DD234274A1 - METHOD FOR PRODUCING NONTIONIC AND ANIONIC BORDER FLUID ACTIVE FERROCENE DERIVATIVES - Google Patents

Abstract

The invention relates to a process for the preparation of novel nonionic and anionic surface-active ferrocene derivatives which can be used as emulsion and suspension formers. According to the invention, ferrocenylalkyl derivatives are phosphorylated with ethylene oxide, chlorosulfonic acid or diphosphoric acid or their intermediates with sodium diethyl phosphite or with triethyl phosphite or reacted with methyl or ethyl magnesium halides. The ethyl (v-ferrocenylalkyl) phosphonates are applied as alkali salt or ammonium salt. In this way, by addition of ethylene oxide nonionic, by sulfation reaction sulfur-containing anionic by phosphorylation phosphoric anionic and by subsequent steps phosphorus-containing nonionic emulsion and suspension formers available.

Description

Field of application of the invention

The invention relates to a process for the preparation of novel nonionic and anionic surfactant ferrocene derivatives which can be used as emulsion and suspension formers.

For the application of ferrocene and ferrocene derivatives as well as other elemental organic and inorganic compounds in the art, for. As the lubricant application and the surface modification, or in medicine and biotechnology for influencing life processes by iron-containing and other elemental or inorganic compounds in many cases, the formation of emulsions or suspensions, alone or together with organic solvents required in water. The application of the process according to the invention for the preparation of nonionic and anionic surface-active ferrocene derivatives serves this type of application of ferrocene, its derivatives and other organometallic and inorganic compounds.

Characteristic of the known technical solutions

For emulsion and suspension processes, mainly nonionic and anionic surfactants are used. The preparation of stable water-soluble surfactant ferrocene derivatives and other organo-transition metal compounds having a surfactant character has hitherto been described only for cationic derivatives of ferrocene and other ff-aromatic transition metal complexes (G. Sonnek and Mitarb., Z. Chemie 21/1981 /, 331 and DD-WP 159842).

Object of the invention

It is the object of the invention to develop for emulsion and suspension processes of elemental organic and inorganic compounds particularly effective nonionic and anionic surface-active compounds which have high interfacial activity in the field of the invention and can thereby enable special molecular interactions against conventional surfactants.

Explanation of the essence of the invention

The object of the invention is achieved by a process for the preparation of novel nonionic and anionic surface active ferrocene derivatives of general formula I,

R ² R ¹ - / Fc / - (-C-) - XI

in the

R ^{1 is} hydrogen, an alkyl or aryl radical,

R ² and R ³ , which may be identical or different, are hydrogen or an alkyl radical, / Fc / a ferrocenyl radical, η is an integer between 1 and 20 and

X is one of the nonionic or anionic hydrophilic radicals customary in surfactants, such as the poly (oxyethylene) group, the dimethyl or diethylphosphoryl group, the sulfate, phosphate, phosphonate, ethylphosphonate or carboxyl group, in accordance with the invention by .omega.-ferrocenylalkanols general formula II,

R ² R ¹ - / Fc / - (-C-) - OH II

in the

R ¹ , R ² , R ³ , / Fc / and η have the abovementioned meanings, are reacted with ethylene oxide or with chlorosulfonic acid or diphosphoric acid with or without solvent under a protective gas atmosphere, or by the invention ω-Ferrocenylalkylchloride the general formula III

R ²

1 ^l

R ¹ - / Fc / - (- S -) - Cl III

j ^п

R ³

in the

R ¹ , R ² , R ³ , / Fc / and η have the abovementioned meanings, with sodium diethyl phosphite or with triethyl phosphite with or without solvent under a protective gas atmosphere first to diethyl (cü-ferrocenylalkyl) phosphonate of the general formula IV,

R ²

R ¹ - / Fc / - (-С-) _п - Р (0) (0С ₂ Н ₅ ) ₂ IV

in the

R ¹ , R ² , R ³ , / Fc / and η have the abovementioned meanings, and then reacted either with an up to four-fold molar excess of methyl or Ethylmagnesiumhalogeniden (Grignard compounds) in ω-Ferrocenylalkyl-dimethyl- or diethylphosphine oxide or with alkali hydroxide by partial hydrolysis in ethyl (ct> -ferrocenylalkyl) phosphonate.

In this way, stable, water-soluble nonionic and anionic emulsion and suspension formers, which contain chemically bound in the organic hydrophobic residue ferrocene, won.

The extraction of nonionic emulsion and suspension formers according to the invention is preferably carried out by addition of ethylene oxide to compounds of formula II by acid catalysis, preferably by means of boron trifluoride etherate, at temperatures between 60 and 100 ° C.

The extraction of sulfur-containing anionic emulsion and suspension formers according to the invention is preferably carried out by sulfation reaction of compounds of formula II by means of chlorosulfonic acid in ethereal solution. This reaction is carried out according to the invention at room temperature.

The extraction of anionic phosphorus-containing emulsion and suspension formers is carried out according to the invention preferably as a phosphorylation reaction of compounds of formula III with sodium diethyl phosphite (Michaelis-Becker reaction), which is advantageously carried out with or without solvent in the temperature range between 90 and 12O ⁰ C. Preferred solvent medium according to the invention is toluene for this reaction.

The extraction of nonionic phosphorus-containing emulsion and suspension formers is carried out according to the invention by reaction of intermediates of phosphorylation according to formula IV with methyl or Ethylmagnesiumhalogeniden to ω-Ferrocenylalkyl-dimethyl or diethylphosphinoxiden at temperatures between 90 and 100 ⁰ C. In this invention, ether after addition distilled off from heptane as a solution medium.

In order to form phosphorus-containing anionic emulsion and suspension formers, organic amine, preferably isobutanolamine, is used according to the invention for salt formation of ethyl (w-ferrocenylalkyl) phosphonate.

Chromatographic methods, preferably with aluminum oxide columns, are particularly suitable for purifying the sulfur-containing anionic emulsion and suspension formers or their intermediates prepared according to the invention. If they are acidic intermediates, the eluent is preferably acidified with acetic acid. Suitable eluents according to the invention are Вепгеп / methanol mixtures, preferably in a mass ratio of 1: 1.

The object of the invention is unexpectedly achieved without hydrolytic, complex-destructive action of the reactants under the reaction conditions according to the invention. The ferrocene-containing nonionic emulsifying and suspending agents prepared according to the invention are readily water-soluble in the corresponding alkyl chain length range, being stable in the aqueous solutions in contrast to most other 77-aromatic complexes and having high interfacial activity, which forms the basis for the emulsion and suspension action of the products represents. It is identified in the embodiments described below by the information on the lowering of the surface tension of the water and the interfacial tension between water and heptane.

Exemplary embodiments Example 1

4-ferrocenyl-butyl-poly (oxyethylene) / 12 EO adduct

In a three-necked flask equipped with spiral stirrer, gas inlet tube and reflux condenser, 2.0 g (7.75 mmol) of 4-ferrocenyl-butan-i-ol are introduced and added after flushing with nitrogen with two drops of boron trifluoride etherate. The flask is heated in an oil bath, and ethylene oxide is provided passed through the well stirred alcohol at reaction temperatures of 80 to 100 ⁰ C, until the desired degree of ethoxylation (12 moles of ethylene oxide per mole of alcohol) is reached. The uptake of ethylene oxide is continuous and is monitored by weight measurement . After 60 minutes, the Etr.ylenoxidzufuhr is interrupted and the oil bath removed. During cooling, nitrogen is introduced.

The reaction product is a mixture of homologous compounds with different polyether chain lengths / Fc / - (CH ₂ ) ₄ - (OCH ₂ CH ₂ ) _n -OH,

the statistical mean of which is an average of 12 moles of ethylene oxide per mole of alcohol, ie η = 12. Poly (oxyethylene) formed as by-products are shaken out with butan-2-one. Yield: 5.9 g of 4-ferrocenyl-butyl-poly (oxyethylene) / i 2 EO adduct. The product is clearly soluble in water. ¹ H NMR spectroscopic data: δ = 4.00 / Fc /; δ = 3.52 (-O-CH ₂ -CHr) _n ; δ = 1.50 (CH ₂ J ₄

Surfactant properties:

a. maximum surface tension decrease Осмс: 46,0mN / m

CMC: 0.7 x 10 ^"4 mol / l

b. maximum interfacial tension lowering (heptane / water)

6,4mN / m

C ₈ : 2.1 · 10 " ⁴ mol / l с contact angle

Similarly, non-ionic ethylene oxide adduct adducts of ω-ferrocenylalkanols of any alkyl chain length can be within the given limits and with any suitable degree of oxethylation.

Example 2

Sodium 7-ferrocenyl-heptyl-i-sulfate

A solution of 2.0 g of 7-ferrocenylheptan-i-ol (6.66 mmol) in 100 ml of absolute diethyl ether is added to a four-necked flask equipped with stirrer, reflux condenser, dropping funnel and gas inlet tube. While passing a nitrogen stream, a solution of 1.0 g of chlorosulfonic acid (8.58 mmol) in 60 ml of ether is slowly added dropwise at room temperature.

To characterize the very unstable in air 7-ferrocenyl-heptyl-1-sulfate, a portion of the filtrate is freed from the ether and the residue immediately taken up in benzene and purified by chromatography on an alumina column. After elution with benzene / ethanol mixture (1: 1), evaporation of the solvent and absorption in dichloromethane, the 7-ferrocenyl-heptyl-1-sulfate can be precipitated with heptane.

Elemental analysis of S- (p-bromobenzyl) -isothiuronium-7-ferrocenyl-heptyl-1-sulfate:

CHN

Re: 48.01% 5.32% 4.48%

Filled: 48.16% 5.05% 4.39%

To convert the 7-ferrocenyl-heptyl-i-sulfate in the sodium-7-ferrocenyl-heptyl-1-sulfate 100 ml of ethanol are added to the filtered ethereal solution and then the ether removed in vacuo, in the thus obtained ethanolic solution takes place Neutralization by adding 0.9 g of solid NaHCO ₃ (50% excess) and stirring the suspension under nitrogen (about seven to eight hours). After filtration and evaporation of the solvent, the residue is extracted with absolute alcohol. The crude product obtained by evaporation of the ethanol is recrystallized in acetone.

Even after repeated recrystallization, the product still contains sodium sulfate and water.

Yield: 2.9 g of sodium 7-ferrocenyl-heptyl-i-sulfate, mixed with 0.6 mol of Na ₂ SO ₄ and 0.2 mol of H ₂ OH% (89 ° C of theory).

Elemental analysis:

C H Fe

calculated: 41.58% 4.80% 11.37%

Filled: 41.48% 4.80% 11.21%

Surfactant properties:

a. maximum surface tension lowering Семе · '42,6mN / m

CMC: 1.2 x 10 ^-3 mol / l

b. maximum interfacial tension lowering (heptane / water) o "civk> 5.0mN / m

Example 3

Isobutanolamine salt of 7-ferrocenyl-heptyl-phosphonsäuremonoethy! Ester in a Vierhalskoiben equipped with stirrer, thermometer, dropping funnel and reflux condenser, a solution of 23.8 g of 7-ferrocenyl-i-chloro-heptane (74.7 mmol) Submitted to 50 ml of absolute toluene. 35.9 g of sodium diethyl phosphite (224.4 mmol), dissolved in 100 ml of toluene, are added dropwise with stirring to the boiling solution. In the course of the phosphonylation, sodium chloride precipitates as a viscous white precipitate. After four hours of reaction, the reaction mixture is allowed to cool and add so much water that the precipitate just dissolves.

There are three phases:

top: organic phase with the 7-ferrocenyl-heptyl-phosphonic acid diethyl ester middle: sodium salt of 7-ferrocenyl-heptyl-phosphonic acid monoethyl ester below: aqueous sodium chloride solution

The organic phase is separated and the remaining two phases extracted several times with ether. From the combined organic phases remains after drying over sodium sulfate and removal of the solvent, a residue of 24.6 g, which is purified by chromatography over an alumina column.

Eluent eluate

1. Petroleum ether 7-ferrocenylM-chloro-heptane

2. Ether / methanol (25: 1) 7-Ferrocenyl-heptyl-phosphonic acid diethyl ester

(14.5 g = 46.3% of theory)

The remaining two phases are acidified and again extracted several times with ether. Drying over sodium sulfate and removal of the solvent 7.5 g of 7-ferrocenyl-heptyl-phosphonic acid monoethyl ester (further 25.7% of theory) remain from the ethereal phase.

Overall, 72% of the theoretical yield of phosphorylation products are recovered.

9.5 g of 7-ferrocenyl-heptyl-phosphonic acid diethyl ester (22.62 mmol) can be by eight-hour saponification in alcoholic sodium hydroxide solution (6 g NaOH / 60 ml of water / 40 ml of ethanol) and after acidification, repeated extraction with ether, drying over

Dissolve sodium sulfate and remove the solvent in 6.9 g of 7-ferrocenyl-heptyl-phosphonic acid monoethyl ester (77.8% of theory).

The isobutanolamine salt is prepared by adding 0.6 g of isobutanolamine (6.74 mmol) dissolved in 8 ml of acetone to a solution of 2.0 g of 7-ferrocenyl-heptyl-phosphonic acid monoethyl ester (5.102 mmol) in 30 ml of acetone at room temperature. Slowly, a yellow precipitate forms, which is filtered off after prolonged standing.

Yield: 1.5 g of isobutanolamine salt of 7-ferrocenylheptylphosphonic acid monoethyl ester (61.1 "/ od. Th.) Melting point: 87 to 90.5 ⁰ C.

Surfactant properties:

a. maximum surface tension reduction

Осмо 44,0mN / m

CMC: 2.1 10 ~ ³ mol / l.

Claims (9)

Invention claim: 1. A process for the preparation of novel nonionic and anionic ferrocene-type surfactants of general formula I, R ² R ¹ - / Fc / - (- S -) _л -х ι in the R ^{1 is} hydrogen, an alkyl or aryl radical, R ² and R ³ , which can be identical or different, represent hydrogen or an alkyl radical / Fc / a ferrocenyl radical,
η is an integer between 1 and 20 and X represents one of the nonionic or anionic hydrophilic radicals customary in surfactants, such as the poly (oxyethylene) group, the dimethyl or diethylphosphoryl group, the sulfate, phosphate, phosphonate, ethylphosphonate or carboxyl group,
characterized in that ω-ferrocenylalkanols of the general formula II, R ² R ¹ - / Fc / - (-C-) _n - OH II R ³ in the R ¹ , R ² , R ³ , / Fc / and η have the abovementioned meanings, be reacted with Ethyloxid or with chlorosulfonic acid or diphosphoric acid with or without solvent under a protective gas atmosphere, or that ω-Ferrocenylalkylchloride the general formula IM, R ²
R ¹ - / Fc / - (-C-) - Cl III in the R ¹ , R ² , R ³ , / Fc / and η have the abovementioned meanings, with sodium diethyl phosphite or with triethyl phosphite with or without solvent under a protective gas atmosphere first to diethy4o) -ferrocenylalkyl) phosphonate of the general formula IV, R ² - / Fc / - (-C-) _n -P (0) (0C ₂ H ₅ ) ₂ IV in the R ¹ , R ² , R ³ , / Fc / and η have the abovementioned meanings, and then converted either with an up to four-fold molar excess of methyl or Ethylmagnesiumhdlogeniden in ω-Ferrocenylalkyl-dimethyl- or -diethylphosphinoxid or with alkali solution by partial hydrolysis in ethyl (ct> -ferrocenylalkyl) phosphonate. 2. The method according to item 1, characterized in that the reaction with ethylene oxide to compounds of formula II at temperatures between 60 and 100 ⁰ C under acidic catalysis, preferably by boron trifluoride etherate occurs. 3. The method according to item 1, characterized in that the reaction is carried out with chlorosulfonic acid to compounds of formula II in ethereal solution at room temperature. 4. The method according to item 1 and 3, characterized in that for the purification of the products preferably chromatographic separation of alumina columns with benzene / methanol mixtures, which are optionally acidified in acid intermediates with acetic acid, takes place. 5. The method according to item 1, characterized in that is used as the phosphorylating agent for compounds of formula III Natriumdiethylphosphit at temperatures of 90 to 120 ⁰ C. 6. The method according to item 1 and 5, characterized in that is used for the phosphorylation reaction of compounds of formula III toluene as a solution medium. 7. The method according to item 1,5und6, characterized in that the reaction of intermediates according to formula IV with methyl or Ethylmagnesiumhalogeniden to co-Ferrocenylalkyl-dimethyl- or -diethylphosphinoxiden is carried out at temperatures between 90 and 100 ° C. 8. The method of item 1, 5, 6 and 7, characterized in that the ether is distilled off to displace the ether in the reaction of intermediates of formula IV with methyl or Ethylmagnesiumhalogeniden after addition of heptane as the solvent. 9. The method according to item 1, 5 and 6, characterized in that the alkali metal salts of ethyl (u> -ferrocenylalkyl) phosphonate with organic amines, preferably with isobutanolamine, are converted into ammonium salts.