DE10063332A1 - Adhesion promoter, useful for dental technology, comprises a compound containing a polymerizable vinylic unit, a hydrophobic flexible spacer and a functional unit containing an adhesive group - Google Patents

Abstract

An adhesion promoter (I) comprises a compound (X, Y, Z) of at least three components, when (X) is a polymerizable vinylic unit, (Y) is a hydrophobic flexible spacer and (Z) is a functional unit containing an adhesive group (Z1).

Description

This invention relates to compounds for use as adhesion promoters between Metal or dental material and a polymerizable material.

The invention is in particular the object of a stable composite between metal / alloy or tooth material and a polymerizable material (Plastic / liquid systems, composites in paste form etc.).

The invention solves this problem according to the features of patent claim 1.

The basic idea is that on the one hand by the detention groups of the mono a strong adhesive interaction with the metal surface arises and on the other hand in the course of curing of the polymerizable material by copolymerization, incorporation into the polymer network takes place.

The polymerizable compounds have entwe as a characteristic feature preferably a phosphonate end group (monomer type 1) or a cyclic Disulfide end group (monomer type 2) and are in solution individually or as Mi used.  

1 Introduction

The connection of similar or different materials with the help of Glue is of great importance in many areas of industrial engineering. It is found Today hardly any industry in which the gluing is not in any form is applied. Also in our daily and professional life are adhesives and the tools and methods of application necessary for their processing self-evident component.

About 50 years ago, adhesives were the first to be used in aircraft construction Application.

By gluing wing flaps or stiffening of exterior walls Alloy / alloys could reduce the total weight and thus a total of Fuel savings can be achieved. Other industries quickly recognized the breadth of application the adhesive technology. Such are applications in vehicle construction, mechanical engineering, bridge construction or in the field of electronics, paper processing or in medical technology. Through consistent development and adaptation to required specific Properties can be applied today in dentistry, and adhesives High-performance hotmelt adhesives even effective on oily or rusty surfaces be applied.

In the field of medical technology, different materials are often used, such as Metals / alloys, ceramics or plastics joined together. to Reliable functionality of the adhesive system used is the property of Biocompatibility required, since in these cases, the adhesive direct contact with the skin of the patient. Is an adhesive system for making Dental restorations used, there is the additional difficulty that the composite also in a constantly watery environment must be durable.  

Further optimizations of the properties of adhesives are becoming great today Efforts are made since their overall industrial application is economical and the potential scope is far from exhausted.  

2. Basics 2.1. Basis of adhesion of the adhesives

The adhesion of an adhesive or adhesive on or to a substrate can take place in three principally different ways [1-4]:

• - Mechanical bond
• - Chemical compound
• - Adhesive composite

The transitions between these three types of composite are fluid, so that in individual cases a clear distinction is almost impossible. However, as a rule, always one of the composite principles predominate.

The composite mechanism of the mechanical bond is based on a principle physical anchoring or crosslinking of adhesive and backing, whose Basis macro or micro anchorage sites as well as anchorages on molecular Level can be. The effect is due to different shapes of the surface of the affected to sticking parts. It is independent of the molecular structure of the Adhesive. In the following discussion, the mechanical bond is not mentioned.

2.1.1. Wetting and wettability

For the adhesives to have good potency, they must be in close contact can come with the surfaces to be bonded. The process of making this close molecular contact between the adhesive and the surface to be bonded is referred to as wetting. The willingness of the surface to be moistened is called wettability [5, 6].  

A measure of the wettability of a surface by a particular liquid is the so-called contact or contact angle, which forms between the two phases.

The wetting of the surface with the adhesive is better, the smaller the Contact angle θ is, d. H. the less pronounced is the teardrop shape. An optimal Wetting is present at a contact angle of zero, the adhesive forms in this Case a quasi monomolecular uniform layer on the substrate surface. An essential condition for a good wetting is that the surface tension (also called surface energy) of the adhesive is smaller or at least equal that of the surface of the solid to be wetted (to be bonded) is.

Fig. 2.1 Schematic representation of the contact angle

This is the reason that solids with high or medium Surface energy, such as metals, porcelain, glass or wood, easier to glue than Plastics. The surface energies of the plastics are often even lower than that the adhesives. This is especially true for polytetrafluoroethylene, which is the cause is that this material is almost impossible to bond [1, 2, 7; 8th].  

From what has been said about wetting and wettability, it becomes immediately clear why attach so much importance to the pretreatment of the surfaces to be bonded is: through the respective pretreatment processes, the material surfaces exposed, whereby only an intimate contact with the adhesive is possible.

2.1.2. Chemistry of the contact surface

The most common adhesive mechanism is the adhesive bond. Under the The term adhesive bond or adhesion is understood to mean all binding mechanisms which cause the cohesion of matter at interfaces. These are in primarily hydrogen bonds, from the Waals interactions as well mechanical anchors due to micro-anchors.

Real covalent chemical bonds can be between glue and Form substrate surface only if both partners have reactive groups. Of course, the partial occurrence is covalent, ionic or metallic Bindings as well as complex bonds should be considered. A good example of this is the silanization of inorganic materials with organosilanes [9-12].

Silanization is the most important and effective surface treatment method of glasses, ceramics, metal oxides, as well as natural and synthetic silicas like sand or quartz [13-19]. Basically, all other solids, which can their surfaces hydroxyl groups, be silanized.

Silanization means surface treatment with special silanes. The silanes have a hybrid character [20, 21], ie they have both an organic and an inorganic molecule content. For example:

CH ₂ = CH-SiCl ₃
vinyltrichlorosilane

(CH ₂ CH-Si (OC ₂ H ₅ ) ₃
vinyltriethoxysilane

3-glycidoxypropyltrimethoxysilane

3-mercaptopropyltrimethoxysilane

3-aminopropyltriethoxysilane

3-Methacryloyloxypropyltrimethoxysilane

Fig. 2.1 Some common organosilanes

Before the respective silane can be coupled to the glass surface, must first hydrolyzes the methoxy, ethoxy or chloride groups attached to the silicon become. This reaction can either take place on the surface itself, or it is in acidic aqueous solution before the coating process [22, 23].

The resulting silanol can with good distribution a uniform coating form on the glass and with its surface hydroxyl groups under formation  Covalent bonds condense or form hydrogen bonds. at This condensation reaction forms coatings on the glass with layer thicknesses between 5 to 20 nm, which are completely hydrophobic and thus water-insoluble.

a. Hydrolysis of the silane

General:

specifically:

b. Binding of the silanol to the glass surface

Fig. 2.2 Reaction of the silane with the glasses

The most important result of a good silanization is the training a chemical bond between matrix resin and the coated glass surface, when the silane used has a suitable organic functional group.

Thus, for example, vinyl or methacrylic silanes can polymerize with double bonds of the matrix resin [24-29], whereas aminosilanes can undergo polycondensation reactions [10, 30] and glasses coated with mercaptosilanes can participate in rubber vulcanization [31]. When selecting the corresponding silane, it is therefore always important to ensure that its organofunctional groups can react with the matrix resin. Fig. 2.3 shows some reaction possibilities as well as a schematic form of the bond between the glass surface and the matrix polymer via the silane coating.

begin

addition

condensation

Fig. 2.3 Reaction possibilities of the organofunctional silane groups 2.1.3. Adhesives for dentistry

In dentistry, the adhesive restoration of damaged hard tooth substance has a special character Meaning attained [32-34]. This technique allows tooth-colored plastics to be firm and firm permanently connect with the enamel. Now you have a lot of Adhesion systems designed to be able to form a chemical compound for Produce dentin. All of these adhesive systems are special ones Methacrylate derivatives [35-39].

These adhesive systems are intended to chemically react either with the inorganic component of dentin [40] (hydroxyapatite) or with the organic component (collagen) [41], but on the other hand because of the methacrylic group with the dental plastic [42, 43] Methacrylate is, connect.

4-meta = 4-methacryloyloxyethyl trimellitate anhydride

NTG-GMA = reaction product of N (p-tolyl) glycine and glycidyl methacrylate

Reaction product of bis-GMA and POCl ₃

2-Methacryloyloxyethylphenylphosphat

Hydroxyethyl methacrylate + glutardialdehyde = GLUMA

Fig. 2.4 Adhesive compounds 2.2. Self-assembled monolayers

Self-Assembled Monolayers (also called Self-Assembly Molecules or Self-Organizing Monolayers abbreviation: SAMs) were already investigated and described in 1940 [44], but it was not until 1983 that this order process was technically exploited [45]. Self-assembled monolayers basically have two different active groups,  in between is a spacer, z. B. aliphatic spacer. A group of them interacts with the metal surface and the other end group acts with a special property or connects to another functional connection. The SAM's form chemical bonds that resist the attack of water and all at the same time prevent electrochemical reactions at the intermediate layers [46, 47].

The self-assembly of the monomolecular layers on a solid surface offers rational process for the preparation of an intermediate layer with a defined Composition, structure and thickness. This also results in a control of chemical and physical properties of the intermediate layers in such different phenomena such as catalysis, corrosion, lubrication and adhesion [48-50].

2.2.1. Self-assembled monolayers of organosulfur compounds

Much of the research reported so far about SAM's relates to Alkanethiols (R-SH) [52-60]. The SAM's are usually more stable than their counterparts  organic crystals, and large areas are much easier to form. infrared spectroscopic [61-65] and electrochemical studies [66-69] were performed and have shown that the self-reactions formed by alkanethiols and dialkyl disulphides Assembled monolayers are highly ordered.

Porter and co-workers [70, 71] proposed that the following reaction equation for electrochemically deposited thiolates could apply to gold from an ethanol / KOH solution. This includes an at least two-stage process, physisorption and then chemisorption.

X- (CH ₂ ) _n -SH _sol → X- (CH ₂ ) _n -SH _ad

Au + X (CH ₂ ) _n -SH _ad → Au-S- (CH ₂ ) _n X + H ⁺ + 1e ^-

Sol .: solution; ad .: Adsorption

The film formed by chemisorption of the alkanethiols on gold desorbs in an alkaline solution (pH <11) by oxidative and reductive reactions.

Au-S- (CH ₂ ) _n CH ₃ + 2 H ₂ O → Au (O) + ^- O ₂ S- (CH ₂ ) _n CH ₃ + 4H ⁺ + 3e ^-

Au-S- (CH ₂ ) _n CH ₃ + e ^- → Au (O) + ^- S- (CH ₂ ) _n CH ₃

The packing density and surface order have great influences on the properties of the SAM's. It has been reported [70-73] that the electrochemically deposited monolayers have similar structures and interlayer properties to those formed by self-assembly of the analogous alkanethiols when the thiols have between 10 and 22 methylene groups in the carbon chain. Among 10 methylene groups, the monolayers are densely packed, but over 22 methylene groups, the monolayers are not properly formed. Lee et al. [74-76] studied structures and friction properties of SAMs of adsorption on Au (111) of three homologous C ₁₇ alkanethiols, heptadecanethiol [HS- (CH ₂ ) ₁₆ CH ₃ ; n-C17], 2,2-dipentadecyl-1,3-propanedithiol {(HSCH ₂ ) ₂ C [(CH ₂ ) ₁₄ CH ₃ ] ₂ ; d-C17}, and 2-pentadecyl-1,3-propanedithiol [CH ₃ (CH _{2) 14} CH (CH ₂ SH) ₂ m-C17]. The results indicate that the film of the nC ₁₇ compounds has the lowest coefficient of friction and the highest relative density, d-C17 has a slightly higher coefficient of friction, and the film of m-C17 has a much higher coefficient of friction. The main reason for this is that m-C17 forms films with inferior packing density and crystal ordering compared to n-C17 and d-C17.

Three factors are important for the construction of the stable alkanethiol monolayer:

• The adsorption of the surface active sulfur groups on the substrate,
• - the distributive interactive interactions between alkyl chains, and
• - the interactions between the functional end groups and the outer one Medium.

Disulfides (R-S-S-R ') have been studied in less detail [46, 77-79], although with them the first monolayers were obtained on gold. It was accepted that on Gold adsorbing disulfides form similar surface species as in the Alkanethiols observed. Hagenhoff et al. [80] have with TOF-SIMS (time-of-flight secondary ion mass spectrometry) measured disulfides on gold and postulated that the Adsorption of disulfides on gold is a two-step process. The first step is the Breakage of the S-S bond; in the second step, the molecules bind individually to the substrates, and thus form the same surface compositions as alkanethiols.

Recently, two Japanese scientists [81] provided direct evidence images by STM (scanning tunneling microscopy) for the dissociative adsorption of unsymmetrical disulfide SAMs on Au (111). They measured the adsorption process of 11-hydroxyundecyl octadecyl disulfide [CH ₃ (CH ₂ ) ₁₇ SS- (CH ₂ ) ₁₁ OH] on gold (111) during the growth period of the SAMs by STM. The results of STM revealed two separate phases which have different orientations and are identical to the length of the molecular group CH ₃ (CH ₂ ) ₁₇ S and HO (CH ₂ ) ₁₁ S.

Dialkyl sulfides have been studied even less, despite their stability to nucleophilic reactions or oxidation compared to thiols or disulfides [77, 82, 83], which is a great advantage in the synthesis of the compounds. There are two different views on the interaction of dialkyl sulfides:
In a series of experiments, some dialkyl sulphides taken up in gold, e.g. For example, diphenylsulfides and ethylphenylsulfides were investigated by linear voltage sweeps (LVS), X-ray photoelectron spectroscopy (XPS), and infrared reflection absorption spectroscopy (IRRAS) [84]. The results of the investigation were explained by the form of cleavage of the CS bond, which involved the formation of the gold thiolate. The studies on disulfides and sulfides on silver by surface-enhanced Raman spectroscopy (SERS) gave the same explanation, ie, in the sense of cleavage of the CS bond [85]. Other researchers [77] studied the adsorption of symmetric and unsymmetrical dialkyl sulfides on gold by XPS and voltammetry measurements and compared film formation of dialkyl sulfides on gold in an ethanol solution by kinetic studies of disulfides and thiols. They postulated that there is no cleavage of the CS bond in adsorption of the sulfides, and that the rate of film formation of the sulfides is much slower than that of the thiols and disulfides (about 3 orders of magnitude).

2.2.2. Self-assembled monolayers of phosphonate compounds

SAMs of alkylphosphonates have been studied for several years [86-88].

Although organosulfur compounds are very useful in bonding with precious metals (Gold, silver, platinum), their affinity to non-noble metals, e.g. As iron, stainless Steel and aluminum, limited.

Many scientists have done painstaking research on alkyl phosphonates different non-precious metals [86, 89-97]. The experimental results point out that phosphonates under certain conditions stable SAM's on can form a number of metals.  

Alkylphosphonic acids are classified as non-noble metals or metal oxides (hydroxides) to form monolayers that are less ordered than alkylthiols on gold [98]. The resistance of the intermediate layers to attacks by the solvent is dependent of the chain length of the methylene groups. The phosphonate with the chain length 8 or longer is SAM's with the most pronounced features. The result is analogous to the thiols.

The films of the phosphonates formed on base metal behave very stably. On Film of phosphonate on aluminum was dipped in water; and after 14 days No major changes in the properties due to the measurement of the Contact angle detected [96]. Desorb the SAMs of the phosphonates on iron oxide only from a temperature of 340 ° C [91]. It is believed that this stability is due to the formation of P-O-M (M = metal) bonds results.

2.2.3. Self-assembled monolayers of other compounds

Carboxylic acids [93, 99] and some DNA nucleobases [100] can also be self-assembled Monolayers train on metal. Siloxanes give SAMs on silica [101, 102]. Carboxylic groups of the carboxylic acid can be reacted with hydroxy groups on the Condense metal surface and form a carboxylate-metal salt. In general  Phosphonic acids combine more strongly with metal oxides than organic acids, but Functional phosphonic acids with long chains are relatively difficult to synthesize. Recent studies found that the adhesion of the carboxylic acids to alumina and other substrates can be greatly increased by pretreatment [103, 104]. The influence of structural parameters (substrates, chain length, end groups) on the Properties of surface bonding, chain conformation, and chemical stability of the Carbonic acid monolayer on alumina, copper, and silver films was included investigated [61, 105-107]. A bond geometry that strongly depends on the metal oxide Substrate is determines the packing density and chain conformation.

The experimental results prove that carboxylic acids are strongest in silver oxide via a bidentate surface bond and most weakly aluminum or Attach copper oxide over a monodentate bond [62, 63, 108].

Furthermore, it has been extensively studied that siloxanes are adsorbed on silica and train SAM's [109-111]. But both her self-organization and her resulting layer structure differ from those of thiols, phosphonates and organic acids. Because of the similarity between the substrate and the Adhesion molecules, the siloxanes can be crosslinked before or after adsorption, alignment and packing of the organic groups from the siloxane backbone and not be controlled by the substrate.  

For the nucleobases of DNA, the mechanism is still unclear. Ratner and Employees [100, 112-114] investigated self-assembled purines and pyrimidines Gold surfaces by AFM (Atomic Force Microscopy). They pointed out that Purine, adenine, thymine and cytosine arranged on gold two-dimensional lattice works training, although only monolayer but no multilayer exist. Compared to the SAMs of the thiols on gold is the rate of monolayer formation of the Nucleobases very slowly (about 24 to 48 hours). It is believed that the N-H group reacts with the surface and then an N-Au bond is formed.  

3. Task

In this work, multifunctional compounds were synthesized in which polymerizable head groups (A-) via hydrophobic-flexible spacer with Bonding groups (B) are linked. These monomers should be used as new adhesion promoters permanent bond between common materials such as plastics, Allow metals / alloys or metal oxides. The length of the Spacers and the end group in the side chain are varied, and it should be the chemical and physical properties depending on the molecular structure be explored.

Accompanying the synthesis of the multifunctional compounds were aptitude tests for Composite strength provided.

The following specifications have been made:

• - Methacrylic acid as a polymerizable group
• - Oligomethylene spacer as a flexible part
• - Sulfur, phosphorus and nitrogen-containing radicals as a bonding group
  

n = 1, 3, 5 or 6; X, Y = -O-, -NH- or -N (CH ₃

) -
R = radicals with different functional groups

Fig. 3.1 Structural formula of the target compounds 4. Presentation of the results 4.1. synthesis strategy

First, selected α, ω-diols or α, ω-diamines were combined on one side with methacrylic acid and from these then linear and branched monomers were prepared with different adhesion groups.

• - Synthesis of building blocks with methacrylic group (A-)
  CH ₂ = C (CH ₃ ) -CO-X- (CH ₂ ) _n -YH
  X, Y = O, NH, NCH ₃ ; n = 2, 6, 10, 12;
• - Synthesis of the A- - B, A - - -B- - -A monomers
  [CH ₂ = C (CH ₃ ) -CO-X- (CH ₂ ) _n -Y-] _m R
  n = 2, 6, 10, 12; X, Y = O, NH; NCH ₃ ;
  R = various radicals with functional groups
  m = 1, at A- -B; m = 2, for A- - -B - - -A
• - Synthesis of the monomers of the star-shaped molecule
  

For the spacer groups in the monomers, flexible alkyl groups of different chain length, -O- (CH ₂ ) ₆ -O-, -O- (CH ₂ ) ₁₀ -O-, -NH- (CH ₂ ) ₁₀ -NH-, and - (CH ₃ ) N- (CH ₂ ) ₁₂ -N (CH ₃ ) - used. As the bonding group (B - -), some sulfur-containing compounds such as sulfide -C (O) CH ₂ SCH ₂ CH ₂ SCH ₂ C (O) -, disulfide -C (O) CH ₂ CH ₂ SSCH ₂ CH ₂ C ( O) -, and the lipoic acid radical introduced. To investigate the influence of different groups on noble metal or non-noble metal, monomers with nucleobase groups, thymine and orotic acid groups, and phosphonoacetyl groups were compared.

The synthesis of the spacer components with polymerizable methacryloyl group (A - - -) was through a classical esterification reaction with a few drops concentrated sulfuric acid as a catalyst in a solution of the corresponding Acid and a diol [115]. In the presentation of Spacer components with amino group became a diamine and Methacrylic anhydride used.

Esterification or amidation of the spacer components with the carboxyl function the adhesive groups by suitable coupling reagents (eg., DCC, CDI or EEDQ) led to the monomers of the type A - - B and A - - -B - - -A.

The starting compound of the star-shaped molecule (A - - -B ¹ - - -B ² ) was a Fmoc-protected phosphotyrosine. The esterification of the compound with the spacer component 10-hydroxydecyl methacrylate was carried out by the coupling reagent DCC. To cleave the Fmoc protecting group, the product was treated with 1,8-diazabicyclo (5.4.0) -7-undecene (DBU).

The synthesized compounds were analyzed by mass spectrometry, IR and NMR spectroscopy and identified by elemental analysis. in the Result report, representative spectra are mapped; find the rest in the appendix.

4.2. Representation of the building block components with terminal methacryloyl groups

[CH ₂ = C (CH ₃ ) -CO] ₂ O + H ₂ N- (CH ₂ ) ₁₀ -NH ₂ → CH ₂ = C (CH ₃ ) -CO-NH- (CH ₂ ) ₁₀ -NH ₂ + CH ₂ = C (CH ₃ ) -CO-OH

4.2.1. Preparation of the ω-hydroxyalkyl methacrylates (I, II)

6-Hydroxyhexyl methacrylate (I) and 10-hydroxydecyl methacrylate (II) were obtained via the azeotropic esterification with 1,6-hydroxyhexanediol or 1,10-hydroxydecanediol with the same molar ratio of methacrylic acid. The two crude products were washed with water, purified on a silica gel column and characterized by mass spectrometry, CHN analysis, ¹ H-NMR and IR spectroscopy.

Tab. 4.1 Signal assignment

In Fig. 4.2 it can be seen that in the product shown there is only one main component (peak 736) and a very small amount of impurity (peak 145). The major component (peak 736) was further analyzed by mass spectrum and a result given in Fig. 4.3.

Tab. 4.2 Fragmentations

MS (CI): MH ⁺

= 243

M / Z fragment 283 [Allyl + M] ⁺ 271 [Ethyl + M] ⁺ 225, 212, 185, etc. Thermal fragments

Tab. 4.3 Assignment

Wave number / cm ^-1 Grouping or vibration 3354 OH Valenzschwgg. 2928 and 2855 aliphatic C-H valence schwgg. 1720 C = O Carbonylschwgg. 1638 C = C Valenzschwgg.

4.2.2. Preparation of methacrylic acid-10-aminodecylamide (III)

A solution of methacrylic anhydride was added to a solution of 1,10- Diaminodecane and N-methylmorpholine in chloroform dropped at RT. To Work-up of the reaction mixture was the crude product as methacrylic acid 10-aminodecylamide hydrochloride crystallized from water, and to Release of the primary amino group was accompanied by the hydrochloride Treated with potassium carbonate solution [116, 117].

Identification:  

Tab. 4.4 Signal assignment

Tab. 4.5 Fragmentations

MS (CI): MH ⁺

= 241

M / Z fragment 281 [Allyl + M] ⁺ 269 [Ethyl + M] ⁺ 223, 211, 154, etc. Thermal fragments

Tab. 4.6 Assignment

Wave number / cm ^-1 Grouping or vibration 3317 NH Valenzschwgg. 2921 u. 2849 aliphatic C-H valence schwgg. 1656 C = O Carbonylschwgg. 1618 C = C Valenzschwgg.

4.3. Representation of the monomers with adhesive groups 4.3.1. Representation of the sulfur-containing monomers 4.3.1.1. Preparation of the monomers with lipoic acid ester

The introductions of the terminal lipoic acid esters were carried out by esterification as in Scheme 1 [118-121].

The esterification with lipoic acid via coupling reagent gave sufficient yields (about 60%). All crude products were purified on a silica gel column with CH ₂ Cl ₂ / CH ₃ OH = 99/1 (v / v) as the eluent.

Identification:  

Tab. 4.7 Signal assignment

Tab. 4.8 Fragmentations

MS (CI): MH ⁺

= 431

M / Z fragment 471 [Allyl + M] ⁺ 459 [Ethyl + M] ⁺ 345, 189, 157, etc. Thermal fragments

Tab. 4.9 Assignment

Wave number / cm ^-1 Grouping or vibration 2934 u. 2858 aliphatic C-H valence schwgg. 1734 and 1719 C = O Carbonylschwgg. 1638 C = C Valenzschwgg.

4.3.1.2. Preparation of the monomers with lipoamide

As a model compound, lipoic acid 2-methacryloyloxyethylamide (.IX.) Was synthesized [122-124]. The crude product was filtered off and then purified on a silica gel column. Further, the compound N was ^α- methacryloyl, N ^ω -lipoyl-1,10-diaminodecane (X) and N ^α -methyl, N ^α -methacryloyl, N ^ω -methyl, N ^ω -lipoyl-1,12-diaminododecane (XI ) with good yield.

Identification:  

Tab. 4.10 Signal assignment

Table 4.11 Fragmentations

MS (CI): MH ⁺

= 429

M / Z fragment 469 [Allyl + M] ⁺ 457 [Ethyl + M] ⁺ 364, 241, 189, etc. Thermal fragments

Tab. 4.12 Assignment

Wave number / cm ^-1 Grouping or vibration 3311 N-H Valenzschwgg. 2923 u. 2850 aliphatic C-H valence schwgg. 1694 and 1641 C = O Carbonylschwgg. 1607 C = C Valenzschwgg.

Tab. 4.13 Signal assignment

Table 4.14 Fragmentations

MS (CI): MH ⁺

= 485

M / Z fragment 525 [Allyl + M] ⁺ 513 [Ethyl + M] ⁺ 455, 420, 297, etc. Thermal fragments

4.3.1.3. Preparation of the monomers 2,2 '- (Ethylenedithio) -diacetic acid bis (2-methacryloyloxyethyl) ester (VII)

The monosulfide compound was prepared analogously to the lipoic acid ester components described above (see Section 4.3.1.1). The esterification by the coupling reagent N, N'-dicyclohexylcarbodiimide (DCC) succeeded with a good yield of 81%. The substance was purified on a silica gel column with CH ₂ Cl ₂ as eluent and identified by mass spectrometry, ¹ H-NMR and IR spectroscopy.

Identification:  

Table 4.15 Fragmentations

MS (CI): M ⁺

= 434

M / Z fragment 349 [CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ OOCCH ₂ SCH ₂ CH ₂ SCH ₂ COOCH ₂ CH ₂ ) ⁺ 305 [CH ₂ = C (CH ₃ ) -COOCH ₂ CH ₂ OOC-CH ₂ SCH ₂ CH ₂ SCH ₂ -CO] ⁺ 231 [CH ₂ = C (CH ₃ ) -COOCH ₂ CH ₂ OOC-CH ₂ SCH ₂ CH ₂ ] ⁺ 113 [CH ₂ = C (CH ₃ ) -COOCH ₂ CH ₂ ] ⁺

4.3.1.4. Preparation of the monomers 3,3'-dithio- dipropionic acid bis (2-methacryloyloxyethyl) ester (VIII)

The starting compound used for the esterification were 3,3'-dithio-dipropionic acid and 2-hydroxyethyl methacrylate. For working up of the product, column separation was carried out on silica gel with CH ₂ Cl ₂ / CH ₃ OH as eluent.

Identification:  

Tab. 4.16 Signal assignment

In Fig. 4.20. the synthesis of thymine-1-acetic acid (XII) is shown. The synthesis was carried out in a two-step one-pot reaction [125, 126]. Thymine was dissolved in aqueous KOH solution and activated at the N1 site. The solution was heated and then slowly added dropwise methyl bromoacetate in slight excess. The nucleophilic substitution took place at the N1 atom of thymine. This was obtained as a non-isolated intermediate of thymine-1-acetic acid methyl ester. Further stirring at room temperature (3-4 h, TLC control) saponified the ester, the product being present in a strongly alkaline medium as a carboxylate ion. Acidification led to the precipitation of thymine-1-acetic acid. The product was filtered off and dried at 40 ° C in an oil pump vacuum.

Identification:  

Table 4.17 Fragmentations

MS (CI): MH ⁺

= 185

M / Z fragment 225 [Allyl + M] ⁺ 213 [Ethyl + M] ⁺ 167 [MH-H ₂ O] ⁺ 139 [M-COOH] ⁺ 127 Reactant contamination

4.3.2.2. Preparation of thymine-1-acetic acid 2-methacryloyloxy ethyl ester (XIII)

The synthesis route of thymine-1-acetic acid 2-methacryloyloxyethylester (XIII) is shown in Fig. 4.19. To activate the carboxylic acid, the coupling reagent 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ) was used [127, 128]. The crude product was washed with 3N HCl and demineralized water and then recrystallized from isopropanol with a good yield (81%).

Identification:  

Tab. 4.18 Signal assignment

Table 4.19 Fragmentations

MS (CI): MH ⁺

= 297

M / Z fragment 337 [Allyl + M] ⁺ 325 [Ethyl + M] ⁺ 229 [MH-CH ₂ = C (CH ₃₎ CO. + H] ⁺ 211 [M-CH ₂ = C (CH ₃ ) COO] ⁺ 167, 127, 113 etc. Thermal fragments

4.3.2.3. Preparation of orotic acid 2-methacryloyloxyethyl ester (XIV)

See Fig. 4.19. The reaction of 2-hydroxyethyl methacrylate with orotic acid was carried out analogously to the synthesis of thymine-1-acetic acid 2-methacryloyloxyethyl ester (XIII). The crude product was recrystallized from isopropanol.

Identification:  

Table 4.20 Fragmentations

MS (CI): MH ⁺

= 269

M / Z fragment 309 [Allyl + M] ⁺ 297 [Ethyl + M] ⁺ 213, 185 pollution 183, 113 u. 69 Thermal fragments

Tab. 4.21 Signal assignment

4.3.2.4. Preparation of orotic acid 10-methacryloyloxydecyl ester (XV)

The esterification was analogous to the reaction to orotic acid 2-methacryloyloxy ethyl ester with 10-hydroxydecyl methacrylate in dimethylformamide. From a solution of n-hexane / acetone: 3/1 (v / v) a white crystallized Solid with melting point 121 ° C from.

Identification:  

Tab. 4.22 Signal assignment

Table 4.23 Fragmentations

MS (CI): MH ⁺

= 381

M / Z fragment 421 [Allyl + M] ⁺ 409 [Ethyl + M] ⁺ 313, 295, 197, 185, 157 etc. Thermal fragments

Tab. 4.24 Assignment

Wave number / cm ^-1 Grouping or vibration 3157 N-H (associated) valence Schwgg. 3029 = C-H Valenzschwgg. 2929, 2857 u. 2820 aliphatic C-H valence skeleton. 1738, 1713 u. 1671 C = O Carbonylschwgg. 1635 C = C Valenzschwgg.

4.3.3.1. Preparation of N ^α -Methacryloyl, N ^ω - (P, P-dimethoxy) - phosphonoacetyl-1,10-diaminodecane (XVI) and N ^α - methyl, N -methacryloyl ^α, N ^ω -methyl, N ^ω - (P, P-dimethoxy) - phosphonoacetyl-1,12-diaminododecane (XVII)

In Fig. 4:29 is the two-stage synthesis of N ^α -Methacryloyl, N ^ω - (P, P-dimethoxy) -phosphonoacetyl-1,10-diaminodecane (XVI), and N ^α -methyl, N ^α - methacryloyl, N ^α -methyl , N ^ω - shown (P, P-dimethoxy) -phosphonoacetyl-1,12-diamino dodecane (XVII). Phosphonoacetic acid P, P-dimethyl ester potassium salt was reacted by a cation exchanger (Amberlyst 15). The product obtained was concentrated by rotary evaporation and then immediately concentrated with DCC, methacrylic acid-10-aminodecylamide (III) or N ^α , N ^ω -dimethyl, N ^α -methacryloyl-1,12-aminododecane (DOMA), which was kindly made available a chloroform solution used. The crude products were purified over a silica gel column each with a yield of 63% and 78%.

Identification:  

Table 4.25 Fragmentations

MS (FAB): MH ⁺

= 391

M / Z fragment 413 [M + Na] ⁺ 306, 292, 241, 224 Thermal fragments

Tab. 4.26 Signal assignment

Tab. 4.27 Signal assignment of Fig. 4.32

Wave number / cm ^-1 Grouping or vibration 3317 N-H-Valenzschwgg. 3059 = C-H Valenzschwgg. 2925, 2852 aliphatic C-H valence skeleton. 1670 and 1651 C = O Carbonylschwgg. (RCO NHR) 1609 C = C Valenzschwgg.

In Fig. 4.33 it can be seen that the product contains only one phosphorus species, which due to the signal position can be assigned to the functional group -CH ₂ -P (O) (OCH ₃ ) ₂ .

Table 4.28 Fragmentations

MS (CI): MH ⁺

= 447

M / Z fragment 487 [Allyl + M] ⁺ 475 [Ethyl + M] ⁺ 415, 377, 334, 295 Thermal fragments

Tab. 4.29 Signal assignment

4.3.3.2. Preparation of N ^α -methacryloyl, N ^ω -phosphonoacetyl-1,10-diaminodecane (XVIII) and N ^α -methyl, N ^α -methacryloyl, N ^ω -methyl, N ^ω -phosphonoacetyl-1,12-diaminododecane (XIX)

Starting with compounds XVI and XVII, N was ^α- methacryloyl, N ^ω -phosphonoacetyl-1,10-diaminodecane (XVIII) and N ^α -methyl, N ^α -methacryloyl, N ^ω -methyl, N ^ω -phosphonoacetyl-1,12 -diaminododecane (XIX) synthesized via methyl cleavage with trimethylbromosilane [129-131]. The crude product XVIII was precipitated from acetone and recrystallized from isopropanol / acetone with a good yield of 89%. The crude product XIX was precipitated from hexane / acetone with a yield of 87%.

Identification:  

Table 4.30 Fragmentations

MS (FAB): [M - H] ^-

= 361

M / Z fragment 389 Reactant contamination. 375 Verunr. Monomethyl elimination product 343, 262 Thermal fragments

Tab. 4.31 Signal assignment

Tab. 4.32 Assignment of Fig. 4.39

Wave number / cm ^-1 Grouping or vibration 3283 N-H-Valenzschwgg. 3065 = C-H Valenzschwgg. 2920, 2847 aliphatic C-H valence skeleton. 1637 C = C Valenzschwgg. 1592 and 1548 C = O Carbonylschwgg. (RCO NHR)

Table 4.33 Fragmentations

MS (FAB): [M - H] ^-

417

M / Z fragment 497 [M + CuOH] ^- 385, 347, 232, 223 Thermal fragments

Tab. 4.34 Signal assignment

Tab. 4.35 Assignment

Wave number / cm ^-1 Grouping or vibration 2926, 2854 aliphatic C-H valence skeleton. 1640 C = C Valenzschwgg. 1621 u. 1580 C = O Carbonylschwgg. (RCO NHR)

In Fig. 4.44 it can be seen that the only signal is 18.6 ppm and agrees with the ³¹ P NMR spectrum of XVIII. It can be assigned as a signal to the group CH ₂ -P (O) (OH) ₂ .

4.3.4.1. Preparation of N-α-Fmoc-O-benzyl-L-phosphotyrosine 10-methacryloyloxydecyl ester (XX)

Fig. 4.45 shows the synthetic route of N-α-Fmoc-O-benzyl-L-phosphotyrosine-10-methacryloyloxydecyl ester (XX). The starting material N-α-Fmoc-O-benzyl-L-phosphotyrosine was activated with the coupling reagent DCC. Thereafter, 10-hydroxydecyl methacrylate (II) was added to this reaction mixture. The product was concentrated by rotary evaporation, taken up with CH ₂ Cl ₂ , purified on a silica gel column to give a light yellowish oil with a yield of 70%.

Identification:  

Tab. 4.36 Signal assignment

Table 4.37 Fragmentations

MS (FAB): [M - H] ^-

= 796

M / Z fragment 706, 618, 600, etc. Thermal fragments

Tab. 4.38 Assignment

Wave number / cm ^-1 Grouping or vibration 3349 N-H, O-H Valence Schwgg. 3065, 3037 = C-H Valenzschwgg. 2927, 2855 aliphatic C-H valence skeleton. 1734, 1718, 1698 C = O Carbonylschwgg. 1638 C = C valence oscillation 1611, 1589, 1512, 1451 Aromatics Ringschwgg.

4.3.4.2. Preparation of O-benzyl-L-phosphotyrosine-10 methacryloyloxydecyl ester (XXI)

The cleavage of the Fmoc protecting group of XXI was carried out contrary to the usual procedure not in piperidine / DMF but in a 2% solution of DBU in CH ₂ Cl ₂ [132, 133]. The crude product was concentrated by rotary evaporation, purified on an alumina column to give a light oil with a yield of 87%.

Identification:  

Table 4.39 Fragmentations

MS (FAB): [MH] ⁺

= 576

M / Z fragment 873, 768, 660 pollution 614 [M + K] + 598 [M + Na] + 508, 486, 406 etc. Thermal fragments

Tab. 4.40 Signal assignment

Tab. 4.41 Assignment

Wave number / cm ^-1 Grouping or vibration 3355 O-H Valenzschwgg. 3063, 3032 = C-H Valenzschwgg. 2928, 2855 aliphatic C-H valence skeleton. 1719 C = O Carbonylschwgg. 1638 C = C Valenzschwgg. 1609, 1509, 1454 Aromatics Ringschwgg.

4.3.4.3. Preparation of N-α-lipoyl-O-benzyl-L-phosphotyrosine 10-methacryloyloxydecyl ester (XXII)

The reaction of XXI with lipoic acid in CH ₂ Cl ₂ solution is carried out with CDI as coupling reagent. The crude product was purified on a silica gel column.

Identification:  

Tab. 4.42 Signal assignment

Table 4.43 Fragmentations

MS (FAB): [MH] ^-

762

M / Z fragment 778, 728 Verunr. 694, 656, 644 etc. Thermal fragments

Tab. 4.44 Assignment

Wave number / cm ^-1 Grouping or vibration 3330 N-H, O-H Valence Schwgg. 3065, 3034 = C-H Valenzschwgg. 2927, 2854 aliphatic C-H valence skeleton. 1737, 1719, 1698 C = O Carbonylschwgg. 1653 C = C Valenzschwgg. 1612, 1513, 1455 Aromatics Ringschwgg.

4.4. Attempts to polymerize

To study polymerizability and properties of the monomers were Polymers of some of the monomers shown synthesized. radical Polymerizations were initiated with UV radiation. It was Irgacure 651 or 2,2-dimethoxy-2-phenyl-acetophenone as a photoinitiator, the thermally to 300 ° C is stable, and upon irradiation with UV light in radicals after a Norrish I photoreactivity decays [134].

The radical polymerization with Irgacure 651 was on the monomers with Lipoic acid residues studied in detail. The monomers and 3 wt% initiator  were dissolved in a little THF, and then with a halogen lamp perpendicular to the exposed vessel for three times 20 min. [135].

For working up the synthesized macromolecular compounds, the Polymer solutions dripped into an excess of methanol. The failed one Precipitate was centrifuged and dried in air.

The polymer shown was identified by ¹ H NMR and IR spectroscopy. Number and weight average molecular weight and molecular weight distribution of the polymer were determined by gel permeation chromatography and thermal properties by DSC.

The polymers of lipoic acid 2-methacryloyloxyethyl ester (IV), lipoic acid-6 methacryloyloxyhexyl ester (V) and lipoic acid 10-methacryloyloxydecyl ester (VI) were presented. In Tab. 4.45 conditions and yields of the Polymerizations listed.  

Tab. 4.45 Polymerization of methacrylates with a lipoyl group

Fig. 4.58- Fig. 4.61 show the IR spectrum, GPC chromatogram, ¹ H-NMR spectrum and DSC diagram of the polylipoic acid 2-methacryloyloxyethyl ester (poly IV). Equal measurements for Poly V and Poly VI were not performed because no suitable solvent was found.

From Table 4.45 it can be seen that the yield of the polymers decreases under the same polymerization conditions with increasing spacer length of the monomers. The result of Fig. 4.58 was obtained by measuring the refractive index of the different fractions of poly IV. The measurement revealed a number average molecular weight of poly IV of 1.3 × 10 5 g / mol, further a number average degree of polymerization Mn / M = about 420, and a dispersity of Mw / Mn = 2.9. The value is consistent with a value of 2 to 3 in a free radical polymerization system.

Tab. 4.46 Assignment

Wave number / cm ^-1 Grouping or vibration 2928, 2855 aliphatic C-H valence skeleton. 1719 C = O Carbonylschwgg.

In the IR spectrum of the polymer (see Fig. 4.59), the absorption band of the C = C valence vibration between 1636 and 1638 cm ^-1 is absent compared to the comparable monomer spectrum. In addition, a significant broadening of the gangs is recorded.

Compared to the ¹ H NMR spectrum of the monomer, the signals of the vinyl protons are absent at 5.5 and 6.1 ppm. The peaks of the resulting methylene protons of the polymer backbone are between 1.9 and 2.3 ppm. In addition, the sharp proton signal of the α-CH ₃ group is at 1.95 ppm to a width between 0.8-1.6 ppm and the signal of the -OCH ₂ group at 4.3 ppm to a width between 3.6 -3.8 ppm shifted.

The thermal property of poly IV was investigated by Differential Scanning Calorimetry (DSC). Due to the additional ester groups in the side chain, it is to be expected that the glass transition point lies between the values known from the literature of -70 ° C. (polydecyl methacrylate, comparable length of the side chain) and -5 ° C. (polyhexyl methacrylate, shorter side chain) [136, 137 ]. Fig. 4.61 confirms a glass transition temperature of -36.1 ° C.

4.5. Composite properties of the compounds

One goal of this work is to create an adhesive bond that connects between Metal and plastic enables to represent. The adhesion of the synthesized compounds were examined by pressure-shear experiments.  

This work was carried out by Girrbach Dental GmbH, Pforzheim the department F performed.

4.5.1. Determination of strength [138, 139]

On metal test specimen made of titanium, a Co-Cr alloy (neocrom FH, NEM-Leg.) and a high gold alloy (Platinor CF 4) was 0.1-1.0 wt% ige solution of a corresponding compound brushed. After evaporation of the solvent was a cylindrical sample (∅ 5 mm, h = 2 mm) of Composite veneering system belleGlass HP polymerized in layers. The Polymerization of the material was carried out according to the manufacturer. Through a Pressure-shear test with a universal testing machine, the initial Bond strength can be determined. Based on already published Test series were to the test specimens after completion one day in water (37 ° C) stored and sheared off after drying from the metal surface.

4.5.2. Experimental results

Table 4.47 shows the experimental results of the different compounds each on Co-Cr-Leg., Titanium and High Gold Leg. listed. The data correspond to an average value of several shear tests.

In order to evaluate the adhesive properties of the compounds, a comparison test with a product already established in the market was carried out under the same conditions. The values from Fig. 4.62 and 4.63 indicate a thoroughly competitive concept.

Table 4.47 Bond strength values in MPa

Fig. 4.62 shows the adhesion strengths of some compounds on a high gold cast alloy. From this it can be seen that two products made by us have a better composite property than a competing product. It can be seen from Table 4.47 that the two compounds, V and VI, are not even the best.

The difference in the absolute values between Fig. 4.62 and Tab. 4.47 resulted from different concentrations of the compounds in the test sample preparation.

Fig. 4.63 shows that our product VI has a much better bond strength on a reduced-gold casting alloy both compared to a blank (comparative test without the addition of a primer) and to a competitor product on the market.

It should be noted that the composite results from first standard tests stemmed, long-term tests to measure the permanent composite strength yet stand.  

5th discussion 5.1. Synthesis of the building block components

The display was made as described in chapter 4.2 "Representation of the block components with terminal methacryloyl groups ".

Three ω-hydroxyalkyl methacrylates were used for further synthesis. Next to the Commercially available 2-hydroxyethyl methacrylate, the 6-hydroxyhexyl and the 10-Hydroxydecylmethacrylat by acid-catalyzed esterification of methacrylic acid with the corresponding α, ω-alkanediols prepared. As a classic catalyst was used concentrated sulfuric acid. It turned out that approaches with a equimolar ratio of diol component to methacrylic acid yields of 60-65% of the desired target product. Regarding the costs involved and the Separation of the dimethacrylate byproduct over a silica gel column proved this Procedure as the cheapest. Absolutely necessary was the addition of hydroquinone to the Veresterungsreaktion, as this unwanted, thermally initiated radical Polymerizations of methacrylic acid or methacrylates were inhibited.

The preparation of the 10-aminodecylmethacrylamide was prepared according to literature [116, 117] carried out. The direct reaction of methacrylic acid with the diamine proved to be unfavorable. The benefits of using methacrylic anhydride are mild Reaction conditions permitting execution at room temperature. In the event of of methacrylic acid chloride as the acylating reagent, a tertiary base was added as HCl. Catcher used and additionally cooled (exothermic reaction of salt formation). In addition, the dripping rate had to be carefully regulated during the reaction become.

5.2. Synthesis of the monomers by esterification

The detention groups were controlled by various activating agents via their Carboxyl group with the terminal alcoholic hydroxy group of Linked block components. A compilation is shown in Table 5.1.

Table 5.1 Comparison of the yield with different coupling reagent

As shown in Table 5.1, DCC is the best condensing agent for this reaction. Moreover, DCC forms in the reaction in many organic solvents poorly soluble urea derivative, which is largely removed by simple filtration can be. The choice of solvent had no significant influence on the Exploit.

In this case, the activation of the carboxyl group takes place by addition to an N = C double bond of the carbodiimide. An alcohol subsequently reacts with the activated component to form a carboxylic acid ester and N, N'-dicyclohexylurea. It is important in this reaction that the N-acylurea formation [119, 122], which occurs as a side reaction by intramolecular rearrangement, is largely suppressed. The addition of 4-N, N-dimethylaminopyridine as the acylation catalyst [140, 141] and a catalytic amount of a strong acid [142, 143], e.g. B. p-toluenesulfonic acid also had a positive effect. Fig. 5.1 shows schematically the reaction path in a carbodiimide condensation.

The carboxylic acids with nitrogen-containing heterocycles were esterified with the coupling reagent EEDQ. DCC, CDI or even the conversion of the carboxylic acids into the corresponding acid chloride with thionyl chloride and longer reaction times (up to 48 hours) and temperature changes did not bring the desired success. By thin layer chromatography, only unreacted starting material could be detected in the reaction mixture. One reason for this could be the poor solubility of the strongly polar starting compounds. Although EEDQ does not require an additional tertiary base, one disadvantage of this coupling reaction is not to mention: the formation of the ethyl ester as a by-product when the alcohol component is not used in large excess over the carboxylic acid. Fig. 5.2 shows the activation mechanism of the EEDQ.

The esterification of N-α-Fmoc-O-benzyl-L-phosphotyrosine with the building block component II succeeded by DCC, however, formed a variety of by-products of which the target compound was difficult to separate. From the literature [144, 145] is It is known that phosphoric diesters can very well be activated with DCC. Nevertheless the achieved yield of 70% of the theory was quite satisfactory.

The Fmoc protecting group is normally cleaved with piperidine in DMF [132]. In Alternatively, a 2% solution of DBU in dichloromethane [133] was used in this work very good yield of 90% used. Dichloromethane can be unlike the high-boiling DMF can be easily removed by distillation.

5.3. Synthesis of the monomers by amidation

The synthesis of monomers having amide group was done with DCC or CDI to give 2- Methacryloyloxyethylliponsäureamid (IX), N ^α -Methacryloyl, N ^ω -liponsäurediamino decane (X), N ^α - methacryloyl, N ^ω - (P, P-dimethoxy ) -phosphonoacetic acid diaminodecane (XV) and N-α-lipoyl-O-benzyl-L-phosphotyrosine-10-methacryloyloxydecyl ester (XIX).

Here, CDI proved to be the most favorable coupling reagent of the lipoic acid amides, after several attempts with DCC failed.

The possible formation of an N-acylurea derivative during DCC activation disturbs the Implementation, leaving the target product only in low yield or not at all is obtained. The synthesis of N-methacryloyl-10-decyl lipoic acid amide (X) was demonstrated unsuccessful attempts of the amide coupling with DCC finally with CDI to the goal. Carbonyldiimidazole reacts with carboxylic acids to acylimidazoles, which are very active Acylating agents are. The by-products, imidazole and carbon dioxide, can be simple be removed from the reaction mixture.

Coupling of the phosphonoacetic acid P, P-dimethyl ester proved to be very successful favorable, before the actual linking reaction, first a conversion of the corresponding potassium salt in the free carboxylic acid with the aid of a suitable Make cation exchanger.

5.4. Influence of chemical structures on the adhesion

According to the International Standard, the bond strengths of our compounds examined by pressure-shear experiments. In principle, all tested compounds showed very good mechanical properties. Of these, sulfur-containing compounds adhere well On high-gold alloys, phosphorus-containing compounds adhere specifically Titanium and Co-Cr alloys and nitrogenous compounds adhere well to gold and nitrogen Co-Cr alloys. It is important that substances with these head groups self-assembling monolayers (SAMs) on the corresponding metals can.

Gold is in the periodic table of the elements in group Ib. It is a precious metal and chemically inert. This makes it an ideal dental material. But because of his Inertness has great difficulty in using gold with an organic material connect. In 1983, Nuzzo and Allara [45] first reported on SAM's of disulfides gold, opening up new avenues for potential applications and processes were.

Our experimental results prove that the sulfides, which act as a bonding group to the Connecting the gold with the plastic have been applied are very effective. Table 4.47 shows that the bond strengths of the lipoic acid ester derivatives to gold no discernible difference as a function of the spacer chain length within the have experimental conditions. Compared to monomers appeared in the Composite capability of poly IV no obvious changes. Porter [70] reported the monolayer formed from disulfides has similar structures and Have interlayer properties like those of the 10 to 22 analog alkanethiols Methylene groups in the carbon chain. Among 10 methylene groups, the Monolayer densely packed, but over 22 methylene groups are not the monolayer properly trained. Our compounds IV, V and VI have similar structures and each 11, 15 and 19 aliphatic carbon atoms and additionally two ester groups in the main chains of molecules. This agrees well with Porter's results.

Table 4.47 also shows that the organomonosulfide is a poorer composite Has strength on gold as the organodisulfide, i. H. SAM's of organomonosulfide  are more labile than those of the organodisulfide. The result is in line with the information provided by Jung et al. [77] agree.

The composite strength of Compound XI (16.8 MPa) differs greatly from that of Compound VI (19.0 MPa). Two reasons could lead to the result. The first Reason is that too long a molecular chain does not lead to an orderly education of the  SAM's leads. The second reason is that the two methyl groups on the Nitrogen atoms of the compound XI represent a spatial hindrance that dense Prevents packing of the molecules on the metal.

Table 4.47 shows that the bond strengths obviously increase (19.0 MPa at VI and 19.8 MPa at X) when diaminodecane as a spacer instead of decanediol is used. One reason could be that a molecule with an amide group stiffer than a comparable molecule with one ester group, a higher one Has melting point and makes a crystal easier. For example, nylon has one higher melting point than the corresponding polyester, d. H. the connection X is lighter crystallize on metal and it will be easier to form SAM's.

It is surprising that the bond strength of compound VIII is greater than that of Compounds IV, V and VI. In the formation of the SAM's of alkanedisulfides Gold is known from the literature [80, 81] that initially a break in the S-S bond of the Disulfides occurs and then an S-Au bond is formed. Both Compounds IV, V and VI are cyclic disulfides, i. H. every molecule can form two S-Au bonds. Even if an S-Au bond is broken, the other survivor conveys the liability. That could be beneficial to education Affect SAM's. Therefore compounds IV, V or VI should have larger composite Strengths as compound VIII show. On the other hand, the detention group has the Compounds IV, V or VI have a ring structure, with the long main chain of the molecule is located at the α-position of the ring. Such a structure can be a problem in the bring spatial packing, which has a negative impact on the formation of SAM's could have. Compared to VI, compound VIII is a linear molecule. To Breakage of the S-S bond results in two separate molecular chains with an S-Au bond. The two opposing factors are likely to affect education at the same time the SAM's. Obviously, as our results show, there is a hindrance steric effect more significant than that resulting from two Au-S bonds positive effect.  

Presumably, compounds with a β-lipoic acid residue would be synthetic [146, 147], better results are obtained, as the molecules with β- Lipoic acid radicals have less spatial impediments and thus easier can form ordered monolayers on a gold surface as those with α- Liponsäureresten.  

6. Experimental part 6.1. Used chemicals and auxiliaries FLUKA AG, Buchs

Bromoacetic acid, N-bromosuccinimide, 1,10-decanediol, N, N'-diisopropylcarbodiimide, 4- N, N-dimethylaminopyridine, 3,3'-dithio-dipropionic acid, 2-ethoxy-1-ethoxycarbonyl-1,2- dihydroquinoline, 2,2 '- (ethylenedithio) -diacetic acid, 1,6-hexanediol, 2- Hydroxyethyl methacrylate, methacrylic acid chloride, orotic acid, phosphonoacetic acid P, P dimethyl ester potassium salt, thymine; Triisopropylsilane, trimethylbromosilane, Triphenylphosphine.

MERCK, Darmstadt

1,1'-carbonyldiimidazole, sodium sulfate, sodium bicarbonate, hydrochloric acid, toluene-4 sulfonic acid monohydrate; Solvents such as acetone, chloroform, dichloromethane, Diethyl ether, N, N-dimethylformamide, ethyl acetate, methanol, tetrahydrofuran.

SIGMA-ALDRICH Chemie GmbH, Steinheim

1,10-diaminodecane, N, N'-dicyclohexylcarbodiimide, deuterochloroform, dimethylsulfoxide-d ₆ , deuterium oxide, DL-α-lipoic acid, methacrylic anhydride.

NOVAbiochem AG, Läufelfingen

N-α-Fmoc-O-benzyl-L-phosphotyrosine.  

6.2. Spectroscopic and analytical methods ¹ H and ³¹ P NMR spetoscopy

Equipment:
Bruker AC 200 (200 MHz)
Bruker DRX 400 (400 MHz)
The NMR spectra were recorded by Mr. U. Ziegler, Dept. Org. Chemie I, University of Ulm.
Solvent: deuterochloroform CDCl ₃

; Dimethyl sulfoxide-d ₆

CD ₃

SOCD ₃

; Deuterium oxide D ₂

O

Mass spectrometry

Device: mass spectrometer SSQ 7000; TSQ 7000
The mass spectra were analyzed by Dr. Ing. G. Schmidtberg, Mass Spectrometry, University of Ulm. For ionization, the methods Chemical Ionization (CI) and Fast Atom Bombardment (FAB) were used.

IR spectroscopy

Device: Bruker FT-IR IFS 113V
The spectra were recorded by Mrs. E. Kaltenecker, Section Vibrational Spectroscopy, University of Ulm.
The solids were measured as KBr pellets.

Elemental analysis

Device: CHN-O-Rapid, Fa. Heraeus
The elemental analyzes were performed by Ms. M. Lang, Department of Analytical Chemistry and Environmental Chemistry, University of Ulm.
The melting points of the synthesized compounds were observed under a Zeiss polarizing microscope with Mettler hot stage.

6.3. Chromatographic methods TLC

For this purpose, DC aluminum foils Kieselgel 60 brand "Alugram Sil G / UV254" of Company Macherey-Nagel, Düren and Merck DC aluminum foil aluminum oxide 60 F254 neutral, used.

column

Packing material:
Silica gel 60, 70-200 μm, from Amicon, Lausanne;
Silica gel 60, 63-200 μm, Merck, Darmstadt.

6.4. Synthesis of the monomer building blocks 6.4.1. Working instructions for the synthesis of 6-hydroxyhexyl methacrylate (.I.) And 10-hydroxydecyl methacrylate (.II.)

To a solution of 8.6 g of methacrylic acid (0.10 mol), 0.10 mol of the corresponding diol and 0.20 g of hydroquinone in 250 ml of toluene, 0.1 ml of concentrated H ₂ SO _{4 was added} dropwise at RT.

The mixture was refluxed on a water separator until the calculated Amount of water had separated.  

After cooling, the mixture was filtered off once washed with 5% NaHCO ₃ solution, then shaken with 4 × 15 ml of water until the wash water is pH-neutral, dried over Na ₂ SO ₄ , filtered and concentrated by rotary evaporation.

The crude product was taken up in dichloromethane and purified over a silica gel column (LM: CH ₂ Cl ₂ / CH ₃ OH = 98/2, v / v).

CH ₂ = C (CH ₃ ) -CO-O- (CH ₂ ) ₆ -OH (I)

characterization

SF: C ₁₀

H ₁₈

O ₃

M = 186 g / mol
Yield: 11.9 g = 65 mmol, 65% of theory; colorless oil
¹

H-NMR:

Illustration

4.1
MS spectrum: Figure in Appendix
IR spectrum: Fig: in appendix

CH ₂ = C (CH ₃ ) -CO-O- (CH ₂ ) ₁₀ -OH (II)

characterization

SF: C ₁₄

H ₂₆

O ₃

M = 242 g / mol
Yield: 14.4 g = 0.60 mol, 60% of theory; colorless oil
¹

H-NMR: Figure in Appendix
MS spectrum:

Illustration

4.3
IR spectrum:

Illustration

4.4

6.4.2. Synthesis of methacrylic acid-10-aminodecylamide hydrochloride and methacrylic acid-10-aminodecylamide (III)

To a solution of 12.90 g of diaminodecane (DAD, 0.075 mol), 15.15 g of N- Methylmorpholine (0.150 mol) in 400 ml of dry chloroform became a solution of 11.57 g of methacrylic anhydride (MAA, 0.075 mol) in 300 ml of chloroform at RT added dropwise within 2 h and then stirred for 2 h at RT.

The reaction was washed twice with 150 ml of 5% NaHCO ₃ solution, then acidified to pH = 8 with 12N HCl. The aqueous phase was separated. From this aqueous solution (pH = 8) crystallize at 2 ° C after 4 h from white needles.

characterization

SF: C ₁₄

H ₂₈

N ₂

O x HCl M = 276 g / mol
Yield: 5.51 g = 18.4 mmol, 24.7% of theory; white needle-shaped crystals
Mp: 132-134 ° C
¹

H-NMR:

Illustration

4.5
MS spectrum: Figure in Appendix
IR spectrum: Figure in Annex

Before further reaction, methacrylic acid-10-aminodecylamide (III × HCl) has to be added to be converted to free amine:

2.0 g (7.23 mmol) of III × HCl is dissolved in 20 ml of a 5% K ₂ CO ₃ solution, and the solution is then extracted with 3 × 15 ml of chloroform. The organic phase is collected and concentrated by rotary evaporation.

characterization

SF: C ₁₄

H ₂₈

N ₂

OM = 240 g / mol
Yield: 1.73 g = 7.23 mmol, 99% of theory; white, flaky crystals
Mp .: 90 ° C
¹

H-NMR: Figure in Appendix
MS spectrum:

Illustration

4.6
IR spectrum:

Illustration

4.7

6.5. Synthesis of Sulfur-Containing Monomers 6.5.1. Synthesis of Lipoic Acid 2-Methacryloyloxyethyl Ester (IV)

To a solution of 0.81 g of 2-hydroxyethyl methacrylate (HEMA, 6.2 mmol), 1.28 g of DL-α- Lipoic acid (LP, 6.2 mmol), a spatula tip 4-N, N-dimethylaminopyridine (DMAP) and a spatula tip of toluene-4-sulfonic acid monohydrate (PTSA) in 30 ml of dry pyridine 1.67 g of DCC (8.1 mmol) were added at RT.

The batch was stirred for 12 h at RT and then concentrated by rotary evaporation.

The residue was taken up in diethyl ether, filtered again and concentrated by rotary evaporation.

The crude product was dissolved in dichloromethane and purified over a silica gel column (eluent: CH ₂ Cl ₂ / CH ₃ OH = 99/1, v / v).

characterization

SF: C ₁₄

H ₂₂

O ₄

S ₂

M = 318 g / mol
Yield: 1.26 g 4.0 mmol, 65% of theory; yellowish oil
¹

H-NMR:

Illustration

4.9
MS spectrum: Figure in Appendix
IR spectrum: Figure in Annex

6.5.2. Synthesis of Lipoic Acid 6-Methacryloyloxyhexyl Ester (V)

To a solution of 0.93 g of 6-hydroxyhexyl methacrylate (HHMA, 5.0 mmol), 1.03 g of LP (5.0 mmol), a spatula tip of DMAP and a spatula tip of PTSA in 30 ml of dry CH ₂ Cl ₂ were added at RT Add 1.13 g of DCC (5.5 mmol).

The batch was stirred for 12 h at RT and then concentrated by rotary evaporation.

The residue was taken up in diethyl ether, filtered again and concentrated by rotary evaporation.

The crude product was dissolved in dichloromethane and purified over a silica gel column (eluent: CH ₂ Cl ₂ / CH ₃ OH = 99/1, v / v).

characterization

SF: _C18

H ₃₀

O ₄

S ₂

M = 374 g / mol
Yield: 1.20 g = 3.1 mmol, 64% of theory; yellowish oil
¹

H-NMR: Figure in Appendix
MS spectrum: Figure in Appendix
IR spectrum: Figure in Annex

6.5.3. Synthesis of lipoic acid 10-methacryloyloxydecyl ester (VI)

To a solution of 0.61 g II (2.5 mmol), 0.52 g LP (2.5 mmol), a spatula tip of DMAP and a spatula tip of PTSA in 20 ml of dry THF at RT 0.57 g DCC (2.8 mmol) was added.

The batch was stirred for 12 h at RT and then concentrated by rotary evaporation.

The solution was taken up in diethyl ether, filtered again and concentrated by rotary evaporation.

The crude product was dissolved in dichloromethane and purified over a silica gel column (LM: CH ₂ Cl ₂ / CH ₃ OH = 99/1, v / v).

characterization

SF: C ₂₂

H ₃₈

O ₄

S ₂

M = 43% / mol
Yield: 0.67 g, 1.55 mmol, 62% of theory; yellowish oil
¹

H-NMR: Figure in Appendix
MS spectrum:

Illustration

4.10
IR spectrum:

Illustration

4.11

6.5.4. Synthesis of Lipoic Acid-2-methacryloyloxyethylamide (IX)

To a solution of 1.03 g of LP (5.0 mmol) in 30 ml of dry chloroform was added Solution of 1.24 g of DCC (6.0 mmol) in chloroform at RT.

To the reaction mixture was added a suspension of 0.83 g of 2-methacrylic acid. aminoethyl ester hydrochloride (5.0 mmol) and 1.02 g of N-methylmorpholine (10.0 mmol) in Chloroform added at RT and then stirred at RT for 12 h, filtered off and concentrated by rotary evaporation.

The crude product was taken up in dichloromethane and purified over a silica gel column (LM: CH ₂ Cl ₂ / CH ₃ OH = 98.5 / 1.5, v / v).

characterization

SF: C ₁₄

H ₂₃

NO ₃

S ₂

M = 317 g / mol
Yield: 0.68 g = 2.1 mmol, 43% of theory; pale yellow solid
Mp .: 49-51 ° C
¹

H-NMR:

Illustration

4.12
MS spectrum: Figure in Appendix
IR spectrum: Figure in Appendix

6.5.5. Synthesis of N ^α -methacryloyl, N ^ω -lipoyl-1,10-diaminodecane (X) and N ^α -methyl, N ^α -methacryloyl, N ^ω -methyl, N ^ω- lipoyl-1,12-diaminododecane (XI)

To a solution of 0.31 g of LP (1.5 mmol) in 20 ml of dry chloroform was added Solution of 0.24 g of CDI (1.5 mmol) in chloroform was added at RT and stirred for 30 min.

To the reaction was added a solution of 0.36 g of III (1.5 mmol) or 0.44 g of DOMA (1.5 mmol) in chloroform at RT and then stirred at RT for 12 h and filtered off.

The reaction was washed with 20 ml of 5% NaHCO ₃ solution, then washed with 20 ml of 3 N HCl and 3 × 20 ml of water. The organic phase was dried over Na ₂ SO ₄ , filtered and concentrated by rotary evaporation.

The crude product X was recrystallized from CH ₂ Cl ₂ . The crude product XI was taken up in dichloromethane and purified over a silica gel column (LM: CH ₂ Cl ₂ / CH ₃ OH = 98/2, v / v).

Characterization: X

SF: C ₂₂

H ₄₀

N ₂

O ₂

S ₂

M = 428 g / mol
Yield: 0.46 g = 1.07 mmol, 72% of theory; white solid
Mp .: 82-87 ° C
¹

H-NMR: Figure in Appendix
MS spectrum:

Illustration

4.13
IR spectrum:

Illustration

4.14

Characterization: XI

SF: C ₂₆

H ₄₀

N ₂

O ₂

S ₂

M = 484 g / mol
Yield: 0.59 g = 1.21 mmol, 81% of theory; yellowish oil
¹

H-NMR:

Illustration

4.15
MS spectrum:

Illustration

4.16
IR spectrum: Figure in Appendix

6.5.6. Working procedure for the synthesis of 2,2 '- (Ethylenedithio) - diacetic acid bis (2-methacryloyloxyethyl) ester (VII) and 3,3'- Dithio-dipropionic acid bis (2-methacryloyloxyethyl) ester (VIII)

To a solution of 0.53 g of 3,3'-dithio-dipropionic acid (2.5 mmol), 0.65 g of HEMA (5.0 mmol), 0.61 g DMAP (5.0 mmol) and 0.095 g PTSA (0.50 mmol) in 30 mL dry Dichloromethane was added at RT 1.13 g DCC (5.5 mmol).

The mixture was stirred at RT for 12 h, filtered off and then concentrated by rotary evaporation.

The residue was taken up in dichloromethane and purified over a silica gel column (LM: CH ₂ Cl ₂ ).

CH ₂ = C (CH ₃ ) COO- (CH ₂ ) ₂ -OOC-CH ₂ = S- (CH ₂ ) ₂ -S-CH ₂ -COO- (CH ₂ ) ₂ -OOCC (CH ₃ ) = CH ₂ (VII)

characterization

SF: _C18

H ₂₆

O ₈

S ₂

M = 434 g / mol
Yield: 0.88 g = 2.02 mmol, 81% of theory; Colorless oil
¹

H-NMR: Figure in Appendix
MS spectrum:

Illustration

4.17
IR spectrum: Figure in Appendix

CH ₂ = C (CH ₃ ) COO- (CH ₂ ) ₂ -OOC- (CH ₂ ) ₂ -SS- (CH ₂ ) ₂ -COO- (CH ₂ ) ₂ -OOCC (CH ₃ ) = CH ₂ (VIII )

characterization

SF: _C18

H ₂₆

O ₈

S ₂

M = 434 g / mol
Yield: 0.63 g = 1.45 mmol, 58% of theory; colorless oil
¹

H-NMR:

Illustration

4.18
MS spectrum: Figure in Appendix

6.6. Synthesis of monomers containing nitrogen-containing hetero cyclen 6.6.1. Synthesis of thymine-1-acetic acid (XII) [125, 126]

10.35 g of thymine (82.5 mmol) were dissolved in 100 mL of aqueous 18% KOH (318 mmol). dissolved and then the reaction solution heated to 65 ° C. 17.15 g Bromoacetic acid methyl ester (124 mmol) was then added with good stirring added dropwise and then stirred at 65 ° C for 2 h. At RT, the reaction solution was still 3-4 h stirred (TLC control). To separate the unreacted thymine, was with Concentrated hydrochloric acid adjusted to pH 5 and then the reaction solution for 2 h at 4 ° C. cooled. The white precipitate (thymine) was separated and the solution with brought concentrated hydrochloric acid to pH = 2 and again cooled at 4 ° C for 2-3 h. The precipitated product (thymine-1-acetic acid) was separated, with water until neutral washed and then dried at 40 ° C for one day in an oil pump vacuum.

characterization

SF: C ₇

H ₈

N ₂

O ₄

M = 184 g / mol
Yield: 9.46 g = 51.3 mmol, 62% of theory; white, flaky crystals
Mp: 262 ° C (See 260-261 ° C Ref. [148])
¹

H-NMR: Figure in Appendix
MS spectrum:

Illustration

4.21
IR spectrum: Figure in Appendix

6.6.2. Synthesis of thymine-1-acetic acid 2-methacryloyloxyethyl ester (XIII)

To a suspension of 0.67 g thymine-1-acetic acid (3.64 mmol) and 2.84 g HEMA (21.8 mmol) in 30 mL CH ₂ Cl ₂ was added a solution of 1.08 g EEDQ (4, 37 mmol) in CH ₂ Cl ₂ at RT.

The batch was stirred at RT for 24 h and then concentrated by rotary evaporation.

The residue was dissolved in chloroform, then washed with 20 ml of 3N HCl and 3 x 20 ml of water. The organic phase was dried over Na ₂ SO ₄ , filtered and concentrated by rotary evaporation. The crude product was precipitated from diethyl ether and recrystallized from isopropanol.

characterization

SF: C ₁₃

H ₁₆

N ₂

O ₆

M = 296 g / mol
Yield: 0.87 g = 2.95 mmol, 81% of theory; white, needle-shaped crystals
Mp .: 100 ° C
¹

H-NMR:

Illustration

4.22
MS spectrum:

Illustration

4.23
IR spectrum: Figure in Appendix

6.6.3. Synthesis of orotic acid 2-methacryloyloxyethyl ester (XIV)

To a suspension of 0.78 g of orotic acid (5.0 mmol) and 3.90 g of HEMA (30.0 mmol) in 30 A solution of 1.48 g EEDQ (6.0 mmol) in DMF at RT was added to DMF.

The batch was stirred at RT for 24 h and then evaporated in an oil pump vacuum.

The crude product was dissolved in chloroform, precipitated from diethyl ether and then recrystallized twice from isopropanol.

characterization

SF: C ₁₁

H ₁₂

N ₂

O ₆

M = 268 g / mol
Yield: 0.86 g = 3.2 mmol, 64% of theory; white, flaky crystals
Mp .: 159-164 ° C
¹

H-NMR:

Illustration

4.25
MS spectrum:

Illustration

4.24
IR spectrum: Figure in Appendix

6.6.4. Synthesis of orotic acid 10-methacryloyloxydecyl ester (XV)

To a suspension of 0.31 g of orotic acid (2.0 mmol) and 1.45 g of 11 (6.0 mmol) in 30 ml DMF was added a solution of 0.59 g EEDQ (2.4 mmol) in DMF at RT.

The batch was stirred at RT for 24 h and then evaporated in an oil pump vacuum.

The residue was dissolved in chloroform, then washed with 20 ml of 3N HCl and 3 x 20 ml of water. The organic phase was dried over Na ₂ SO ₄ , filtered and concentrated by rotary evaporation.

The crude product was precipitated from diethyl ether and dried in an oil pump vacuum.

characterization

SF: C ₁₉

H ₂₈

N ₂

O ₆

M = 38% / mol
Yield: 0.28 g = 0.74 mmol, 37% of theory; white, flaky crystals
Mp .: 121 ° C
¹

H-NMR:

Illustration

4.26
MS spectrum:

Illustration

4.27
IR spectrum:

Illustration

4.28

6.7. Synthesis of monomers with phosphonoacetic acid terminated 6.7.1. Synthesis of N ^α -Methacryloyl, N ^ω - (P, P-dimethoxy) phosphono -acetyl-1,10-diaminodecane, and N ^α -methyl, N ^α (.XVI.) - methacryloyl, N ^ω -methyl, N ^ω - (P, P-dimethoxy) phosphonoacetyl-1,12-diaminododecane (XVII)

0.62 g phosphonoacetic acid P, P-dimethyl ester potassium salt (3.0 mmol) and 0.60 g Amberlyst 15 (cation exchanger) was stirred at RT in 15 ml of chloroform for 2 h, filtered off and evaporated. To this approach, a solution of 0.61 g of III (2.5 mmol) was added. or 0.74 g DOMA (2.5 mmol) and 0.62 g DCC (3.0 mmol) in 20 ml dry chloroform added. Thereafter, the reaction mixture was stirred at RT overnight, filtered off and rotated.

The residue was taken up again in chloroform and the organic phase was shaken out once with aqueous HCl solution (pH = 1-2) and three times with water. The organic phase was dried over Na ₂ SO ₄ , filtered and concentrated by rotary evaporation. The residue was purified over a silica gel column (LM: CH ₂ Cl ₂ / CH ₃ OH = 96/4, v / v).

Characterization: XVI

SF: _C18

H ₃₅

N ₂

O ₅

PM = 390 g / mol
Yield: 0.61 g = 1.56 mmol, 63% of theory; white solid
Mp .: 60-62 ° C
¹

H-NMR:

Illustration

4.31
³¹

P-NMR:

Illustration

4:33
MS spectrum:

Illustration

4.30
IR spectrum:

Illustration

4:32

Characterization: XVII

SF: C ₂₂

H ₄₃

N ₂

O ₅

PM = 446 g / mol
Yield: 0.84 g = 1.88 mmol, 75% of theory; colorless oil
¹

H-NMR:

Illustration

4:35
³¹

P-NMR:

Illustration

4:36
MS spectrum:

Illustration

4:34
IR spectrum: Figure in Appendix

6.7.2. Synthesis of N ^α -methacryloyl, N ^ω -phosphonoacetyl-1,10-diaminodecane (XVIII) and N ^α -methyl, N ^α -methacryloyl, N ^ω -methyl, N ^ω -phosphonoacetyl-1,12-diaminododecane (XIX)

To a solution of 0.15 g of XVI or 0.18 g of XVII (0.39 mmol) and 0.01 g of hydroquinone monomethyl ether (inhibitor), 0.14 g of trimethylbromosilane (0.92 mmol) in 5 ml absolute dichloromethane added. The reaction was stirred under reflux for 3 h and then evaporated. 3 ml of methanol was added and stirred for 2 h. The Crude product XVIII was precipitated from acetone and from isopropanol / acetone  recrystallized. The crude product XIX was precipitated from hexane / acetone and dissolved in Dried oil pump vacuum.

Characterization: XVIII

SF: C ₁₆

H ₃₁

N ₂

O ₅

PM = 362 g / mol
Yield: 0.124 g = 0.343 mmol, 89% of theory; white solid
Mp .: 137 ° C
¹

H-NMR:

Illustration

4:38
³¹

P-NMR:

Illustration

4:40
MS spectrum:

Illustration

4:37
IR spectrum:

Illustration

4:39

Characterization: XIX

SF: C ₂₀

H ₃₉

N ₂

O ₅

PM = 418 g / mol
Yield: 0.14 g = 0.34 mmol, 87% of theory; colorless, viscous oil
¹

H-NMR:

Illustration

4:42
³¹

P-NMR:

Illustration

4:44
MS spectrum:

Illustration

4:41
IR spectrum:

Illustration

4:43

6.8. Synthesis of N-α-Lipoyl-O-benzyl-L-phosphotyrosine-10 methacryloyloxydecyl ester (XXII) 6.8.1. Synthesis of N-α-Fmoc-O-benzyl-L-phosphotyrosine-10 methacryloyloxydecyl ester (XX)

To a solution of 1.38 g of II (5.6 mmol), 1.63 g of N-α-Fmoc-O-benzyl-L-phosphotyrosine (2.8 mmol), 0.69 g of DMAP (5.6 mmol) and 0.11 g of PTSA (0.56 mmol) in 30 ml of dry Dichloromethane at RT, a solution of 1.24 g of DCC (6.0 mmol) in dichloromethane added.

The mixture was stirred at RT for 12 h, filtered off and then concentrated by rotary evaporation.

The residue was taken up in dichloromethane and purified over a silica gel column (LM: CH ₂ Cl ₂ / CH ₃ OH / CH ₃ COOH = 94/6/4, v / v).

characterization

SF: _C45

H ₅₂

NO ₁₀

PM = 797 g / mol
Yield: 1.58 g = 1.99 mmol, 70% of theory; pale yellowish oil
¹

H-NMR:

Illustration

4:46
MS spectrum:

Illustration

4:47
IR spectrum:

Illustration

4:48

6.8.2. Working procedure for the cleavage of the Fmoc protective group of N- α-Fmoc-O-benzyl-L-phosphotyrosine-10-methacryloyloxy decyl

To cleave the Fmoc protecting group, 0.40 g of XX (0.50 mmol) in 5 mL of CH ₂ Cl ₂ / DBU = 98/2 (w / w) was stirred at RT until the reaction was complete (TLC control). , The solution was concentrated by rotary evaporation, taken up in CH ₂ Cl ₂ and purified over an alumina column (LM: CH ₂ Cl ₂ / ClCH ₃ OH = 90/10, v / v).

Characterization: XXI

SF: C ₃₀

H ₄₂

NO ₈

PM = 575 g / mol
Yield: 0.25 g = 0.44 mmol, 87% of theory; white solid
¹

H-NMR:

Illustration

4:50
³¹

P-NMR:

Illustration

4:52
MS spectrum:

Illustration

4:49
IR spectrum:

Illustration

4:51

6.8.3. Synthesis of N-α-Lipoyl-O-benzyl-L-phosphotyrosine-10 methacryloyloxydecyl ester (XXII)

To a solution of 0.20 g of XXI (0.35 mmol) in dichloromethane was added a mixture of 0.083 g LP (0.40 mmol) and 0.093 g DCC (0.45 mmol) in dried dichloromethane added. After 4 hours of stirring at RT (turnover control with TLC) was the Neck rotated.

The residue was taken up in dichloromethane and purified over a silica gel column (LM: CH ₂ Cl ₂ / CH ₃ OH = 92/8, v / v).

characterization

SF: C ₃₈

H ₅₄

NO ₉

PS ₂

M = 763 g / mol
Yield: 0.12 g = 0.157 mmol, 45% of theory; white solid
¹

H-NMR: Figure
³¹

P-NMR:

Illustration

4:56
MS spectrum:

Illustration

4:54
IR spectrum:

Illustration

4:55

6.9. Working instructions for the polymerization of the monomers

150 mg of monomer and 3% by weight of 2,2-dimethoxy-2-phenyl-acetophenone (photoinitiator) are dissolved in 2 ml of THF. The batch is 15 min. illuminated with a halogen lamp perpendicular to the open vessel. Thereafter, the procedure is stopped, the solution evaporated again with 3 wt .-% initiator and 2 ml of THF and exposed again over the same period. Then the residue is taken up in a little THF, precipitated in methanol. Thereafter, the precipitate is dried in air.
Yield:
Poly IV: 85% d. Th .; Mn = 133 × 10 ³ , Mw = 386 × 10 ³ , Mw / Mn = 2.905
Poly V: 82% d. Th .;
Poly VI: 68% d. Th.

6.10. Working procedure for determining the strength

The solutions of the compounds synthesized by us were used in concentrations of 0.1 to 1.0 wt .-% with alcohols prepared as a solvent.

On the looped metal specimen (12.5 × 12.5 × 2 mm) made of titanium, a Co-Cr Alloy (neocrom FH, NEM-Leg.) And a high gold alloy (Platinor CF 4) a solution of a corresponding substance was brushed on. An airing was introduced to evaporate the solvent. Thereafter, a cylindrical sample (∅ 5 mm, h = 2 mm) of the composite veneering system belleGlass HP layer by layer on the Polymerized on connections. The polymerization of the material was carried out after Manufacturer's instructions. By a pressure-shear test with a universal testing machine the initial bond strengths could be determined. In reference to already published test series were to the test specimens after completion a day in Stored water (37 ° C) and sheared off after drying from the metal surface.  

7. Summary

In the present work, several monomers with polymerizable Groups and detention groups are synthesized in different ways and some of them be polymerized. These monomers may possibly act as new adhesion promoters in a metal-plastic composite can be used.

In the previous preparation of the methacrylic building block components, flexible alkyl groups of different chain length, -O (CH ₂ ) ₆ O-, -O (CH ₂ ) ₁₀ O-, -NH (CH ₂ ) ₁₀ NH- and -N (CH ₃ ) (CH ₂ ) ₁₂ N (CH ₃ ) - used as a spacer group. Via the alkyl spacers, the monomers were linked to disulfide, phosphate or phosphonate groups as well as to nitrogen-containing heterocycles.

Methacrylic acid was reacted with the diols (1,6-hexanediol and 1,10-decanediol) converted classical acid-catalyzed esterification to the corresponding monoesters. 1,10-Diaminodecane and methacrylic anhydride provided the monoamide.

The adhesive components were linked via their carboxyl group with the free OH or NH ₂ - functions of the spacer. Various coupling reagents were used. Esterifications of the sulfur-containing carboxylic acids with DCC proceeded in good yields. In contrast, analogous reactions of the nitrogen-containing heterocycles with DCC, CDI, and thionyl chloride gave unsatisfactory results; only EEDQ led to a successful coupling here. For the amidation of lipoic acid CDI was used.

For the synthesis of the monomer with P 14278 00070 552 001000280000000200012000285911416700040 0002010063332 00004 14159hosphonate adhesion group, the Potassium salt of P, P-Dimethoxyphosphonessigsäure by a cation exchanger in converted to the free carboxylic acid, which is then activated with DCC and with a  Aminospacer was reacted in good yield. The cleavage of the methyl esters was quite easy with trimethylbromosilane.

To construct a star-shaped molecule with three different functional groups initially an Fmoc-protected phosphotyrosine with the OH-containing methacrylic Spacer component esterified with DCC. Subsequently, the by splitting off the Fmoc protecting group with DBU-released α-amino group of the tyrosine derivative with CDI converted to the corresponding Liponsäureamid.

Some monomers with lipoic acid adhesion group were reacted with the photoinitiator 2,2- Dimethoxy-phenylacetophenone polymerized to fairly poorly soluble polymers.

The synthesized compounds were identified and characterized by mass, ¹ H NMR, ³¹ P NMR, and IR spectra, as well as by elemental analysis.

To assess the adhesive properties of the newly synthesized substances was their Bond strength tested by first pressure-shear experiments on some metals. ever In the manner of the metal, the compounds show a strong relationship with respect to the adhesive groups pronounced selectivity. Thus, the phosphonate group has a good affinity for titanium and to a chromium-cobalt alloy, the disulfide group adheres better to a High gold alloy, and the nitrogen-containing heterocyclic group has an affinity for Chromium-cobalt alloy and high-gold alloy. Within the experiments show the compounds with increasing spacer length no obvious change.  

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Claims (7)

1. adhesion promoter for adhesion promotion between a metal or a metal alloy on the one hand and a polymerizable material, in particular plastic, on the other hand, in particular for dental technology, characterized by a compound (X, Y, Z) th of at least three compo th, wherein the first component (X) is a polymerizable vinylic unit, the second component (Y) is a hydrophobic flexible spacer, and the third component (Z) is a functional unit which contains an attachment group (Z1). 2. Adhesion promoter according to claim 1, characterized in that the third Kompo (Z) contains another functional group (Z2), which has an organic Chain with the second component (Y) and the adhesion group (Z1) is connected. 3. Adhesion promoter according to claim 1, characterized in that the first unit (X) comprises groups of the following structure:
4. Adhesion promoter according to claim 1, characterized in that the second unit (Y) methacrylic block components having alkyl groups with different (selectable) chain length (n, preferably = 10 or 12) of the following structure:
5. Adhesion promoter according to claim 1, characterized in that the adhesion group (Z1) of the third unit (Z) is a cyclic disulfide of the following structure:
6. Adhesion promoter according to claim 1, characterized in that the adhesion group (Z1) of the third unit (Z) is a phosphonate of the following structure:
7. Adhesion promoter according to claim 1, characterized in that the functional group (Z2) of the adhesion group (Z) comprises groups of the following structure: