1 tetralone

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Structural formula
Structural formula of 1-tetralone
General
Surname 1 tetralone
other names
  • α-tetralone
  • 1-oxotetralin
  • 3,4-dihydro-1 (2 H ) -naphthalenone
  • 1,2,3,4-tetrahydro-1-naphthalenone
Molecular formula C 10 H 10 O
Brief description

clear light yellow to dark brown liquid

External identifiers / databases
CAS number 529-34-0
EC number 208-460-6
ECHA InfoCard 100.007.692
PubChem 10724
Wikidata Q522228
properties
Molar mass 146.19 g mol −1
Physical state

liquid

density

1.099 g cm −3 (25 ° C )

Melting point

2-7 ° C

boiling point
  • 255-257 ° C
  • 113–116 ° C (8 hPa)
Vapor pressure

2.7 Pa (20 ° C)

solubility

practically insoluble in water, soluble in diethyl ether , benzene , toluene and p- xylene

Refractive index
  • 1.5672 (20 ° C, 589 nm)
  • 1.5695
safety instructions
GHS labeling of hazardous substances
07 - Warning

Caution

H and P phrases H: 302
P: 264-301 + 312-330-501
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

1-Tetralone is a bicyclic aromatic hydrocarbon with an α- keto group (benzocycloalkanone), which can also be understood as benzo-fused cyclohexanone and is used as a raw material for agrochemicals and pharmaceuticals.

Occurrence and representation

The basic body of the α-tetralons also occurs in natural substances, such as B. in the so-called Aristelegone A (4,7-dimethyl-6-methoxy-1-tetralone) from the Aristolochiaceae family used in traditional Chinese medicine .

1-tetralone by oxidation of tetralin

As early as 1933 by Heinrich Hock described, tends tetralin to autoxidation and forms, with oxygen in the air gradually 1- hydroperoxide . The heavy metal ion-catalyzed air oxidation of tetralin with Cr 3+ or Cu 2+ in the liquid phase leads via the hydroperoxide to a mixture of the intermediate stage 1-tetralol and the end product 1-tetralone.

Oxidation of tetralone to 1-tetralone

Because the boiling points of the main component 1-tetralone (255–257 ° C) and the secondary component 1-tetralol (255 ° C) are practically identical, the latter is removed by chemical conversion.

1-tetralone by Friedel-Crafts reaction of 4-phenylbutyric acid

The starting compound 4-phenylbutyric acid (the sodium salt of which sodium phenylbutyrate is used to treat hyperammonaemia ) can be obtained from 3-benzoylpropionic acid via catalytic hydrogenation on a palladium contact with a yield of 96%. 3- Benzoylpropionic acid itself can be obtained from benzene and succinic anhydride in a yield of 77 to 82% by a Haworth reaction named after Robert Downs Haworth (a variant of the Friedel-Crafts reaction ) .

A more recent patent claims the synthesis of 4-phenylbutyric acid via Friedel-Crafts acylation of benzene and γ-butyrolactone with aluminum chloride at 60 ° C and working up with dilute sodium hydroxide solution and subsequent acidification in 94% crude yield and 81% pure yield.

The intramolecular cyclization of 4-phenylbutyric acid to 1-tetralone in 75 to 86% yield can be brought about by heating with polyphosphoric acid .

Cyclization of 4-phenylbutyric acid to 1-tetralone

The acid-catalyzed cyclization can also be carried out with methanesulfonic acid . This reaction path with yields between 23 and 80% has been described as a working method for chemistry classes.

Also by adding catalytic amounts of strong Lewis acids , such as. B. the relatively easily accessible bismuth (III) bis (trifluoromethanesulfonyl) amide Bi (NTf 2 ) 3 , 4-phenylbutyric acid can be quantitatively converted into 1-tetralone at 180 ° C.

1-tetralone by Friedel-Crafts reaction of 4-phenylbutyric acid chloride

Significantly shorter reaction times than the Friedel-Crafts acylation with 4-phenylbutyric acid make it possible to use the acid chloride (by reaction with phosphorus pentachloride ) with superstoichiometric amounts of tin (IV) chloride SnCl 4 , with total yields of 85 to 91 according to method B of the specification % be achieved.

Synthesis of 1-tetralone via 4-phenylbutyric acid chloride

4-Phenylbutyric acid chlorides with electron donating groups ( electron donors ) can be cyclized to 1-tetralones under mild reaction conditions in yields greater than 90% in the solvent hexafluoroisopropanol HFIP, which forms strong hydrogen bonds .

1-tetralone by Friedel-Crafts reaction of γ-butyrolactone

The acylation of benzene with γ-butyrolactone with excess aluminum chloride by method A gives α-tetralone in yields of 91 to 96%.

Synthesis of 1-tetralone with gamma-butyrolactone

The disadvantage of many variants of Friedel-Crafts acylation is the use of large amounts of AlCl 3 , polyphosphoric acid or PCl 5 for the preparation of the acid chlorides used, which cause considerable work-up costs and waste volumes.

The use of solid acidic catalysts based on zeolites and aluminosilicates for the reaction of benzene with γ-butyrolactone was also proposed, but no information was given on their efficiency. In this way is connected to the six-membered ring lactone δ-valerolactone the seven-membered ring-ketone 1-benzosuberone accessible.

Synthesis of dimethyl-α-benzosuberone synthesis

properties

1-Tetralone is a clear, light yellow to dark brown liquid with a faint odor that is practically immiscible with water. Α-Tetralone is miscible with non-polar organic solvents.

Applications

1-Tetralone can be reduced to tetralin with lithium in liquid ammonia in a Birch reduction with 96% yield.

Reactions of 1-tetralone with Li in ammonia

If the process management is changed and aqueous ammonium chloride solution is added after the ammonia has evaporated, the keto group is reduced to the secondary alcohol and 1-tetralol is obtained in 70% yield.

With calcium in liquid ammonia at −33 ° C, reduction to 1-tetralol takes place in 81% yield.

The methylene group α to the keto group is particularly reactive and is converted from formaldehyde in the form of trimeric paraldehyde in the presence of the trifluoroacetic acid salt of N-methylaniline to 2-methylene-1-tetralone with yields of up to 91%.

Synthesis of 2-methylene-1-tetralone from 1-tetralone

The 2-methylene ketone can be stored at temperatures below −5 ° C, but polymerizes completely within 12 hours at room temperature.

The Pfitzinger reaction of isatin with 1-tetralone produces the 3,4-dihydro-1,2-benzacridine-5-carboxylic acid known as tetrophane .

Synthesis of tetrophane

The reactivity of the α-methylene group is also made use of by the reaction of 1-tetralone with methanol at 270–290 ° C, in which 2-methyl-1-naphthol is formed in 66% yield with dehydration and formation of the aromatic naphthalene ring system .

Synthesis of 2-methyl-1-naphthol

In the reaction of the oxime of 1-tetralone with acetic anhydride , with aromatization of the cycloalkanone ring, N- (1-naphthyl) acetamide is formed, which, like 1-naphthylacetic acid, acts as a synthetic auxin .

Synthesis of N- (1-naphthyl) acetamide

The tertiary alcohol formed in the Grignard reaction of 1-tetralone with phenylmagnesium bromide reacts with acetic anhydride with elimination of water to form 1-phenyl-3,4-dihydronaphthalene, which is dehydrated with elemental sulfur to 1-phenylnaphthalene in a total yield of approx. 45%.

Synthesis of 1-phenylnaphthalene from 1-tetralone

The ruthenium (II) -catalyzed arylation of 1-tetralone using phenylboronic acid neopentylglycol ester gives 8-phenyl-1-tetralone in up to 86% yield.

Synthesis of 8-phenyl-1-tetralone from 1-tetralone

1-Tetralone reacts with 5-aminotetrazole and an aromatic aldehyde in a multicomponent reaction under microwave radiation to form a four-membered heterocyclic ring system.

Multicomponent reaction of 1-tetralone with aminotetrazole and aromatic aldehyde

By far the most important application of 1-tetralone is in the synthesis of 1-naphthol by aromatizing dehydrogenation, e.g. B. on platinum catalysts at temperatures of 200 to 450 ° C.

Synthesis of 1-naphthol from 1-tetralone

1-naphthol is the starting material for the insecticide carbaryl and the beta blockers propranolol and nadolol , as well as for the antidepressant sertraline and the anti- protozoal therapeutic atovaquone .

The use of the 1-tetralons as a poison against clothes moths has not caught on on the market, despite its "hardly any unpleasant smell on the human sensory organs".

Individual evidence

  1. ↑ a b c d e Entry on α-Tetralone at TCI Europe, accessed on November 25, 2017.
  2. ↑ a b c d e f data sheet α-Tetralon at Sigma-Aldrich , accessed on November 25, 2017 ( PDF ).
  3. ^ A b William M. Haynes: CRC Handbook of Chemistry and Physics, 97th Edition . CRC Press, Boca Raton, FL, USA 2016, ISBN 978-1-4987-5429-3 , pp. 3-504 .
  4. ↑ a b c H.R. Snyder, FX Advertiser: α-Tetralone In: Organic Syntheses . 20, 1940, p. 94, doi : 10.15227 / orgsyn.020.0094 ; Coll. Vol. 3, 1955, p. 798 ( PDF ).
  5. ↑ a b c d C.E. Olson, AR Bader: α-Tetralone In: Organic Syntheses . 35, 1955, p. 95, doi : 10.15227 / orgsyn.035.0095 ; Coll. Vol. 4, 1963, p. 898 ( PDF ).
  6. ↑ a b D.-M. Cui, M. Kawamura, S. Shimada, T. Hayashi, M. Tanaka: Synthesis of 1-tetralones by intramolecular Friedel-Crafts reaction of 4-arylbutyric acids using Lewis acid catalysts . In: Tetrahedron Lett. tape 44 , no. 21 , 2003, p. 4007-4010 , doi : 10.1016 / S0040-4039 (03) 00855-4 .
  7. ↑ Data sheet 1-Tetralone, 97% from AlfaAesar, accessed on November 25, 2017 ( PDF )(JavaScript required) .
  8. ↑ P.-C. Kuo, Y.-C. Li, T.-S. Wu: Chemical constituents and pharmacology of the Aristolochia species . In: eJTCM . tape 2 , no. 4 , 2012, p. 249-266 , doi : 10.1016 / S2225-4110 (16) 30111-0 .
  9. ↑ H. Hock, W. Susemihl: Autoxidation of hydrocarbons: About a tetrahydro-naphthalene peroxide obtained by autoxidation (I. Commun.) . In: Ber. German Chem. Ges. Volume 66 , no. 1 , 1933, pp. 61-68 , doi : 10.1002 / cber.19330660113 .
  10. ↑ S. Bhattacharjee, Y.-R. Lee, W.-S. Ahn: Oxidation of tetraline to 1-tetralone over CrAPO-5 . In: Korean J. Chem. Eng. tape 34 , no. 3 , 2017, p. 701-705 , doi : 10.1007 / s11814-016-0310-4 .
  11. ↑ Patent US4473711 : Liquid-phase process for oxidation of tetralin. Applied on August 6, 1981 , published on September 25, 1984 , applicant: Union Carbide Corp., inventor: RW Coon. ‌
  12. ^ William M. Haynes: CRC Handbook of Chemistry and Physics, 97th Edition . CRC Press, Boca Raton, FL, USA 2016, ISBN 978-1-4987-5429-3 , pp. 3-502 .
  13. ↑ LF Somerville, CFH Allen: β-Benzoylpropionic acid In: Organic Syntheses . 13, 1933, p. 12, doi : 10.15227 / orgsyn.013.0012 ; Coll. Vol. 2, 1943, p. 81 ( PDF ).
  14. ↑ Patent US6372938B1 : Synthesis of 4-Phenylbutyric acid. Applied on May 21, 2001 , published on April 16, 2002 , applicant: SR Burzynski, inventor: SR Burzynski, L. Musial. ‌
  15. ↑ V. Premasagar, VA Palaniswamy, EJ Eisenbraun: Methanesulfonic acid catalyzed cyclization of 3-arylpropanoic and 4-arylbutanoic acids to 1-indanones and 1-tetralones . In: J. Org. Chem. Band 46 , no. 14 , 1981, pp. 2974-2976 , doi : 10.1021 / jo00325a028 .
  16. ↑ MS Holden, RD Crouch, KA Barker: Formation of α-tetralone by intramolecular Friedel-Crafts acylation . In: J. Chem. Educ. tape 82 , no. 6 , 2005, p. 934-935 , doi : 10.1021 / ed082p934 .
  17. ↑ S. Antoniotti, E. Dunach: Facile preparation of metallic triflate and triflimidates by oxidative dissolution of metal powders . In: Chem. Commun. tape 8 , 2008, p. 993-995 , doi : 10.1039 / B717689A .
  18. ↑ H. Motiwala, RH Vekariya, J. Aubé: Intramolecular Friedel-Crafts acylation reaction promoted by 1,1,1,3,3,3-hexafluoro-2-propanol . In: Org. Lett. tape 17 , 2015, p. 5484-5487 , doi : 10.1021 / acs.orglett.5b02851 .
  19. ↑ SDK develops new catalyst for tetralone synthesis. In: Showa Denko KK News Release 2004. Showa Denko KK, accessed December 1, 2017 .
  20. ↑ a b Patent DE357063 : Process to protect fur and woolen fabrics against moths and other insects. Filed on October 25, 1921 , published on August 15, 1922 , Applicant: United chemical factories north Julius & Co ..
  21. ^ SS Hall, SD Lipsky, FJ McEnroe, AP Bartels: Lithium-ammonia reduction of aromatic ketones to aromatic hydrocarbons . In: J. Org. Chem. Band 38 , no. 18 , 1971, p. 2588-2591 , doi : 10.1021 / jo00817a004 .
  22. ↑ Z. Marcinow, PW Rabideau: Metal-ammonia reduction of α-tetralone. Competition between ring reduction, carbonyl reduction, and dimer formation . In: J. Org. Chem. Band 53 , no. 9 , 1988, pp. 2117-2119 , doi : 10.1021 / jo00244a054 .
  23. ↑ JR Hwu, YS Wein, Y.-J. Leu: Calcium metal in liquid ammonia for selective reduction of organic compounds . In: J. Org. Chem. Band 61 , no. 4 , 1996, pp. 1493-1499 , doi : 10.1021 / jo951219c .
  24. ↑ J.-L. Gras: Methylene ketones and aldehydes by simple, direct methylene transfer: 2-Methylene-1-oxo-1,2,3,4-tetrahydronaphthalene In: Organic Syntheses . 60, 1981, p. 88, doi : 10.15227 / orgsyn.060.0088 ; Coll. Vol. 7, 1990, p. 332 ( PDF ).
  25. ↑ I. Yuranov, L. Kiwi-Minsker, A. Renken: One-step vapor-phase synthesis of 2-methyl-1-naphthol from 1-tetralone . In: Appl. Catal. A . tape 226 , no. 1–2 , 2002, pp. 193-198 , doi : 10.1016 / S0926-860X (01) 00902-4 .
  26. ↑ MS Newman, WM Hung: An improved aromatization of α-tetralone oximes to N- (1-naphthyl) acetamides . In: J. Org. Chem. Band 38 , no. 23 , 1973, p. 4073-4074 , doi : 10.1021 / jo00987a029 .
  27. ↑ R. Weiss: 1-Phenylnaphthalene In: Organic Syntheses . 24, 1944, p. 84, doi : 10.15227 / orgsyn.024.0084 ; Coll. Vol. 3, 1955, p. 729 ( PDF ).
  28. ↑ K. Kitazawa, T. Kochi, F. Kakiuchi: Ruthenium-catalyzed arylation of ortho CH bond in an aromatic with an arylboronate: 8-Phenyl-1-tetralone In: Organic Syntheses . 87, 2009, pp. 209-217, doi : 10.15227 / orgsyn.087.0209 ; Coll. Vol. 11, 2009, pp. 1210-1216 ( PDF ).
  29. ↑ GP Kantin, M. Krasavin: Reaction of α-tetralone, 1 H -tetrazol-5-amine, and aromatic aldehydes upon microwave irradiation - a convenient method for the synthesis of 5,6,7,12-tetrahydrobenzo [h] tetrazolo [5,1-b] quinazolines . In: Chem. Heterocycl. Compd. tape 52 , no. 11 , 2016, p. 918-922 , doi : 10.1007 / s10593-017-1985-0 .
  30. ↑ Patent DE2421745 : Process for the production of α-naphthol by catalytic dehydrogenation of α-tetralone. Applied on May 6, 1974 , published on November 20, 1975 , Applicant: Sumitomo Chemical Co., Ltd., Inventor: K. Kudo, T. Ohmae, A. Uno. ‌
  31. ↑ C. Kaiser, T. Jen, E. Garvey, WD Bowen, DF Colella, JR Wardell Jr .: Adrenergic agents. 4. Substituted phenoxypropanolamine derivatives as potential β-adrenergic agonists . In: J. Med. Chem. Volume 20 , no. 5 , 1977, pp. 687-689 , doi : 10.1021 / jm00215a014 .
  32. ↑ Patent DE2258995 : 2,3-cis-1,2,3,4-tetrahydro-5 [2-hydroxy-3- (tert-butylamino) propoxy] -2,3-naphthalenediol. Applied December 1, 1972 , published June 7, 1973 , Applicant: ER Squibb & Sons, Inc., Inventor: FR Hauck, CM Cimarusti, VL Narayan. ‌
  33. ^ ME Condon et al .: Nondepressant β-adrenergic blocking agents. 1. Substituted 3-amino-1- (5,6,7,8-tetrahydro-1-naphthoxy) -2-propanols . In: J. Med. Chem. Volume 21 , no. 9 , 1978, p. 913-922 , doi : 10.1021 / jm00207a014 .
  34. ↑ K. Vukics, T. Fodor, J. Fischer, I. Fellevári, S. Lévai: Improved industrial synthesis of antidepressant sertraline . In: Org. Process Res. Dev. Band 6 , no. 1 , 2002, p. 82-85 , doi : 10.1021 / op0100549 .
  35. ^ BN Roy, GP Singh, PS Lathi, MK Agarwal: A novel process for synthesis of Atovaquone . In: Indian J. Chem. 52B, 2013, p. 1299-1312 ( res.in [PDF]).