δ-valerolactone

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Structural formula
Structural formula of delta-valerolactone
General
Surname δ-valerolactone
other names
  • 5-valerolactone
  • Tetrahydro-2 H -pyran-2-one
  • 5-hydroxyvaleric acid lactone
  • 5-pentanolide
  • Oxan-2-one
Molecular formula C 5 H 8 O 2
Brief description

colorless to yellowish or light brown liquid

External identifiers / databases
CAS number 542-28-9
EC number 208-807-1
ECHA InfoCard 100.008.007
PubChem 10953
Wikidata Q903610
properties
Molar mass 100.11 g mol −1
Physical state

liquid

density
  • 1.056 g cm −3 at 20 ° C
  • 1.079 g cm −3 at 25 ° C
Melting point

−13 ° C

boiling point
Vapor pressure
  • 0.088 hPa at 20 ° C
  • 0.84 mbar at 50 ° C
solubility
Refractive index
  • 1.4553 (25 ° C)
  • 1.4560 to 1.4580 (20 ° C)
safety instructions
GHS labeling of hazardous substances
05 - Corrosive

danger

H and P phrases H: 318
P: 280-305 + 351 + 338
Toxicological data
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

δ-valerolactone ( delta-valerolactone , oxan-2-one) is the pyranoid lactone of 5-hydroxyvaleric acid (5-hydroxypentanoic acid), while the positionally isomeric tetrahydropyranones oxan-3-one and oxan-4-one are cyclic ether ketones.

δ-valerolactone is mainly used as a monomer for polyester , the positionally isomeric furanoid γ-valerolactone (4-hydroxypentanoic acid lactone) as a biogenic fuel and as a “green” solvent.

Manufacturing

In the hydrogenation of 5,6-dihydro-2 H -pyran-2-one - accessible in 25% yield by reacting 3-butenic acid with paraldehyde in a mixture of concentrated sulfuric acid and glacial acetic acid with a ferrocene- based palladium (II) -Complex, delta-valerolactone is obtained in 99% yield.

Hydrogenation of 5,6-dihydro-2H-pyran-2-one to δ-valerolactone

δ-valerolactone is obtained in 96% yield in the cyclization of 5-bromovaleric acid - e.g. B. from dihydropyran by acidolysis to δ-hydroxyvaleraldehyde, subsequent oxidation to δ-hydroxyvaleric acid and reaction with hydrobromic acid - with tetraalkylammonium fluorides

Cyclization of 5-bromovaleric acid to delta-valeolactone

A more common synthesis route is the Baeyer-Villiger oxidation of cyclopentanone with peroxytrifluoroacetic acid, which gives δ-valerolactone in 96% yield.

Baeyer-Villiger oxidation of cyclopentanone to delta-valerolactone

The oxidation can also be carried out in the presence of molybdenum complexes with hydrogen peroxide . A “green” route with a very good yield of 98% shows the oxidation of cyclopentanone with hydrogen peroxide and a lipase .

For the large-scale production of δ-valerolactone, the easily accessible 1,5-pentanediol seems to be the most suitable starting material. B. can also be isolated by distillative separation of the complex, so-called oil / on substance mixture in the oxidation of cyclohexane to cyclohexanol / cyclohexanol. The oxidation of 1,5-pentanediol is by copper compounds, such as. B. catalysed copper chromite . Carrying out the reaction at temperatures above 200 ° C. is decisive for the conversion of the starting material and the purity of the product, a conventional stirred reactor proving to be unsuitable since 30-35% polymeric by-products are formed when attempting to completely convert 1,5-pentanediol.

In a tubular reactor, on the other hand, the reaction proceeds much more specifically to the product, which, under catalysis with a copper (II) oxide and zinc oxide mixed catalyst, delivers pure δ-valerolactone in 86% yield.

Oxidation of 1,5-pentanediol to delta-valerolactone

An industrial process carries out the catalytic dehydrogenation in a tubular reactor on two catalyst layers with different contents of copper oxide with the carrier gas hydrogen and a temperature gradient of 300 ° C to 260 ° C with practically complete 1,5-pentanediol conversion, a δ-valerolactone selectivity of 96 % and a δ-valerolactone purity of> 99%.

properties

Pure δ-valerolactone is a water-clear, colorless liquid with an ester-like odor, which reacts slightly acidic in aqueous solution. It solidifies at −13 ° C, boils at 230 ° C and has a dynamic viscosity of 3.41 mPa · s at 20 ° C. The flash point is 110.5 ° C, the ignition temperature is 414 ° C. At temperatures above 370 ° C, δ-valerolactone begins to decompose.

Applications

δ-Valerolactone is used as a versatile intermediate for coatings of the polyester, polyurethane, acrylic and vinyl types.

5-chloropentanoyl chloride can be produced from δ-valerolactone by reaction with phosgene in the presence of 3-picoline in yields of up to 87% and purities of> 98%,

Synthesis of 5-chlorovaleric acid from delta-valerolactone

as the starting substance for a number of intermediate stages of drugs, such as. B. antivirals , phosphodiesterase-3 inhibitors such as cilostazol or anticoagulants such as apixaban is used more widely.

Similar to the much more frequently used ε-caprolactone , δ-valerolactone of appropriate purity can be achieved by cationic ring-opening polymerization, e.g. B. with trifluoromethanesulfonic acid methyl ester to poly-δ-valerolactone and with other lactones or δ-hydroxycarboxylic acids also by anionic and also by enzymatic polymerization using lipases to form copolymer polyesters, which are interesting as possible implant materials because of their biodegradability, biocompatibility and their permeation behavior .

Ring-opening polymerization of delta-valerolactone

Because of the tendency towards depolymerization from the end of the chain ( back-biting ) and the lower reactivity of the six-membered lactone ring in δ-valerolactone compared to the seven-membered ε-caprolactone, polymers with comparatively lower molar masses are produced in enzymatic ring-opening polymerization, but they do so when used thermophilic esterases at least had number-average molar masses of M n > 2.000 g / mol and make the poly-δ-valerolactone obtained appear suitable for use as hydrophobic soft segments in thermoplastic elastomers or as active ingredient carriers for controlled drug release.

The controlled living polymerization of δ-valerolactone leads with the catalyst trifluoromethanesulfonimide to poly-δ-valerolactone with the corresponding catalyst content z. B. with M n = 9.600 g / mol and in the presence of functional initiators, such as. B. N- (2-hydroxyethyl) maleimide to terminally functionalized telechelic poly-δ-valerolactones with controlled molecular weights and low polydispersity .

Individual evidence

  1. ↑ a b c d e f Entry on delta-valerolactone in the GESTIS substance database of the IFA , accessed on February 5, 2017(JavaScript required) .
  2. ↑ a b c d data sheet δ-valerolactone from Sigma-Aldrich , accessed on June 10, 2015 ( PDF ).
  3. ↑ a b c L.E. Schniepp, HH Geller: Dehydrogenation of 1,5-pentanediol . In: J. Amer. Chem. Soc. tape 69 , no. 6 , 1947, pp. 1545-1545 , doi : 10.1021 / ja01198a517 .
  4. ↑ a b c d e f BASF, Safety Data Sheet, page no longer available , search in web archives: delta-Valerolactone@1@ 2Template: Dead Link / worldaccount.basf.com
  5. ↑ a b Entry on δ-valerolactone at TCI Europe, accessed on February 5, 2017.
  6. ↑ M. Nakahawa, J. Saegusa, M. Tonozuka, M. Obi, M. Kiuchi, T. Hino, Y. Ban: 5,6-Dihydro-2H-pyran-2-one and 2H-Pyran-2-one . In: Org. Synth., Coll. Vol. Volume 6 , 1977, pp. 462-454 , doi : 10.15227 / orgsyn.056.0049 .
  7. ↑ HM Ali, AA Naiini, CH Brubaker Jr .: Selective reduction of conjugated double bonds with molecular hydrogen and palladium (II) complexed to ferrocenylamine sulfide catalysts . In: Tetrahedron Lett. tape 32 , no. 40 , 1991, pp. 5489-5492 , doi : 10.1016 / 0040-4039 (91) 80065-E .
  8. ↑ LE Schniepp, HH Geller: Preparation of Dihydropyran, δ-Hydroxyvaleraldehyde and 1,5-Pentanediol from Tetrahydrofurfuryl Alcohol . In: J. Am. Chem. Soc. tape 68 , no. 8 , 1946, pp. 1646-1648 , doi : 10.1021 / ja01212a085 .
  9. ↑ R. Gaudry, L. Berlinguet: Étude de la synthèse de la proline par cyclisation d'un acid valérianique dihalogéné . In: Can. J. Research . 27b, no. 4 , 1949, pp. 282-292 , doi : 10.1139 / cjr49b-030 .
  10. ↑ T. Oii, H. Sugimoto, K. Doda, K. Maruoka: Esterification of carboxylic acids catalyzed by in situ generated tetraalkylammonium fluorides . In: Tetrahedron Lett. tape 42 , no. 52 , 2001, p. 9245-9248 , doi : 10.1016 / S0040-4039 (01) 02035-4 .
  11. ↑ a b N. Isenberg, JB Leibsohn, VE Merola: 5-Bromopentanoic acid and 2,5-dibromopentanoic acid . In: Canadian Journal of Chemistry . 40, 1962, p. 831, doi : 10.1139 / v62-126 .
  12. ^ SE Jacobson, R. Tang, F. Mares: Oxidation of cyclic ketones by hydrogen peroxide catalysed by Group 6 metal peroxo complexes . In: J. Chem. Soc., Chem. Commun. 1978, p. 888-889 , doi : 10.1039 / C39780000888 .
  13. ↑ AJ Kotlewska, F. van Rantwijk, RA Sheldon, IWCE Arends: Epoxidation and Baeyer-Villiger oxidation using hydrogen peroxide and a lipase dissolved in ionic liquids . In: Green Chem. Band 13 , no. 8 , 2011, p. 2154-2160 , doi : 10.1039 / C1GC15255F .
  14. ↑ Patent DE10100552 : Method and device for the distillative work-up of 1,6-hexanediol, 1,5-pentanediol and caprolactone. Registered on January 9, 2001 , published on July 11, 2002 , applicant: BASF AG, inventor: M. Gall, G. Kaibel, T. Krug, H. Rust, F. Stein. ‌
  15. ↑ S. Oka: Synthesis of δ-valerolactone . In: Bull. Inst. Chem. Res., Kyoto University . tape 39 , no. 4-5 , 1961, pp. 322-324 ( [1] ).
  16. ↑ Patent EP2373637 : Process for the production of delta-valerolactone in the gas phase. Registered on December 2, 2009 , published on May 22, 2013 , applicant: BASF SE, inventor: R. Pinkos, C. Bauduin, A. Paul, G. Fritz, H. Wagner. ‌
  17. ^ BASF brochure, Solvent-borne and high-solids coatings
  18. ↑ Patent WO2001064614 : Process for the production of chlorocarboxylic acid chlorides. Registered on February 28, 2001 , published on September 7, 2001 , applicant: BASF AG, inventor: A. Stamm, H.-J. Kneuper, J. Henkelmann, T. Weber, R. Busch. ‌
  19. ↑ Patent EP0509469 : Synthetic compounds suitable for the therapy of infections caused by rhinoviruses. Filed April 15, 1992 , published October 21, 1992 , Applicant: Repla Chemical Ltd., Inventor: M. Artico, F. Corelli, S. Massa, A. Mai. ‌
  20. ↑ Pharmaceutical Substances: Syntheses, Patents and Applications of the most relevant APIs . Published by Axel Kleemann, Jürgen Engel, Bernhard Kutscher, Dietmar Reichert, Thieme Verlag, 5th Edition, Sept. 2008, ISBN 978-3-13-558405-8
  21. ↑ J. Wang, P. Wang, L. Liu, H. Zhang, Z. Shang, Synthesis of apixaban intermediate , J. Hebei Univ. Sci. Technol., 35 , 334, (2014).
  22. ↑ a b H.R. Kricheldorf, R. Dunsing, A. Serra: Polylactones. 10. Cationic polymerization of δ-valerolactone by means of alkylating agents . In: Macromolecules . tape 20 , no. 9 , 1987, pp. 2050-2057 , doi : 10.1021 / ma00175a002 .
  23. ↑ P. Kurcok, J. Penczek, J. Franek, Z. Jedlinski: Anionic polymerization of lactones. 10. Anionic block copolymerization of δ-valerolactone and L-lactide initiated with potassium methoxide . In: Macromolecules . tape 25 , no. 9 , 1992, pp. 2282-2289 , doi : 10.1021 / ma00035a001 .
  24. ↑ S. Kobayashi: Lipase-catalyzed polyester synthesis - A green polymer chemistry . In: Proc. Jpn. Acad. Ser. B Phys. Biol. Sci. tape 86 , no. 4 , 2010, p. 338–365 , doi : 10.2183 / pjab.86.338 , PMC 3417799 (free full text).
  25. ↑ H. Cao, H. Han, G. Li, J. Yang, L. Zhang, Y. Yang, X. Fang, Q. Li: Biocatalytic Synthesis of Poly (δ-Valerolactone) Using a Thermophilic Esterase from Archaeoglobus fulgidus as Catalyst . In: Int. J. Mol. Sci. tape 13 , no. 10 , 2012, p. 12232-12241 , doi : 10.3390 / ijms131012232 .
  26. ↑ R. Kakuchi, Y. Tsuji, K. Chiba, K. Fuchise, R. Sakai, T. Satoh, T. Kakuchi: Controlled / Living Ring-Opening Polymerization of δ-Valerolactone Using Triflylimide as an Efficient Cationic Organocatalyst . In: Macromolecules . tape 43 , no. 17 , 2010, p. 7090-7094 , doi : 10.1021 / ma100798u .