CA2065005A1

CA2065005A1 - Photoactive compounds

Info

Publication number: CA2065005A1
Application number: CA002065005A
Authority: CA
Inventors: Harry G. Heller; John Whittall
Original assignee: Individual
Current assignee: MTM Research Chemicals Ltd
Priority date: 1989-07-24
Filing date: 1990-07-20
Publication date: 1991-01-25
Also published as: ZA905759B; WO1991001312A1; EP0484390A1; AU6050490A; JPH05504545A; GB8916860D0; IE902673A1

Abstract

Photoactive compounds having general formulae (III) are provided in which A represents oxygen or NR1 wherein R1 represents hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, aralkyl having 7 to 9 carbon atoms, aryl having 6 to 14 carbon atoms, which may be substituted with one or more halogen or alkoxy groups having 1 to 20 carbon atoms, or alkaryl having 7 to 22 carbon atoms; P1 represents a 5-substituted-3-furyl, 3-thienyl, or 3-pyrryl group, said 5-substituted-3-furyl, 3-thienyl and 3-pyrryl groups being unsubstituted or substituted in the 2-position, said optional 2-substituents being selected from alkyl groups having 1 to 20 carbon atoms and aralkyl groups having 7 to 12 carbon atoms, and said 5-substituents being selected from (i) aryl groups having 6 to 14 carbon atoms, substituted with a group of the formula -NR7R8 wherein R7 and R8 each represent hydrogen or alkyl having 1 to 20 carbon atoms or together with the nitrogen atom to which they are attached represent a 1-pyrrolidine, a 1-piperidine, or a morpholine group, and (ii) heterocyclic groups selected from 2-thienyl, 3-thienyl, 2-furyl and 3-furyl groups, said last-mentioned 2-thienyl, 3-thienyl, 2-furyl and 3-furyl groups being unsubstituted or substituted by one or more C1-3 alkyl groups or halogen atoms; P2 represents alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, aralkyl having 7 to 9 carbon atoms, aryl having 6 to 14 carbon atoms which may be unsubstituted or substituted with one or more halogen atoms, or alkaryl having 7 to 22 carbon atoms; and F>C=
represents a substituted methylene group, having at least two carbon atoms.

Description

W O 91/01312 2 0 5 ~ O Q ~ PCT/GB90/~1118 ~OVEL PHOTOA~TIVE COMPOUNDS

This invention relates to a novel class of photoactive compounds and to processes for their production.
As used herein, the expression "photosctive compound" is defined as a compound which undergoes a structural change (hereinafter referred to as a "photoactive change") when subjected to electromagnetic radiation of a selected wavelength or wavelengths and undergoes a reversal to its original structure when subjected to thermal energy or to electromagnetic radiation of another wavelength and wherein the distinct structural forms interact differently with electromagnetic radiation. For example they may have different spectral absorption characteristics which can manifest themselves by the structural forms having different observable colours and often different dispersivities and refractive indices.
Photoactive compounds as defined above which undergo major colour changes on conversion between their respective structural forms are referred to as "photochromic compounds".
Photochromic compounds have a wide range of uses, e.g. in the manufacture of image and data recording media and in display systems.

~3UE~3TiTUTE SHEET

.:
~. : ' ' . .,~

W O 91/01312 2 0 6 5 0 ~ 5 PCT/GB90/01118 , An important class of photochromic compounds is based on bismethylenesuccinic anhydride or "fulgide" (I).

O
Il ,. .

2 ~ \
0 (I) CH2~ \~/

.
Such compounds are exemplified by those described in G~-1442628, GB 1464603, GB 2002752 and US 4220708. Thus, for example US-4220708 describes and claims a class of compounds of the formula ; A ~
~ ~ (II) 1~ .
O
; wherein X represents oxygen or NR6, R6 being hydrogen or an alkyl, aryl or aralkyl group;
R represents an alkyl or aryl group;
A represents a 3-furyl, 3-thienyl, 3-benzofuryl or 3-benzothienyl group; and ~-B represents an adamantylidene group or the grouping , R2 ' ::

~UB5TITUTE ~;HEEt ., ,- . : . ', `: ~ :

:
W O 91/0131~ 2 0 6 5 0 ~ ~ i PCT/GB90/01118 in which R2 and R3 independently represent an alkyl.
aryl, or a heterocyclic group containing a 3-furyl or 3-thienyl ring or one of R2 and R3 represents hydrogen and the other represents an alkyl or aryl group.

By appropriate selection of substituents on the 3-furyl, 3-thienyl, 3-benzofuryl and 3-benzothienyl groups represented by A
and by appropriate selection of groups X, R and B, photochromic compounds having a range of properties may be produced. Compounds of formula II in which B represents an adamantylidene group are preferred as they have a high quantum efficiency for bleaching of their coloured forms. They further show good thermal stability and the ability to undergo a large number of colour change cycles without substantial deterioration in the character of the absorption spectra as a result oP the formation of so-called "fatigue products"
of irreversible side reactions.
However the preferred compounds of US 4220708 in which B
represents adamantylidene are expensive to produce owing to the high cost of adamantanone used as a starting material. Also, for the known compounds and their coloured forms, only a relatively restricted number of characteristic wavelengths may be used to induce a photochromic change in structure and compounds having only a relatively restricted range of characteristic absorption wavelengths are available. These disadvantages impose limitations.
where for example it is wished to mass-produce data storage media economic 1ly, or where it is necessary to prcduce a photochromic SUBSTITUTE ~HEET

;:
- . , - .. ~ , ..
- . . '~
:

W 0 91/~1312 2 ~ ~ ~ 0 0 ~ ~^r compomnd having optical characteristics which match the characteristic ~avelengths of available sources of electromagnetic radiation, e.g. semi-conductor diode lasers.
A further difficulty with many known compounds is their limited solubility in organic solvents and limited capacity to form solid solutions with plastics materials. Photochromic compounds having a higher solubility than known compounds would be desirable in many fields. For example ln the production of security printing inks and varnishes it is desirable for the components of the inks to be soluble in the liquid ink base. In other methods of printing, higher solubility would enhance the formulation of solid solutions in plastics materials. Similarly :in order to produce thin, uniform coatings on data storage media, it is advantageous to use a coating fluid containing a photochromic compound in the dissolved state.
Currently available photochromic materials of limited solubility fail to satisfy these criteria.
Our International Patent Application No PCT/GB89/00155 describes and claims photochromic compounds having the general -formula O p2 pl~ pl~
F>C* ~ A or ~ A

O

(IIIa) (IIIb) `~UBSTITUTE ~HEET
:

- . .. -; - . . . .. . . . - . . . .

.- . : -:. , ~ .
.~- . . . "
..
- . : . ..

W O 91/01312 2 ~ ~ ~ O O ~ PCT/GB90/01118 wherein the substituents P , P , F>C*, L>C~ and A are defined as follows:
A represents oxygen or NR wherein R represents hydrogen, alkyl having l to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, aralkyl having 7 to 9 carbon atoms, aryl having 6 to 14 carbon atoms, which may be substituted with one or more halogen or al~oxy groups having l to 20 carbon atoms, or alkaryl having 7 to 22 carbon atoms;
pl represents 2 3-furyl, a 3-thienyl, a 3-pyrryl, a 3-ben7Ofuryl or a 3-benzothienyl group, each of which may be unsubstituted or subs~ituted by substituents defined below;
p2 represents a Cl_20 alkyl, a C3_l2 Y
C7_9 aralkyl, a C6_l4 aryl (which may be unsubstituted or substituted by one or more halogen atoms) or a C7 22 alkaryl group; and F>C* and L>C* represent a substituted or unsubstituted bridged polycyclic hydrocarbon residue containing from 7 to 20 carbon atoms in a polycyclic system, said residue having a plane of asymmetry which is par~llel to the plane which includes the single bonds extending from ca-bon atom C~ and the anhydride or imide ring, any substituents on the bridged polycyclic hydrocarbyl residue being selected from alkyl groups having l to 4 carbon atoms, halogen atoms and hydroxy groups.
According to the aforementioned International Application, the optional substituents on the 3-furyl, 3-thienyl and 3-pyrryl groups may be in the 2- and/or 5-positions.

SUBSTIT~JTE ~HEET

. . . . ...................... ` ~- ` .

. : ~ , - .
- ;.

: :
W O 91/01312 2 Q 6 ~ O Q S PCT/GB90/01118 The optional 5-substituents are selected from (i) Cl_20 alkyl groups, (ii) C3 12 cycloalkyl grouPs. , (iii) C3_l2 cycloalkenyl groups, (iv) C6 14 aryl groups, which are unsubstituted or substituted (a) with one or more alkoxy groups, (b) with a group of the formula -NR7R8, wherein ~7 and R8 each represent hydrogen or Cl 20 alkyl or together with the nitrogen to which they are attached represent a l-pyrrolidine, a l-piperidine or a l-morpholine group), or (c) with one or more halogen atoms, (V) C7_12 aralkyl groups, (vi) halogen atoms, and (vii) heterocyclic groups selected from 2-thienyl, 3-thienyl, 2-furyl and 3-furyl groups, said heterocyclic groups (vii) being unsubstituted or substituted by one or more Cl 3 alkyl groups or halogen atoms.

We have now found that a class of compounds of related structure to the aforementioned compounds of formulae (IIIa) and (IIIb) have particularly advantageous properties and particularly are capable of undergoing photoactive change to coloured forms with a range of colours that extends beyond that obtainable with the previously produced compounds. In particular, the new class of compounds according to the invention exhibit particularly advantageous bathochromic shifts and hyperchromic effects.

~UBSTITUTE 8HE~T

-, . - ... . ~ . - - '. . . .
.. ` . .

- :. ., . .- , ;; , , ;;
- , ,, , :
W O 91/01312 2 0 6 ~ O ~ ~ PCT/GB90/01118 -- 7 ~

According to the present invention there is provided a photoactive compound having the general formula pl ~ A
F>

(III) in which A represents oxygen or NRl wherein Rl represents hydrogen, alkyl having l to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, aralkyl having 7 to 9 carbon atoms, aryl having 6 to 14 carbon atoms, which may be substituted with one or more halogen or alkoxy groups having l to 20 carbon atoms, or alkaryl having 7 to 22 carbon atoms;
.- pl represents a 5-substituted 3-furyl, 3-thienyl, or 3-pyrryl group, said 5-substituted 3-furyl, 3-thienyl and 3-pyrryl groups being unsubstituted or substituted in the 2-position, said SUE3STITLJTE SHEEl~

.. - , . . . ..... .. .

W O 91/01312 2 ~ Q a PCT/GB90/01118 optional 2-substituents being selected from alkyl groups having l to 20 carbon atoms and aralkyl groups having 7 to 12 carbon atoms, and said 5-substituents being selected from (i) aryl groups having 6 to 14 carbon atoms, substituted with a group of the formula -NR7R8 wherein R7 and Rô each represent hydrogen or alkyl having l to 20 carbon atoms or together with the nitrogen atom to which they are attached represent a l-pyrrolidine, a l-piperidine, or a morpholine group, and (ii) heterocyclic groups selected from 2-thienyl, 3-thienyl, 2-furyl and 3-furyl groups, said last-mentioned 2-thienyl, 3-thienyl, 2-furyl and 3-furyl groups being unsubstituted or substituted by one or more Cl 3 alkyl groups or halogen atoms;
p2 represents alkyl having l to 20 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, aralkyl having 7 to 9 carbon atoms.
aryl having 6 to 14 carbon atoms which may be unsubstituted or ~ -substituted with one or more halogen atoms, or alkaryl having 7 to 22 carbon atoms; and F>C= represents a substituted methylene group, having at least two and preferably from 2 to 20 carbon atoms.
In a preferred class of compounds, F>C= is an unsubstituted hydrocarbyl radical. However the invention also includes compounds in which wherein F>C= is a substituted hydrocarbyl radical, e.g. one having one or more substituents selected from hydroxy, oxo, halogen, -S03H and COOH.

.. . ', ' ' ' ' :' ` ' ' ' ' ' ' ~ "~ ' , ' , ' .. , ' ' : ' .

. ' . ' ' ' ' ' ' '. . .. . ' ~ . , j. .

_ g _ Specific exa~ples of groups F>C= include those having the structure in which R and R3 independently represent hydrogen, Cl 20 6-14 aryl, C7_l2 alkaryl, C7 12 aralkyl, C3 12 cycloalkyl, heterocyclic group containing 5-12 atoms arranged in one, two or three rings (including bicyclic structures) and having at least one hetero-atom selected from N, S and O (with the proviso that R2 and R3 are not both hydrogen~, or R and R3 together represent a divalent cyclic or polycyclic hydrocarbyl group.
One or more of said al~yl, aryl, alkaryl, aralkyl, cycloarlkyl, heterocyclic or polycyclic groups representing Rl and R2 may be substituted for example by one or more of the substituents referred to above in relation to F>C=.
In a preferred class of compounds, symbol F>C represents V / C33/ C= ~

SUBSTITUTE SHEET

- . ... - . . .......... ;. . ............. . - .. .. .

, . .. . . ... .. . ~ . . ..

:

W O 91/01312 2 0 6 ~ O O S PCTIGB90/01118 From amongst the de~inition of pl above. the following structures re preferred.
f~ '.
X Q y where Q is oxygen or sulfur, Y is Cl_4 ~lkyl :
X is selected from;

(a) a 4-substituted phe~yl group to the formula ~.
R`N ~

wherein R3 and R each represents a C1 4 alkyl group : or together with the nitrogen atom to which they are attached form a pyrrolide, piperidine or morpholine group.
, (b) a 2-thiophene group optionally substit1ted in the 3- and/or 5-positions by a Cl 4 alkyl group.

(c) a 3-thiophene group optionally substituted in the 2-and/or 5-position with Cl 4 alkyl groups.
.
SUBSTlTUTE ~iHEET
-' - . , . ., . :. . . .
. - . -, . . , . i, :

W O 91/01312 ~ ~ ~ 5 ~ ~ PCT/GB90/01118 Examples of coopounds according to the invention which are preferred are those in which P represents:
5-(p-diethylaminophenyl)-2-methyl-furan-3-yl, 5-(p-piperidinophenyl)-2-methyl-furan-3-yl, 5-(p-pyrrolidinophenyl)-2-methyl-furan-3-yl, 5-(2-thienyl)-2-methyl-furan-3-yl, 5-(3-thienyl)-2-methyl-furan-3-yl, 5-(2,5-dimethyl-3-thienyl)-2-methyl-furan-3-yl, 5-(2-thienyl)-furan-3-yl, or 5-(2,5-dimethyl-3-thienyl)-furan-3-yl.

As indicated above, the compounds of formulae (III) are photoactive. That is to say compounds of formulae (III) are capable of undergoing a structural change when subjected to electromagnetic radiation of a selected wavelength or wavelengths and undergo a reversal to their original form when subjected to thermal energy or to electromagnetic radiation of another wavelength.
The use of the compounds of formula III in the manufacture of image and data recording media thus forms a further aspect of the invention.

SUBSTITUTE ~;HEET

W 0 91~01312 2 0 6 ~ O ~ ~ PCT/GB90/01118 The compounds of the invention of formula (III) may be prepared by the Stobbe condensation from a lower dialkyl succinates, e.g. diethyl succinate.
Advantageously a modification to conventional Stobbe reaction conditions is employed which will be discussed in further detail below and forms a further aspect of the invention.
Various sequences of reaction may be used, e.g. the sequences referred to as "Sequence l" and "Sequence 2" below.
The ~roduction of compounds of formulae (III) by Sequence l is as follows:
Seouence l In a first step a ketone (VI) is reacted with a di-lower alkyl succinate (VII, R = lower Cl 4 alkyl) CH -COOR FC>=C-COOR
1 2 >
F>=O ~ ¦ I

(VI) (VII) (VIII) to yield condensation product VIII. The reaction is carried out in the presence of a basic catalyst e.g. as described in more detail below.
Condensation product VIII is esterified to form the diester (IX, R = lower alkyl) which is then reacted with a ketone PlCOPZ
F>C=C-COOR F>C=C-COOH
+ plcoP2 >
CHz-COOR 1 ~ -COOR

p2 (IX) (X) SU BSTITUTE S H E~ET

.

-~ . . . .
. ~ .
. ~

Half-ester X is hydrolysed to form the corresponding dicarbcxylic acid and then converted into the desired compound of formula III by treatment with 8 dehydrating agent (e.g. 2n acyl halide) to form a compound in which A is oxygen, which in turn can be converted into a compound in which A represents NRl by reacting with an amine H2NR .
The production of compounds according to the invention by Sequence 2 will now be described.
Sequence 2 In a first step, a ketone P COP may be reacted with a di-lower alkyl succinate (VII, R=lower Cl 4 alkyl) l 2 CH2-COOR > CH2-COOH
P COP
CH2-COOR ,/C-COOR
,pl /

(VII) (XI) to yield a condensation product XI. The reaction is carried out in the presence of a basic catalyst, e.g. as described in more detail below.
Condensation prodùct XI is esterified to form the diester (XII, R=lower alkyl) which is then reacted with a ketone (VI).

CH2-COOR F>C=C-COOR
¦ I F>CO
C~7 (VI) > c//c C

(XIII) (XII) SUBSTtTUTE ~;HEET

, .: . . . .. : . . .. . . . . . .

W O 91/01312 2 0 6 5 0 0 ~ PCT/GB90/01118 _ la -Half-es~er (XIII) is hya-olysed ~o form the corresponding dicarboxylic acid and then converted into the desired compounds IIIa and mIIb as desc-ibed above.
Conventionally, in car-ying out a Stobbe condensation in wnich a ketone is condensed with a dialkyl succinate. the reaction is generally carried out in ethanol or t-butanoi, esing sodium ethoxide or potassium t-butoxide as catalyst respec~ively.
Alternatively the reaction has been carried out in ;oiuene, usin~
sodiu~ hyc_ide plus a t ace of ethanol. as catalyst.
Yields ootainaoie with e.~isting react on ~e~ a ar.d ca~alys~s can be low, partic lar~y when the reactants are ste-ically hindered.
.~s indicated in the aforementioned International Pa~ent Application No. PCT/GBo9/0015~, it has unexpectedly been found that a particular catalyst/reaction medium combination gives improved high yields.
Thus according to this procedure, a condensation product between a lower alkyl ester of succinic acid ~or a methylene derivative of succinic acid in which at least one of the hydrogen atoms of the methylene groups is replaced by a subs;ituent whicn does not interfere with the reaction) and a ketone, is formed by reacting said ester and said ketone in the presence of an aroma~ic hydrocarbon, preferably toluene, and an alkali metal alkoxide, preferably potassium t-butoxide.
Applied to the production of compounds according to the invention, (Sequence l) there is provided a process for producing a compound of formula 5U~3STITUTE 5HEET

.
.
.

WO 91/01312 2 ~ ~ 3 0 () !~ PCI~GB90/01118 r > C= C~OOR
( VIII ) c,U,2~00H

wnerein R and F>C are as defined above which comprises rescting a di-lower alkyl succinate of general formula CH .COOR
1 2 (VII) C'~2 COOR

whereln ?~ is as derinea above wi-h a ketone o. .ormuia F>C=CO (XIII) wherein F>C is as de~ined above, characterised in that the reaction is carried out in a reaction medium comprising toluene and in the presence of potassium t-butoxide as catalyst.
The resulting compound of formula (VIII) may then be este-if_ed to form a compound of formula IX :
:

F> C=C--COOR
(IX) ~ ,, CH2--COOR :

and reacted with a ketone of formula P1COP2, wnerein pl and p2 are zs defined above to form 2 compound of formula ~

~IUBSTITU I E SHEET

W 0 91/01312 2 0 6 5 O O ~ PCT/GB90/01118 According to (Sequence 2) there is provided a process for producing a compound of fo-mula ¦ (XI) /C--COOR
vl~ , wAerein R, pl ar.d D- are as defined above which comprises reac ing a di-iowe~ aikyl succ nate of general formula C'2 COOR
I (VII) CH2.COOR

wherein R is as cefined above with a ketone of formula D -, p CO ~ XIII) wherein pl and p2 are as defined above, characterised in that the reaction is czrried out in a reaction medium comprising toluene and in the presence of potassium t-butoxide as catalyst.
The resulting compound of formula (VI.-) may then be ester~fied to fo-m a compound of formula IX

.

~ -COOR

P p2 and reacted with a ketone of formula F>CO (XII_), to form a compound of formuia (III).

~3UBSTITUTE ~;HEET

- . , . . . . . ~ . .. .

: .: , W O 91/01312 2 0 ~ ~ O Q 5 PCT/GB90/01118 .he proauc~lon ~I photoa_~ ve co~Dounas accor-ing ~o th~ lnven~-on.
znd thei~ ~?~ cai proper-ies ~;'1 now D' desc.~De~ o~e de~a -:~e following _xamDies.

Exam~lQ 1 E-c~-5-(p-Die,hy,aminorinenyl)-2-metnyl-3-furyl2thylicene(isoDroDyiibenej succinic annydride (Vla. Z = aiethyiamino) The ketone (I, R = diethylamino) (5 9, 18 mM) was abded to a solution of potassium t-butoxide (2.3~ 9, 21 mM) in tetrahydrofuran (7~ nl) and the mixture cooled below 5C. Diethyl isopropyiidene succinate (2a, R = elhyl) (4.74 g, 22 mM) in tetrahydrofuran (2~ ml) was added dropwise with stirring.
When the addition was complete, the reaction mixture was stirred at room temperature for 1 hour. Water (25 ml) W2S added and tetrahydrofuran and water were removed under reduced pressure.
Water (25 ml) was added and the aqueous solution was extracted with ether ~ :
to remove neutral biDroducts. The aqueous layer was very carefully acidified liberate the half-ester (lla, Z = diethylamino) whicn was extracled with chloroform and dried over anhydrous magnesium sulphate. The ex~rac~ was filtered and the solvent removed. The residual iight brown oil of the half ester was hydrolysed by boiiing with 10% ethanolic potassium hydroxide (20 ml) for 1 hour. The mixture was cooled, water (25 ml) W2S added, and most of the ethanol removed by distillation under reduced pressure. The solution was very carefully acidified with ~ M hyarochloric acid to liberate the diacid (Illa, Z = diethylamino) which was extracted with chloroform, dried over .
anhydrous magnesium sulphate and filtered. The solvent was removed from the filtrate to leave the biacid which was conver;ed into the fulgides (IVa, Z =diethylamino) (both isomers) by treatment with acetyl chloride (20 rnl) followed by removal of the excess acetyl chloriae unber reduced pressure.
The mixture of E- and Z-fulgides were recn/stallised from ethanol.

EET

. .. . ~ .. .- . . . .. . . .. ... .

., . ;.. ... ..
. . : ~, :. .

~ i ... ., ~ .

Wo 91/01312 2 0 6S Q~ pcr/GB9o/ol3l8 _xamole ~ - -p-Piperiaincphenyl)-~-me~hyl-3-furvietnyiic~nc (isc~,^pylicane) succinic annydride (IVa Z = aiethyiaminoj The reaction was carriea out as Tcr Example 1 exce?t t ~t ketcne (I. Z =
?iperidino) (5 9) was used in place of ketone (1. Z = biethylamino).

-xamole 3 E-cc-5-(p-Pyrrolidinophenyl)-2-methyl-3-Turylethylidene~isopro,oyiibene) succinic anhydride (IVa Z = pyrrolidino) The reaction was carried out as for Example 1 except that ketone (1 Z = ~ .
pyrrolidino) (~ g) was used in place of ketone (1 Z = diethylamino).
The coloured form in toluene after irradiation of the (E) fulgide (IVc. Z =
pyrroiidino) has a molar extinction coefficient OT over 2~.250 dm~cm-~m^l-~.
at 588 nm the maximum cf the absorption banc in the visibie recic ..
, Examo!e 4 E-c~-5-(p-Diethylaminophenyl)-2-methyl-3-furylethylidene(abamantylidene j succinic anhydride (IVd. Z = diethylamino) The reaction was carried out as for Example 1 except that diethyi adamantylidene succinate (6 9) (2di R = ethyl) was used in place OT diethyl isopropylidene succinate (2a R = mëthyl).
The coloured form in toluene after irradiation OT the (E)-Tulgide (IVd. Z =
diethylamino) has a mo~ar extinction coefficient OT over 18 500 dm~ cm-~mol-1 at 612 nm the maximum of the absorp~ion banb in the visibie region.

~3UBSTITUTE SHEFT

: .

~ n '~ PCrlGB90101118 WO 91/01312 ~ lJ 3 -~2mDle ~
_--~-(2~.hienyl)-~-,mQTnyl-3-,'ur/ir-thyiiCiene(iSODrC?yiibr-r_ ) su. ^inic 2nhycride (-va, X_ 2-thienyl).

I ne ketone (1, X= 2-thienyl) (10 9, 48 mM) was 2baed to a solulicn OT
uotas-aium t-i~utoxide (6.46 9, ~ mM) in tetrahydrofurcn (2~v~ ml). T ile miXlUre W25 cooled below 5C 2nd diethyl isopropylidene suc-inG;e (22, R =
ethyl) (1 0.2a 9, 48 mM) wzs added dro?wise with stirring. After 1 hour, Ih re2clion mix~ure was allowed to warm up to room temper2~_re 2r.c wcs s,irred for a fur~her 12 hours. Mcst of the tet,ahy~rolulan wcs remover urc_r reauceci pressure ana ether (100 ml) was 2cibeci. The elhe!ea, soiu~icn ','~'-â
exlr~c~ed wilh waler 2nd the c^,"~ined csueous ex~,2r~-a w re _^;ai,lea w,~.- .
c ,n~. nycrocnloric 2c,c. The iiberaled hclf-esler (3a, X _-2-.hienyi. R = e W2S extracted ~ith ether. The elher layer W25 crieb over arînyarous magnesium sulphate and filterecl. Solvenl was removeb frc~ tne ,iilr2te 2ra the residual dark oil containing the half-ester (14.7 9) was hydrolysed wi;h ~ :
10% ethanolic polassium hydroxide (150 ml). On cooling, the dipotassium salt ot the diacid (4a, X= 2-thienyl) crystallised. The ~alt was filterea off, dissolved in water and acidified with concentrated hydrochloric acid, giving the diacid in 68% yield. The diacid (5.14 9, 15 mM) wzs dissolved in ether (150 ml) and treated with acetyl cnloride (10 ml). Excess 2celyl chlorice cnd ether were removed by distillation and the E-fulgide (va, X = 2-thienyl) was c ys.Gliised from a mix~ure of ethanol, acelic ac.c, anb elhyl -ce.^-~e. givinS
yellow crys;als 1 82-4C. :

Ex2m~1P 6 E-a-v~-(3-thienyl)-2-methyl-3-furylethyiidene(isoDropyiidene) succinic anhydride ~5a, X = 3-thienyl).

The reaction was carried out zs for example ~ except that tne ke~one (1, X=
3-thienyl) was used in place OT ketone (1, X= 2-thienyl). .

The Z-isomer of the proauc~ w2s oDtainea câ c^~urleSS crvs.2is ,rvm elnar,vi m.?. 1 .g-1~0C.
SUBSTlTUTE SHEET

WO 91/0131_ 2 0 ~ PCl~GB90/OlllB

cxamr~e 7 c--5-(2~-cilll2tnyl-3-thienyi)-3-furyie~hyii~eneiis~J?r~ yiiG-ne) sucrinic anhydride (52. X = 2.5-dimethyl-3-,hienyl).

The reaclion was carried out 2S ior examDle ~ eXcepl tr,_' the ketone (1, X =
2,~-dimethyl-3-thienyl) was used in place of ketone (1, X = thienyl).

The produc. was oJtained 25 r,ear c~louness crysL2!s..,..~. 16~-16r~C.

Cxamcle 8 E-o-5-(2-thienyl)-3-furylethylidene(dicyclopropyimethyiene) succinic anhydride (::)b X = 2-thienyl).

The reaction was carried out as for example 5 except that dimethyl dicyclopropylmethylene succinate (2b, R = methyl) was used in place of diethyl isopropylidene succinate (2a, R = ethyl).

Examole g E-c~-~-(2-thienvl)-3-furylethylidene (adamantyliaene)suc--lc annyoride '-c.
X = 2-thienyl).

The reaction w2s carried out as for example ~ except that dimethyl adamantylidene succinate (2c, R = methyl) W2S used in place of diethyl isopropylidene succinate (2a, R = ethyl).

SUE3STITUTE ~;HEET

- ~ . . ~ . ~ . , ", WO 91tO1312 ~ O () ~ PCT/GB90/01118 ,, ~ .

, _xamr~i- 10 E-cL-5-(2,5-dimethyl-3-thienyl)-3-furyiethyiiaene(bicyc!opropylmethylene) succinic anhydride (5b, X = 2.5-ciimethyl-3-thienyl).

2,5-Dimethyl-3-acetylthiopnene (1, X = 2,5-dimethyl-3-thienyl) (50 9, 0.33 M) and dimethyl dicyclopropylmethyiene suc_,nate (2c, R = methyl) (74 9, 0.33 M) in dry toluene (100 mi) was csaed dropwise, with s~irrins, over 1 nour to potassium t-butoxide (60 9, 0.53 M) in dry toluene (500 ml) at 0C. After 1.a hours water (1 1) was adbeb anc the aqueous layer s-parated. Acibi,ica~ion (5M HCI) and extraction with ether (2 x 300 ml) gave a solution which was dried (Mg S04) and filtered Removal _f soivent from the filtrate gave a near quantitative yield of crude half-ester (~b, X = 2,5-dimethyl-3-thienyl). The half-ester was hydrolysed with KOH (50 9) in isopropanol (500 ml) by boiling for 1 hour. The reaction mixture was left overnight. The potassium salt of the diacid was filtered off, washed with acetone (1 1) and suspended in dry toluene (500 ml) and Na2CO3 (20 g) added. Acetyl chloride (~0 ml) was added dropwise with stirring over 1 hour. After a fur~her 30 min, the solution was filtered, and the solid residue was washed with acetone (2 x 75 ml). The organic solutions were combined and the solvent removed. The fulgide (~, X = 2,~-dimelhyl-3-thienyl) (both isomers) was crvs;allised from 2-propanol.
Yield 26.~ 9.

SU~STITUTE ~HEET

Claims

1. A photoactive compound having the general formula (III) in which A represents oxygen or NR1 wherein R1 represents hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, aralkyl having 7 to 9 carbon atoms, aryl having 6 to 14 carbon atoms, which may be substituted with one or more halogen or alkoxy groups having 1 to 20 carbon atoms, or alkaryl having 7 to 22 carbon atoms;
P1 represents a 5-substituted 3-furyl, 3-thienyl, or 3-pyrryl group, said 5-substituted 3-furyl, 3-thienyl and 3-pyrryl groups being unsubstituted or substituted in the 2-position, said optional 2-substituents being selected from alkyl groups having 1 to 20 carbon atoms and aralkyl groups having 7 to 12 carbon atoms, and said 5-substituents being selected from (i) aryl groups having 6 to 14 carbon atoms. substituted with a group of the formula -NR7R8 wherein R7 and R8 each represent hydrogen or alkyl having 1 to 20 carbon atoms or together with the nitrogen atom to which they are attached represent a 1-pyrrolidine. a 1-piperidine.
or a morpholine group, and (ii) heterocyclic groups selected from 2-thienyl, 3-thienyl, 2-furyl and 3-furyl groups, said last-mentioned 2-thienyl, 3-thienyl, 2-furyl and 3-furyl groups being unsubstituted or substituted by one or more C1-3alkyl groups or halogen atoms;
P2 represents alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, aralkyl having 7 to 9 carbon atoms.
aryl having 6 to 14 carbon atoms which may be unsubstituted or substituted with one or more halogen atoms, or alkaryl having 7 to 22 carbon atoms; and F>C= represents a substituted methylene group, having at least two carbon atoms.

2. A compound according to Claim 1 wherein F>C= has from 2 to 20 carbon atoms.

3. A compound according to Claim 1 or Claim 2 wherein F>C= is a hydrocarbyl radical.

4. A compound according to Claim 1 or Claim 2 wherein F>C= is a substituted hydrocarbyl radical. having one or more substituents selected from hydroxy, oxo, halogen, -SO3H and COOH.

5. A compound according to Claims 1 to 4 in which F>C= has the structure in which R2 and R3 independently represent hydrogen, C1-20 alkyl, C6-14 aryl, C7-12 alkaryl, C7-12 aralkyl, C3-12 cycloalkyl, a heterocyclic group containing 5-12 atoms arranged in one, two or three rings (including bicyclic structures) and having at least one hetero-atom selected from N, S and 0 (with the proviso that R2 and R3 are not both hydrogen) or R2 and R3 together represent a divalent cyclic or polycyclic hydrocarbyl group.

6. A compound according to Claim 5 wherein one or more of said alkyl, aryl, alkaryl, aralkyl, cycloalkyl, heterocyclic or polycyclic groups representing R2 and/or R3 is substituted by one or more substituents as defined in Claim 4.

7. A compound according to Claim 4 wherein the symbols F>C
represents

8. A compound according to any preceding claim wherein P2 represents methyl.

9. A compound according to any preceding claim wherein P1 represents a group or structure where Q is oxygen or sulfur.
Y is C1-4 alkyl X is selected from:

(a) a 4-substituted phenyl group to the formula wherein R3 and R4 each represents a C1-4 alkyl group or together with the nitrogen atom to which they are attached form a pyrrolide, piperidine or morpholine group.

(b) a 2-thiophene group optionally substituted in the 3 and/or 5-position by a C1-4 alkyl group.

(c) 2 3-thiophene group optionally substituted in the 2-and/or 5-position with C1-4 alkyl groups.

10. A compound according to any preceding claim wherein the moieties F>C= are selected from groups of the following formulae:

11. A compound according to any preceding claim wherein P1 represents 5-(p-diethylaminophenyl)-2-methyl-furan-3-yl, 5-(p-piperidinophenyl)-2-methyl-furan-3-yl, 5-(p-pyrrolidinophenyl)-2-methyl-furan-3-yl, 5-(2-thienyl)-2-methy1-furan-3-yl, 5-(3-thienyl)-2-methyl-furan-3-yl, 5-(2,5-dimethyl-3-thienyl)-2-methyl-furan-3-yl, 5-(2-thienyl)-furan-3-yl, or 5-(2,5-dimethyl-3-thienyl)-furan-3-yl.

12. A compound according to any preceding claim wherein P2 represents a methyl group.

13. Use of a coupound as claimed in any of Claims 1 to 11 in the manufacture of image and data recording media.