,4′-biphenol molecule
Displayed structure of a 4,4′-biphenol molecule
3D model of a 4,4′-biphenol molecule
3D model of a 4,4′-biphenol molecule
Names
Preferred IUPAC name
[1,1′-Biphenyl]-4,4′-diol
Other names
4,4′-Dihydroxybiphenyl
4,4′-Diphenol
4,4′-Biphenyldiol
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.002.001 Edit this at Wikidata
EC Number
  • 202-200-5
KEGG
UNII
  • InChI=1S/C12H10O2/c13-11-5-1-9(2-6-11)10-3-7-12(14)8-4-10/h1-8,13-14H checkY
    Key: VCCBEIPGXKNHFW-UHFFFAOYSA-N checkY
  • InChI=1/C12H10O2/c13-11-5-1-9(2-6-11)10-3-7-12(14)8-4-10/h1-8,13-14H
    Key: VCCBEIPGXKNHFW-UHFFFAOYAM
  • Oc2ccc(c1ccc(O)cc1)cc2
Properties
C12H10O2
Molar mass 186.210 g·mol−1
Appearance colorless or white solid
Melting point 283 °C (541 °F; 556 K)
Boiling point Sublimes
Insoluble in water
Soluble in ethanol and ether
Hazards
Flash point > 93.3 °C (199.9 °F; 366.4 K)
Safety data sheet (SDS) MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkYX markN ?)

4,4′-Biphenol is an organic compound with the formula (C6H4OH)2/ It is one of three symmetrical isomers of biphenol. It is a colourless crystalline solid with a high melting point. It is primarily used in the production of polymers, particularly liquid crystals where it imparts high thermal stability, and PPSU-type polysulfone (also called polyphenylenesulfone, or Radel R).

Synthesis

The industrial synthesis of 4,4′-biphenol was developed in the 1960s by Allan Hay, while working at the historic General Electric Research Laboratory. The reaction is driven by the formation and dimerisation of phenol radicals. As the direct oxidative coupling of phenols gives a mixture of isomers, 4,4′-biphenol is instead prepared from 2,6-di-tert-butylphenol, where para-coupling is the only possibility. A reaction with oxygen produces phenol-radicals which undergo rapid dimerisation, ultimately forming a diphenoquinone.

Synthesis of 4.4'-biphenol from 2,6-di-tert-butylphenol. Isobutylene is eliminated in the final stage.

This intermediate is reduced to the tetra-butyl-biphenyl derivative by a reaction with two equivalents of 2,6-di-tert-butylphenol, in an oxygen-free environment (with the radicals generated dimerising to form additional tetra-butyl-biphenyl). In the final step, high temperature dealkylation is performed to remove the butyl groups, producing the desired 4,4′-biphenol product. If groups less bulky that t-butyl are used then polyphenylene ethers such as poly(p-phenylene oxide) can be produced.

Safety

4,4'-Biphenol exhibits estrogenic SAR.

See also

References

  1. ↑ Chen, Guoliang; Du, Fangyu; Zhou, Qifan; Liu, Dongdong; Fang, Ting; Shi, Yajie; Du, Yang (2018-01-31). "Dimerization of Aromatic Compounds Using Palladium-Carbon-Catalyzed Suzuki–Miyaura Cross-Coupling by One-Pot Synthesis (Supporting Information)". Synlett. 29 (6): 779–784. doi:10.1055/s-0036-1591892. ISSN 0936-5214. S2CID 104289422.
  2. ↑ Parker, David; Bussink, Jan; Van De Grampel, Hendrik T.; Wheatley, Gary W.; Dorf, Ernst-Ulrich; Ostlinning, Edgar; Reinking, Klaus; Schubert, Frank; Jünger, Oliver; Wagener, Reinhard (2012). "Polymers, High-Temperature". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a21_449.pub4. ISBN 978-3-527-30673-2.
  3. 1 2 Hay, A.S. (January 1965). "Dehydrogenation reactions with diphenoquinones". Tetrahedron Letters. 6 (47): 4241–4243. doi:10.1016/S0040-4039(01)89114-0.
  4. 1 2 3 Hay, Allan S. (April 1969). "p,p'-Biphenols". The Journal of Organic Chemistry. 34 (4): 1160–1161. doi:10.1021/jo01256a098.
  5. ↑ Helmut Fiege; Heinz-Werner Voges; Toshikazu Hamamoto; et al. (2002). "Phenol Derivatives". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_313. ISBN 3527306730.
  6. ↑ O’Brien, M. K.; Vanasse, B. (2004). "Vanadium(IV) Chloride". In Paquette, L. (ed.). Encyclopedia of Reagents for Organic Synthesis. New York, NY: J. Wiley & Sons. doi:10.1002/047084289X.rv001. ISBN 0471936235.
  7. ↑ Hay, Allan S. (April 1962). "Polymerization by oxidative coupling. II. Oxidation of 2,6-disubstituted phenols". Journal of Polymer Science. 58 (166): 581–591. Bibcode:1962JPoSc..58..581H. doi:10.1002/pol.1962.1205816634.
  8. ↑ Kuiper, George G. J. M.; Lemmen, Josephine G.; Carlsson, Bo; Corton, J. Christopher; Safe, Stephen H.; Van Der Saag, Paul T.; Van Der Burg, Bart; Gustafsson, Jan-Åke (1998). "Interaction of Estrogenic Chemicals and Phytoestrogens with Estrogen Receptor β". Endocrinology. 139 (10): 4252–4263. doi:10.1210/endo.139.10.6216. PMID 9751507.