Polyyne

Ichthyothereol is a polyyne that occurs in plants in the genus Ichthyothere and is highly toxic to fish

In chemistry, a polyyne /ˈpɒlɪʌɪn/ is any organic compound with alternating single and triple bonds; that is, a series of consecutive alkynes, (−C≡C−)
n with n greater than 1. The simplest example is diacetylene or buta-1,3-diyne, H−C≡C−C≡C−H.

These compounds have also been called oligoynes,[1] or carbinoids after "carbyne" (−C≡C−)
∞, the hypothetical allotrope of carbon that would be the ultimate member of the series.[2][3] The synthesis of this substance has been claimed several times since the 1960s, but those reports have been disputed.[4] Indeed, the substances identified as short chains of "carbyne" in many early organic synthesis attempts[5] would be called polyynes today.

Polyynes are distinct from polyacetylenes, polymers formally obtained by polymerization of acetylenes. The backbones of polyacetylenes have alternating single and double bonds n. In biochemistry and plant biology, "polyacetylene" is routinely used to describe naturally occurring polyynes and related species.[6]

Along with cumulenes, polyynes are distinguished from other organic chains by their rigidity, which makes them promising for molecular nanotechnology. Polyynes have been detected in interstellar molecular clouds where hydrogen is scarce.

Synthesis

The first reported synthesis of polyynes was performed in 1869 by Carl Glaser, who observed that copper phenylacetylide (CuC2C6H5) undergoes oxidative dimerization in the presence of air to produce diphenylbutadiyne (C6H5C4C6H5).[3]

Interest in these compounds has stimulated research into their preparation by organic synthesis by several general routes. Many such procedures involve a Cadiot–Chodkiewicz coupling or similar reactions to unite two separate alkyne building-blocks or by alkylation of a pre-formed polyyne unit.[7]

Simple polymers

Using various techniques, polyynes H(−C≡C−)
nH with n up to 4 or 5 were synthesized during the 1950s.[8] Around 1971, T. R. Johnson and D. R. M. Walton developed the use of end-caps of the form −SiR
3, where R was usually an ethyl group, to protect the polyyne chain during the chain-doubling reaction using Hay's catalyst (a copper(I)-TMEDA complex).[8][9] With that technique they were able to obtain polyynes like Et
3Si–(C≡C)
m–SiEt
3 with m up to 8 in pure state, and with m up to 16 in solution.

Alkynes with the formula H(−C≡C−)
nH and n from 2 to 6 can be detected in the decomposition products of partially oxidized copper(I) acetylide (Cu+
)
2C2−
2 (an acetylene derivative known since 1856 or earlier) by hydrochloric acid. A "carbonaceous" residue left by the decomposition also has the spectral signature of (−C≡C−)
n chains.[10]

Organometallics

Organometallic polyynes capped with metal complexes are well characterized. As of the mid-2010s, the most intense research has concerned rhenium (ReCnRe, n=6-20),[11] ruthenium (RuRuCnRuRu, n=8-20),[12] iron (FeC12CFe),[13] platinum (PtCnPt, n=16-28),[14] palladium (ArCnPd, n=6-10),[15] and cobalt (Co3CnCo3, n=14-26)[16] complexes.

Examples of known organometallic polyynes.

Stability

Long polyyne chains are said to be inherently unstable in bulk because they can cross-link with each other in an exothermal (indeed explosive) reaction.[4] Explosions are a real hazard in this area of research.[17] They can be fairly stable, even against moisture and oxygen, if they are end-capped with suitable inert groups (such as tert-butyl or trifluoromethyl) rather than hydrogen atoms,[18] especially bulky ones that can keep the chains apart.[1] In 1995 the preparation of carbyne chains with over 300 carbons was reported using this technique.[18] However the report has been contested by a claim that the detected molecules were fullerene-like structures rather than long polyynes.[4]

A polyyne compound with 10 acetylenic units (20 atoms), with the ends capped by Fréchet-type aromatic polyether dendrimers, was isolated and characterized in 2004.[1] As of 2010, the polyyne with the longest chain yet isolated had 22 acetylenic units (44 atoms), end-capped with tris(3,5-di-t-butylphenyl)methyl groups.[19]

Polyyne chains have also been stabilised to heating by co-deposition with silver nanoparticles,[20] and by complexation with a mercury-containing tridentate Lewis acid to form layered adducts.[21] Long polyyne chains encapsulated in double-walled carbon nanotubes have also been shown to be stable.[22]

Structure

Synthetic polyynes of the form R−(−C≡C−)
n−R, with n about 8 or more, often have a smoothly curved or helical backbone in the crystalline solid state, presumably due to crystal packing effects.[23] For example, when the cap R is triisopropylsilyl and n is 8, X-ray crystallography of the substance (a crystalline orange/yellow solid) shows the backbone bent by about 25–30 degrees in a broad arch, so that each C−C≡C angle deviates by 3.1 degrees from a straight line. This geometry affords a denser packing, with the bulky cap of an adjacent molecule nested into the concave side of the backbone. As a result, the distance between backbones of neighboring molecules is reduced to about 0.35 to 0.5 nm, near the range at which one expects spontaneous cross-linking. The compound is stable indefinitely at low temperature, but decomposes before melting. In contrast, the homologous molecules with n=4 or n=5 have nearly straight backbones that stay at least 0.5 to 0.7 nm apart, and melt without decomposing.[24]

Natural occurrence

Biological origins

A wide range of organisms synthesize polyynes.[6][25] These chemicals have various biological activities, including as flavorings and pigments, chemical repellants and toxins, and potential application to biomedical research and pharmaceuticals.

8,10-Octadecadiynoic acid

The simple fatty acid 8,10-octadecadiynoic acid is isolated from the root bark of the legume Paramacrolobium caeruleum of the Showy Mistletoe (Loranthaceae) family and has been investigated as a photopolymerizable unit in synthetic phospholipids.[7]

Thiarubrine B

Thiarubrine B is the most prevalent among several related light-sensitive pigments that have been isolated from the Giant Ragweed (Ambrosia trifida), a plant used in herbal medicine. The thiarubrines have antibiotic, antiviral, and nematocidal activity, and activity against HIV-1 that is mediated by exposure to light.[26]

Falcarindiol

Falcarindiol is the main compound responsible for bitterness in carrots, and is the most-active among several polyynes with potential anticancer activity found in Devil's club (Oplopanax horridus). Other polyynes from plants include oenanthotoxin and cicutoxin. Polyynes including falcarindiol can be found in Apiaceae vegetables like carrot, celery, fennel, parsley and parsnip where they show cytotoxic activities.[27] Aliphatic C(17)- polyynes of the falcarinol type were described to act as metabolic modulators[28][29] and are studied as potential health-promoting nutraceuticals.[30]

Ichthyothereol

Ichthyothere is a genus of plants whose active constituent is a polyyne called ichthyothereol. This compound is highly toxic to fish and mammals.[31] Ichthyothere terminalis leaves have traditionally been used to make poisoned bait by indigenous peoples of the lower Amazon basin.[31]

Z-Dihydromatricaria acid

Dihydromatricaria acid is a polyyne produced and secreted by the soldier beetle as a chemical defense.[32]

In space

The octatetraynyl radicals and hexatriynyl radicals together with their ions are detected in space where Hydrogen is rare.[33] Moreover, there have been claims[34] that polyynes have been found in astronomical impact sites on Earth as part of the mineral Chaoite, but this interpretation has been contested.[35] See Astrochemistry.

See also

References

  1. 1 2 3 Gibtner, Thomas; Hampel, Frank; Gisselbrecht, Jean-Paul; Hirsch, Andreas (2002). "End-cap stabilized oligoynes: Model compounds for the linear sp carbon allotrope carbyne". Chemistry, a European Journal 8 (2): 408–432. doi:10.1002/1521-3765(20020118)8:2.
  2. ↑ Heimann, R.B.; Evsyukov, S.E.; Kavan, L., eds. (1999). Carbyne and carbynoid structures. Physics and Chemistry of Materials with Low-Dimensional Structures 21. p. 452. ISBN 0-7923-5323-4.
  3. 1 2 Chalifoux, Wesley A.; Tykwinski, Rik R. (2009). "Synthesis of extended polyynes: Toward carbyne". Comptes Rendus Chimie 12 (3-4): 341–358. doi:10.1016/j.crci.2008.10.004. In Avancés récentes en chimie des acétylènes – Recent advances in acetylene chemistry
  4. 1 2 3 Kroto, H. (November 2010). "Carbyne and other myths about carbon". RSC Chemistry World.
  5. ↑ Akagi, K.; Nishiguchi, M.; Shirakawa, H.; Furukawa, Y.; et al. (1987). "One-dimensional conjugated carbyne — synthesis and properties". Synthetic Metals 17 (1–3): 557–562. doi:10.1016/0379-6779(87)90798-3.
  6. 1 2 Minto RE; Blacklock BJ (July 2008). "Biosynthesis and function of polyacetylenes and allied natural products". Prog Lipid Res 47 (4): 233–306. doi:10.1016/j.plipres.2008.02.002. PMC 2515280. PMID 18387369.
  7. 1 2 Xu, Zhenchun; Byun, Hoe Sup; Bittman, Robert (1991). "Synthesis of photopolymerizable long-chain conjugated diacetylenic acids and alcohols from butadiyne synthons". J. Org. Chem. 56 (25): 7183–7186. doi:10.1021/jo00025a045.
  8. 1 2 Eastmond, R.; Johnson, T.R.; Walton, D.R.M. (1972). "Silylation as a protective method for terminal alkynes in oxidative couplings: A general synthesis of the parent polyynes H(C≡C)
    n    H     (n = 4–10, 12)". Tetrahedron 28 (17): 4601–16. doi:10.1016/0040-4020(72)80041-3.
  9. ↑ Johnson, T.R.; Walton, D.R.M. (1972). "Silylation as a protective method in acetylene chemistry: Polyyne chain extensions using the reagents, Et
    3    Si(C≡C)
    m    H     (m = 1,2,4) in mixed oxidative couplings". Tetrahedron 28 (20): 5221–36. doi:10.1016/S0040-4020(01)88941-9.
  10. ↑ Cataldo, Franco (1999). "From dicopper acetylide to carbyne". Polymer International 48 (1): 15–22. doi:10.1002/(SICI)1097-0126(199901)48:1.
  11. ↑ Dembinski, Roman; Bartik, Tamás; Bartik, Berit; Jaeger, Monika; Gladysz, J. A. (2000-02-01). "Toward Metal-Capped One-Dimensional Carbon Allotropes:  Wirelike C6−C20 Polyynediyl Chains That Span Two Redox-Active (η5-C5Me5)Re(NO)(PPh3) Endgroups". Journal of the American Chemical Society 122 (5): 810–822. doi:10.1021/ja992747z. ISSN 0002-7863.
  12. ↑ Cao, Zhi; Xi, Bin; Jodoin, Diane S.; Zhang, Lei; Cummings, Steven P.; Gao, Yang; Tyler, Sarah F.; Fanwick, Phillip E.; Crutchley, Robert J. (2014-08-27). "Diruthenium–Polyyn-diyl–Diruthenium Wires: Electronic Coupling in the Long Distance Regime". Journal of the American Chemical Society 136 (34): 12174–12183. doi:10.1021/ja507107t. ISSN 0002-7863.
  13. ↑ Sakurai, Aizoh; Akita, Munetaka; Moro-oka, Yoshihiko (1999-08-01). "Synthesis and Characterization of the Dodecahexaynediyldiiron Complex, Fp*−(C⋮C)6−Fp* [Fp*= Fe(η5-C5Me5)(CO)2], the Longest Structurally Characterized Polyynediyl Complex". Organometallics 18 (16): 3241–3244. doi:10.1021/om990266i. ISSN 0276-7333.
  14. ↑ Zheng, Qinglin; Gladysz, J. A. (2005-08-01). "A Synthetic Breakthrough into an Unanticipated Stability Regime:  Readily Isolable Complexes in which C16−C28 Polyynediyl Chains Span Two Platinum Atoms". Journal of the American Chemical Society 127 (30): 10508–10509. doi:10.1021/ja0534598. ISSN 0002-7863.
  15. ↑ Pigulski, Bartłomiej; Gulia, Nurbey; Szafert, Sławomir (2015-10-22). "Synthesis of Long, Palladium End-Capped Polyynes through the Use of Asymmetric 1-Iodopolyynes". Chemistry – A European Journal: n/a–n/a. doi:10.1002/chem.201502737. ISSN 1521-3765.
  16. ↑ Bruce, Michael I.; Zaitseva, Natasha N.; Nicholson, Brian K.; Skelton, Brian W.; White, Allan H. (2008-08-15). "Syntheses and molecular structures of some compounds containing many-atom chains end-capped by tricobalt carbonyl clusters". Journal of Organometallic Chemistry 693 (17): 2887–2897. doi:10.1016/j.jorganchem.2008.06.007.
  17. ↑ Baughman, R.H. (2006). "Dangerously Seeking Linear Carbon". Science 312 (5776): 1009–1110. doi:10.1126/science.1125999. PMID 16709775.
  18. 1 2 Lagow, R.J.; Kampa, J.J.; Han-Chao Wei; Battle, Scott L.; et al. (1995). "Synthesis of linear acetylenic carbon: The "sp" carbon allotrope". Science 267 (5196): 362–7. doi:10.1126/science.267.5196.362. PMID 17837484.
  19. ↑ Chalifoux, Wesley A.; Tykwinski, Rik R. (2010). "Synthesis of polyynes to model the sp-carbon allotrope carbyne". Nature Chemistry 2: 967–971. doi:10.1038/nchem.828.
  20. ↑ Casari, C. S.; Cataldo, F.; et al. (2007). "Stabilization of linear carbon structures in a solid Ag nanoparticle assembly". Applied Physics Letters 90: 013111. doi:10.1063/1.2430676.
  21. ↑ Gabbai, F. P.; Taylor, T. J. (March 24, 2006). "Supramolecular Stabilization of α,ω-Diphenylpolyynes by Complexation to the Tridentate Lewis Acid [o-C6F4Hg]3". Organometallics 25 (9): 2143–2147. doi:10.1021/om060186w.
  22. ↑ Zhao, C.; Shinohara, H. (2011). "Growth of Linear Carbon Chains inside Thin Double-Wall Carbon Nanotubes". Journal of Physical Chemistry C 115 (27): 13166–13170. doi:10.1021/jp201647m.
  23. ↑ Szafert, Slawomir; Gladysz, J. A. (2006-11-01). "Update 1 of: Carbon in One Dimension:  Structural Analysis of the Higher Conjugated Polyynes". Chemical Reviews 106 (11): PR1–PR33. doi:10.1021/cr068016g. ISSN 0009-2665.
  24. ↑ Eisler, Sara; Slepkov, Aaron D.; Elliott, Erin; Thanh Luu; et al. (2005). "Polyynes as a model for carbyne: Synthesis, physical properties, and nonlinear optical response". Journal of the American Chemical Society 127 (8): 2666–76. doi:10.1021/ja044526l. PMID 15725024.
  25. ↑ Annabelle, L.K.; Shi Shun; Tykwinski, Rik R. (2006). "Synthesis of Naturally Occurring Polyynes". Angewandte Chemie International Edition 45 (7): 1034–57. doi:10.1002/anie.200502071. PMID 16447152.
  26. ↑ Block, Eric; Guo, Chuangxing; Thiruvazhi, Mohan; Toscano, Paul J. (1994). "Total Synthesis of Thiarubrine B [3-(3-Buten-1-ynyl)-6-(1,3-pentadiynyl)-1,2-dithiin], the Antibiotic Principle of Giant Ragweed (Ambrosia trifida)". J. Am. Chem. Soc. 116 (20): 9403–9404. doi:10.1021/ja00099a097.
  27. ↑ Zidorn, C.; Jöhrer, K.; Ganzera, M.; Schubert, B.; et al. (2005). "Polyacetylenes from the Apiaceae Vegetables Carrot, Celery, Fennel, Parsley, and Parsnip and Their Cytotoxic Activities". J. Agric. Food Chem. 53 (7): 2518–23. doi:10.1021/jf048041s. PMID 15796588.
  28. ↑ Atanasov, AG; Blunder, M; Fakhrudin, N; Liu, X; Noha, SM; Malainer, C; Kramer, MP; Cocic, A; Kunert, O; Schinkovitz, A; Heiss, EH; Schuster, D; Dirsch, VM; Bauer, R (Apr 2013). "Polyacetylenes from Notopterygium incisum--new selective partial agonists of peroxisome proliferator-activated receptor-gamma". PLOS ONE 8 (4): e61755. doi:10.1371/journal.pone.0061755. PMC 3632601. PMID 23630612.
  29. ↑ Ohnuma, T; Anan, E; Hoashi, R; Takeda, Y; Nishiyama, T; Ogura, K; Hiratsuka, A (2011). "Dietary diacetylene falcarindiol induces phase 2 drug-metabolizing enzymes andblocks carbon tetrachloride-induced hepatotoxicity in mice through suppression of lipid peroxidation". Biol Pharm Bull. 34 (3): 371–8. doi:10.1248/bpb.34.371. PMID 21372387.
  30. ↑ Christensen, LP (Jan 2011). "Aliphatic C(17)-polyacetylenes of the falcarinol type as potential health promoting compounds in food plants of the Apiaceae family". Recent Pat Food Nutr Agric 3 (1): 64–77. doi:10.2174/2212798411103010064. PMID 21114468.
  31. 1 2 Cascon, Seiva C.; Mors, Walter B.; Tursch, Bernard M.; Aplin, Robin T.; Durham, Lois J. (1965). "Ichthyothereol and Its Acetate, the Active Polyacetylene Constituents of Ichthyothere terminalis (Spreng.) Malme, a Fish Poison from the Lower Amazon". Journal of the American Chemical Society 87 (22): 5237–5241. doi:10.1021/ja00950a044. ISSN 0002-7863.
  32. ↑ Eisner, Thomas; Eisner, Maria; Siegler, Melody (2005). "40. Chauliognathus lecontei (a soldier beetle)". Secret Weapons: Defenses of Insects, Spiders, Scorpions, and Other Many-legged Creatures. Harvard University Press. pp. 185–188. ISBN 9780674018822.
  33. ↑ Duley, W. W.; Hu, A. (2009). "Polyynes and interstellar carbon nanoparticles". Astrophys. J. 698: 808. Bibcode:2009ApJ...698..808D. doi:10.1088/0004-637X/698/1/808.
  34. ↑ El Goresy, A.; Donnay, G. (1968). "A New Allotropic Form of Carbon from the Ries Crater". Science 151: 363–364. doi:10.1126/science.161.3839.363.
  35. ↑ Smith, P. P. K.; Busek, P. R. (1982). "Carbyne Forms of Carbon: Do They Exist?". Science 216 (4549): 984–986. doi:10.1126/science.216.4549.984.
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