WO2012003599A1 - Procédés pour la synthèse de ligands à base de di(triazacyclononane) - Google Patents

Procédés pour la synthèse de ligands à base de di(triazacyclononane) Download PDF

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Publication number
WO2012003599A1
WO2012003599A1 PCT/CN2010/001008 CN2010001008W WO2012003599A1 WO 2012003599 A1 WO2012003599 A1 WO 2012003599A1 CN 2010001008 W CN2010001008 W CN 2010001008W WO 2012003599 A1 WO2012003599 A1 WO 2012003599A1
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WO
WIPO (PCT)
Prior art keywords
dtne
water
bis
mmol
triazacyclonon
Prior art date
Application number
PCT/CN2010/001008
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English (en)
Inventor
Ronald Hage
Jean Hypolites KOEK Jean Hypolites KOEK
Stephen William Russell
Xiaohong Wang
Lodewijk Van Der Wolf
Jianrong Zhang
Wei Zhao
Original Assignee
Unilever Plc
Unilever N.V.
Hindustan Unilever Limited
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 Unilever Plc, Unilever N.V., Hindustan Unilever Limited filed Critical Unilever Plc
Priority to PCT/CN2010/001008 priority Critical patent/WO2012003599A1/fr
Priority to BR112013000236-0A priority patent/BR112013000236B1/pt
Priority to ES17151457T priority patent/ES2764203T3/es
Priority to ES11803066.7T priority patent/ES2621881T3/es
Priority to CA2804475A priority patent/CA2804475C/fr
Priority to EP11803066.7A priority patent/EP2590952B1/fr
Priority to IN119MUN2013 priority patent/IN2013MN00119A/en
Priority to US13/808,565 priority patent/US8907082B2/en
Priority to EP17151457.3A priority patent/EP3176155B1/fr
Priority to PL11803066T priority patent/PL2590952T3/pl
Priority to HUE17151457A priority patent/HUE049652T2/hu
Priority to CN201180042920.4A priority patent/CN103180302B/zh
Priority to PT171514573T priority patent/PT3176155T/pt
Priority to CA3052591A priority patent/CA3052591A1/fr
Priority to PCT/CN2011/001104 priority patent/WO2012003712A1/fr
Publication of WO2012003599A1 publication Critical patent/WO2012003599A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D255/00—Heterocyclic compounds containing rings having three nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D249/00 - C07D253/00
    • C07D255/02—Heterocyclic compounds containing rings having three nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D249/00 - C07D253/00 not condensed with other rings

Definitions

  • the present invention concerns the synthesis of binucleating macrocyclic ligands that may be used to form complexes that have utility as bleach and/or oxidation catalysts.
  • Manganese complexes containing the ligands Me 3 TACN (1,4,7- trimethyl-1, , 7-triazacyclononane) and Me-DTNE (1,2-bis- (4, 7-dimethyl ⁇ 1, 4, 7-triazacyclonon-l-yl ) -ethane) are of interest for different bleaching of cellulosic and other substrates .
  • Ts 4 -DTNE The reaction with 1, 4-ditosyl-l, 4, 7-triazacyclonone with 2 equivalents of ditosyl-ethyleneglycol in DMF yielded Ts 4 -DTNE is also disclosed in Inorg. Chem. 1985, 24, 1230; Inorg.
  • Ts -DTNE has also been obtained using 0, 0' N, ' -tetratosyl- N, ' -bis (2-hydroxyethyl) ethylenediamine and ethylenediamine (Synthesis 2001, 2381-2383; Inorg. Chem. 2007, 46(1), 238- 250; Green Chem. 2007, 9, 996-1007).
  • the binucleating triazacyclononane ligand can be obtained in a reasonable yield.
  • the purity level is insufficient to obtain the dinuclear manganese complex ( [Mn IV Mn Ii:i ( ⁇ - ⁇ ) 2 ( ⁇ -OAc) (Me 4 -DTNE) ] 2+ ) in high yield, an additional purification step, such as vacuum destination is needed. Although this gives then a high purity material, the yield loss is quite substantial.
  • Reaction of 1, 4-di (arylsulfonate) -1, 4, 7-triazacyclonane with dihaloethane in a solvent, optionally, in the presence of water, and a base yields 1, 2-bis- (4, 7-diarylsulfonate-1, 4, 7- triazacyclonon-l-yl) -ethane in high yield.
  • Removing the arylsulfonate protecting groups and then reacting further with formaldehyde and formic acid in one-pot reaction yields e 4 -DTNE (1, 2-bis- (4, 7-dimethyl-l, 4, 7-triazacyclonon-l-yl ) - ethane) .
  • the present invention provides a method of producing a compound of formula (C) , the method comprising the following step:
  • bridging element of the form ZCH 2 CH 2 Z, wherein P is an arylsulfonate protecting group and Z is a halogen selected from: Cl; Br; and, I.
  • one-pot synthesis/reaction is a strategy to improve the efficiency of a chemical reaction whereby a reactant is subjected to successive chemical reactions in just one reactor. This is much desired by chemists because avoiding a lengthy separation process and purification of the intermediate chemical compound would save time and resources while increasing chemical yield.
  • the present invention provides a one-pot method for the preparation of 1, 2-bis- ( 4 , 7-dimethyl-l, 4 , 7 , - triazacyclonon-l-yl) -ethane (Me-DTNE) the method comprising deprotecting a compound of formula (C) :
  • a method for obtaining Me 4 DTNE is provided.
  • a preferred synthetic scheme for obtaining e 4 DTNE is
  • 1, 4-di (arylsulfonate) -1, 4, 7-triazacyclonane reacts with 1,2- dihaloethane in a solvent and a base, wherein the water level in the solvent is between 0 and 90%.
  • the 1,2- dihaloethane is preferably selected from 1 , 2-dibromoethane , 1, 2-diodoethane and 1, 2-dichloroethane, with 1,2- dibromoethane being most preferred.
  • solvents such as acetonitrile, dimethylformamide (dmf) , xylene, toluene, dioxane, 1-butanol, 2-butanol, t-butanol, 1-propanol, and 2-propanol.
  • the solvent may contain
  • the water content of the solvent may be between 0 and 90%.
  • the base used for the coupling of 1 , 4-di (arylsulfonate) - 1, 4, 7-triazacyclonane with dihaloethane should not be too strong; the base used for the coupling reaction is
  • a tosyl group is used as protecting group for the secondary amines of the 1 , 4 , 7-triazacyclonane moiety.
  • the tosyl group (abbreviated Ts or Tos) is CH 3 C 6 H 4 S0 2 .
  • This group is usually derived from the compound 4-toluene sulfonyl chloride, CH 3 C 6 H 4 S0 2 C1, which forms esters and amides of toluene sulphonic acid.
  • the para orientation illustrated (p-toluenesulfonyl) is most common, and by convention tosyl refers to the p-toluenesulfonyl group.
  • Tosylate refers to the anion of p-toluenesulfonic acid (CH 3 C 6 H 4 SO 3 "" ) . Whilst the tosyl group is the preferred protecting group other
  • arylsulfonyl groups (ArS0 2 ) will function to provide the advantages of the present invention.
  • ArS0 2 arylsulfonyl groups
  • arylsulfonyl employed is a benzenesulfonate .
  • Preferred solvents are acetonitrile, 1-butanol, 2-butanol, t-butanol, and dimethylformamide (dmf) . These solvent are preferably used with additional water, preferably between 10 and 90%. Most preferably, acetonitrile/H 2 0 is used, as 1,2- bis (4, 7-arylsulfonate-1, 4, 7-triazacyclonon-l-yl) -ethane obtained is of higher purity than using other solvents. This allows the formation of the Me 4 -DTNE ligand of higher purity and therefore the ligand does not need to be distilled prior using for the complexation step with manganese.
  • the protecting groups of 1 , 2-bis ( 4 , 7-arylsulfonate-1 , 4 , 7- triazacyclonon-l-yl) -ethane are removed by treatment with an acid to yield 1 , 2-bis ( 1 , 4 , 7-triazacyclonon-l-yl) -ethane .
  • the preferred acid used for deprotection is concentrated
  • the 1, 2-bis (1, , 7-triazacyclonon-l-yl) -ethane is preferably methylated by reaction with formaldehyde and subsequent reduction.
  • reaction with formaldehyde and formic acid (Eschweiler-Clarke methylation) are the
  • formaldehyde can be for example found in US 4,757,144.
  • the Me 4 -DTNE ligand can be extracted using a C5-C8 hydrocarbon as solvent.
  • the C5-C8 is preferably selected from pentane, hexane, heptane, octane, cyclopentane,
  • the ligand obtained is best vacuum distilled before further complexing with manganese salts.
  • the ligand may be purified by precipitating as HC1 salt, after which the free Me 4 -DTNE ligand was obtained by addition of
  • Ts 4 -DTNE 1 , 2-bis ( 4 , 7-ditosyl-l , 4 , 7- triazacyclonon-l-yl) -ethane)
  • TS4-DTNE (93.3% purity) (25 g, 26 mmol) and 96% sulphuric acid (59.2 mL, composed of 56.8 mL concentrated H 2 S0 4 (98%) plus 2.4 mL water) were stirred at 110°C (oil bath) in a 1 L 3-necked flask overnight.
  • TS4-DTNE 52 g (77% purity), 44.5 mmol
  • 96% sulphuric acid 130.6 mL, composed of 125.6 mL concentrated H 2 S0 4 (98%) plus 5ml water
  • the green filtrate was evaporated (the water bath temperature ⁇ 45 °C) .
  • the residual dark green oil was co-evaporated with ethanol and ethyl acetate to facilitate the removal of most of the remaining water. Dark green oils were taken up in ethanol, and the insoluble white salts separated by filtration were washed with ethanol. After removing all ethanol, the dark green oil was obtained again. The small amount of ethanol was added and stirred for 2 min. Then the large amount of ethyl acetate was added. The green solid was precipitated immediately.
  • Me 4 -DTNE (89.3% purity with 1.3% Me 3 -TACN) (765 mg,2 mmol); EtOH/H 2 0 (2:1, v/v) : 20 mL; MnCl 2 H 2 0 (840 mg, 4.2 mmol);
  • UV-Vis purity of 91.1%, the yield of 86.8% the weight of the compound (g) ⁇ the purity of the compound (%)/the calcd. weight of the compound (g) ) .
  • Total chloride amount was 11.17 %.
  • Me 4 -DTNE 70.5% purity with 22.8% Me 3 -TACN
  • MnCl 2 '4H 2 0 2.22 g, 11.2 mmol
  • NaAc(166 mg, 2 mmol) 1 M of H 2 0 2 in water (15 mL, 15 mmol) ; 1.5 M of NaOH (7.5 mL, 11.25 mmol); 1 M of HAc (2.5 mL, 2.5 mmol).
  • the yield (%) the weight of the compound (g) * the purity of the
  • Total chloride amount was 10.35 %.
  • Total chloride amount was 10.91 %.

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

Abstract

La présente invention concerne un procédé amélioré de synthèse de ligands à base de di(triazacyclononane) consistant à faire réagir le 1,4-di(arylsulfonate)-1,4,7-triazacyclononane dans le dihaloéthane de façon à produire du 1,2-di(4,7-diarylsulfonate-1,4,7-triazacyclonon-1-yl)-éthane qui est déprotégé dans un milieu acide de façon à donner du 1,2-di(1,4,7-triazacyclonon-1-yl)-éthane, puis à faire réagir le 1,2-di(1,4,7-triazacyclonon-1-yl)-éthane avec du formaldéhyde et de l'acide formique dans une réaction monotope de façon à obtenir du 1,2-di(4,7-diméthyl-1,4,7-triazacyclonon-1-yl)-éthane.
PCT/CN2010/001008 2010-07-06 2010-07-06 Procédés pour la synthèse de ligands à base de di(triazacyclononane) WO2012003599A1 (fr)

Priority Applications (15)

Application Number Priority Date Filing Date Title
PCT/CN2010/001008 WO2012003599A1 (fr) 2010-07-06 2010-07-06 Procédés pour la synthèse de ligands à base de di(triazacyclononane)
BR112013000236-0A BR112013000236B1 (pt) 2010-07-06 2011-06-05 método de produzir um composto, e, sal protonado
ES17151457T ES2764203T3 (es) 2010-07-06 2011-07-05 1,2-bis-(4,7-dimetil-1,4,7-triazaciclonon-1-il)-etano y producto intermedio para la síntesis del mismo
ES11803066.7T ES2621881T3 (es) 2010-07-06 2011-07-05 1,2-Bis-(4,7-dimetil-1,4,7-triazaciclonon-1-il)-etano e intermedio del mismo
CA2804475A CA2804475C (fr) 2010-07-06 2011-07-05 1,2-di-(4,7-dimethyl-1,4,7-triazacyclonon-1-yl)-ethane et intermediaire correspondant
EP11803066.7A EP2590952B1 (fr) 2010-07-06 2011-07-05 1,2-di-(4,7-diméthyl-1,4,7-triazacyclonon-1-yl)-éthane et intermédiaire correspondant
IN119MUN2013 IN2013MN00119A (fr) 2010-07-06 2011-07-05
US13/808,565 US8907082B2 (en) 2010-07-06 2011-07-05 1,2-bis-(4,7-dimethyl-1,4,7-triazacyclonon-1-yl)-ethane and intermediate for the synthesis of same
EP17151457.3A EP3176155B1 (fr) 2010-07-06 2011-07-05 1,2-bis- (4,7-dimethyl-1,4,7-triazacyclonon-1-yl) -éthane et intermédiaire pour sa synthèse
PL11803066T PL2590952T3 (pl) 2010-07-06 2011-07-05 1,2-bis-(4,7-dimetylo-1,4,7-triazacyklonon-1-ylo)-etan i jego produkt przejściowy
HUE17151457A HUE049652T2 (hu) 2010-07-06 2011-07-05 1,2-bisz-(4,7-dimetil-1,4,7-triazaciklonon-1-il)-etán és intermedier annak szintézisére
CN201180042920.4A CN103180302B (zh) 2010-07-06 2011-07-05 1,2-二(4,7-二甲基-1,4,7-三氮杂环壬-1-基)-乙烷及其中间体
PT171514573T PT3176155T (pt) 2010-07-06 2011-07-05 1,2-bis-(4,7-dimetil-1,4,7-triazaciclonon-1-il)-etano e intermediário para a síntese do mesmo
CA3052591A CA3052591A1 (fr) 2010-07-06 2011-07-05 1,2-di-(4,7-dimethyl-1,4,7-triazacyclonon-1-yl)-ethane et intermediaire correspondant
PCT/CN2011/001104 WO2012003712A1 (fr) 2010-07-06 2011-07-05 1,2-di-(4,7-diméthyl-1,4,7-triazacyclonon-1-yl)-éthane et intermédiaire correspondant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2010/001008 WO2012003599A1 (fr) 2010-07-06 2010-07-06 Procédés pour la synthèse de ligands à base de di(triazacyclononane)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006125517A1 (fr) * 2005-05-27 2006-11-30 Unilever Plc Procede de blanchiment

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006125517A1 (fr) * 2005-05-27 2006-11-30 Unilever Plc Procede de blanchiment

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HANKE, DIETER ET AL.: "Synthesis and X-ray and Neutron Structures of anti-[L2Rh2(H)2(mu-H)2](PF6)2 (L= 1,4,7-Trimethyl-1,4,7-triazacyclononane) and a Related Species Containing a syn-[Rh2(FH)2(mu-H)2]2+ Core. Isolation of [L2Fe2(mu-H)3]BPh4", INORGANIC CHEMISTRY, vol. 32, no. 20, 1993, pages 4300 - 4305 *
WIEGHARDT, KARL ET AL.: "Coordination Chemistry of the Bimacrocyclic, Potentially Binucleating Ligand 1,2-Bis(1,4,7-triaza-1-cyclononyl)ethane (dtne). Electrochemistry of Its First Transition Series Metal(II,III) Complexes. Characterization of the New Hemerythrin Model Complex [Fez(dtne)(mu-O)(mu-CH3C02)Z]Br2H2O", INORGANIC CHEMISTRY, vol. 24, no. 8, 1985, pages 1230 - 1235 *

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