WO1996022972A1 - Procede de preparation de quinones et d'hydroquinones substituees - Google Patents

Procede de preparation de quinones et d'hydroquinones substituees Download PDF

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Publication number
WO1996022972A1
WO1996022972A1 PCT/FI1996/000047 FI9600047W WO9622972A1 WO 1996022972 A1 WO1996022972 A1 WO 1996022972A1 FI 9600047 W FI9600047 W FI 9600047W WO 9622972 A1 WO9622972 A1 WO 9622972A1
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WO
WIPO (PCT)
Prior art keywords
formula
hydroquinone
quinone
alkyl sulfide
spectrum
Prior art date
Application number
PCT/FI1996/000047
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English (en)
Inventor
Osmo Hormi
Anu Moilanen
Original Assignee
Neste Oy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Neste Oy filed Critical Neste Oy
Priority to AU44889/96A priority Critical patent/AU4488996A/en
Publication of WO1996022972A1 publication Critical patent/WO1996022972A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the invention relates to a process for the preparation of substituted quinones and hydro ⁇ quinones by a new, simple method.
  • the invention relates in particular to a process for the preparation of long-chain, alkyl sulfide substituted quinones and hydroquinones.
  • Substitu ⁇ ted quinones and hydroquinones prepared by the process according to the invention can be used in the preparation of new liquid crystal polymers.
  • R is a long-chain alkyl group containing 8-18 C atoms.
  • the repeating of reactions (1) and (2) produces the formation of disubstituted quinones.
  • An object of the present invention is, however, to prepare from the starting material according to Formulae (I) and (II) stated above, in a manner deviating from that in th said publication, via monosubstituted quinones according to Formula II, monosubstitute hydroquinones according to Formula (IN).
  • alkyl sulfide substituted hydroquinone according to Formula (IV), in which R is a long -chain alkyl chain containing 8-18 atoms, can be prepared by a process which is characterized in what is stated in th characterizing clause of Claim 1.
  • the process according to the invention comprises the following reactions (1) and (2):
  • quinone according to Formula (I) and a long- chain thiol according to Formula (II) are thus first allowed to react with each other in a nucleophilic addition reaction in the presence of alcohol in a nitrogen atmosphere to form addition products according to Formula in.
  • the addition products can be produced almost quantitatively by means of a mixing reaction at room temperature, the material amount of quinone being double that of thiol.
  • alcohol preferably isopropanol
  • the reaction product i.e. monosubstituted quinone according to Formula (III) precipitates out directly from the reaction mixture.
  • the obtained product can be recrystal- lized either from isopropanol or from toluene, depending on which thiol is used in the reaction.
  • the monosubstituted quinone of Formula (III), prepared by the procedure described above, must be further reduced in order that an alkyl sulfide substituted hydroquinone according to Formula (IV) can be formed.
  • the reduction for the production of the desired end product according to Formula (IV) is now accomplished according to the present invention rapidly and easily by using as the reducing agent sodium dithionite, Na 2 S 2 O 4 .
  • the reducing agent is dissolved in water, preferably up to a saturated solution, and the obtained solution is added to the substituted quinone to be reduced, dissolved in a suitable solvent.
  • the solvent used may be, for example, tetrahydrofuran (THF) or methylene chloride (CH 2 C1 2 ).
  • THF tetrahydrofuran
  • CH 2 C1 2 methylene chloride
  • the reaction mixture is stirred at room temperature until complete reduction occurs.
  • the reduction can be verified, for example, from an organic layer on a thin sheet or from the turning of the orange-yellow quinone solution into a light, yellowish hydroquinone solution.
  • the long-chain thiol compound, i.e. long-chain mercaptan, used as the starting material contains, as stated above, an alkyl chain having 8-18 C atoms.
  • the alkyl chain contains 8, 12 or 18 carbon atoms, in which case the desired reduced end product obtained is respectively 2-octylmercapto-l,4-hydroquinone, 2-dodecylmercapto-l,4- hydroquinone or 2-octadecylmercapto-l,4-hydroquinone.
  • the monosubstituted hydroquinones according to Formula (IV), prepared by the process according to the present invention, can be used in the preparation of liquid crystal polymers. It has been observed that these compounds improve the compatibility of liquid crystal polymers with cheaper aliphatic polymers, whereupon less expensive liquid crystal polymers are obtained as a result.
  • Figures 1-12 depict various spectra for alkyl sulfide substituted quinones and hydroquinones prepared by the process according to the invention.
  • FIGs 6a and 6b IR spectrum of 2-dodecylmercapto-l ,4-benzoquinone (6a) and MS spectrum of 2-dodecylmercapto-l ,4-hydroquinone (6b).
  • Figure 7 400 MHz *H NMR spectrum of 2-dodecylmercapto-l,4-benzoquinone.
  • FIGS 9a and 9b MS spectrum of 2-octylmercapto-l,4-benzoquinone (9a) and MS spectrum of 2-octylmercapto-l,4-hydroquinone (9b).
  • Figures 10 a and b IR spectrum of 2-octylmercapto-l,4-benzoquinone (10a) and IR spectrum of 2-octylmercapto-l,4-hydroquinone (10b).
  • the HRMS values indicate the length of the carbon chain.
  • Tables 1 and 2 show interpretations of the spectra of the quinone and hydroquinone structures.
  • H a , H b , and H c indicate hydrogen atoms at positions 3, 5 and 6 of the benzene ring.
  • H x and H y indicate hydrogen atoms in the OH groups at positions 1 and 4 of the hydroquinone structure.
  • Table 1. Interpretation of the quinone structures, Figures 3, 7 and 11.
  • the products prepared by the process according to the invention are desired alkyl sulfide substituted benzo- quinones and hydroquinones.
  • the reaction was carried out in an N 2 atmosphere at room temperature.
  • the flask was equipped with a reflux condenser, a magnetic stirrer, and a thermometer.
  • 20 mmol (2J6 g) of 1 ,4-benzoquinone was dissolved in 30 ml of isopropanol (the dissolving could be promoted by heating the reaction mixture).
  • the obtained product was filtered, and more of the product proper could be filtered out from the filtrate after 24 h.
  • the product was recrystallized from isopropanol in the case of 1-octanethiol or 1-dodecanethiol and from toluene in the case of 1-octadecane.
  • the percent yield for all thiols was approx. 90 %.
  • Recrystallized substituted quinones prepared according to Example 1 were reduced in order to obtain the desired hydroquinone compounds.
  • the reduction was carried out by using sodium dithionite Na 2 S 2 O 4 as the reducing agent.
  • the quinone form was dissolved in THF or CH 2 C1 2 , to which Na 2 S 2 O 4 , dissolved in water up to a saturated solution, was added.
  • the solutions were mixed together at room temperature, and complete reduction to hydroquinones was verified from an organic layer on a thin sheet (solvent system: 25 % ethyl acetate/75 % n-hexane).
  • Tables 3 and 4 show the R, values and melting points of the substituted quinone structures and hydroquinone structures.
  • quinone compounds are UV-active and hydroquinone compounds are well colored with iodine.
  • the reduction was also verified visually in a change of the orange-yellow quinone solution into a light yellowish hydroquinone solution. The time taken by the reduction was a few minutes on this scale.
  • the reaction was carried out in an N 2 atmosphere at room temperature.
  • the flask was equipped with a power stirrer, a reflux condenser, a thermometer, and a drop funnel.
  • the yield from the reaction was approx. 25 % (in the instruction, 32.4 %).
  • FIGURE 1 la MS spectrum of 2-octadecylmercapto-l,4-benzoquinone lb MS spectrum of 2-octadecylmercapto-l,4-hydroquinone
  • FIGURE 2 2a IR spectrum of 2-octadecylmercapto-l,4-benzoquinone 2b IR spectrum of 2-octadecylmercapto-l,4-hydroquinone
  • FIGURE 3 400 MHz ⁇ NMR spectrum of 2-octadecylmercapto-l,4- benzoquinone
  • FIGURE 4 400 MHZ l H NMR spectrum of 2-octadecylmercapto-l,4-hydroquinone
  • FIGURE 5 5a MS spectrum of 2-dodecylmercapto-l,4-benzoquinone 5b MS spectrum of 2-dodecylmercapto-l, -hydroquinone
  • FIGURE 6 6a IR spectrum of 2-dodecylmercapto-l,4-benzoquinone (top)
  • FIGURE 7 400 MHz ⁇ NMR spectrum of 2-dodecylmercapto-l,4-benzoquinone
  • FIGURE 8 400 MHz ⁇ NMR spectrum of 2-dodecylmercapto-l,4-hydroquinone
  • FIGURE 9 9a MS spectrum of 2-octylmercapto-l,4-benzoguinone 9b MS spectrum of 2-octylmercapto-l, -hydroquinone
  • FIGURE 10 10a IR spectrum of 2-octylmercapto-l,4-benzoquinone
  • FIGURE 11 400 MHz ⁇ NMR spectrum of 2-octyl ercapto-l,4-benzoquinone
  • FIGURE 12 400 MHz ⁇ NMR spectrum of 2-octylmercapto-l,4-hydroquinone

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention se rapporte à un nouveau procédé de préparation d'hydroquinones substituées par sulfure d'alkyle, répondant à la formule (IV), selon lequel des quinones substituées par sulfure d'alkyle, de la formule (III), sont initialement préparées, et des hydroquinones substituées par sulfure d'alkyle, de la formule (IV), sont obtenues à partir de ces quinones par réduction à l'aide de dithionite de sodium. Le procédé selon l'invention est simple et rapide et permet d'obtenir ces composés au moyen d'une réaction quasi quantitative et à l'aide de matériaux de départ économiques, disponibles dans le commerce. Les composés préparés selon ce procédé peuvent être utilisés, notamment, dans la préparation de polymères à cristaux liquides.
PCT/FI1996/000047 1995-01-23 1996-01-23 Procede de preparation de quinones et d'hydroquinones substituees WO1996022972A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU44889/96A AU4488996A (en) 1995-01-23 1996-01-23 Method for the preparation of substituted quinones and hydroquinones

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI950269A FI950269A (fi) 1995-01-23 1995-01-23 Menetelmä substituoitujen kinonien ja hydrokinonien valmistamiseksi
FI950269 1995-01-23

Publications (1)

Publication Number Publication Date
WO1996022972A1 true WO1996022972A1 (fr) 1996-08-01

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AU (1) AU4488996A (fr)
FI (1) FI950269A (fr)
WO (1) WO1996022972A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7718722B2 (en) 2000-11-21 2010-05-18 Flexsys America L.P. Alkylthio- and aryl(heteroyl)thio-substituted p-phenylenediamines, their manufacture and their use in rubber

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1157030B (de) * 1962-01-16 1963-11-07 Bayer Ag Vogelabschreckmittel
US4377634A (en) * 1977-09-06 1983-03-22 Fuji Photo Film Co., Ltd. Method for forming high contrast photographic image

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1157030B (de) * 1962-01-16 1963-11-07 Bayer Ag Vogelabschreckmittel
US4377634A (en) * 1977-09-06 1983-03-22 Fuji Photo Film Co., Ltd. Method for forming high contrast photographic image

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
CHEMICAL & PHARMACEUTICAL BULLETIN, Volume 16, No. 2, February 1968, S. UKAI et al., "Reaction of Phenol Derivatives with Sulfoxides. II.1. A New Method of Synthesis of Monothio Derivatives of p-Benzoquinone2", pages 195-201. *
CHEMICAL ABSTRACTS, Volume 100, No. 16, 16 April 1984, (Columbus, Ohio, USA), SERGEEV V.A. et al., "Synthesis and Properties of Oligomeric Benzoquinone-Bisthiophenol Adducts", page 28, Abstract No. 122010g; & VYSOKOMOL. SOEDIN., SER. A, 1984, 26(1), 151-159. *
CHEMICAL ABSTRACTS, Volume 117, No. 5, 3 August 1992, (Columbus, Ohio, USA), BOROVKOV V.V. et al., "Synthesis of the Capped Photosynthetic Model System Based on Mesoporphyrin II", page 893, Abstract No. 48182x; & KHIM. GETEROTSIKL. SOEDIN., 1991, 10, 1419-1423. *
CHEMICAL ABSTRACTS, Volume 52, No. 7, 10 April 1958, (Columbus, Ohio, USA), MASUO AKAGI et al., "Antioxidative Effect of Phenolic Compounds Containing Sulfur for Fats and Oils", Abstract No. 5330i; & YAKUGAKU ZASSHI, 1957, 77, 1121-1123. *
DERWENT'S ABSTRACT, No. 94-148871/18, Week 9418; & SU,A,1 796 618, (MOSC FINE CHEM TECHN INST), 23 February 1993. *
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Volume 61, 1939, J.M. SNELL et al., "The Reaction of Thiol Compounds with Quinones", pages 450-453. *
SYNTHESIS, Volume 11, 1989, S. BITTNER et al., "Synthesis of Phenylenedithiodiquinones", pages 868-869. *
ULLMANNS ENCYKLOPAEDIE DER TECHNISCHEN CHEMIE, Band 20, "4., Neubearbeitete und Erweiterte Auflage", pages 130, 141. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7718722B2 (en) 2000-11-21 2010-05-18 Flexsys America L.P. Alkylthio- and aryl(heteroyl)thio-substituted p-phenylenediamines, their manufacture and their use in rubber

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Publication number Publication date
FI950269A0 (fi) 1995-01-23
FI950269A (fi) 1996-07-24
AU4488996A (en) 1996-08-14

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