FR2657082A1 - Non-centrosymmetric polymolecular combinations and their uses especially in non-linear optics - Google Patents

Abstract

The invention relates to non-centrosymmetric polymolecular combinations and to their uses especially in non-linear optics. The compounds according to the invention contain at least the following repeat unit (I): in which C is an organic structure containing a system of double bonds providing a stable, substantially two-dimensional conformation and 2 Jc sets, sites capable of forming hydrogen bonds with G; in which G is an organic structure containing a system of double bonds providing a stable, substantially two-dimensional conformation and 2 Jg sets, sites capable of forming hydrogen bonds with C; in which B is a radical, the orientation of which is desired, capable of providing, for example, a high N.L.O. activity; in which the ":" sign symbolises the hydrogen bonding system established between one of the said C sets and one of the said G sets; in which K symbolises a hydrocarbon chain system.

Description

The invention relates to non-centrosymmetric polymolecular associations and their uses in particular in non-linear optics.

 More precisely, the invention relates to polymolecular associations whose motifs are oriented in the same direction using the specificity of the hydrogen bonding systems, according to a concept known as molecular recognition. This type of compound, hereafter designated by polymer, solves many problems, and has many applications.

 In order not to burden the description, the problem posed by the non-orientation of the patterns will only be developed in the latter in the field of non-linear optics, and in particular in the case of polymers active in O.N.L. (non-linear optics).

 As J. Zyss and I. Ledoux indicate in the article published in "L'ECHO des RECHERCHES", 1st quarter 1987 under the title "Organic molecules and optical signal processing", the development of optical telecommunications requires the realization of components using materials of high non-linear second or third order susceptibility.

 Many compounds, both inorganic and organic, are used in different forms such as solutions, polymers, doped polymers, monomolecular layers, liquid crystals, single crystals, liquid crystal polymers or the like.

 Organic compounds are very interesting because the synthesis of a very wide variety of products is generally possible. In addition, most organic compounds have a high resistance to external aggressions (humidity, acidity, oxidation, etc.) and can be added to materials such as polymer films or the like.

 J.F. Nicoud and R.J. Twieg in their thesis entitled "Design and synthesis of organic molecular compounds for efficient second harmonic generation" Ed. D.S. CHEMLA and J. ZYSS, 1987 list different molecules likely to be active in nonlinear optics.

 These molecules have as carbon skeleton chains generally comprising aromatic rings substituted on the one hand by electron donor groups and on the other hand, electron acceptor groups.

 The delocal i sati on of the electrons generates strong hyperpol ari sabi lity of the third and second orders when the molecule is non-centrosymmetric.

 Significant research efforts are continually being developed to discover and manufacture new compounds with activity in nonlinear optics.

Numerous patterns are already known having activity in non-linear optics
These patterns are generally made up of at least one electron donor group and at least one electron acceptor group linked together by pi electron conjugation systems (conjugated double bonds and / or aromatic systems).

In a large number of cases these patterns are inserted physically or chemically in a polymer and it is arranged so that the orientation of these patterns deviates sufficiently from the random distribution to obtain the property of being active in non-optical linear
In general, the selective orientation is obtained by subjecting the polymer with its patterns to the fluid being to an electric field, then it is stabilized by solidification and / or crosslinking of the polymer.
the main part of the research focused on the choice and improvement of the active units and on their insertion into the polymer and on the stability of the anisotropy following their oriented insertion.

 during these studies, however, it was shown that the results were all the better when the elementary patterns were large and had a high polarity - polarizability.

 Conceptually, one of the best means of obtaining such a combination of properties would be to produce patterns which would oligomerize, or even polymerize, always keeping the same orientation of the donor and acceptor groups.

 To date and to the knowledge of the applicant, no system of this type has given satisfaction or even been studied.

 The problem of the orientation of the patterns arises "mutatis mutandis" in various other fields such as that of dielectrics.

This is why one of the aims of the present invention is to provide a means of associating several patterns, for example active in ONL (Optics No
Linear) so that they have the same orientation
Another object of the present invention is to provide polymolecular associations forming sequences of repeating units oriented in the same direction, sequences which in the following description will be designated by the term "polymers".

These aims and others which will appear subsequently are achieved by a non-centrosymmetric polymereroid compound comprising at least the following recurring motif (I)
BC: G (I)
I
K in which C is an organic structure comprising a double bond system ensuring a substantially flat stable conformation and 2 sets Jc of sites capable of forming hydrogen bonds with G in which G is an organic structure comprising a double bond system ensuring a conformation stable substantially flat and 2 sets Jg of sites capable of forming hydrogen bonds with C in which B is radical whose orientation is desired, for example, capable of ensuring a high ONL activity; in which the sign "symbolizes the hydrogen bonding system established between one of said sets of C and one of said sets of G; in which K symbolizes a system of hydrocarbon chain (s)
Said hydrogen bonding system being such that to each site D of structure C corresponds a site A of structure G and to each site D of structure G corresponds a site A of C; the sites D and A being respectively functions carrying at least one hydrogen atom capable of giving hydrogen bonds and functions carrying a doublet capable of forming a hydrogen bond.

There are at least two sites per so-called site sets.

Advantageously, said sites D are chosen independently from the group consisting of:
NH;
OH ;
SH;
CH;
Advantageously, said sites A are independently chosen from the group of functions comprising an oxygen, nitrogen or sulfur atom, and in particular the following functions = O; O; = N; = N-; -NOT ; = S;
4
The best results are achieved when the D sites are independently selected from the group consisting of: NH, OH, and when the A sites are independently selected from the group consisting of \ II = 0; O; = N; -NOT-.

The control of the specific orientation can be considerably facilitated by playing on the K system of hydrocarbon chain (s)
Control can also be obtained by arranging so that each type of site game does not have internal symmetry.

 The sequential arrangement of the sites of each game can be such that there is symmetry or not.

 These two types of measures are not contradictory and can be used simultaneously.

 The sites are advantageously located topologically so that the z i ai intra-molecular hydrogen bonds are as weak as possible, and in particular weaker than the intermolecular bonds between the site concerned and its counterpart.

In general, the sets of sites of the same structure have an axis of symmetry which makes it possible to deduce a set of sites by knowing the other. This symmetry does not necessarily extend to the rest of the structure.

 The axes of symmetry of Jc and Jg are preferably parallel to each other.

To obtain good results, a set of sites of a structure, must not be able to be associated with a set of the same structure, (ie to give associations of the type Jg: Jg or Jc: Jc ) as strongly as the associations Jc: Jg. An odd number of sites per game allows for example to observe this constraint.

For each structure, a site can be common to the two games.

The sets of associated sites (Jc Jg) can be deduced from the associations known in biology, and in particular in genetics: for example, we can cite the associations:
Cytosine - Isocytosine
Guanine - Cytosine
Adenine - Uracile
Mention may also be made of artificial associations such as di-amino pyridine and derivatives of the barbiturates specified below or of the type of those described by T Ross Kelly et al (JACS 1987, 109, 6 549- 6 551).

The number of hydrogen bonds generated by the coupling of Jc: Jg is at least equal to 2, to obtain sufficient solidity of the bond. With the number of hydrogen bonds, the stability of the polymers increases. The upper limit is only a matter of molecular engineering.

However, in general this number does not exceed 5 in known associations.

The polymer according to the invention can be stabilized for certain applications by creating covalent bonds transforming the polymeroid into a polymer or into an oligomer. It is also possible to provide, on each structure, substituents having unsaturations which may give rise to polymerizations with or without crosslinking.

 In the case of application to 1 'O.N.L. (non-linear optics), those skilled in the art will appreciate how easy it is to make the double bond system of the structures according to the invention coincide with that required by the active patterns in O.N.L.

et des dérivés de l'acide barbiturique de formule II suivante :

avec K représentant un système de -ou- une chaine(s) alcoyle.The description of the invention will continue taking as paradigm of the association of structures C and G, that of the triamino pyrimidines of formula I as follows:

and barbituric acid derivatives of the following formula II:

with K representing a system of -or- an alkyl chain (s).

Structures I and II could combine in a cyclic hexameric system (3 structures I and 3 structures II alternately). However, polymeroid chains with a preferred orientation were formed.

 These sequences are obtained by dissolving the compounds of compounds I and II in a polar, preferably aprotic, solvent such as chloroform and methylene chloride. These sequences are first soluble and have relatively few patterns according to the invention.

 When the above solutions are concentrated, the "molecular mass" (polymolecular associatXon mass or supramolecular mass) of polymeroid increases, it forms crystal structures shown in FIG. I corresponding to the sequence of Figure II.

In the case of the application of the invention to non-linear optics, systems derived from compounds I and II can easily be produced, for example that in which B represents a para-cyano phenyl radical or else the following recurring unit:

The following nonlimiting examples illustrate the invention.

Example I 1. l-Dicvanononane
A solution of malononitrile (10.0 g, 0.15 mole) in dry dimethylsulfoxide (25 ml) is added dropwise to the sodium hydride suspension. (6.7 g of a 55-60% dispersion in mineral oil, ca 0.16 mol) in dimethyl sulfoxide (25 ml) over a period of 2 hours].

The resulting anionic solution is added dropwise to the mixture of 1-bromoctane (87.0 g, 0.15 mole) and dimethylsulfoxide with vigorous stirring.

When the addon is complete, the reaction mixture of the quasi-solid has been dissolved in water (600 ml) and extracted with chloroform.

The aqueous phase is slightly acidified with dilute hydrochloride acid, and again extracted with chloroform; the organic phases are combined, washed with water (x 3), and dried over sodium sulfate. The solvent is evaporated and the residue distilled at approximately 1 Torr. (102 Pa)
A fraction recovered between 108-130 ° C, is identified as the compound specified in the title, 15.2 g (56%) of colorless liquid. H (CDCl3) 0.87 (3 H, br t, CH3), 1.27 L 10 H, br s, -2) 5 CH3), 1.60 (2 H, m, (CN) 2
CH CH2 CH2], 2.02 (2 H, m, (CN) 2 CH CH2), and 3.70 (IH, t, J 6.9 Hz, (CN) 2
CH); m / z 177 (MI, 14%), 163 (26, M - CH3), 149 (12, M - CH2 CH3), and 135 (34, M- (CH2) 2 CH3).

Example 2 5 - Octvl - 2. 4. 6 - Drimidinetriamine
A solution of sodium ethanolate is prepared from sodium (382 mg, 16.6 mmol) and ethanol (15 ml).

Guanidinium hydrochloride (1.06 g, 11.1 mmol) and 1, 1-dicyanononane (1.78 g, 10.0 mmol) are added; the mixture is heated at reflux for 3 hours then filtered hot.

The bulky precipitate separated during cooling, which was collected on a filter and washed with a small amount of cold ethanol, gives white crystals of the compound specified in the title (0.988 g (42%), melting point 132-133 C , max. (CHCl3) 3526 (NH), 3419 (NH), 2928 (CH2,
CH3), 2856, 1604 (NH), 1577, and 1477 cm-1; H (CDCl3) 0.86 (3 H, br t, CH3), 1.25 (10 H, br s, (CH2) 5 CH3), 1.45 (2 H, m, Ar CH2 CH2), 2.20 (2 H, t , J 7.5 HZ, ArCH2) and 4.41 (6 H, br s, NH2); c (CDCl3) 161.8 (C-2 or C-4 (6)), 160.4 (C-2 or C-4 (6)), 88.2 (C-5), 31.8 (Ar CH2), 29.8, 29.6 , 29.3, 27.9, 24.4, 22.7, and 14.1 (CH3); m / z 237 (M +, 6%) and 138 (100, Ar Cl2 +.).

Example 3 1 1 - Dicanohexadecane
An intimate mixture of hexadecylmalonamide (1.00 g, 3.06 mmol) and phosphorus pentoxide (1.00 g, 7.05 mmol) is heated in an apparatus sold under the name of Kugelrohr, at 200 ° C., and under a vacuum of 0.5 Torr (70 Pa).

The colorless oil distilled from the dark brown reaction mixture, which solidifies to give an off-white crystalline solid, gives 0.72 g (81%) H (CDCl3) 0.87 (3H, br t, CH3), 1.25 ( 26 H, br s, (CH2) 13CH3), 1.60 (2H, m, (CN2 CH CH2) 2.00 (2 H, m, (CN) 2 CHCH2), 3.70 (1H, t, J 6.9
HZ, (CN) 2CH).

Example 4 1- (2,2- Dicvanoethvl) naDhthvlene
An intimate mixture of a -naphthylmethylmalonamide (1.00 g, 4.13 mmol) and phosphorus pentoxide (1.3 g, 9.16 mmol) is heated to 200 ° C. in a device sold under the name of Kugelrohr, and under a vacuum of 0.5 Torr.

The yellow mixture, distilled from the dark brown reaction mixture, which after a long period turns into an oily yellow solid, gives 0.61 g (72%) H (CDCl3) 3.80 (2H, d J 7.7 HZ, Ar CH2) , 4.07 (1H, dd, J 7.1 and 8.1 HZ, (CN) 2CH), 7.45-7.63: (4H, m, Ar-H), and 7.81-7.96 (3H, m,
Ar-H); m / z 206 (M +, 20%) and 141 (100, Ar CH2 ±).

Example 5 5 - Hexadecvl - 2.4.6 - Dvrimidinetri ami ne
A solution of sodium ethanolate is prepared from sodium (190 mg, 8.3 mmol) and ethanol (10 mil).

Guanidinium hydrochloride (536 mg, 5.6 mmol) and 1,1-dicyanoheptadecane (1.45 g, 5.0 mmol) are added, then the mixture is heated to reflux for 3 hours, and is filtered hot.

A precipitate of white solid was recovered on a filter from the filtrate, after cooling, giving the compound specified in the title (1.18 g, 68%) in the form of a white solid, melting point 137.5-138.5 "C
H (CDCl3) 0.87 (3 H, br t, CH3), 1.24 (26 H, br s, (CH2) 13 CH3 1.45 (2H, m, Ar CH2 Cru2), 2.20 (2H, br t, Ar CH2) and 4.36 (6H, br s, NH2) m / z (FAB +) 350 (MH +, 100 X).

Example 6 5 - (a naohthvlmethvl) - 2. 4. 6 - Drimidinetriamine
A solution of sodium ethanolate is prepared from sodium (220 mg, 9.56 mmol) and ethanol (10 ml).

Guanidinium hydrochloride (600 mg, 6.28 mmol) and 1- (2, 2-dicyanoethyl) naphthylene (1.18 g, 5.72 mmol) are added and the mixture is heated at reflux for 3 hours, cooled to room temperature, and filtered.

The filter cake is washed with ethanol (x 1) and water (x 3), and dried under vacuum giving the compound specified in the title, in the form of a moderately soluble beige powder (0.82 g, 54% ).

Recrystallization from chloroform gives white microcrystals melting point 276-277 C (dec.) G H (CDCl3) 4.08 (2H, s, Ar CH2), 4.33 (4H, br s, 4- and 6-NH2) , 4.49 (2H, br s, 2-NH2), 7.21 (1H, dt, J 1.1 and 7.1
Hz, ArH), 7.37 (1H, t, J 7.7 Hz, Ar-H), 7.56 (2H, m, Ar-H) 7.76 (1H, d, J 8.3 Hz, Ar-H), 7.90 (1H, dd , J 2.4 and 7.0 Hz, Ar-H), and 8.12 (1H, d, J 7.5
Hz, Ar-H); m / z 265 (M +, 100%).

Example 7 5.5-DihexadecYl-2.4.6-Dvrimidinetrione
A solution of sodium ethanolate is prepared from sodium (1.0 g, 0.043 mmol) and ethanol (25 ml).

Diethylhexadecylmalonate (9.1 g, 0.015 mole) and urea (1.35 g, 0.022 mole) are then added, then the mixture is heated at 100 ° C. for 6 hours.

The resulting white suspension is diluted with water and 3/4 of the ethanol decreases under reduced pressure. On acidification to PH6 with dilute hydrochloric acid, a white precipitate is separated which is filtered and dried, giving 5.08 g (59%) of the compound specified in the title in the form of an amorphous white solid. The product could be crystallized from ethanol, melting point 112-114 C. dH (CDCl3) 0.87 (6H, br t, CH3), 1.24 (56H, br s, (CH2) 14 CH3), 1.94 (4H, m, 5-CH2), and 7.82 (2H, br s, N-H); m / z (FAB +) 577 (MH +, 49%).

Example 8 <2.2-Dicvanoethvl) ferrocene
Trifluoroacetic anhydride (311 μl, 462 mg, 2.2 mmol) and pyridine (324 B1, 316 mg, 4.0 mmol) are added to the suspension of ferrocenylmethylmalonamide (300 mg, 1.0 mmol) in anhydrous dioxane (2 mil), at 0 C.

The mixture is allowed to return to room temperature and after 12 hours, it is poured into water and extracted with chloroform. The organic extract is dried over sodium sulfate and evaporated to give a crude product in the form of a brown solid (255 mg of reasonable purity by NMR and thin layer chromatography.

Chromatography (CH2Cl2) gives dark orange crystals (99 mg, 37X). H (CDCl3) 3.11 (2H, d, J 6.7 Hz, Ar-CH2), 3.72 (1H, t, J 6.7 Hz, (CN) 2CH), 4.16 (5H, s ,, CgHg), 4.21 (2H, t , J 1.8 Hz, C5H4), and 4.28 (2H, t,
J 1.8 Hz, C5H4).

Example 9 5- Ferrocenvlmethvl-2.4,6- ovrimidinetriamine
A sodium ethanolate solution is prepared from sodium (15 mg 0.65 mmol) and ethanol (1 ml).

Then added guanidinium hydrochloride (35 mg, 0.37 mmol) and a solution of (2,2-dicyanoethyferrocene (85 mg, 0.32 mmol) in methanol the mixture is heated to reflux for 3 hours, cooled to room temperature and filtered.

The cake is washed with water (x 3) and ethanol (x 1), then dried under vacuum, thus giving the compound specified in the title, in the form of a moderately soluble beige solid (20 mg, 19%).

g H (CDCl3) 3.36 (2H, s, Ar CH2), 4.08 (2H, d, J 1.7 Hz, C5H4), 4.13 (7H, s, C5H4 and CsHs), 4.42 (2H, br, s, 2-NH2 ), and 4.48 (4H, br s, 4- and 6-NH2).

Example 10 5.5- Dir2 - (2-methoxvethoxv) ethvll - 2.4.6- pvrimidinitrione
A solution of sodium ethanolate is prepared from sodium (0.80 g, 0.035 mole) and ethanol (15 ml).

Di- (2-methoxy-ethoxyethyl) malonate (4.10 g, 0.011 mole) of diethyl and urea (1.00 g, 0.017 mole) are then added; the mixture is heated at high reflux for 21 hours.

Water (50 ml) is added and virtually all of the ethanol is removed under reduced pressure. No precipitate is observed after acidification to PH5 with dilute hydrochloric acid; thus the solution is evaporated and the residue is taken up in 1: 1 ethanol-chloroform, giving a cloudy solution. This was filtered through diatomaceous earth and evaporated to give a pale gold resin of marginal purity. H (CDC13) 2.30 (4H, t, J 5.8 Hz, 5-CH2), 3.31 (6H, s, OCH3), 3.44 (12 H, m, CH20 CH2 CH2 CH20
CH3) and 8.1 (2H, v br, NH).

Example 11
Complex between 5. 5-Diethl-2,4,6-pvrimidinetrione and 5-butvl 2 * 4.6- evrimidinetriamine
A solution of 5,5-diethyl-2,4,6-pyrimidinetrione (101.6 mg, 0.55 mmol) in chloroform (15 mi) is mixed with a solution of 5-butyl-2,4,6-pyrimidinetriamine (100.0 mg , 0.55 mmol), in chloroform (25 ml).

Following this short induction period, the solution gradually becomes cloudy and a precipitate is observed.

After 12 hours, the mixture is filtered giving the compound specified in the title (163 mg, 81%) in the form of a white crystalline solid, (melting point 213-214 C), (gradually heated) or 228-229 C (quickly heated).

Recrystallization from ethanol gives larger crystals (melting point 215-216 C). v max (KBr) 3474, 3304, 3106, 2959, 2838, 2583, 1707, 1650, 1562, 1458, 1421, 1361, 1320, 1254, 1177, 1143, 930, 871, 637, 530, and 443 cm-l ; H (CDC13) 0.90 (9H, m, CH3), 1.40 (4H, m, CH2 CH2
CH3), 2.00 (4H, br q, 5-CH2 in pyrimidinetrione), 2.18 (2H, br t, 5-CH2 in pyrimidinetriamine), 5.80 (4H, br s, 4- and 6-NH2), and 6.57 (2H, br s, 2-NH2).

Example 12
Complex between 5-octyl- 2,4,6-Dvrimidinetriamine and 5.5-DiethYl-2 46-pvrimidinetrione
A solution of 5,5-diethyl-2,4,6-pyrimidinetrione (184.2 mg, 1.00 mmol) in chloroform (20 mi) is mixed with a solution of 5-octyl-2,4,6-pyrimidinetriamine ( 237.4 mg, 1.00 mmol) in chloroform (15 ml).

No precipitate is observed after standing for 12 hours at room temperature; the solvent is evaporated off, giving the compound specified in the title in the form of a white microcrystalline solid (melting point 205-206 C), the crystallization of which only raised the melting point to 207-208 " C. v max (CHCl3) 3517, 3455, 3348, 3225, 2971, 2929, 2856, 1693, 1639, 1577, 1439, 1383, 1316, 1278, 1239, and 418 cm-1; g H (CDCl3) 0.89 ( 9H, m, CH3), 1.26 (10H, br s, (CH2) sCH3) 1.45 (2H, br s, Ar CH2 CH2), 1.99 (4H, br g, 5-CH2 in pyrimidinetrione), 2.16 (2H, br t, 5-CH in pyrimidinetriamine), 6.17 (4H, br s, 4- and 6-NH2), 7.11 (2H, br s, 2-NH2), and 13.6 (2H v br, NH in pyrimidinetrione) ;; jc (CDCl3) 178.9 (C-4 (6) in pyrimidinetrione), 160.3 (pyrimidinetriamine), 158.0 (pyrimidinetriamine), 156.9 (C-2 in pyrimidinetrione), 85.5 (C-5 in pyridinetriamine), 57.0 (C-5 in pyrimidinetrione), 32.2 (5-CH2 in pyrimidinetrione), 31.8 (5-CH2 in pyrimidinetriamine), 29.8 (pyrimidinetriamine), 29.5 (pyrimidinetriamine), 29.2 (pyr imidinetriamine), 27.5 (pyrimidinetriamine), 23.8 (pyrimidinetriamine), 22.6 (pyrimidinetriamine), 14.1 (CH3 in pyrimidinetriamine), and 9.7 (CH3 in pyrimidinetrione).

Example 13
Complex between 5.5-Dibutvl-2.4.6-ovrimidinetrione - 5-butyl 2.4.6-pvrimidinetriamine
A solution of 5,5-dibutyl-2,4,6-pyrimidinetrione (240.3 mg 1.00 ml) in chloroform (20 ml) is mixed with a solution of 5-butyl-2,4,6-pyrimidinetriamine (181.2 mg, 1.00 mmol) in chloroform (80 ml).

After a short induction period, the solution gradually becomes cloudy and a precipitate is observed. After 12 hours, the mixture is filtered giving the compound specified in the title (470 mg), in the form of white solvated crystals, melting point 267-268 C (sublimation).

Example 14
Complex between 5,5-Di- [2- (2-methoxyethoxy) ethyl)] -2.4 6-pvrimidinetrione and 5-butvl-2.4.6-pvrimidinetriamine
A solution of 5,5-di- (2- (2-methoxyethoxy) ethyl] - 2,4,6 - pyrimidinetrione (332 mg, 1.0 mmol) in chloroform-methanol (2: 1, 50 ml) is mixed with a solution of 5-butyl-2,4,6 pyrimidinetriamine (181 mg, 1.0 mmol) in chloroform (80 ml) The solution is evaporated to give the title compound, in the form of a semi-crystalline solid egg shell.

Example 15 Comolex between 5,5-diethvl-2,4,6-nyrimidinetrione and 5 (a naDhthylmethvl) -2,4,6-pyrimidinetriamine
A solution of 5,5-diethyl-2,4,6-pyrimidinetrione (184.2 mg, 1.00 mmol) in chloroform (20 ml), is mixed with a hot solution of 5- (a naphthyl methyl) -2,4, 6tpyrimidinetriamine (265.3 mg, 1.00 mmol) in chloroform (130 ml).

A precipitate is formed almost immediately by mixing the two solutions.

After standing for 2 hours, the mixture is filtered giving the compound specified in the title (515 mg) in the form (solvated) of white crystals, melting point 276-278 C.

Example 16 Comolex between 5,5-dibutvl-2,4, 6-ovrimidinetrione and 5-octyl-2.4,6 -Dvrimidinetriamine
A solution of 5,5-dibutyl -2,4,6 -pyrimidinetrione (600.8 mg, 2.5 mmol) in chloroform (25 ml) is mixed with a solution of 5-octyl -2,4,6-pyrimidinetriamine (593.4 mg , 2.5 mmol) in chloroform (25 ml).

No precipitation is observed in one hour of time; then the solution is evaporated, giving the compound specified in the title in the form of a white solid, (melting point, 215-216 C.) g H (CDCl3) 0.86 (9H, m,
CH3), 1.26 (18H, br s, CH2) 5 CH3 in pyrimidinetriamine and (CH2) 2 CH3 in pyrimidinetrione), 1.45 (2H, br m, Ar CH2 CH2), 1.93 (4H, br m, 5-CH2 in pyrimidinetrione), 2.16 (2H, br t, 5-CH2 in pyrimidinetriamine), 6.06 (4H, br s, 4- and 6- NH2), 6.98 (2H, br s, 2-NH2), and 13.6 ( 2H, v br, NH in pyrimidinetrione) ;; #c (CDCl3) 177.5 (C-4 (6NH in pyrimidinetrione), 160.8 (pyrimidinetriamine), 158.8 pyrimidinetriamine), 155.0 (C-2 in pyrimidinetrione), 86.1 (C-5 in pyrimidinetriamine), 55.8 (C- 5 in pyrimidinetrione), 39.2 (5-CH2 in pyrimidinetrione), 31.8 (5-CH2 in pyrimidinetriamine), 29.9, 29.7, 29.6, 29.3, 27.6, 27.2, 26.1, 24.0, 22.8, 22.6, 14.1 and 13.7.

Example 17
Complex between 5.5-Dihexadecyl-2,4,6-pyrimidinetrione and 5-hexadecvl -2,4,6-Dvrimidinetriamine
A solution of 5,5-dihexadecyl -2,4,6-pyrimidinetrione (115.4 mg, 0.20 mmol) in chloroform (25 ml) is mixed with a solution of 5-hexadecyl-2,4,6-pyrimidinetriamine ( 69.9 mg, 0.20 mmol) in chloroform (25 ml).

The solution is evaporated to give the compound specified in the title, in the form of a powder of white micro-crystals; melting point 170-175 C after softening around 140 C.

(CDCl3) 0.87 (9H, br t, CH3), 1.23 (82 H, br s, (CH2) 13 CH3 in pyrimid
Ar CH2 CH2), 1.92 (4H, br s, 5-CH2 in pyrimidinetrione), 2.16 (2H, br t, 5-CH2 in pyrimidinetriamine, and 5.3 (v br).

Example 18
Complex between 5,5-Dibutvl-2,4,6-rimidinetrione and 5- (naphthylmethyl) -2,4,6-pvrimidinetriamine
A solution of 5,5 -dibutyl-2,4,6-pyrimidinetrione (120.2 mg, 0.50 mmol) in chloroform (10 ml) is mixed with a hot solution of 5- (naphthylmethyl) -2,4,6-pyrimidinetriamine (132.7 mg, 0.50 mmol) in chloroform (60 ml).

A precipitate is formed almost immediately upon mixing the two solutions.

After standing for 2 hours, the mixture is filtered to give the compound specified in the title (223 mg, 88%) in the form of a white crystalline powder; melting point 315-316 C.

Example 19
Complex between 5,5-Di-F2 (2-methoxvethoxv) ethv11-2,4,6 -pvrimidinetrione and 1.3 5-triazine -2.4.6 -triamine
A solution of 5,5-Di- [2- (2-methoxyethoxy) -ethyl] -2,4,6-pyrimidinetrione (332 mg, 1.0 mmol) in 10 ml of water is mixed with a solution of 1.3 , 5-triazine -2,4,6-triamine (126 mg, 1.0 mmol) in water (40 ml).

After a short induction period, a large precipitate is filtered, washed with water and dried.

The title compound (40 mg, 9%) is a solid of white insoluble microcrystals, melting point 315-316 C

Claims (8)

 K in which C is an organic structure comprising a double bond system ensuring a substantially flat stable conformation and 2 sets Jc, of sites capable of forming hydrogen bonds with G in which G is an organic structure comprising a double bond system ensuring a substantially flat stable conformation and 2 sets of Jg, of sites capable of forming hydrogen bonds with C in which B is a radical whose orientation is desired, capable of ensuring, for example a high activity O, NL  !  ::! :  : C: G:  B  CLAIMS 1) Non-centrosymmetric polymeroid compound characterized in that it comprises at least the following recurring motif (I) Said binding system being such that to each site D and C corresponds a site A of G and to each site D of G corresponds a site A of C; the sites D and A being respectively functions carrying at least one hydrogen atom capable of giving hydrogen bonds and functions carrying a doublet capable of forming a hydrogen bond. C and one of the so-called games of G; in which K symbolizes a hydrocarbon chain system;  ":" in which the sign symbolizes the hydrogen bonding system established between one of the said sets of 2) Compound according to claim 1 characterized in that the structure C has an axis of symmetry allowing to deduce one of said sets of sites by knowing the other. 3) Compound according to one of claims 1 to 2 characterized in that the structure G has an axis of symmetry making it possible to deduce one of the said sets of sites by knowing the other. 4) Compound according to one of claims 1 to 3 characterized in that by the fact that said D sites are independently selected from the group consisting of: N-H; OH 5) Compound according to one of claims 1 to 4 characterized in that said sites A are independently selected from the group consisting of: = 0; 0; = N; -NOT-. 6) Compound according to one of claims 1 to 5 characterized in that a site is common to said two sets of sites of structure C. 7) Compound according to one of claims 1 to 6 characterized in that a site is common to said two sets of sites of structure G. 8) Active material in nonlinear optics characterized in that it contains a compound according to one of claims 1 to 7.