10-Undecin-1-ol - 10-Undecin-1-ol

Structural formula
10-Undecinol-Struktur
General
Name 10-Undecin-1-ol
other names
  • 10-Undecinol
  • 10-Undecyn-1-ol
Sum formula C11H20O
Brief description

colorless [1] to light yellow [2] liquid

External identifiers / databases
CAS number 2774-84-7
PubChem 76015
Wikidata Q18571289
characteristics
Molar mass 168.28 g · mol −1
Physical state

liquid

density
boiling point
solubility

practically insoluble in water, soluble in alcohols such as methanol [4] and ethanol , in chlorinated hydrocarbons such as dichloromethane [5] and chloroform [6] , and in tetrahydrofuran

Refractive index
  • 1,4565 (20 °C)[1]
  • 1,4573 (20 °C)[3]
safety instructions
GHS hazard labeling [2]
no GHS pictograms
H and P phrases H: no H-phrases
P: no P-phrases [2]
As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions . Refractive index: Na-D line , 20 ° C

10-Undecin-1-ol is a naturally occurring, linear alkynol with a terminal ethynyl group . It is easily accessible synthetically from 10-undecen-1-ol or 10-undecinic acid or methylundecinoate.

Occurrence

10-Undecin-1-ol occurs in considerable amounts (10.74%) in the pseudobulbs of Bulbophyllum kaitense Reichb.f. , a species of epiphytes native to India, which are used in traditional medicine ( Ayurveda ) and local natural medicine treatments as anti-inflammatory and antimicrobial medicinal drugs . [7]

Manufacturing

Reduction of 10-undecynic acid with lithium aluminum hydride in diethyl ether gives 10-undecynol in a yield of 89% of theory. [3]

10-Undecynol can be obtained in 93% yield by isomerization of 2-Undecyn-1-ol (from the reaction of propargyl alcohol with n-Octyllithium) [8] .

10-Undecinol aus 2-Undecinol

The displacement of the internal triple bond at the chain end succeeds smoothly with the potassium amide of 1,3-diaminopropane . [9]

Analogously to the preparation of 10-undecynoic acid from undecylenic acid , 10-undecyn-1-ol can be obtained from 10-undecen-1-ol by bromination of the double bond and subsequent double dehydrobromination with sodium amide in liquid ammonia in 60% yield. [10]

Another synthetic route starts from the methyl ester of 10-undecinic acid, which is reduced to 10-undecynol in 63% yield with tetraisopropyl orthotitanate and polymethylhydrosiloxane (PMHS). [11]

10-undecinol from 10-undecynoic acid methyl ester

characteristics

In its pure state, 10-Undecin-1-ol is a clear, colorless liquid that solidifies to a waxy mass at temperatures below 5 ° C. Like undecylenic acid, 10-undecinol also has a fungicidal effect, although this is limited by its even lower solubility in water. Inclusion compounds with methylated β-cyclodextrin increase the water solubility and thus the bioavailability of such solubilized 10-undecinol, which lead to a considerably increased effectiveness against phytopathogenic fungi such as Rosellina necatrix . [12]

Applications

10-Undecinol is an important component in a synthesis route to the insect pheromone bombykol , which acts as a sexual attractant in the silk moth. [13] A convergent stereospecific synthesis is based on the starting materials 10-undecynol and 1-pentyne . [14]

In analogy to the preparation of 10,12-docosadiyne-1,22-diacid from 10-undecynoic acid by oxidative Glaser coupling , 10-undecin-1-ol can be obtained in the variant of the Eglinton reaction with copper (II) acetate in pyridine and catalytic amounts of copper (I) chloride are linked in 68% yield to the corresponding α, ω-diol 10,12-docosadiyne-1,22-diol. [10]

10,12-Docosadiin-1,22-diol

The simple thiol-in addition of mercaptoethanol to the ethynyl group of 10-undecynol leads to a vinyl thioether derivative which, as a diol component, reacts with MDI ( methylenediphenyl isocyanate ) to form linear polyurethanes. [15]

Thiol-In-Addition zu Vinylthioethern

The terminal ethynyl group makes 10-undecinol a suitable molecule for click chemistry , e.g. B. for thiol-in coupling reactions. [16] For example, 10-undecinol (together with 10-undecynoic acid and 10-undecynoic acid methyl ester) reacts in a photoinitiated thiol-yne reaction with 3,6-dioxa-1,8-dithiol in the presence of the photoinitiator DMPA (2,2-dimethoxy -2-phenylacetophenone) to comb-like oligothioethers, which can be used as functional polyols for polyurethane syntheses. [17]

Oligothioether durch Thiol-In-Addition an 10-Undecinol

Another click reaction, the copper (I) iodide- catalyzed azide-alkyne cycloaddition (CuAAC, copper (I) -catalyzed azide-alkyne cycloaddition ), leads to the conversion of TBDMS ( tert- butyldimethylsilyl) -protected glutaric acid half-ester of 10-undecinol with the bis- azide 1,5-diazido-3-oxapentane [bis (2-azidoethyl) ether] in 86% yield to substituted 1,2,3-triazoles . [18]

Bola-bis-triazole from 10-undecinol

The resulting polymerizable bolaamphiphil can serve as a model compound for membrane-spanning lipids, which give the membranes of the archaea's biological domain extreme stability against high thermal (up to 121 ° C), osmotic (approx. 30% NaCl solution) and hydrolytic (pH 0) stress . [19] The length of the hydrophobic chain between the two hydrophilic head groups of the bistriazole bolaamphiphile should be sufficient to span the approximately 35 Angstrom thick lipid bilayer of biomembranes.

Individual evidence

  1. a b c d data sheet 10-Undecyn-1-ol from AlfaAesar, accessed on October 29, 2014 ( PDF )(JavaScript required) .
  2. a b c d Data sheet 10-Undecyn-1-ol, ≥95.0% (GC) from Sigma-Aldrich , accessed on December 26, 2014 ( PDF ).
  3. a b c L.D. Bergel'son, Y.G. Molotkovskii, M.M. Shemyakin: Unsaturated acids and macrocyclic lactones: I. Synthesis of diacetylenic and dienic macrocyclic lactones. In: Zh. Obshch. Khim. Band 32, 1962, S. 58–64 (CA: 57.14930 (1962)).
  4. S. Inayama, T. Tatewaki, S. Okada: Solid-state polymerization of conjugated hexayne derivatives with different end groups. In: Polymer J. Band 42, 2010, S. 201–207 , doi : 10.1038 / pj.2009.326 .
  5. H. Woo, Y. You, T. Kim, G.-J. Jhon, W. Nam: Fluorescence ratiometric zinc sensors based on controlled energy transfer. In: J. Mater. Chem. Band 22, 2012, S. 17100 , doi : 10.1039 / c2jm33366j .
  6. G.W. Kabalka, M. Varma, R.S. Varma, P.C. Srivastava, F.F. Knapp Jr.: Tosylation of alcohols. In: J. Org. Chem. Band 51 , No. 12, 1986, S. 2386–2388 , doi : 10.1021 / jo00362a044 .
  7. A. Kaliarasan, S.A. John: GC-MS Analysis of Bulbophyllum Kaitense Rechib., pseudobulbs eastern ghats of India. In: Int. J. Chem. Appl. Band 3 , No. 3, 2011, S. 215–220 (PDF (Memento vom 16. Februar 2015 im Internet Archive)).
  8. H. Winarno: Rapid isomerization of alkynol by potassium aminopropylamide reagent. In: Indo. J. Chem. Band 7 , No. 3, 2007, S. 320–323 (Online).
  9. L. Brandsma: Preparative Acetylenic Chemistry. In: Studies in Organic Chemistry 34. Elsevier, 1988, ISBN 0-444-42960-3, S. 245–246.
  10. a b H. Bader, H. Ringsdorf: Liposomes from α,ω-dipolar amphiphiles with a polymerizable diyne moiety in the hydrophobic chain. In: J. Polym. Sci., Polym. Chem. Ed. Band 20 , No. 6, 1982, S. 1623–1628 , doi : 10.1002 / pol.1982.170200622 .
  11. M. T. Reding, S. L. Buchwald: An inexpensive air-stable titanium-based system for the conversion of esters to primary alcohols. In: J. Org. Chem. Band 60 , No. 24, 1995, S. 7884–7890, doi:10.1021/jo00129a031.
  12. T. L. Neoh, T. Tanimoto, S. Ikefuji, H. Yoshi, T. Furuta: Improvement of antifungal activity of 10-undecyn-1-ol by inclusion complexation with cyclodextrin derivatives. In: J. Agric. Food Chem. Band 56 , No. 10, 2008, S. 3699–3705 , doi : 10.1021 / jf.0731898 .
  13. T. Sakurai, T. Nakagawa, H. Mitsuno, H. Mori, Y. Endo, S. Tanoue, Y. Yasukochi, K. Touhara, T. Nishioka: Identification and functional characterization of a sex pheromone receptor in the silkmoth Bombyx mori. In: Proc. Natl. Acad. Sci. Band 101 , No. 47, 2004, S. 16653–16658, doi:10.1073/pnas.0407596101.
  14. N. Miyaura, H. Suginome, A. Suzuki: New stereospecific syntheses of pheromone bombykol and its three geometrical isomers. In: Tetrahedron. Band 39 , No. 20, 1983, S. 3271–3277 , doi : 10.1016 / S0040-4020 (01) 91575-3 .
  15. R.J. González-Paz, G. Lligadas, J.C. Ronda, M. Galià, V. Cádiz: Thiol-yne reaction of alkyne-derivatized fatty acids: Thiol-reactive linear polyurethane. In: J. Renew. Mater. Band 1, 2013, S. 187 , doi : 10.7569 / JRM.2013.634114 .
  16. R. Hoogenboom: Thiol-yne chemistry: A powerful tool for creating highly functional materials. In: Angew. Chem. Int. Ed. Band 49 , No. 20, 2010, S. 3415–3417 , doi : 10.1002 / anie.201000401 .
  17. C. Lluch, G. Lligadas, J.C. Ronda, M. Galià, V. Cádiz: Thiol-yne approach to biobased polyols: Polyurethane synthesis and surface modification. In: abiosus e.V., 6th Workshop on fats and oils as renewable feedstock for the chemical industry. 2013, S. 67 ( online [PDF]).
  18. G.M. Mitchell: Design and synthesis of a macrocyclic phospholipid. (online).
  19. Archaeal Lipids. In: SBKB, PSI-Nature Structural Biology Knowledgebase. doi:10.3942/psi_sgkb/fm_2012_12.