DD159842A3 - PROCESS FOR PREPARING NEW ORGANO TRANSITION METAL COMPOUNDS WITH TENSID CHARACTER - Google Patents

Abstract

Reaction of omega-haloalkyl transition metal compounds with triacylamides results in the organo-transition metal compounds according to the invention, which offer themselves for a novel modification of surfaces via surfactant adsorption layers. Such compounds can also be used for catalyst preparations and surface finishes. The reaction of the starting materials is carried out in polar solvents under inert gas atmosphere in Molverhaelnis between 5: 1 to 1:10 at temperatures between 0 and 100 degrees C, most advantageously in a closed vessel. Subsequently, the products obtained are purified by chromatography.

Description

Title of the invention

Process for the preparation of novel organo-transition metal compounds having a surfactant character

Field of application of the invention

The invention relates to a process for the preparation of novel surfactant-type organo-transition metal compounds. Compounds of this type are suitable for novel modification of surfactant adsorption layer interfaces. Such compounds can be used for the catalyst preparation and for the surface treatment.

Characteristic of the known technical solutions

The preparation of 1Γ-aromatic-transition metal complexes with sufficient solubility and surfactant character in an aqueous medium has not yet been described *

Object of the invention

It is the object of the invention to prepare surfactant-type organic transition metal compounds according to a simple method from Oo -haloalkyl transition metal compounds; , ,

Explanation of the essence of the invention

This object is achieved according to the invention by a process for the preparation of novel organo transition metal compounds of general formula I,

R ²

R ⁴

x ^@

in the R is a ^ -aromatic transition metal complex radical with elements of the 6 'to 8' subgroup of the Periodic Table _a in particular glycopentadienyl manganese tricarbonyl,

2 mesitylene tricarbonyl or ferrocene, R, R and R represent hydrogen, identical or different alkyl, cycloalkyl, alkenyl or aryl radicals, X is halogen, preferably chlorine or bromine, and h can assume the values 1 to 3.2, in which kr-haloalkyl transition metal compounds of general formula II,

R ¹ - (CH ₂ ) _n - χ ^1τ

in which R and X have the abovementioned meaning, with trialkyl amines of the general formula III,

_3

2 · 4 TTT

, R- Ν '- R * IH

in which R to R have the abovementioned meaning, are reacted in polar solvents under a protective gas atmosphere * The implementation erfplgt preferably in the loading ratio of 1: 5, but are molar ratios of Il to III between 5: 1 and. 1:10 possible.

Suitable polar solvents are alcohols, in particular the low molecular weight alcohols from C. to C _4, for example ethanol, as well as nitrobenzene, dimethylformamide or water, in particular, suitable. ,

It is advantageous to carry out the reaction in a one-pot process. To this end, the ω-haloalkyl transition metal compound optionally also diluted with a solvent is added to the amine III which has been initially introduced in the solvent at room temperature. Optionally II · The reaction can then be carried out in a closed vessel, such as sealed tube and autoclave, or in an open vessel under a protective gas atmosphere "The reaction is carried out between O to 100 ⁰ C, preferably between 70 to 90 ° C ·

In order to isolate the products produced according to the invention, it is often sufficient to remove the solvent and the excess reactant in a water-jet pump vacuum under possibly slight heating.

The Feinroinigung itself is carried out by chromatographic means of silica gel (particle size 100 to 200, in order, flow agent: alcohols of chain length C. to C., especially methanol).

With the compounds according to the invention, the technique is enriched by a substance with new properties which are lacking the known quaternary ammonium compounds. Namely, the novel compounds contain a TT aromatic complex with different transition metals in the hydrophobic part of the molecule instead of an aliphatic or araliphatic radical the boundary surfaces by formation of Tensidadsorptionsschichten, as was detected at fluid interfaces in aqueous medium by measuring the surface tension. "In this way, particularly structured metal-containing monolayers can be produced · This method is for the catalyst preparation of large. Meaning·

The essential difference of this new type of surfactant in comparison to the previously known surfactants is therefore that with these compounds, in contrast to the normal action of surfactants, the occupation of interfaces with metal-containing compounds is made possible. This is for example the result of the determined concentration surface chip

• 1-7 HfD -JCi Ώ O .. * 4; i. i-i ♦> r?

"2.

tion curve (CMC ~ ca. 10 tmol / 1), which proves the formation of a fluid adsorption layer with a metal-containing compound. "

According to the process of the invention, the various-8th organo transition metal compounds having a surfactant character of hitherto unknown composition are easy to prepare. The products obtained according to the invention can be used, optionally without expensive purification operation, as active component for catalyst preparation or surface modification (also of metals).

Another advantage of the erfindungegemäßen method is that easily manufactured starting compounds ^ Ä "N * Nesmejanov, -L * M" Korneva and M _e I "Rybi-nskaja, Koordinationechemie (USSR) 3, 1394 (1977} 7 are used and the required amines are available ·

embodiments

Example 1 . _

y-iCyclopentadienylmangaritricarbonylJ-heptyltrimethyl-

ammonium chloride ·

To 1.6 g (5 mmol) of 7-chloroheptyl-cyclopentadienylmangantricarbonyl in 2 ml of abs · ethanol are added 2.4 g (41 mmol) of trimethylamine in 3 ml of abs. Ethanol under! ^ - Atmosphere placed in a bomb tube and heated for about 6 hours at 80 to 90 ⁰ C * Then the solvent and the excess amine distilled off *

-As a residue remains a pale yellow viscous liquid, - the crystallized after long standing, "A fine cleaning is carried out by preparative Dünnschichtchrornatographie or column chromatography (silica gel 100 to 200 u, eluent: methanol) * Yield: 1.8 g (96% of Theory) MS ς m / e 34.5 (M-CH ₃ Cl)

0 /

Cl content: over "9.0 70 ge f. 8.4 % i

Example 2

, S-iCyciopentadienyimangantricarbonylJ-pentyldimethyldodecylammoniumchlorid

To 0.5 g (16 mmol) of 6-chloro-pentyl-cyclopentadienyl manganese tricarbonyl in 4 ml abs. Ethanol are 3.4 g (16 mmol) of dimethyl-dodecylamine in 4 ml of ethanol under NU atmosphere in a bomb tube and heated at 80 to 90 ⁰ C for about 6 hours.

Subsequently, the solvent is distilled off.

The separation of the excess amine is carried out by means of chromatography or by conversion into the hydr.chloride and subsequent filtration (partial crystallization),

The residue remaining is a pale yellow viscous liquid "which crystallizes after several days." Yield: 0.75 g (90 % of theory) MS: m / e 471 (M-CH ₃ Cl) Cl content calc. 6.8 % F _# 6.2 %.

Example 3

3- (Mesityl-chromtricarbony1) -propy1-trimethylammonium bromide

To 1 g (2 _r 7 mmol) of S-bromo-propyl-mesityl-chromotricarbonyl. in 10 ml of ethanol, 0.8 g (14 mmol) of trimethylamine in 5 ml of ethanol under N 2 atmosphere in a bomb tube and heated Etv \ / a 5 hours at 80 C. »Then the solvent and the excess Ämin are distilled off ·

The residue remaining is a yellow-green crystalline residue which is recrystallised in ethanol.

Yield * I ₁ O g '(91% of theory) MS ί m / e 339 (M-CH ₃ Br) Br-Gehalti about 18.4% _e'

gef "17.9 %. ·

Example 4:

7 ~ Ferrocenyl-heptyltrimethylammonium chloride To 1.8 g (5.6 mmol) of 7-ferrocenylheptylchloriä in 3 ml of abs * ethanol are 3.3 g (56 mmol) of trimethylamine in 4 ml of abs. Ethanol under N ₂ atmosphere in a bomb tube and heated for about 8 hours at 80 ⁰ C * -Finally the solvent and the excess amine distilled off ·

Yellow crystals remain as residue. Purification takes place by crystallization in ethanol-ethyl acetate mixtures.

Yield: 1.6 g. (80.9% of theory) MS. : m / e 327 (M-CH ₃ Cl)

Cl content: over 9.38%

ge1> 9.6-6 % '

Claims (4)

·· £ .11 fey z 1 Introduction sans p.rue h Process for the preparation of novel organo-transition metal compounds having a surfactant character of the general formula I ₁ R ^{2 1} O- - (CH ₂ J _n - ^ - R in the R is a ^ -aromatic transition metal complex radical with elements of the 6th to 8th subgroup of the Periodic Table, in particular cyclopentadienyl manganese tricarbonyl, mesitylene tricarbonyl or ferrocene, 2. » Process according to item 1, characterized in that the reaction of II with III in a molar ratio between 5 ί 1 and 1 ί 10, preferably 1: 5, is carried out * 2 3 4 · R, R and R are hydrogen, same or different Represent alkyl, cycloalkyl, alkenyl or aryl radicals,
X is halogen, preferably chlorine or bromine, and η can assume the values 1 to 12, characterized in that to-haloalkyl transition metal compounds of general formula II, R ¹ - (CHg) _n - X II in which R and X have the abovementioned meaning, with trialkylamines of the general formula III, 'R ³ R ² - N - R ⁴ III in which R to R have the abovementioned meaning, in polar solvents under a protective gas atmosphere at temperatures between 0 to 100 ⁰ C, in particular between 70 to 90 ⁰ C, to be implemented. ··. β 3 * Method according to item 1 and 2, characterized in that are used as polar solvents alkenols, in particular low molecular weight alkanols having 1 to 4 carbon atoms such as ethanol, and nitrobenzene, dimethylformamide or water « 4, method according to item 1 to 3 _t, characterized in that the organo-transition metal compounds are subsequently purified by chromatography »