NEW 2,2'-AZINO-BIS-THIAZOLINES AS PRECURSORS TO AIR-STABLE RADICALS

NOUVELLES 2,2'-AZINO-BISTHIAZOLINES COMME PRECURSEURS DE RADICAUX STABLES DANS L'AIR

Claims

What we claim is:

1) New compounds of the general formula:
Image
where:
R F is an organic halogenated organic radical, alkyl, aryl, aryl-alkyl, alkyl-
aryl, heterocyclic, alkyl-heterocyclic, heterocyclic-alkyl-, in which at least
than 40% of the hydrogen atoms are replaced by either chlorine or
fluorine, possibly including catenary heteroatoms in the for of -O-, =N-,
-S-, =P-, =(P=O) -, -SO-, -SO2- from 1 to 28 carbon atoms, or is part of
a polymer chain or network.
R is an organic radical from 1 to 400 carbon atoms, or is part of a polymer
chain or network.
R1 is H or R
2) Compound according to claim 1 characterised in that R F is F, Cl, CF3, C n
F2n+1,
HC n F2n+1-, CF3O-, C n F2n+1O-, HC n F2n+1O-, CF3S-, C n F2n+1S-,
HC n F2n+1S-, ClC n F2n+1-, ClC n F2n+1O-, ClC n F2n+1S-, BrC n F2n+1-, BrC n
F2n+1O-,
BrC n F2n+1S-, IC n F2n+1-, IC n F2n+1O-, IC n F2n+1S-, CH2=CHC n F2n+1-,
CH2=CHC n F2n+1O-, CH2=CHC n F2n+1S-, R2OC n F2n+1-, R2OC n F2n+1O-,
R2OC n F2n+1S-, CF3CH2-, CF3CH2O-, (CF3)2CH-, (CF3)2CHO-, CHF2-, CHF2O-,
CHF2S-, CClF2-, CClF2O-, CClF2S-, , CClF2-, CCl2FO-, CClF2S-, CCl3,-
CCl3O-, C6F5-, CF3C6F4-, C6F5O-, CF3C6F4O-, 3,5-(CF3)2C6H2-, C6Cl5-,
C6Cl5O-, FSO2CF2-, ClSO2(CF2)n-, -SO3(CF2)n-, -SO3(CF2)n-, -CO2(CF2)n-,
-SO3(CF2)n-, -2O3P(CF2)n-, FSO2N(-)SO2(CF2)n-, CF3SO2N(-)SO2(CF2)n-,
C n F2n+1SO2N(-)SO2(CF2)n-, R1SO2N(-)SO2(CF2)n-, FSO2(CF2)n-, ClSO2(CF2)n-,
-SO3(CF2)n-, -SO3(CF2)n-, -CO2(CF2)n-, -SO3(CF2)n-, C n F2n+1SO2N(-)(CF2)n-,
R1SO2N(-)(CF2)n- where R2 has a similar definition than R, and 2 <= n
<= 12.

1


3) Compound according to claim 1 characterised in that R is an alkyl, alkenyl,
an
aryl-alkyl, an aryl-alkenyl, an alkyl-aryl, an aryl-alkenyl, an alkyl-
heterocyclic,
heterocyclic-alkyl, from 1 to 28 carbon atoms, possibly including catenary
heteroatoms in the for of ~O~, =N~, ~S~, =P~, =(P=O)~, ~SO~, ~SO2~ possibly
bearing various functionalities

4) Compound according to claim 3 characterised in that the various
functionalities
include negative or positive ion-bearing groups, hydroxy, amine, solvating or
complexing capabilities, double bonds and polymerization-active
functionalities.

5) Compound according to claim 3 characterized in that R is chosen from C p
H2p+1~,
C6H5~, C6H5C p H2p~, C p H2p+1C6H4~, C p H2p+1C6H4C r H2r~, CH2=CHC p H2p~,
CH2=CHC6H5~, CH2=CHC6H4C p H2p+1~, CH2=CHC p H2p C6H4~, Image,
HOC p H2p~, (HO)CH2CH(OH)C p H2p~, HO[C2H4O]q C r H2r~, C p H2p+1O
[C2H4O]q C r H2r~(HO)CH2C2H4OC2H4~, HOC6H5~, HOCH2C6H5~,
HOC p H2p+1C6H4~, HOC6H4C p H2p+1~, HO C p H2p C6H4 C p H2p~,
CH2=CHC(=O)OC p H2p~, CH2=CHC(=O)OC6H4~, CH2=CHC(=O)OC6H4~,
CH2=CHC(=O)OC p H2p C6H4~, CH2=CHC(=O)OC p H2p C6H4 C r H2r~,
CH2=C(CH3)C(=O)OC p H2p~, CH2=C(CH3)C(=O)OC6H4~,
CH2=C(CH3)C(=O)OC p H2p C6H4~, CH2=C(CH3)C(=O)OC p H2p C6H4C r H2r~,
-O2CC p H2p~, -O2CC6H4~, [-O2C]2C6H3~, [-O2C]3C6H3~, -O2C C p H2p C6H4~,
-O2CC p H2p C6H4C r H2~, -O3SC p H2p~, -O3S C6H4~, [-O3S]2C6H3~, [-O3S]3C6H3~,
-O3SC p H2p C6H4~, -O3S C p H2p C6H4C r H2r~, -2O3PC p H2p~, -2O3PC6H4~,
[-2O3P]2C6H3~, [-2O3P]3C6H3~, -2O3PC p H2p C6H4~, -2O3PC p H2p C6H4C r H2r,
CF3SO2N(-)O2SC p H2p~, CF3SO2N(-)O2SC6H4~, [CF3SO2N(-)O2S]2C6H3~,
[CF3SO2N(-)O2S]3C6H3~, CF3SO2N(-)O2SC p H2p C6H4~,
CF3SO2N(-)O2SC p H2p C6H4C r H2r~, N.ident.CN(-)O2SC p H2p~, N.ident.CN(-
)O2SC6H4~,
[N.ident.CN(-)O2S]2C6H3~, [N.ident.CN(-)N(-)O2S]3C6H3~, N.ident.CN(-)O2SC p
H2p C6H4~,
N.ident.CN(-)O2SC p H2p C6H4C r H2r~, (N.ident.C)2C(-)O2SC p H2p~,
(N.ident.C)2C(-)O2SC6H4~,
[(N.ident.C)2C(-)N(-)O2SC2C6H3~, [(N.ident.C)2C(-)N(-)O2S]3C6H3~,
(N.ident.C)2C(-)N(-)O2SC p H2p C6H4~, (N.ident.C)2C(-)N(-)O2SC p H2p C6H4C r
H2r~,
[C s H2s+1]3(+)NC p H2P~, ([C s H2s+1]3(+)NC6H4~,[C s H2s+1]3(+)NC6H3~,
{[C s H2s+1]3(+)N}3C6H3~, [C s H2s+1]3(+)C p H2p C6H4~,
[C s H2s+1]3(+)NC p H2p C6H4C r H2r~, [C s H2s+1]3(+)NC p H2p~,
([C s H2s+1]3(+)PC6H4~,[C s H2s+1]3(+)~PC6H3~,{[C s H2s+1]3(+)P}3C6H3~,
[C s H2s+1]3(+)PC p H2p C6H4~, [C s H2s+1]3(+)PC p H2p C6H4C r H2r~,
([C s H2S+1]2(+)SC6H4~,[C s H2s+1]2(+)SC6H3~, {[C s H2s+1]2(+)S}3C6H3~,
[C s H2s+1]2(+)SC p H2p C6H4~,[C s H2s+1]2(+)SC p H2p C6H4C r H2r~, C s
H2s+n(+)[NC4H4]~,
C s H2s+1(+)[NC3H3N]C p H2p~, [C s H2s+1O]3Si Cp H2p~, [C s H2s+1O]2Si(CH3) C
p H2p~
Where: (1<n, p<=48), (0 <=s<=18)
6) Compound according to claim 1 characterised in that is formed form two
moieties
A~B, either A or B, alternatively A and B being chosen from:



Image

3


Image

4


Image

5



Image

6



Image
7) Polymer or co-polymers characterised in that they are prepared from the
polymerisation or copylmerisation of compounds according to claim 1 containing
active functionalities in R, R' of R F
8) Polymers or co-polymers characterised in that it comprises the repeat
units:
Image
where Q is a divalent organic radical containing between 1 and 240 carbon
atoms and possibly including catenary heteroatoms in the for of -O-, =N-,
-S-, =P-, =(P=O) -, -SO-, -SO2-
9) Polymer or co-polymers characterised in that it comprises the repeat units:



Image
where Image represents a divalent organic radical containing between 1 and
240 carbon atoms and possibly including catenary heteroatoms in the for of
-O-, =N-, -S-, =P-, =(P=O) -, -SO-, -SO2-.
10) Compounds according to claim 1 to 9 characterised in that the azino-bis-
thiazoline units can form a radical cation and possibly a radical di-cation.
11) Compounds according to claim 10 characterised in that the radical canon is
stable
to air and to water.
12) Compound according to claim 1, as discrete molecule or under polymeric
form
characterised in that it is used as a redox mediator.
13) Compound according to claim 1 as discrete molecule or under polymeric form
characterised in that it is used as an assay for laccases.
14) Compound according to claim 1 as discrete molecule or under polymeric form
characterised in that it is used as redox shuttle for lithium batteries,
either with
liquid electrolytes or with polymeric electrolytes.
15) Compound according to claim 1 as discrete molecule or under polymeric form
characterised in that it is used as active component for electrochromic
windows.
16) Compound according to claim 1 as discrete molecule or under polymeric form
characterised in that it is used a mediator for redox fuel cells on the
positive
electrode side.
17) Compound according to claim 1 as discrete molecule or under polymeric form
characterised in that it is used a mediator for bleaching paper pulp and
fibers with
oxygen.

8

Description

CA 02448618 2003-09-11
NEW 2,2'-AZINO-BIS-THIAZOLINES
AS PRECURSORS TO AIR-STABLE RADICALS
Invention by Michel Armand, Amer Hammami, Hicham Cavalie,
What we claim is:
1 ) New compounds of the general formula:
R
where:
RF is an organic halogenated organic radical, alkyl, aryl, aryl-alkyl, alkyl-
aryl, heterocyclic, alkyl-heterocyclic, heterocyclic-alkyl-, in which at least
than 40% of the hydrogen atoms are replaced by either chlorine or
fluorine, possibly including catenary heteroatoms in the for of -O-, =N-,
-S-, =P-, =(P=O) -, -SO-, -SOz- from 1 to 28 carbon atoms, or is part of
a polymer chain or network.
R is an organic radical from 1 to 400 carbon atoms, or is part of a polymer
chain or network.
R' isHorR
2) Compound according to claim 1 characterised in that RF is F, Cl, CF3,
C"Fz"+i,
HC"Fzn+i-, CF30-, C~Fz~+~O-, HC"Fz~+lO-, CF3S-, CnFzn+iS-,
HC"Fzn+tS-,C1C"Fz"~-i-, C1C"Fzn+~O-, CICnFz~+iS-, BrC"Fzn+~-, BrC"Fz~+i0-,
BrC"Fz"+i S-, I CnFz"+1-, I C~F2n+i O-, I C"FZn+~ S-, C Hz=CHC"Fz"+i-,
CHz=CHCnFzn+10-~ CHz=CHCnFzn+1S-, RzOCnFzn+1-, RzOCnFzn+10-,
RZOCnFzn+~S-, CF3CHz-, CF3CHz0-, (CF3)2CH-, (CF3)zCHO-, CHF2-, CHFzO-,
CHFZS-, CCIFz-, CC1F20-, CC1FZS-, , CCIzF-, CClzFO-, CC1FZS-, CC13,-
CC13O-, C6F5-, CF3C6F4-, C6FSO-, CF3C6F4O-, 3,S-(CF3)zC6H2-, C6C15-,
C6C150-, FSOZCFz-, CISOz(CFz)ri , -S03(CFz)~ , -S03(CFz)~ , 'COz(CFz)ri ,
-S03(CFz)ri , 'z03P(CFz)n , FSO2N~-~SOz(CFz)n , CF3SOZN~-~SOz(CFz)n ,
C~Fz"+1SOZN~-~SOz(CFz)"-, R'SOZN~-~SOz(CFz)n , FSOz(CFz)~ , CISOz(CFz)ri ,
-S03(CFz)n-, 'S03(CFz)ri , ~COz(CFz)p , -S03(CFz)~ , CnFz~+~ S02N~ ~(CFz)n ,
R' S02N~~?(CFz)~ where Rz has a similar definition than R, and 2 < n < 12.
., .,
RF' RF


CA 02448618 2003-09-11
3) Compound according to claim 1 characterised in that R is an alkyl, alkenyl,
an
aryl-alkyl, an aryl-alkenyl, an alkyl-aryl, an aryl-alkenyl, an alkyl-
heterocyclic,
heterocyclic-alkyl, from 1 to 28 carbon atoms, possibly including catenary
heteroatoms in the for of -O-, =N-, -S-, =P-, =(P=O)-, -SO-, -SOZ- possibly
bearing various functionalities
4) Compound according to claim 3 characterised in that the various
functionalities
include negative or positive ion-bearing groups, hydroxy, amine, solvating or
complexing capabilities, double bonds and polymerization-active
functionalities.
5) Compound according to claim 3 characterized in that R is chosen from
CpHZp+1-,
C6H5-, C6HSCpHZp , CpH2p+IC6H4-~ CpHzp+IC6HaCrH2T ~ CHz=CHCpHzp ,
CH2=CHC6H5-, CH2=CHC6H4CpH2p+1-, CHZ=CHCPHZpC6H4-, O CpH~,- ,
HOCpHZp , (HO)CHZCH(OH)CpH2p , HO[CZH40]aCrHZ~ , CpHZp+10
U2H40~qCrH2r (HO)CHZCZH40CzH4-, HOC6H5-, HOCHZC6H5-,
HOCpH2p+IC6Ha-, HOC6HaCPH2p+1-, HO CpH2pC~H4 CPHZp ,
CH2=CHC(=O)OCPHZp , CH2=CHC(=O)OC6H4-, CHZ=CHC(=O)OC6H4-,
CH2=CHC(=O)OCpH2pC6H4-, CHZ=CHC(=O)OCpH2pC6Hy CrH2t-,
CHZ=C(CH3)C(=O)OCPHZP , CHz=C(CH3)C(=O)OC6H4-,
CHZ=C(CH3)C(=O)OCpH2pC6H4-, CHZ=C(CH3)C(=O)OCpH2pC6H4CrH2r-,
OZCCpHZp , 02CC6Hq-, [ 02C~2C6I"13-~ L 02C~3C~H3m OzC CpH2pC6H4-
OZCCpHZpC6H4CrH2,.-, 03SCpH2p , 03S C6H4-, [ O3S]ZC6H3-, C 03S]3C6H3-,
03SCpHZpC(Hq-s 03.5 CpH2pC6H4CrH2t ~ 203PCpH2p , 203PC(H4-,
[ 203P]ZC6H3-, [ 203P]3C6H3-, z03PCpH2pC(,H4-, ZO3PCPHZpC6H4CrH2r,
CF3SOZN~ ~OZSCpHZp , CF3SOZN~ ~OZSC6H4-, [CF3SO2N~ ~OZSJ2C6H3-,
jCF3SOzN~ ~OZS]3C6H3-, CF3SOzN~ ~OzSCpH2pC6H4-,
CF3SOZNt ~OZSCpHZpC6H4C,H2r-, N~CNt ~OZSCpHzp , N-CND ~OZSC6H4-,
[N---CN( )OZS]zC6H3-, [N~CN~ >Nc ~OZS]3C6H3-, N~CNt ~OZSCpH2pC6Hd-,
N---CND ~OZSCpH2pC6H4CrHz~ , (N=C)ZC( )OZSCpHzP , (N-C)ZC( )OZSC6H4-,
L(N$C)aC~ ~OZS~2C6H3-, ~(N$C)2Cc >Nc >OZS~3C6H3-s
(N~C)ZC~-~N~-~OZSCpH2pC6H4-, (N=C)ZC~-?N~'~OZSCpH2pC6H4C~Hz,~,
[CSHzs+1]3t+~NCpHZP ~ UCSHzs+a3~+~NC6H4-,[CSHzs+1]3~+~NC6H3-,
~~CsH2s+1~3~+~N~3C6H3-~ ~CsH2s+1~3~+~CpH2pC6H4-,
~CsH2s+1~3~+~CpH2pC6HqCrH2r--~ ~CsH2s+1~3~+~NCpH2p ,
(~CsH2s+1~3~+~PC6H4-,~CsH2s+1~3~+~PC6H3-, ~~CsH2s+1~3~+~P~3C6H3-~
~CsH2s+1~3~+~PCPHZPC6H4 > ~CsH2s+1~3~+~PCPHZpC6H4CrH2W~
(LCSH2S+n2~+~SC6H4-,[CSHZs+y2~+~SCsH3-, ~LCsH2s+1]2~+~s}sC6H3-
~CsH2s+1~2~+~SCPHZPC6H4 s ~CsH2s+1]a~+~SCpHzpCsHaCrH2a~ CsH2s+n+~LNCaHa]-
CsH2s+1~+~LNC3H3N~CPH2P ~ ~CsH2s+lOJ3s1 CpHZp-~ ~CsH2s+10~251(CH3) CpH2p-
Where: ( 1 < n, p < 48), (0 < s < 18)
6) Compound according to claim 1 characterised in that is formed form two
moieties
A-B, either A or B, alternatively A and B being chosen from:


CA 02448618 2003-09-11
H3 ~ H3 ~ H3
N N N
N= ~N t--N
F3C ~ S C2F5 _' S CeFs ' ~S
12H5 l2Hs 12H5
N N N
~N N- N
F3C ~S/ C2Fs 1S C4F9 ~S
13H7 13H7 13H7
N N N
N N= N
F3C ~ S C2Fs _ S C4F9 ~ S
sHl3 ~ sHl3 ~ sHl3
N N N
N N ~N
F C 'S C F \ S C4F9 ~ ~S
8H17 ~ 8H17 ~ 8H17
N N N
N ~N r--N
C ~S CzFs "S C4F9 "S
C12H2s 1 lzH2s 1 l2Hzs
IIIN N N
N N~ N
~ S C2F5 -. S CaFs w S
F3C
16H33 ~ 16H33 ~ 12H25
N N N
N ~N- ~N
F3C ~g C2Fs ~S C4F9 'S
C18H37 118H37 118H37
IN N N
---N J--N t--N
F3C ~S~ C2Fs "S C4F9 "S


CA 02448618 2003-09-11
N
~N
F3C ' S C2Fs CaFs
IHs IH3
N N
J--N- r---N
H3C0--C 'S HgCS-C ~S
Fp F2
I Hs ( Hs
N N
r--N= 1--N=
C2Hs0-F ~S~ C2HsS- z ~ ~S
2
I H3 ~ H3
N N
N J---N
~S
H3C0-(C2H40)n-F2 S H3C0-(CZH4S)n-F
2
IH3 IH3
N N
----N ~N
OOC-(H2C)p-O--F S OOC-(H2C)p-S- z S
2
IH3 IH3
N N
r--N- J--N
OaS -(HzC)P - O - C S OsS-(HzC)P - S- C ~ ~S
F2 F2
H3
N
02S-N-S02 j--N
I F3 IH2C)P-S-F ~S
z


CA 02448618 2003-09-11
H3
N
O2S-N-SO2 N
F3 ~H2C)P-O-C S
F2
I H3 CHs
N
N- O N
_ H2 _ S
CI-F2 S H2 C O
2
Hs CH3
N
~N- N
H H S
Br-C \S HO-C? C? O-C
F2 F2
I H3 I H3
N N
t--N O r--N
II H2 H ~2
F2HC S H2C=H-C-O-C-C-O-F S
2
I H3 CH3
N
j-N= CHg O N
H
HF2C-C S H2C= ~ -II-O-Cp C? O-C S
F2 F2
C H3
N
t--N
H_ _ ~S
H2C H C2 O F
2
Hp O
H2 ~ -C-OH (CH2)P-CH \CH2
N
N
N ~
r--N-
F3C S FsC ~S


CA 02448618 2003-09-11
H2C-C? (O-C? CHz)n-OCHa (CHz)p-N=C=O
N
N ~N
S
F3C ~ S F3C
(CHz)PrC00 ICHz)P-O II H CHz
N O
N- ~N
~S
FaC S F3C
(GHz)P-SOa (CHz)P-O-C-C-CHz
Ha
N
N- ~N
F C S FaG ~ S
3
_ CHa
IGHz)P-SOz-N-SOz-CFa (GHz)P-N~
CH3
N N
~N- N
FsG ~ S FaC w S
+/CHa (CHz)P-CH=CHz
ICHz)P-N,\CHa
\\ N
N CHa
S N
~ S F3C
F3C
N
J--N
FaC ,S


CA 02448618 2003-09-11
OCH3
~N
N
N ~
J-- N =
~N
S F3C S
F3C
/CH3
N/
N
~N
F C ' F3C 'S
7) Polymer or co-polymers characterised in that they are prepared from the
polymerisation or copylmerisation of compounds according to claim 1 containing
active functionalities in R, R' of RF
8) Polymers or co-polymers characterised in that it comprises the repeat
units:
~nr"
n
where Q is a divalent organic radical containing between 1 and 240 carbon
atoms and possibly including catenary heteroatoms in the for of -O-, =N-,
-S-, =P-, =(P=O) -, -SO-, -SOZ-
9) Polymer or co-polymers characterised in that it comprises the repeat units:


CA 02448618 2003-09-11
R~ N S RF
~N-N I
S
3P ~ R
R
where vw~n, represents a divalent organic radical containing between 1 and
240 carbon atoms and possibly including catenary heteroatoms in the for of
-O-, =N-, -S-, =P-, =(P=O) -, -SO-, -SOZ-.
10) Compounds according to claim 1 to 9 characterised in that the azino-bis-
thiazoline units can form a radical cation and possibly a radical di-cation.
11) Compounds according to claim 10 characterised in that the radical canon is
stable
to air and to water.
12) Compound according to claim 1, as discrete molecule or under polymeric
form
characterised in that it is used as a redox mediator.
13) Compound according to claim 1 as discrete molecule or under polymeric form
characterised in that it is used as an assay for laccases.
14) Compound according to claim 1 as discrete molecule or under polymeric form
characterised in that it is used as redox shuttle for lithium batteries,
either with
liquid electrolytes or with polymeric electrolytes.
15) Compound according to claim 1 as discrete molecule or under polymeric form
characterised in that it is used as active component for electrochromic
windows.
16) Compound according to claim 1 as discrete molecule or under polymeric form
characterised in that it is used a mediator for redox fuel cells on the
positive
electrode side.
17) Compound according to claim 1 as discrete molecule or under polymeric form
characterised in that it is used a mediator for bleaching paper pulp and
fibers with
oxygen.
R