FR2615187A1 - New amides containing polyethoxylated chains, processes for their synthesis and their applications - Google Patents

Abstract

New amides containing polyethoxylated chains, processes for their manufacture and their applications. The invention relates to new amides corresponding to the formula: in which R is a hydrocarbon, fluorocarbon or partially hydrogenated fluorocarbon chain, n and n' are integers, which are identical or different, between 1 and 10; Z and Z' are alkyl or aralkyl groups, which are identical or different, containing from 1 to 10 carbon atoms. It also relates to processes for the synthesis of these products and their applications, especially as surface-active agents, in particular as emulsifying agents for making microemulsions.

Description

dans laquelle
R est une chaîne hydrocarbonée, fluorocarbonée ou fluorocarbonée partiellement hydrogénee, en particulier du'type perfluoroalkylméthylene, contenant 4 a 18 atomes de carbone.The present invention relates to new industrial products corresponding to the formula

in which
R is a partially hydrogenated hydrocarbon, fluorocarbon or fluorocarbon chain, particularly of the perfluoroalkylmethylene type, containing 4 to 18 carbon atoms.

 n and n 'are integers, identical or not between 1 and 10.

 Z and Z 'are identical or different alkyl or aralkyl groups having from 1 to 10 carbon atoms.

 The products of the invention find applications as surfactants.

They can also be used as extractants of metal ions.

 An increasing interest is now being focused on monodisperse nonionic surfactants having a well-defined hydrophilic part, especially those comprising a perfluorinated chain.

dans lesquels R est un groupement alkyle constituent des produits tensio-actifs bien connus et commercialement développés.Products of the form

in which R is an alkyl group are well known and commercially developed surfactants.

 They are obtained in reactions using ethylene oxide and always leading to polydisperse mixtures difficult to purify.

Moreover, it is known that amide-type products have terminal alcohol functions which lead to equilibrium of the form.

ont été décrits notamment dans la thèse de T. GARTISER soutenue à NANCY, le 15 Novembre 1982.On connaît également des produits de la forme

Such equilibria are particularly reported in "Non Ionic Surfactants
Chemical Analysis. John CROSS (1987) p. 15. "
Perfluorinated chain amide products of the form

have been described in particular in the thesis of T. GARTISER supported in NANCY, November 15, 1982.We also know products of the form

 However, these products, even when they comprise a perfectly defined number of ethoxylated groups, are always involved in equilibria of the type mentioned above and can not therefore be envisioned in applications requiring pure products, such as This is the case when we are looking for the formation of microemulsions.

 The present invention provides products which, while having the advantages of polyethoxylated chain amide type products, can be obtained perfectly pure, which allows to consider various applications including the formation of microemulsions.

où R, n, n', Z, Z' ont la forme exprimée précédemment
Une telle amine n'est généralement pas commerciale.Elle peut être obtenue de différentes façons en particulier a partir d'une réaction de couplage entre La benzylamine ou une forme N-bloquée de la diéthanolamine et une forme activée d'un alcoxyéthanol (HOC2H4OZ) ou d'un alcoxypolyéthoxyéthanol (HO(C2H4O)n Z) avec
La réaction de couplage entre la benzylamine et la forme activée de l'alcoxyéthanol ou de l'alcoxypolyéthoxyéthanol conduit à une forme N-bloquée de l'amine par un groupement benzyle que l'on élimine classiquement. Comme groupement activant de la fonction alcool, on choisira avantageusement le chlorure de l'acide p-toluènesulfonique qui conduira au tosylate correspondant, cependant, d'autres formes peuvent être utilisées, des dérivés halogénés par exemple.Le déblocage de la fonction amine sera réalisé classiouement, par exemple par hydrogénation catalytique ; ce premier mode de préparation est repré senté par le schéma 1 suivant, où le catalyseur d'hydrogénolyse est le palladium. The present invention also provides methods for obtaining these compounds. A first method consists in reacting an amine of the form with an acid halide or other activated form of RCOOH acid.

where R, n, n ', Z, Z' have the form previously expressed
Such an amine is generally not commercially available. It can be obtained in various ways, in particular from a coupling reaction between benzylamine or an N-blocked form of diethanolamine and an activated form of an alkoxyethanol (HOC2H4OZ). or an alkoxypolyethoxyethanol (HO (C2H4O) n Z) with
The coupling reaction between benzylamine and the activated form of alkoxyethanol or alkoxypolyethoxyethanol results in an N-blocked form of the amine by a benzyl group which is conventionally removed. As an activating group of the alcohol function, the p-toluenesulphonic acid chloride which will lead to the corresponding tosylate will advantageously be chosen, however, other forms may be used, for example halogenated derivatives. The deblocking of the amine function will be carried out. classiouement, for example by catalytic hydrogenation; this first method of preparation is represented by the following scheme 1, in which the hydrogenolysis catalyst is palladium.

où + désigne le groupement phényle et Ts le groupement p-toluène sulfonique.Diagram 1

where + denotes the phenyl group and Ts the p-toluene sulphonic group.

 A second method for synthesizing the amine is to make a coupling reaction between an N-blocked form of diethanolamine and an activated form of an alkoxypolyethoxyethanol or an alkoxyethanol. Depending on the coupling conditions, after deblocking the amine formed, either a symmetrical amine (n = n ') or an asymmetric amine (n') will be obtained.

 The N - blocking of the amine can be done for example by tritylation.

The activation of the alkoxyethanol or the alkoxypolyethoxyethanol can be done by tosylation. By way of example, by performing the coupling in the
THF at reflux and with an excess of alcohol, we will arrive at a symmetrical product; by operating in the refluxing ether and then in the refluxing THF and playing on the stoichiometry, we will end up with an asymmetrical or symmetrical product. The deblocking of the coupling product is conventionally carried out with an acidic solution, for example a solution of hydrochloric acid.

b) Dissymétrique

Déblocage

This second method can be schematized as follows
Figure 2

b) Dissymmetrical

unblocking

It will be advantageous to use diagram 1 to make an amine of the forre
HN (C2H40Z) 2, either of Schemes I or 2 to make amines
HN [(C2H4) n Z] 2 with n>, 2.

où n et n' sont des entiers égaux ou différents et Z et Z' sont des groupements tels que définis précédemment. The amine thus formed will then be reacted on an activated form of the acid.
RCOOH, for example, on the chloride of this acid, according to the following scheme 3
Figure 3

where n and n 'are integers equal or different and Z and Z' are groups as defined above.

avec n > 1. Another method making it possible in particular to avoid the subsequent reactions of blocking and unblocking, consists in following the following diagram.

with n> 1.

 The present invention also relates to the applications of the products according to the invention, in particular as nonionic surfactants.

In fact, the products of the present invention, in particular those in which Z = CH 3 have interesting surfactant properties, in particular when R is a perfluorinated or partially fluorinated alkyl chain, can lower the surface tension of batteau up to values of the order of 20 mN · m, or even for example 16 mNm in the case of

The products in which R is an alkyl group make it possible to lower the surface tension of water up to values of the order of 30 to 35 mN.m -1.
The products of the present invention can be used as emulsifiers to form microemulsions consisting of a mixture of a product according to the invention, water and an "oil". water insoluble liquid as defined by LN PRINCE in Acad Press, New York 1977, of the fluorocarbon, perfluorocarbon, hydrocarbon type, optionally substituted.

As "oil", perfluorodecalin, e.g. for the fluorinated products, 1 decane for example, for hydropenated products, the microemulsions thus obtained constitute single-phase, isotropic, clear and stable solutions for a defined temperature range, composed of an aqueous solution of surfactant (Products of 1 invention) in which an "oil" (perfluorodecalin for example) is dispersed in the form of globules whose size may vary from a few tens to a few hundred Angstroms.

 The products of the invention show parallel complexing properties vis-à-vis the metal ions, which allows to consider their application as extractant in liquid-liquid extraction.

 The following examples are given in a non-limiting manner and will better highlight the scope and interest of the invention.

EXAMPLE 1

selon le schéma 1. 1.1. Tritylation de la diéthanolamine.Synthesis of

according to diagram 1. 1.1. Tritylation of diethanolamine.

In a reactor equipped with a magnetic stirring system and a
dropping funnel, 6.34.10 moles (66.6 g) of diethanol
amine in 270 ml of dimethylformamide. After cooling
To the OOC mixture, 170 ml of dichloromethane containing 3.17.10 moles (80.2 g) of trityl chloride are added over about 80 minutes.

After complete addition, the magnetic stirred solution is left
at room temperature for 24 hours. The solution is then washed
with 150 ml of ether and 200 ml of H 2 O. A precipitate is formed
after a few minutes ; we filter, then we recrystallize in a
chloroform / petroleum ether mixture.

 The product obtained is a pink solid: 80 g. Yield: 80%.

 The product is monitored by TLC and proton NMR.

1.2. Activation in the form of monomethyl ether tosylate of diethylene glycol.

In a reactor equipped with a magnetic stirring system and a
3.50 mole (40 g) of diethylene
glycolmonomethylether in 80 ml of pyridine. After chilling
solution at 0 C, a solution is slowly added (90 min)
6.6.10-1 mole (126 g) of para-toluenesulphonyl chloride in
180 ml of pyridine. After complete addition, allow to return
mixing at room temperature; after stirring for 4 hours,
the mixture is added to an aqueous phase and then extracted
The organic phase is then washed in the presence of a
aqueous acid solution (5% HCl: 100 ml). Again, extraction
with ether. After drying the organic phase over sodium sulphate
gnesium, filter and evaporate the solvent.

The product obtained is a colorless liquid: obtained 70 g. Rende
77%. Purification of the product for identification has been
made by silica column chromatography.

 The product is monitored by TLC and proton NMR.

1.3. Condensation of trityldiethanolamine on tosylate.

In a reactor equipped with a refrigerant and a stirring system
55 ml of 50% sodium hydroxide are introduced into this solution.
a mixture of 2.3 × 10 moles (8 g) is added directly.
of tritylated diethanolamine, 6.9 × 10 -2 moles (19 g) of diethylenes
tosylated glycolmonomethylether, 10% (~ 3 g) of tetrabutylammonium
hydrogen sulfate in 65 ml of tetrahydrofuran as solvent.

The mixture is refluxed for 14 hours with good
agitation. After reaction, the solution is diluted with 100 cc
distilled water, then extracted with ethyl ether. The gold phase
is dried over sodium sulphate, filtered, and then
evaporated. The expected product is purified on column by chromato
high performance liquid graphy.

Mass of the product
Yield: 73%.

 Control is by TLC, proton NMR identification.

1.4. Unblocking of the amine.

In a reactor equipped with a stirring system and a light bulb
to bromine, 20 ml of a 5% aqueous solution of HCl are introduced. The
solution is stirred at room temperature; we add in 10 minutes
a solution of tritylaminobis (triethyleneglycolmonomethylether),
1.34.10 moles (7.5 g) in 40 ml of methanol. After addition
complete, the mixture is left at room temperature for 15 minutes.

The tritylcarbinol is then filtered, the solvent evaporated until
that the volume of the residue is substantially equal to the volume of the phase
aqueous initial. It is then extracted with ether (30 ml); the sentence
The aqueous solution is then brought to basic pH by adding a solution
saturated sodium bicarbonate. We evaporate the water, we addi
dichloromethane (50 ml) on the solid residue obtained; we
stir 15 minutes, filter the remaining solid, dry the phase on
finally, the solvent is evaporated.

 3.78 g of a yellow liquid are obtained.

 Yield: 80%.

 Control is by TLC and proton NMR identification.

1.5. Condensation on C6F13CH2COCl.

In a reactor equipped with magnetic stirring and a bulb
bromine, 10-2 mol (3.3 g) of amino bis (triethylene
glycolmonomethyl ether), 10-2 mol (1.01 g) of triethylamine in
25 ml of tetrahydrofuran. After cooling the solution to 0 ° C., 9.10 mol of the acid chloride are added over a period of 30 minutes.
fluorinated. The reaction mixture is stirred at 0 ° C.
during 3 hours. The solution is then diluted with 30 ml of a
0.1 N HCl solution and extracted with 3 volumes (100 ml) of ether.

The organic phase is washed with a saturated aqueous solution of
sodium bicarbonate, then dried over sodium sulfate; the
solvent is evaporated under vacuum.

The control is done by TLC and proton NMR. The yield is
90% with respect to the acid chloride.

 EXAMPLE 2

Preparation of

The procedure is as in Example 1, replacing C6Fl3CH2 C10 O with C8F17CH2 COCl: the product is obtained in a yield of 90% relative to the acid chloride.

 EXAMPLE 3

Synthesis of

By proceeding as in Example 1, replacing C6F13CH2COCl by C1oF21CH2COCl gives a yield of 85% relative to the acid chloride.

 EXAMPLE 4

Preparation of

The procedure is as in Example 1, replacing the monomethyl ether of diethylene glycol with monomethyl ether of triethylene glycol.

The corresponding tosylate is formed in the same way. The product is a painless liquid whose purification for identification is made by chromatography on a silica column: the final yield is 83% relative to the acid chloride.

EXAMPLE 5

Synthesis of

The procedure is as in Example 1, replacing the acid chloride C6F13CH2COCl with another activated form of the acid, namely the BOP reagent, cf. J. Chem. Res. (S) 182 (M) 2118 L1977j.

In a reactor equipped with a stirring system and a dropping funnel, 1.29 × 10 3 mol (400 mg) of amino bis (triethylene glycol monomethyl ether), 1.29 × 10 -3 mol (167 mg) of diisopropylethylamine are introduced. 1.20.10 mol (571 mg) of the reagent (BOP) in 25 ml of acetonitrile. At room temperature, 1.19.10 moles (457 mg) of fluorinated acid (C6F13-COOH) are added over 30 minutes. The reaction mixture is stirred at 200C for 2 hours. The solution is then diluted with 20 ml of a HCl solution (0.1) and extracted with 3 volumes of 20 ml of ether. The organic phase is washed with a saturated aqueous solution of sodium bicarbonate and then dried over sodium sulfate, the solvent is evaporated under vacuum. Yield: 40%

Control by NMR and Infra-Red.

 EXAMPLE 6

Preparation of

In a reactor equipped with a stirring system and an addition funnel, 1.25 × 10 3 mol (500 mg) of amino bis (tetraethyleneglycol-monomethyl ether), 1.25 × 10 mol (162 mg) of diisopropyl-ethylamine, a catalytic amount (15 mg) of dimethylaminopyridine (DMAP) in 25 ml of tetrahydrofuran. At room temperature, 1.15 × 10 3 mol (218 mg) of decanoyl chloride (C 9 H 19 ClOCl) are slowly added. Stirring is maintained at ambient temperature for 5 hours. The solution is then diluted with 30 ml of an acidic aqueous solution (0.1 N HCl) and extracted twice with 45 ml of ether. The organic phase is washed in the presence of a saturated aqueous solution of sodium bicarbonate and then dried over sodium sulfate. The solvent is evaporated under vacuum. Yield: 85%.

Control is done by Infra Red, CCM. The refractive index
N is 1.457.

7.1. Tritylation de la diéthanolamine.EXAMPLE 7
Preparation of

7.1. Tritylation of diethanolamine.

 The procedure is as in Example 1.1.

7.2. Selective blocking in the form of benzyl diethylene glycol.

In a tricolor equipped with a stirring system and a refrigerant,
40 g of a 50% sodium hydroxide solution, 84.8 g (8.10-1) are introduced.
mole) of diethylene glycol, 25.2 g (2.10-2 mol) of
benzyl. The mixture is then refluxed for 6 hours. Re
cooling of the reaction mixture, extraction with 3 volumes of
160 ml of ether after adding 200 ml of H 2 O. Sulphate drying
magnesium. Evaporation of the solvent under vacuum. The gross product
is purified by distillation. Yield 75%.

 TLC control.

7.3. Activation as a tosylate.

The procedure is as in Example 1.3. We obtain C6H5 CH2 (C2H4O) 2
SO2C6H5CH3 with a yield of 80%. The identification of this
product is made by proton NMR.

7.4. Deprotection of the amine.

avec un rendement de 80 %.
Le produit est identifié par RMN du proton.The procedure is as in Example 1.4. We get the amine

with a yield of 80%.
The product is identified by proton NMR.

7.5. The amine obtained in 7.4 is reacted. on the acid chloride
C2F13 CH2 COCl according to the procedure set forth in 1.5.

C6F13 CH2
The amide yield is 80%.

with a
The identification is made by proton NMR.

EXAMPLE 8

selon le schéma 2.Preparation of

according to scheme 2.

8.1. Activation in the form of monomethyl ether diethyl tosylate
glycol.

 The procedure is as in Example 1.2.

8.2.- Condensation of benzylamine on tosylate.

In a tricolor equipped with a stirring system, a light bulb
bromine and a condenser, 2.5 × 10 moles (2.75 g) are introduced.
of benzylamine, 5.5.10 moles (6 g) of sodium carbonate in
25 ml of acetonitrile. At room temperature, add slowly
a solution of 5.5.10 moles (15.5 g) of diethylenesylate
glycol-monomethyl ether in 50 ml of acetonitrile. After addition
When complete, the mixture is refluxed (620C) for 15 hours.

The mixture is then filtered. The solid residue is washed with ether
in order to recover the maximum of product. The filtrate is evaporated
under vacuum.

 The crude product is diluted with 40 ml of an acidic aqueous solution.

This aqueous phase is extracted once in the presence of 60 ml
of ether. Basification of the aqueous phase, followed by extraction
ether. Drying on sodium sulphate, then evaporation
solvent in vacuo.

avec un rendement de 75 %. We obtain

with a yield of 75%.

The identification is made by proton NMR, CCM and measurement of 20
the refractive index (nD = 1.489).

8.3. Unblocking of the amine by hydrogenation.

In a hydrogenation reactor, 5.4 × 10 moles (1 000 g) are introduced.
benzylamino Ebis (diethyleneglycolmonomethyl ether 7 in
15 ml of ethanol, 10% by weight of palladium on charcoal. We are "purging"
the reactor containing the mixture twice with nitrogen, then once
to hydrogen and allowed to react under 80 bar of hydrogen under
stirring and at room temperature for 8 h. After reaction,
it is "purged" twice with nitrogen, it is filtered on cellite. Solvent
is hunted under reduced pressure.

 The product obtained is a yellow liquid. The yield is 85%.

Control is by TLC and proton NMR; the refraction index
is nD20 = 1.449.

 8.4. Condensation on the acid chloride.

 We proceed as in Example 1.5.

 C6F13 CH2 CON [(C2H40) 2 CH32 2 is obtained in a yield of 92%.

 Control is by Infra Red CCM and proton NMR.

 EXAMPLE 9

Formation of microemulsions.

9.1. With 15% C8F17 CH2CON [(C2H4O) 3CH3] 2, 4% perfluorodecalin
and the addition of water is obtained by simple stirring, at a
temperature between 0 and 30 C, a microemulsion. If we
raises the temperature to 340C, we observe a turbid phase that re
spontaneously forms the microemulsion by returning to 30 C.

9.2. With 15% C6F13 CH2 CON [(C2H $ O) 3 CH3] 2, 3% perfluorode
caline and the complement in water, we obtain by simple agitation
a microemulsion at a temperature between 0 and 330C.

9.3. With 15% C8F17 2CON [C2H40) 2 CH3] 2, 6% perfluorodeca
line and the complement in water, we obtain, by simple agitation,
a microemulsion at a temperature between 0- and 160C.

9.4. With 15% C10F21CH2CON [(C2H4O) 3 CH3] 2, 20% perfluoro
decalin and the complement in water, we obtain, by simple agitation,
a stable microemulsion at a temperature of 26 to 40 C.

 EXAMPLE 10

Characterization of the surfactant properties.

The table below gives for some products of the invention
Surface tension and Micellar concentration values
Criticality (CMC) measured at room temperature as well as
of HLB calculated according to the formula of GRIFFIN (J. Soc.Chem.Chem.Chem.
5, 249).

<tb><SEP> Voltage
<tb><SEP> Superficial <SEP> C <SEP> M <SEP> C
<tb><SEP> products <SEP> (mN.m-1) <SEP> (mole / liter) <SEP> H <SEP> L <SEP> B
<tb> C6F13CH2CON <SEP> [(C2H4O) 2 <SEP> CH3] <SEP> 2 <SEP> 16 <SEP> 3.63.10-4 <SEP> 8.54
<tb> C6F13CH2CON <SEP> [(C2H4O) 4 <SEP> CH3] <SEP> 2 <SEP> 18 <SEP> 8.76.10-4 <SEP> 10.0
<tb> C6F13CH2CON <SEP> [(C2H4O) 4 <SEP> CH3] <SEP> 2 <SEP> 24 <SEP> 1.10-3 <SEP> 11.2
<tb> C8F17CH2CON <SEP> [(C2H4O) 3 <SEP> CH3] <SEP> 2 <SEP> 20 <SEP> 1.34.10-5 <SEP> 7.28
<tb> C9H19CON <SEP> [(C2H4O) 4 <SEP> CH3] <SEP> 2 <SEP> 31 <SEP> 5.10-3 <SEP> 15.3
<Tb>

Claims (11)

1. New amides corresponding to the formula:

 in which R is a partially hydrogenated hydrocarbon, fluorocarbon or fluorocarbon chain containing 4 to 18 carbon atoms. Z and Z 'are identical or different alkyl or aralkyl groups having from 1 to 10 carbon atoms. n and n 'are integers identical or not between 1 and 10, 2. New amides according to claim 1 wherein Z and Z 'are methyl groups. 3. New amides according to claim 1 or 2 wherein R is an alkyl perfluorinated group. 4. New amides according to claim 1 or 2 wherein R is a perfluoroalkylmethylene group. 5. Process for preparing the products according to one of Claims 1 to 4, characterized in that an amine of the form is reacted.

 on an activated form of RCOOH acid. The process according to claim 5 wherein the activated form of the acid belongs to the group consisting of the halides of the acid. RCOOH and the form of the acid activated RCOOH. the BOP reagent. 7. Process according to claim 5 or 6, characterized in that the amine is obtained from a coupling reaction between benzylamine or an N-blocked form of diethanolamine and an activated form of an alkoxyethanol or of an alkoxypolyethoxyethanol. 8. Application of the products according to one of claims 1 to 4 or resulting from the process according to one of claims 5 to 7 to make microemulsions with an "oil" and water. 9. Application of the products according to claim 3 or 4 for mictoemulsions with a fluorinated "oil", for example perfluorodecalin and water. 10. Application of the products according to one of claims 1 to 4 for lowering the surface tension of water. 11. Application of the products according to one of claims 1 to 4 as metal complexing agents.