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EP2590507A2 - Use of beta-isophorone as solvent - Google Patents

Use of beta-isophorone as solvent

Info

Publication number
EP2590507A2
EP2590507A2 EP11725679.2A EP11725679A EP2590507A2 EP 2590507 A2 EP2590507 A2 EP 2590507A2 EP 11725679 A EP11725679 A EP 11725679A EP 2590507 A2 EP2590507 A2 EP 2590507A2
Authority
EP
European Patent Office
Prior art keywords
isophorone
solvent
use according
beta
weight
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP11725679.2A
Other languages
German (de)
French (fr)
Inventor
Emmanouil Spyrou
Lars Hellkuhl
Marina Grammenos
Andrea Henschke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
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 Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of EP2590507A2 publication Critical patent/EP2590507A2/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/603—Unsaturated compounds containing a keto groups being part of a ring of a six-membered ring, e.g. quinone methides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents

Definitions

  • the invention relates to the use of ⁇ -isophorone as a solvent.
  • Isophorone also called ⁇ -isophorone, is due to its excellent
  • Solution properties and its low price used as a solvent especially in the field of pesticides (see, for example, CN 101569312, RU 2263449, DE 32 25 940, US 3,281, 234, US 3,253,021), but also in various large industrial
  • Coating process eg. B. in coil coating.
  • the object of the present invention was to find suitable substitutes for isophorone
  • the invention relates to the use of ⁇ -isophorone as a solvent, in particular as a solvent for pesticides and for large industrial coating processes, eg. B. coil coating.
  • Another object of the present invention is the use of ß-isophorone in coating compositions, in particular in primers, topcoats, clearcoats, adhesives or sealing materials.
  • ⁇ -isophorone has heretofore been used exclusively as an intermediate, e.g. in the synthesis of ketoisophorone (eg EP 808 816), an initial building block e.g. B. for the
  • ⁇ -isophorone differs from ⁇ -isophorone in the location of the double bond. In ⁇ -isophorone, the double bond is in conjugation to the carbonyl moiety, while it is farther away in ⁇ -isophorone. This is no longer to be expected with unwanted Michael addition reactions, which are known to be responsible for cancer-causing effects.
  • ⁇ -Isophorone can be produced inexpensively from ⁇ -isophorone by a simple rearrangement and distillative removal with almost 100% yield. This is evidenced by a whole series of patents and references (eg CN 1660752, EP 1 063 220, EP 1 063 219, EP 957 075, JP 1 1/255706, JP 1 1/049712, EP 842 918, DE 196 39 570, EP 488 045, DE 37 35 21 1, Journal of Organic Chemistry (1978), 43 (9), 1821-3).
  • ⁇ -isophorone As compared to ⁇ -isophorone, ⁇ -isophorone has very similar dissolution properties (see experimental part), as already shown by the octanol-water partition coefficient (log P value): ⁇ -isophorone is 1, 7, ⁇ -isophorone at 1, 4, whereas a conventional substitute such as 3,3,5-trimethylcyclohexanone (TMC-On) is 2.5.
  • ⁇ -isophorone boiling point 190 ° C., prepared from ⁇ -isophorone (DE 198 21 379, Degussa)
  • TMCon boiling point 188-192 ° C., Evonik-Degussa GmbH
  • ⁇ -isophorone and ⁇ -isophorone solve the two most common crop protection agents PHENMEDIPHAM and PROPANIL equally in at least 55 wt .-%. Although TMC-on dissolves PROPANIL, it does not dissolve phenmedipham in 55% by weight. Therefore, ⁇ -isophorone is useful as a substitute for ⁇ -isophorone.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Dentistry (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Toxicology (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to the use of ß-isophorone as solvent.

Description

Verwendung von ß-lsophoron als Lösemittel  Use of β-isophorone as solvent
Die Erfindung betrifft die Verwendung von ß-lsophoron als Lösemittel. The invention relates to the use of β-isophorone as a solvent.
Isophoron, auch α-lsophoron genannt, wird aufgrund seiner hervorragenden Isophorone, also called α-isophorone, is due to its excellent
Lösungseigenschaften und seines günstigen Preises als Lösungsmittel eingesetzt, vor allem im Bereich Pflanzenschutzmittel (siehe z. B. CN 101569312, RU 2263449, DE 32 25 940, US 3,281 ,234, US 3,253,021 ), aber auch bei verschiedenen großindustriellen Solution properties and its low price used as a solvent, especially in the field of pesticides (see, for example, CN 101569312, RU 2263449, DE 32 25 940, US 3,281, 234, US 3,253,021), but also in various large industrial
Beschichtungsverfahren, z. B. im Coil-Coating. Coating process, eg. B. in coil coating.
Der Einsatz von Isophoron wird aber heutzutage eingeschränkt, da Isophoron als  However, the use of isophorone is limited today because isophorone as
toxikologisch potentiell gefährlich eingestuft wird und den R-Satz R 40 trägt (Verdacht auf krebserzeugende Wirkung). Der Grund für diesen Verdacht könnte in der Struktur von Isophoron begründet sein, genau genommen in der α,β-ungesättigten Carbonylgruppierung. Solche Gruppierungen sind allgemein dafür bekannt, dass sie das Risiko für eine Krebs erzeugende Wirkung tragen. toxicologically potentially hazardous and carries the R-phrase R 40 (suspected carcinogenic effect). The reason for this suspicion might be due to the structure of isophorone, more specifically the α, β-unsaturated carbonyl moiety. Such moieties are generally known to carry the risk of carcinogenic effects.
So hat es in der Vergangenheit nicht an Versuchen gefehlt, Isophoron durch andere  There has been no lack of attempts in the past, isophorone by others
Lösemittel zu ersetzen. Aber entweder reichten die Lösungseigenschaften nicht aus (z. B. 3,3,5-Trimethylcyclohexanon), oder der Siedepunkt war zu unterschiedlich, oder die To replace solvents. But either the solution properties were not sufficient (eg 3,3,5-trimethylcyclohexanone), or the boiling point was too different, or the
Alternativen waren einfach zu kostspielig. Alternatives were just too expensive.
Aufgabe der vorliegenden Erfindung war es, geeignete Ersatzstoffe für Isophoron The object of the present invention was to find suitable substitutes for isophorone
bereitzustellen. Überraschend wurde gefunden, dass ein Isomer von α-lsophoron, das ß-lsophoron, die geforderten Eigenschaften besitzt. provide. Surprisingly, it has been found that an isomer of α-isophorone, the β-isophorone, has the required properties.
Gegenstand der Erfindung ist die Verwendung von ß-lsophoron als Lösemittel, insbesondere als Lösemittel für Pflanzenschutzmittel sowie für großindustrielle Beschichtungsprozesse, z. B. Coil-Coating. Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von ß-lsophoron in Beschichtungsmitteln, insbesondere in Primern, Decklacken, Klarlacken, Klebstoffen oder Dichtmaterialien. ß-lsophoron wurde bislang ausschließlich als Zwischenprodukt verwendet, z.B. in der Synthese von Ketoisophoron (z. B. EP 808 816), ein Ausgangsbaustein z. B. für die The invention relates to the use of β-isophorone as a solvent, in particular as a solvent for pesticides and for large industrial coating processes, eg. B. coil coating. Another object of the present invention is the use of ß-isophorone in coating compositions, in particular in primers, topcoats, clearcoats, adhesives or sealing materials. β-isophorone has heretofore been used exclusively as an intermediate, e.g. in the synthesis of ketoisophorone (eg EP 808 816), an initial building block e.g. B. for the
Vitamin-E Synthese. ß-lsophoron unterscheidet sich von α-lsophoron durch die Lage der Doppelbindung. In α-lsophoron liegt die Doppelbindung in Konjugation zur Carbonylgruppierung, während sie in ß-lsophoron weiter entfernt liegt. Damit ist nicht mehr mit unerwünschten Michael-Additions- Reaktionen zu rechnen, die bekanntlich für Krebs erzeugende Wirkungen verantwortlich gemacht werden. Vitamin E synthesis. β-isophorone differs from α-isophorone in the location of the double bond. In α-isophorone, the double bond is in conjugation to the carbonyl moiety, while it is farther away in β-isophorone. This is no longer to be expected with unwanted Michael addition reactions, which are known to be responsible for cancer-causing effects.
a-lsophoron ß-lsophoron 3,3,5-Trimethylcyclohexanon  a-isophorone β-isophorone 3,3,5-trimethylcyclohexanone
ß-lsophoron ist aus α-lsophoron durch eine einfache Umlagerung sowie der destillativen Abtrennung mit nahezu 100 % Ausbeute kostengünstig herstellbar. Davon zeugen eine ganze Reihe von Patentschriften und Literaturstellen (z. B. CN 1660752, EP 1 063 220, EP 1 063 219, EP 957 075, JP 1 1/255706, JP 1 1/049712, EP 842 918, DE 196 39 570, EP 488 045, DE 37 35 21 1 , Journal of Organic Chemistry (1978), 43(9), 1821 -3). ß-lsophoron hat verglichen mit α-lsophoron sehr ähnliche Lösungseigenschaften (siehe experimentellen Teil), wie auch schon durch den Oktanol-Wasser-Verteilungskoeffizient (log- P-Wert) deutlich wird: α-lsophoron liegt bei 1 ,7, ß-lsophoron bei 1 ,4, wohingegen ein herkömmlicher Ersatzstoff wie 3,3,5-Trimethylcyclohexanon (TMC-On) bei 2,5 liegt. β-Isophorone can be produced inexpensively from α-isophorone by a simple rearrangement and distillative removal with almost 100% yield. This is evidenced by a whole series of patents and references (eg CN 1660752, EP 1 063 220, EP 1 063 219, EP 957 075, JP 1 1/255706, JP 1 1/049712, EP 842 918, DE 196 39 570, EP 488 045, DE 37 35 21 1, Journal of Organic Chemistry (1978), 43 (9), 1821-3). As compared to α-isophorone, β-isophorone has very similar dissolution properties (see experimental part), as already shown by the octanol-water partition coefficient (log P value): α-isophorone is 1, 7, β-isophorone at 1, 4, whereas a conventional substitute such as 3,3,5-trimethylcyclohexanone (TMC-On) is 2.5.
Bevorzugt wird eine Reinheit an ß-lsophoron von > 95 Gew.-%, besonders bevorzugt > 98 Gew.-% und ganz besonders bevorzugt >99 Gew.-%, verwendet. A purity of β-isophorone of> 95% by weight, more preferably> 98% by weight and very particularly preferably> 99% by weight, is preferably used.
Im experimentellen Teil soll nachgewiesen werden, dass die Lösungseigenschaften von ß-lsophoron ähnlich sind zu α-lsophoron, insbesondere in Bezug auf die beiden am häufigsten in α-lsophoron gelösten Pflanzenschutzmittel PROPANIL und PHENMEDIPHAM, die heutzutage in bis zu 55 Gew.-% in α-lsophoron gelöst werden. Experimenteller Teil In the experimental part, it should be demonstrated that the dissolution properties of β-isophorone are similar to α-isophorone, in particular with respect to the two crop protection agents PROPANIL and PHENMEDIPHAM, which are most frequently dissolved in α-isophorone and are present in up to 55% by weight in α-isophorone be solved. Experimental part
Einsatzstoffe:  Starting Materials:
α-lsophoron: Siedepunkt 215 °C, Evonik-Degussa GmbH  α-isophorone: boiling point 215 ° C, Evonik-Degussa GmbH
ß-lsophoron: Siedepunkt 190 °C, Hergestellt aus α-lsophoron (DE 198 21 379, Degussa) TMCon: Siedepunkt 188 - 192 °C, Evonik-Degussa GmbH  β-isophorone: boiling point 190 ° C., prepared from α-isophorone (DE 198 21 379, Degussa) TMCon: boiling point 188-192 ° C., Evonik-Degussa GmbH
PROPANIL: Schirm  PROPANIL: umbrella
PHENMEDIPHAM: Chemos  PHENMEDIPHAM: Chemos
Allgemeine Arbeitsvorschrift: General procedure:
70 Teile PHENMEDIPHAM bzw. PROPANIL wurden in 30 T des Lösemittels gegeben und danach gut verrührt. Nach 2 h Rühren wurde der Rückstand abzentrifugiert und die überstehende klare Lösung in einen Rundkolben gewogen. Das Lösemittel wurde bei 0,06 mbar und 130 °C vollständig abdestilliert und der Rundkolben zurückgewogen. Dabei ergaben sich für die unterschiedlichen Lösemittel folgende Löslichkeiten (in Gew.-%):  70 parts of PHENMEDIPHAM or PROPANIL were added to 30 T of the solvent and then stirred well. After stirring for 2 h, the residue was centrifuged off and the supernatant clear solution was weighed into a round-bottomed flask. The solvent was completely distilled off at 0.06 mbar and 130 ° C and the round bottom flask weighed back. The following solubilities (in% by weight) were obtained for the different solvents:
* nicht erfindungsgemäße Vergleichsbeispiele * not comparative examples according to the invention
Lediglich α-lsophoron und ß-lsophoron lösen die beiden gängigsten Pflanzenschutzmittel PHENMEDIPHAM und PROPANIL gleichermaßen in mindestens 55 Gew.-%. TMC-on löst zwar PROPANIL, nicht aber Phenmedipham in 55 Gew.-%. Daher ist ß-lsophoron als Ersatzstoff für α-lsophoron geeignet. Only α-isophorone and β-isophorone solve the two most common crop protection agents PHENMEDIPHAM and PROPANIL equally in at least 55 wt .-%. Although TMC-on dissolves PROPANIL, it does not dissolve phenmedipham in 55% by weight. Therefore, β-isophorone is useful as a substitute for α-isophorone.

Claims

Patentansprüche: claims:
1 . Verwendung von ß-lsophoron als Lösemittel. 1 . Use of β-isophorone as solvent.
2. Verwendung nach Anspruch 1 als Lösemittel für Pflanzenschutzmittel. 2. Use according to claim 1 as a solvent for crop protection agents.
3. Verwendung nach Anspruch 1 für Beschichtungsprozesse. 3. Use according to claim 1 for coating processes.
4. Verwendung nach Anspruch 3 für das Coil-Coating. 4. Use according to claim 3 for the coil coating.
5. Verwendung nach Anspruch 1 bis 3 in Beschichtungsmitteln, insbesondere in Primern, Decklacken, Klarlacken, Klebstoffen oder Dichtmaterialien. 5. Use according to claim 1 to 3 in coating compositions, in particular in primers, topcoats, clearcoats, adhesives or sealing materials.
6. Verwendung nach Anspruch 1 bis 5 mit einer Reinheit an ß-lsophoron von 6. Use according to claim 1 to 5 with a purity of ß-isophorone of
> 95 Gew.-%, besonders bevorzugt > 98 Gew.-% und ganz besonders bevorzugt > 95 wt .-%, particularly preferably> 98 wt .-% and most preferably
> 99 Gew.-%. > 99 wt .-%.
EP11725679.2A 2010-07-06 2011-06-07 Use of beta-isophorone as solvent Withdrawn EP2590507A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010030995A DE102010030995A1 (en) 2010-07-06 2010-07-06 Use of beta-isophorone as a solvent
PCT/EP2011/059325 WO2012004073A2 (en) 2010-07-06 2011-06-07 USE OF β-ISOPHORONE AS SOLVENT

Publications (1)

Publication Number Publication Date
EP2590507A2 true EP2590507A2 (en) 2013-05-15

Family

ID=44627103

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11725679.2A Withdrawn EP2590507A2 (en) 2010-07-06 2011-06-07 Use of beta-isophorone as solvent

Country Status (5)

Country Link
US (1) US8846979B2 (en)
EP (1) EP2590507A2 (en)
CN (1) CN102958360A (en)
DE (1) DE102010030995A1 (en)
WO (1) WO2012004073A2 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3079656B1 (en) * 2018-03-27 2020-11-27 Commissariat Energie Atomique 3D RESISTIVE MEMORY
CN111066800A (en) * 2019-12-26 2020-04-28 安徽久易农业股份有限公司 Prothioconazole series missible oil and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030018223A1 (en) * 1999-12-28 2003-01-23 Yoshikazu Takamatsu Process for the preparation of cyclohexanol

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3253021A (en) 1961-04-17 1966-05-24 Hooker Chemical Corp 3, 4-dihalo-n-acylphenylhydroxylamines
US3281234A (en) 1964-06-23 1966-10-25 Pennsalt Chemicals Corp Herbicidal composition and method
US3397120A (en) * 1967-01-13 1968-08-13 Exxon Research Engineering Co Purification of dihydroisophorone by plural distillation and isomerization
CH605535A5 (en) 1974-04-11 1978-09-29 Hoffmann La Roche
DE3225940A1 (en) 1982-07-10 1984-01-12 A. Nattermann & Cie GmbH, 5000 Köln HERBICIDE EMULSION CONCENTRATES
DE3735211A1 (en) 1987-10-17 1989-04-27 Huels Chemische Werke Ag METHOD FOR PRODUCING BETA-ISOPHORONE FROM ALPHA-ISOPHORONE
GB2243551A (en) * 1990-05-01 1991-11-06 Kemira Oy Herbicidal solution
DE59104781D1 (en) 1990-11-30 1995-04-06 Hoffmann La Roche Process for the production of beta-isophorone.
DE19619570A1 (en) 1996-05-15 1997-11-20 Degussa Process for the preparation of ketoisophorone
DE19639570A1 (en) 1996-09-26 1998-04-02 Degussa Process for the preparation of 3,5,5-trimethylcyclohexa-3-en-1-one (β-isophorone) by isomerization of 3,5,5-trimethylcyclohexa-2-en-1-one (alpha-isophorone)
JPH10139713A (en) 1996-11-15 1998-05-26 Daicel Chem Ind Ltd Production of 3,5,5-trimethylcyclohex-3-en-1-one
JP4138932B2 (en) 1998-03-10 2008-08-27 新日本石油株式会社 Method for producing trimethylhydroquinone
JPH1149712A (en) 1997-08-01 1999-02-23 Nippon Petrochem Co Ltd Method for producing trimethylhydroquinone
DE19821379A1 (en) 1998-05-13 1999-11-18 Degussa Improved process for the preparation of 3,5,5-trimethylcyclohexa-3-en-1-one (beta-isophorone by isomerization of 3,5,5-trimethylcyclohexa-2-en-1-one (alpha-isophorone) (II)
JPH11342342A (en) * 1998-06-01 1999-12-14 Daicel Chem Ind Ltd Oxidation catalyst and oxidation method using the same
FR2795408B1 (en) 1999-06-22 2001-08-24 Atofina CONTINUOUS PROCESS FOR MANUFACTURING 3,5,5-TRIMETHYL CYCLOHEXA- 3-IN-1-ONE (BETA-ISOPHORONE)
FR2795409B1 (en) 1999-06-22 2001-08-24 Atofina CONTINUOUS MANUFACTURING PROCESS OF 3,5,5-TRIMETHYL CYCLOHEXA- 3-IN-1-ONE (BETA-ISOPHORONE)
RU2263449C1 (en) 2004-05-06 2005-11-10 Закрытое акционерное общество "Щелково Агрохим" Herbicide composition
CN1259299C (en) 2004-12-10 2006-06-14 浙江大学 A kind of synthetic technique of β-isophorone
CN101182288A (en) * 2007-12-05 2008-05-21 浙江大学 Method for preparing oxyisophorone by heterogeneous oxidation
CN101569312B (en) 2009-06-05 2012-05-02 贵州大学 A pesticide compound containing pymetrozine and thiamethoxam, its preparation method and application

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030018223A1 (en) * 1999-12-28 2003-01-23 Yoshikazu Takamatsu Process for the preparation of cyclohexanol

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
HUANG YUWEI ET AL: "EN translation of: The chemical equilibrium and reaction kinetics of isomerization of [beta] - isophorone to [alpha] - isophorone", CHEMICAL ENGINEERING AND EQUIPMENT, vol. 5, 1 January 2007 (2007-01-01), pages 9 - 11, XP055257400 *
HUANG YUWEI: "The chemical equilibrium and reaction kinetlce of fsomerization of [beta]-isophorone to [alpha]-isophorone", CHEMICAL ENGINEERING AND EQUIPMENT, 1 May 2007 (2007-05-01), pages 9 - 11, XP055208636, Retrieved from the Internet <URL:http://en.cnki.com.cn/Article_en/CJFDTOTAL-FJHG200705004.htm> [retrieved on 20150819] *
R. M. LOPACHIN ET AL: "MOLECULAR MECHANISMS OF THE CONJUGATED - UNSATURATED CARBONYL DERIVATIVES: RELEVANCE TO NEUROTOXICITY AND NEURODEGENERATIVE DISEASES", TOXICOLOGICAL SCIENCES, vol. 104, no. 2, 13 December 2007 (2007-12-13), pages 235 - 249, XP055257403, ISSN: 1096-6080, DOI: 10.1093/toxsci/kfm301 *
See also references of WO2012004073A2 *

Also Published As

Publication number Publication date
WO2012004073A3 (en) 2012-03-08
CN102958360A (en) 2013-03-06
US20140005438A1 (en) 2014-01-02
DE102010030995A1 (en) 2012-01-12
WO2012004073A2 (en) 2012-01-12
US8846979B2 (en) 2014-09-30

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