10,12-docosadiyne-1,22-diacid
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| General | ||||||||||
| Surname | 10,12-docosadiyne-1,22-diacid | |||||||||
| Molecular formula | C 22 H 34 O 4 | |||||||||
| Brief description |
white to blue solid or flakes, light gray powder |
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| properties | ||||||||||
| Molar mass | 362.50 g mol −1 | |||||||||
| Physical state |
firmly |
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| solubility |
almost insoluble in water, soluble in methanol , dichloromethane , chloroform and tetrahydrofuran |
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| As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions . | ||||||||||
10,12-docosadiyne-1,22-diacid is a long-chain linear dicarboxylic acid with a conjugated diacetylene group in the middle , the crystals of which turn intensely blue on the surface through pressure, heat treatment and especially through high- energy radiation ( UV or gamma radiation ) and when heated over Color irreversibly red at 120 ° C. The dicarboxylic acid has pronounced hydrophobic and hydrophilic molecular structures and is the starting compound of so-called bolaamphiphiles based on the throwing weapon of South American gauchos .
Manufacturing
10,12-docosadiinedioic acid is obtained in an oxidative dimerization in the sense of a Glaser coupling in the presence of copper (I) chloride at 70 ° C. by introducing air into an alcoholic solution of 10-undecynoic acid with a yield of 90%. In the variant of the Hay coupling , the solubilizing effect of TMEDA achieves shorter reaction times with very good yields even at room temperature and with the introduction of oxygen.
Through complete catalytic hydrogenation of the diacetylene group in the molecule, the naturally occurring 1,22-docosanedioic acid (phellogenic acid) occurs in cork .
properties
10,12-docosadiinedioic acid is a white crystalline solid which, when exposed to UV radiation, polymerizes topochemically to a polydiacetylene with the formation of a conjugated mesomeric en-yne bond system. The high absorption coefficient of the resulting chromophore causes the crystal surfaces to have an intense blue color. When the monomer crystals of conjugated diacetylenes with polar end groups below their melting point are tempered, polymerization to form deeply colored polymer crystals also occurs.
(The angled representation of the substituents R 1 and R 2 in the 1,4-position of the diene group in the lower part of the figure does not correspond to the sp hybridization present therein (bond angle 180 °), but serves to better illustrate the 1,4-linkage that takes place in the Polymerization of the conjugated triple bonds of substituted diacetylenes).
The blue color changes irreversibly to red when heated above 120 ° C. With further heating or irradiation, as well as in certain solvents, polydiacetylenes can turn yellow permanently.
The causes for the temperature-induced color transitions of polydiacetylenes ( thermochromism ) at the molecular level are controversially discussed in the literature. The blue-red color change is said to be based on a phase transition of the entire system of polymer chain, alkyl chains, and polar and space-filling end groups, which leads to the deformation of the conjugated en-yne polymer chain and thus the effective conjugation length.
Applications
10,12-docosadiinedioic acid and 1,5-diaminopentane form a nylon salt similar to the AH salt for the production of PA 6.6 , from which two-dimensionally crosslinked polymers can be produced. One level of polymerization is formed by the polymerization of the diacetylene groups, the other by the polycondensation of the nylon salt, creating a network of polydiacetylenes that is connected in a vertical direction via polyamide chains. Moldings made from such nylon salts and polymerized under pressure and temperature are characterized by high crystallinity, strength and rigidity, which are comparable to those of metals.
With the amino acid arginine , 10,12-docosadiinedioic acid also forms salts that form hydrogels in water , in which nanofibers are formed. Irradiation with UV light can bring about topochemical polymerisation in these nanofibers to form polydiacetylenes with a color change from white to orange.
The injection of 10,12-docosadiinedioic acid solutions into solutions of p-xylylenediamine in THF produces porous spherical particles of specific porosity and pore size through ionic interactions between carboxyl and amino groups. Polymerization with UV light (254 nm) leads to blue, non-fluorescent particles which, when heated to 110 ° C for 36 hours, turn red and show red fluorescence. The particles show high thermal stability compared to conventional polydiacetylene materials and are suitable as chemical sensors.
Polymer 10,12-docosadiindioic acid forms nanocomposite materials with zinc oxide , which produce different color effects in different organic solvents and are suitable as sensors for organic liquids. Films of similar composition can serve as chromatic sensors for temperature, chemical and material stress, and the like. a. also as sensors for traces of explosives such as trinitrotoluene .
Esterification of 10,12-docosadiindioic acid with hydroxyazobenzenes and cholesterol leads to liquid-crystalline materials that can be processed into thin films. The films can be exposed by irradiation with a helium-cadmium laser and the color image obtained can be fixed by cooling, which could allow access to rewritable recording materials.
Functional esters of 10,12-docosadiynedioic acid form photopolymerizable layers on solid substrates, which use a photolithographic process to provide colored images and are suitable for the construction of thermal and chemical sensors. The blue, non-fluorescent phase of the polymeric diesters has an absorption peak at approx. 630–640 nm, the red fluorescent phase at approx. 540–550 nm. The irreversible color change from blue to red in polymeric 10, which occurs at temperatures above 78 ° C. 12-docosadiindioic acid can also be used as a marker for the usability of ammunition after intense heat exposure.
10,12-docosadiyne-1,22-diacid is also suitable for building up bolaamphiphiles in which there are two polar head groups at the end of a long hydrophobic hydrocarbon chain. The conversion of both terminal carboxy groups leads to symmetrical bolaamphiphiles with the schematic structure (A)
The implementation of only one carboxy group or the targeted derivatization of both with different and differently sized substituents leads to asymmetrical bolaamphiphiles of the schematic structure (B).
In water, bolaamphiphiles form lyotropic phases of various shapes, such as spheres, cylinders, discs or vesicles .
Individual evidence
- ↑ GFS Organic Chemicals, 10,12-Docosadiynedioic acid 98%, Item 3113, http://www.e-digitaleditions.com/i/83298/62
- ↑ a b Data sheet 10,12-Docosadiynedioic acid 95% at AlfaAesar, accessed on 2014-10-20 ( PDF )(JavaScript required) .
- ↑ A. Alissandratos, N. Baudendistel, B. Hauer, K. Baldenius, S. Flitsch, P. Halling: Biocompatible functionalization of starch . In: Chem. Commun. tape 47 , 2010, p. 683-685 , doi : 10.1039 / C0CC02908D .
- ↑ a b c d e f A. Seher: The constitution of isanoic and isanolic acid . In: Liebigs Ann. Chem. Band 589 , no. 3 , 1954, pp. 222-238 , doi : 10.1002 / jlac.19545890308 .
- ^ A b J. Lee, O. Yarimaga, CH Lee, Y.-K. Choi, J.-M. Kim: Network polydiacetylene films: preparation, patterning and sensor applications . In: Adv. Funct. Mater. tape XX , 2011, p. 1–8 , doi : 10.1002 / adfm.201002042 .
- ↑ a b A. Wu, Y. Gu, H. Tian, JF Federici, Z. Iqbal: Effect of alkyl chain length on chemical sensing of polydiacetylenes and polydiacetylenes / ZnO nanocomposites . In: Colloid Polym. Sci. 2014, doi : 10.1007 / s00396-014-3365-y .
- ↑ a b Patent US20120315481 : Porous diacetylene particles, synthesis method thereof. Filed April 6, 2012 , published December 13, 2012 , Applicant: Korea University Research and Business Foundation, Inventor: DJ Ahn, DH Yang.
- ↑ a b Data sheet 10,12-Docosadiynedioic acid, 95% from AlfaAesar, accessed on December 26, 2014 ( PDF )(JavaScript required) .
- ^ AS Hay: Oxidative coupling of acetylenes. II . In: J. Org. Chem. Band 27 , no. 9 , 1962, pp. 3320-3321 , doi : 10.1021 / jo01056a511 .
- ↑ F. Zetzsche, M. Bähler: Investigations on the cork VII. Phellogenic acid (contribution to the behavior of the α-oxy acids in the potash melt) . In: Helv. Chim. Acta . tape 14 , no. 4 , 1931, p. 852-856 , doi : 10.1002 / hlca.19310140425 .
- ↑ G. Wegner: Topochemical polymerization of monomers with conjugated triple bonds . In: Makromol. Chem. Band 154 , 1972, p. 35-48 , doi : 10.1002 / macp.1972.021540103 .
- ↑ M. Schott: The colors of polydiacetylenes: a commentary . In: J. Phys. Chem. B . tape 110 , 2006, p. 15864–15868 , doi : 10.1021 / jp0638437 ( PDF ).
- ↑ Patent US4814404 : Diacetylene-nylon salt compound and method for production of two-dimensional macromolecular crystals and shaped articles using said compound. Filed August 27, 1987 , published March 21, 1989 , Applicant: Agency of Industrial Science & Technology, MITI, Inventors: H. Matsuda, H. Nakanishi, M. Kato, Y. Tanaka, K. Nakayama.
- ↑ M. Mukai, M. Kogiso, M. Aoyagi, M. Asakawa, T. Shimizu, H. Minamikawa: Supramolecular nanofiber formation from commercially available arginine and a bola-type diacetylenic diacid via hydrogelation . In: Polymer J. Band 44 , 2012, p. 646–650 , doi : 10.1038 / pj.2012.46 .
- ↑ A. Patlolla, JL Zunino III, DP Schmidt, Z. Iqbal, DR Skelton: ZnO: Polydiacetylene films as chromatic sensors . In: Tech Connect World . 2010 ( online ( memento of March 4, 2016 in the Internet Archive )).
- ↑ N. Tamaoki, Y. Aoki, M. Moriyama, M. Kidowaki: Photochemical phase transition and molecular realignment of glass-forming liquid crystals containing cholesterol / azobenzene dimesogenic units . In: Chem. Mater. tape 15 , no. 3 , 2003, p. 719-726 , doi : 10.1021 / cm020234c .
- ^ JL Zunino III, DR Skelton, Z. Iqbal: Thermal indicating paints for ammunition assurance
- ↑ Patent US8722418 : Thermal indicating composition. Registered on March 6, 2012 , published on May 13, 2014 , applicant: The United States of America as represented by the Secretary of the Army, inventor: JL Zunino III, Z. Iqbal.
- ^ R. Nagarajan: Self-assembly of bola amphiphiles . In: Chem. Eng. Commun. tape 55 , no. 1-6 , 1987, pp. 251-273 , doi : 10.1080 / 00986448708911931 .