(Thio) (meth) acrylate monomers, intermediate compounds for...

Details (Thio) (meth) acrylate monomers, intermediate compounds for... (Thio) (meth) acrylate monomers, intermediate compounds for...

2001-09-20

2002-10-29

Lipman, Bernard (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C549S011000, C549S018000, C549S021000, C549S022000, C549S031000, C549S032000, C549S037000

Reexamination Certificate

active

06472488

ABSTRACT:

The present invention relates, in general, to novel (thio)(meth)acrylate monomers, preferably mono(thio)(meth)acrylate monomers, which are useful for the formulation of polymerizable compositions leading to transparent homopolymers and copolymers that are suitable for optical and ophthalmic uses.
The polymerizable compositions according to the invention allow the manufacture of moulded articles made of transparent polymer, which is preferably thermoplastic, by polymerization in moulds or by injection-moulding.
The transparent polymers obtained, which have refractive indices of medium to high value, 1.54 or more, are particularly suitable for optical and ophthalmic uses.
Among the optical uses of the polymers according to the invention, mention may be made of wave guides and optical fibres.
Among the ophthalmic uses of these polymers, mention may be made of spectacle lenses and contact lenses.
In general, novel monomers according to the present invention are functional monomers of mono(thio)(meth)acrylate or mono- and di(meth)acrylate type bearing a 5- to 8-membered heterocycle consisting of hydrogen, carbon and sulphur atoms and having at least two endocyclic sulphur atoms. Preferably, the heterocycle is 6- or 7-membered, better still
6
-membered. Also preferably, the number of endocyclic sulphur atoms is 2 or 3. The heterocycle can optionally be fused with a substituted or unsubstituted C
5
-C
8
aromatic or polycyclanic ring, preferably a C
6
-C
7
ring.
When the heterocycle of the functional monomers according to the invention contains 2 endocyclic sulphur atoms, these endocyclic sulphur atoms are preferably in positions 1-3 or 1-4 of the heterocycle. According to the invention, the monomer is preferably also a thio(meth)acrylate monomer. Lastly, the monomers according to the invention preferably have molar masses of between 150 and 400, preferably 150 and 350 and better still between 200 and 300.
More particularly, the novel functional monomers according to the invention correspond to the formula
in which Z represents H or CH
3
(preferably CH
3
) and X represents O or S, and
when X represents S, Y represents a radical of formula:
where R
1
and R
2
are chosen from H, alkyl radicals, preferably C
1
-C
4
alkyl radicals and better still the CH
3
radical, or alternatively R
1
and R
2
together form a (CH
2
)
5
radical, and n
1
is an integer from 0 to 2 inclusive, and
when X represents O, Y represents the radical (a) defined above or a radical chosen from the radicals of formulae:
in which n
2
is equal to 1 or 2, R
3
represents H or an alkyl radical, preferably a C
1
-C
4
alkyl radical and better still a CH
3
radical, R
4
represents H or an alkyl radical, preferably a C
1
-C
4
alkyl radical and better still a CH
3
or C
2
H
5
radical, and R
5
is a divalent radical chosen from the groups of the following formulae:
in which:
A denotes an aryl group, preferably a C
6
-C
12
aryl group and better still a phenyl group, or an alkyl group, preferably a C
1
-C
6
alkyl group,
R′ and R″ denote, independently of each other, H, an alkyl group, preferably a C
1
-C
6
alkyl group, aryl, preferably phenyl, or R′ or R″ can be a group
where R
a
is an alkylene group, preferably a C
1
-C
6
alkylene group, in particular a —CH
2
— group, and R
b
is H or CH
3
,
n takes the values 0 or 1 and 0≦m (integer ≦4), and
 R
6
denotes H or CH
3
, and
Cy denotes a substituted or unsubstituted aryl ring, preferably a phenyl, tolyl or norbornyl ring.
Preferably, R
5
is a divalent radical chosen from:
The monomers according to the invention which are particularly recommended are the thio(meth)acrylate monomers corresponding to the formula (A) above in which X represents a sulphur atom and Y is a radical of formula (a).
The monomers according to the invention can be prepared by various known synthetic processes.
Among the mono(thio)(meth)acrylic monomers which are preferred according to the invention, mention may be made of the monomers of formulae:
Among the di(meth)acrylic monomers which are preferred according to the invention, mention may be made of the monomers of formulae:
in particular the dimethacrylate.
The remainder of the description gives various examples of the synthesis of the monomers according to the invention.
I.1 Synthesis of the Diesters Ia, IIIa and IVa
0.2 mol of ethyl mercaptoacetate (2 eq) in 30 ml of toluene and 1 ml of concentrated sulphuric acid is introduced into a 250 ml three-necked flask equipped with a condenser.
The reaction mixture is brought to a temperature of 80° C., followed by dropwise addition of either 0.1 mol of formaldehyde as a 36% solution in water (stabilized with methanol) in the case of the preparation of compound Ia, or 0.1 mol of acetone or cyclohexanone in the case of compounds IIIa and IVa.
After this addition, the reaction mixture is maintained at 100° C. for 2 hours. Stirring is then continued overnight at room temperature.
The reaction mixture is concentrated under reduced pressure. The residue is taken up in dichloromethane and washed successively with 5% sodium hydroxide solution and then with water.
The organic phase is dried over sodium sulphate, filtered and then concentrated under reduced pressure.
The product thus obtained is purified by distillation under reduced pressure.
Yield=76%. Boiling point=126° C./0.1 mmHg.
Yield=78% Boiling point=131° C./0.1 mmHg.
Yield=96% Boiling point=165° C./0.3 mmHg.
I.2 Dieckmann Cyclization: Use of Sodium Methoxide in Ether
0.1 mol (2 eq) of freshly prepared sodium methoxide is suspended in 70 ml of anhydrous ether; 0.05 mol (1 eq) of diester dissolved in 20 ml of anhydrous ether is added dropwise at room temperature. The reaction mixture is then stirred for ten hours at reflux. The reaction mixture is allowed to cool to room temperature and is then poured into a water-ice-acetic acid mixture.
The aqueous phase is extracted with twice 60 ml of ether. The ether phases are washed with dilute sodium hydrogen carbonate solution and then with water.
The organic phase is dried over sodium sulphate and concentrated under reduced pressure.
The &bgr;-keto esters thus obtained are used crude in the remainder of the synthesis.
I.3 Decarboxylation of &bgr;-keto Esters in Hydrochloric Acid Medium
0.05 mol of &bgr;-keto ester and 120 ml of 1N hydrochloric acid solution are introduced into a round-bottomed flask equipped with a condenser. The reaction mixture is maintained at 100° C. for a minimum of 20 hours. The reaction mixture is taken up in 100 ml of ethyl acetate. The aqueous phase is neutralized with sodium hydroxide solution to pH 5.
The organic phase is then washed successively with water and then with saturated sodium chloride solution.
The organic phase is dried over sodium sulphate and then concentrated under reduced pressure.
The thiacycloalcan-3-ones thus obtained will be purified by chromatography on silica gel.
Yield=79% relates to the preceding two steps. Melting point=101° C.
Yield=28% relates to the preceding two steps. Purification eluent: 9% ethyl acetate/91% petroleum ether.
Yield=88% relates to the preceding two steps. Purification eluent: 10% ethyl acetate/90% petroleum ether.
I.4 Reduction of a Ketone with LiAlH
4
in THF
0.05 mol (1 eq) of lithium aluminium hydride suspended in 20 ml of anhydrous tetrahydrofuran is introduced, under a nitrogen atmosphere, into a three-necked flask fitted with a condenser, a stirrer and a dropping funnel.
0.05 mol (1 eq) of the ketone obtained in step I.3, dissolved in 10 ml of tetrahydrofuran, is then added dropwise at room temperature.
After addition, the reaction mixture is refluxed for 12 hours. The solution is then allowed to cool to room temperature. The reaction mixture is cooled to 0° C. in order to be hydrolysed with 20 ml of water.
The solution is then poured into 60 ml of 10% sulphuric acid solution. The organic phase is separated out and the aqueous phase is extracted with three times 60 ml of ether. The combined ether phase

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