Synthesis and photochromic properties of functional diarylethenes with a [1,3]dithiol-2-one (Thione) bridging unit

Article abstract of DOI:10.1080/15421400590946451

In designing new photochromic compounds for optical data storage and photoswitching devices, the synthesis of a series of 4,5-diaryl-1,3-dithiol-2- one and 4,5-diaryl-1,3-dithiol-2-thione, which are suitable building blocks for incorporation with fluorophore, is herein reported. Our strategy needs the preliminary preparation of diarylalkynes, obtained by successive Sonogashira-Hagihara coupling-reactions in good yields (63-92%). A combination of these synthetic precursors with diisopropylxanthogen disulfide leads to the corresponding 4,5-diaryl-1,3-dithiol-2-ones under radical conditions with excellent yields (54-70%). The thionation of these compounds is obtained nearly quantitatively with phosphorous pentasulfide.

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Synthesis and Photochromic
Properties of Functional
Diarylethenes with a
[1,3]dithiol-2-one (Thione)
Bridging Unit
a
a
a
N. Impagnatiello , A. Heynderickx , C. Moustrou
a
&
a
A. Samat
Université de la Méditerranée, Faculté des
Sciences de Luminy, Marseille Cedex, France
Version of record first published: 31 Aug 2006.
To cite this article: N. Impagnatiello , A. Heynderickx , C. Moustrou & A. Samat
(
[
2005): Synthesis and Photochromic Properties of Functional Diarylethenes with a
1,3]dithiol-2-one (Thione) Bridging Unit, Molecular Crystals and Liquid Crystals,
430:1, 243-248
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Mol. Cryst. Liq. Cryst., Vo l. 43 0, pp. 24 3 –2 48, 20 05
Co py ri g h t # T ay l o r & Fr an ci s In c.
I SSN : 1 54 2- 14 0 6 pri n t =15 63- 528 7 on l i ne
DOI : 1 0. 1 08 0/ 1 54 2 14 0 0 59 094 6451
Synthesis and Photochromic Properties of Functional
Diarylethenes with a [1,3]dithiol-2-one (Thione)
Bridging Unit
N. Impagnatiello
A. Heynderickx
C. Moustrou
A. Samat
Un iv e rs it e´ d e la M e´ dit e rra n e´ e , F a cu lt e´ de s S cie n ce s de L u m in y ,
M ars e ille C ede x , F ra n ce
In designing new photochromic compounds for optical data storage and photo-
switching devices, the synthesis of a series of 4,5-diaryl-1,3-dithiol-2-one and
4
,5-diaryl-1,3-dithiol-2-thione, which are suitable building blocks for incorpor-
ation with fluorophore, is herein reported. Our strategy needs the preliminary
preparation of diarylalkynes, obtained by successive Sonogashira-Hagihara
coupling-reactions in good yields (63–92%). A combination of these synthetic
precursors with diisopropylxanthogen disulfide leads to the corresponding
4
,5-diaryl-1,3-dithiol-2-ones under radical conditions with excellent yields
(54–70%). The thionation of these compounds is obtained nearly quantitatively
with phosphorous pentasulfide.
Keywords: 1 ,2 -dia ryla lk yn es; 4,5- di ar yl -1 ,3 -d it hi ol -2 -o ne; 4,5- diar yl-1,3- dithiol-2- th io ne ;
p hot oc hrom is m; s ynth esis
INTRODUCTION
In t he la st fe w y ea rs, t he i ncre a sin g d em a n d fo r op t i c a l d a t a st ora g e
[
1 ] an d p ho t o s wi t chi ng d ev i ces [ 2] ha s l ed t o t he d ev e l op men t of
ne w p ho t o c h r o m ic co mp o un d s. A mon g t he ma ny kn ow n p hot oc hrom ic
sy s te m s , 1, 2 -d ia ry l et he nes d er iv a t i ve s [ 3] ha v e rec ei v ed t he mos t
Add res s c orr es pond en c e t o C . Mo u st r ou , Un iv er si t e´ d e la M e´ d it er r a n e´ e , G CO M 2,
UM R CNRS 6 1 1 4, F a cu l t e´ d es Sc i en c es d e Lu mi n y, C as e 90 1, 13 28 8 M ar s ei lle Ce d e x
0
9, Fr a nc e. E-m a il: mo u st r ou @ lu mi n y.u ni v-mr s.f r
24 3

2
44
N. Impagnatiello et al.
attention because of their remarkable fatigue resistance, thermal and
chemical stability. To prevent cis–trans photoisomerization, the most
common 1,2-diarylethenes, containing maleic anhydride [4], malei-
mide [5], perfluorocyclopentene and cyclopentene units [6], include a
five-membered cycloalkene.
Each bridging unit has its advantages and disadvantages. The two
first systems are readily accessible but are sensitive to acidic con-
ditions and exhibit degradation in the presence of oxygen [7].
Although the photochromic properties of the diarylperfluorocyclopen-
tenes are highly attractive, their synthesis are not trivial and the
expensive volatile starting material octafluorocyclopentene is a major
disadvantage.
Branda’s group [8–10] and Irie’s group [11] described supramol-
ecular photochromic switches based on bis(thienyl)ethene where the
thiophene rings are linked to fluorescent unit. The reversible pro-
perty changes during the photoisomerization reaction, such as the
refractive index [12], dielectric constant, redox potential and lumi-
nescence [13] can be used to achieve a non-destructive readout
[
10]. Further development of new systems based on the 1,2-diaryl-
ethene is warranted.
Working from the assumption that 4,5-diaryl-1,3-dithiol-2-one
(
thione) photoswitch moiety fused with fluorophores could regulate
the fluorescence property (Scheme 1), we herein present a new series
of diarylethenes based on the 1,3-dithiol-2-one (thione) bridging unit.
We conclude with preliminary data on the photochromic properties
of these compounds.
The radical methodology used in constructing the 1,3-dithiol-2-one
moiety, represents a significant addition to the current literature
methodology.
S C H EM E
1

Synthesis and Photochromic Properties of Functional Diarylethenes
24 5
RESULTS AND DISCUSSION
Synthesis
Am o ng t h e va r io us me t hod s f or i nt rod uci ng a l ky ny l g rou p s on a roma t i c
nu c le i, t he m o st p ow e rf ul a nd use f u l i s t he P d -ca t a l y zed cro ss- coup l i ng
re a c ti o n o f ha l o ge noa re n es w i t h t er m i nal a lk y nes , w hi c h w a s rep o rt ed
f o r t he fi rs t t ime b y Sonogashira-Hagihara [1 4 ] a nd Cassar [1 5 ] i n
1
9 75 . A va r ia ti o n of t h i s sy nt he t i c p ro c ed u re i nv o l v es t he use of p ro-
t e ct i ng gr o up s [16 ] . C oup l in g of ha l og e n oa r e nes w i t h t he com m erc ia l l y
a v ai lab le 2- m e t hy lb ut - 3- y n- 2 -o l p ro vi d e s t he 3 -a ry l a l k y nol [1 7 ].
Th is c o mp o un d g ene ra t es ‘in situ’ a t er mi na l a ry l a cet y l ene moi et y
(
b y r e mo v a l o f t he p ro t e ct i ng g r ou p ), w hi c h c an b e i nv o l v ed i n a n ot he r
Sonogashira c o up li ng t o a ff o r d d i ar yl a l k ynes [1 8 ]. T hi s a p p ro a ch w a s
use d t o t h e e ff i ci en t p re p a ra t io n of b i st h ie ny le t hy nes 4 a nd 5 a s
il l us t ra t e d in S c hem e 2 .
T he s ynt h e s is of i od ot h i op h en e 1 a nd 2 wa s a ccom p l i she d b y usi ng
t h e p ro c e d ur e d e scr ib e d b y Gronowitz [ 19 ] . I n t he p res ence of a ca t a -
ly t ic am o u nt o f [P d Cl ( PP h ) ] a nd C uI , t he cl a ssi c Sonogashira rea c-
2
3 2
t io n o f 1 an d 2 w i th t he co mm er ci al l y a va i la bl e 2 -me t h y l b ut -3 -y n- 2 -ol
in Et N H (r o o m t em p er a t ure , 1 5 h) a ff o rd ed 3 a nd 4 i n 9 2 % a nd 8 5 %
2
y ie ld r e sp e c ti ve l y. A mo d if i ed v er sio n of t he Sonogashira coup l i ng ca r-
ri e d o ut und e r p h a se- t ra ns f er co nd it i on [ 20 ], a l lo w e d t he sy nt hes i s of
co mp o un d 4 an d 5. R ea c t i on of 3 a nd 4 w i th th e i r res p ect i v e p rec urso rs
SCHEME 2 R eag e n t s a n d co n dit io ns : ( i) [ P dC l ( P P h ) ] , C u l, E t N H ,
2
3 2
2
ꢁ
H C ꢀC C (C H
3
)
3
OH , 2 0 C , 1 5 h ; ( ii) [ P d( P P h
3
)
4
] , C u l, b e n z en e , a q . 5 . 5 N N a O H,
C l, re f lu x , 2 0 h ; ( iii) is o prop ylx a n t h ic dis u lf ide , A I B N , t o lu e n e,
1 0 , t o lu en e , re f lu x .
þ
P hC H
re f lu x ; ( iv ) P
2 3
Ne t
4
S

2
46
N. Impagnatiello et al.
ꢁ
an d 2 at 70 C f or 2 0 h, i n t he p re sen ce of b e nz y lt r ie t hy l a mmo ni um
1
ch lo ri d e as p ha s e- t ra nsf e r a ge nt , a qu eou s 5. 5 N Na O H a s b a s e, b e n-
z e ne as s o lve nt , a nd a mi x t ure of [ Pd ( PPh ) ] a nd CuI a s ca t a l y st s,
3
4
g a ve 4 an d 5 in 7 4 % a nd 6 3 % y ie ld re sp ect i v el y . T he fo rma t i on of
t he 1, 3 -d it hio l- 2 -o nes i s ob t a i ned i n on ly one st ep fro m com m erc ia l l y
a v ai lab le d iis o p ro p y lx a nt ho g en d i sul f i d e a nd a l ky nes 4 a nd 5 und er
ra d ic al c o nd it io n s. C onv er si on o f 4 a nd 5 t o 6 a nd 7, w a s ef fi ci ent l y
a cc o m p lis he d by t re at e me nt w i t h d i iso p ro py l x a n t hog en d i sul f i d e a nd
AIB N , in r e flux i ng b enz e ne [ 21 ] . The b uil di ng s b l ock s 6 a nd 7 w ere
iso lat e d af t e r c hr om a t og ra p hy i n 8 0 % a nd 5 4 %. P hosp h orus p ent a s ul -
f ide (P S ) ha s b e en em p lo y ed f or ef f ec ti ng t he conv e rs i on of ca rb ony l
4
1 0
g r o up t o t hi o c arb o ny l g r ou p [ 22 ] . Tr ea t e me nt of t he 1 , 3- d i t hi ol -2 -o ne 6
a n d 7 w it h P S , i n re fl ux i n g t ol ue ne, a ll ow e d t he i r nea rl y q ua nt i t a t -
4
10
iv e c o nve r s io n to t he co rre sp o nd in g 1 ,3 - d i t hi ol - 2 -t hi one 8 a nd 9 (9 6 %
a n d 98 % r e sp e ct i ve l y) . Thi s sy n t he ti c st r a te gy w a s ex t end e d t o p re-
p ar e a d it hia n ap ht hen e d er iv a t i ve . The n, t h e sy nt hes i s of p hot oc h ro-
m ic t ar g e t s 14 a nd 15 w er e re a li z ed a cco rd i ng t o t he Sche me 3 .
T he 2- lit hi o be n zo [ b] t hio p he ne, ob t a ine d i n situ fro m t he rea ct i on of
co mm e r cia l be n z o [b] t hio p he n e w i th n- bu ty ll i t hi um, w a s t ra p p ed w i t h
io d o m e t ha ne t o g iv e 2 -m et hy l be nzo [b] t hio p he n e 10 i n q ua nt i t i ve y i el d .
Tre a t me nt o f 10 w i t h i od i ne i n p re s en ce of i od i c a ci d i n a ci d cond i t i ons
a f fo r d ed 11 in 93 %. A Sonogashira co u p l in g of 11 w i t h a n ex ces s of
2
- m e t hy l-3 -yn -o l a ff o r d ed 12 i n 9 0 %. A not her Sonogashira rea ct i on,
ꢁ
ꢁ
SCHEME 3 R ea ge n t s a n d co n dit io ns : ( i) 2 . 1 e q n - B u li, E t
2
O , ꢂ7 8 C ! 2 0 C ,
ꢁ
ꢁ
t h en C H
3
I ꢂ78 C ! rt ; ( ii) I
2
, H I O
3
, C H
3
C O OH , H
2
O , H
2
S O
4
, 70 C , 3 h ; ( iii)
ꢁ
[
P dC I ( P Ph ) ] , C u I , E t N H, H CꢀC C ( C H ) O H , 2 0 C , 4 da y s ; ( iv ) K O H,
2
3 2
2
3 2
ꢁ
Me O H, T olu en e , re f lu x , 6 h ; ( v ) 14, [ P dC I
v i) is opr opy lxa nt h ic dis u lf ide , A I B N, t o lu en e , re f lu x ; ( v ii) P
re fl ux .
2
( P P h
3
)
2
] , C u I , E t N
2
H , 6 0 C , 2 0 h ;
(
4
S
10 , t o lu e n e,

Synthesis and Photochromic Properties of Functional Diarylethenes
24 7
ca r rie d o u t und er p ha se t ra nsf e r co nd it i ons [2 0 ], of 12 w i t h i t s p rec u r-
so r 11, gi ve s 13 in 8 0%. The ra d i ca l a d d it i on of t he d i i sop rop y l x ant h o -
g en d is ulf id e [2 1] on t o 13, g iv e s t he 1 ,3 - d i t hi ol - 2 -on e 14 i n g oo d y i el d
(
7 0 %). T he t hio nat i on of 14 usi n g P 4 S 1 0 i n ref l uxi ng t ol uen e [2 2 ]
a f fo r d e d 15 in e xc el l ent y ie l d ( 96 %) .
Photochromic Behavior
An e xa m pl e is giv e n w i th co mp ou nd 15. The p hot oc yc l i za t i on of 15 w a s
ꢂ5
a c hie v e d by ir rad i a t i on of a cy cl oh ex an e so lut i o n (3 . 1 0 ) i n p res ence
o f ai r at w av e le ng t h co rre sp o nd i ng t o t he a b sorp t i on b a nd of t he
o p e n -r ing is o m er ( F i g. 1 ).
At t he p ho t o s t a t io na r y st a t e ob t a i ne d i n a b ou t 4 mi n, t he a b sorp t i on
o f t he c o lo re d f orm i s 5 22 nm . Se ve ra l cy cl es p hot oc ol ora t i o n =
p h o t o d e co lo r at io n ( res p ec t iv e l y usi ng 3 74 nm a nd 5 2 2 nm w a v e-
le ng th s) ha ve be en a chi ev ed , sho w in g t h e g oo d rev ers ib i l i t y of t he
ꢂ5
FIGURE 1 UV - Vis a bs o rpt io n s pe ct ra ch a n g e o f 15 ( 3 . 1 0 M in cy clo h e x a n e)
m e as u red at ro om t e mpe ra t u re, a t dif f e ren t s t a g e s o f t h e ph o t o ch ro mic re a c-
t ion . C on t in u ous irrdia t io n ( 3 74 n m ). ( a ) s t a rt ing o pe n - rin g is o m er , ( b ) a f t e r
irra diad iat ion f o r
2
m in u te s , ( c)
4
m inu t e s .

2
4 8
N. Impagnatiello et al.
sy st e m . A m o re ex t e nd ed st ud y of t he p hot oc hem ica l p rop e rt ie s of
t h e se s ys t e m s is i n p ro gr es s.
CONCLUSION
We ha ve d e sc r ibe d a sy nt he t i c st r at e g y f or t he p rep a ra t i on of a ser ie s
o f ne w p ho t o c h r om ic 4 ,5 - di a ry l -1 ,3 - d it hi ol - 2 - one s a nd 4 , 5- d i a ry l- 1 , 3 -
d i th io l- 2- t hio ne s. The y co nst i t ue g oo d b ui l di ng b l ock s fo r t h e d esi g n
o f p ho t o ch ro m ic- f luo ro p ho re co mp o un d s. 1 , 3- t hi ol e- 2 -t hi one s w ere
sy nt he t i z e d t o o f or t ha t a i m.
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