DE102013009918A1 - Method for the production of iminium salts and onium salts, which enable high-contrast imaging in electron microscopy - Google Patents

Abstract

Stressed anion exchange or complex formation reactions also produce stressed iminium and onium salts, which make it possible to coat surfaces and make them electrically conductive, so that these deliver particularly high-contrast images in electron microscopic examinations.

Description

I. Subject of the invention

The invention describes processes for the preparation of iminium salts and onium salts, which are suitable for coating sample surfaces and making them electrically conductive, so that they can be examined by electron microscopy, resulting in particularly high-contrast images.

II. State of the art

Organic onium salts have been known for a long time. They acquired preparative significance in the years around 1970 in connection with the development of phase-transfer catalysis ^[1] .

After a number of onium salts have become known which have melting points below 100 ° C or are even liquid at room temperature, the term "ionic liquids" has been coined for such compounds ^[2-5] .

The ionic liquids are now playing an important role in all areas of applied chemistry. The ionic liquids can be tailor made to suit the field of application. In addition to the nature and structure of the cationic part, the nature of the anion determines the properties of the ionic liquid. It is therefore not surprising that there are a number of methods to produce ionic liquids by anion metathesis [Review: Ref. (3)] and thus optimally adapt their purpose. It ionic liquids have been described, the complex anions such. AlCl ₄ ^- , BCl ₄ ^- , CuCl ₂ ^- or SnCl ₃ ^- contain [abstract: Ref. (3)].

Originally, ionic liquids had been designed as substitutes for organic solvents because they are non-volatile due to their negligible vapor pressure. Of course, the cations of the ionic liquids should not participate in the reactions to be carried out therein. Quaternary ammonium and phosphonium ions, pyridinium and imidazolium ions were classified as largely inert [Ref. (3)].

In contrast, liquid iminium salts were not initially considered to be ionic liquids because they contain reactive cations. Meanwhile, liquid iminium salts have been used to break down wood into its constituents ^[6] .

Some iminium salts - especially chlorides - are hygroscopic and therefore often difficult to characterize analytically. This difficulty can be overcome by the salts are converted by anion exchange or anion modification in non-hygroscopic compounds. There were z. B. N, N, N ', N'-tetramethyl chloroformamidiniumchlorid and N, N, N', N'-tetramethyl-cyanformamidiniumchlorid in the corresponding Hexachloroantimonate, perchlorates, Tetrafluoroborate and Tetraphenylborate converted ^[7] . From N, N ', N''- peralkylated guanidinium chlorides were. Hexachloroplatinate produced ^[8] .

As we have now found, salts that are suitable for coating electrically non-conductive materials and thus provide observation objects that can not only be examined by electron microscopy, but also provide particularly high-contrast images, can be represented by several methods.

Such salts are particularly easily obtainable by anion metathesis on iminium, ammonium, saturated and unsaturated heterocyclic ammonium, phosphonium and sulfonium salts. For this one can use the following procedure.

a) By anion exchange

The combination of an iminium ion with different anions leads to iminium salts, which differ in their properties - in particular their solubility behavior from each other. So can be z. For example, iminium chlorides can be readily converted to the corresponding bromides and iodides by reaction with sodium iodide in acetone, acetonitrile, DMF, etc., with sodium chloride precipitating. If the conversion of iminium chlorides into the corresponding iodides is carried out in the presence of iodine, iminium iodide-iodine adducts are formed, for example. B. I ₃ anions or higher homologs. Starting from iminium tetrafluoroborates, iminium salts with the most varied anions can be obtained by reacting the iminium tetrafluoroborates with the corresponding potassium salts containing the anion to be introduced brings. The poor solubility of the resulting potassium tetrafluoroborate ensures the quantitative course of the anion exchange.

In the presence of complex acids such as HBF ₄ , HSbCl ₆ , HSnCl ₃ , H ₂ PtCl ₆ , on ammonium, iminium and analogous salts, the cations remain unchanged. The resulting salts containing complex anions are sparingly soluble in organic media and precipitate and therefore can be obtained almost quantitatively.

b) By converting anions into complex anions.

Iminium halides can be converted to the corresponding iminium metal halides by addition of metal halides. This is how z. Example, from hexamethyl-guanidiniumchlorid with the addition of aluminum chloride, antimony pentachloride, bismuth trichloride or lead chloride hexamethylguanidinium tetrachloroaluminate, hexachloroantimonate, tetrachlorobismutate or trichloroplumbat.

c) By conversion of the hydroxy groups of acids into metal oxy groups.

In acid anions containing additional acid functions (eg dibasic or tribasic acids), the acidic hydroxy groups can be converted into the corresponding metal oxy groups by addition of metal hydroxides or metal alcoholates (neutralization).

III. embodiments

Synthesis N, N ', N' '- persubstituted guanidinium salts

N- (2-hydroxy) ethyl-N, N ', N', N ", N" -pentamethylguanidinium chloride (1aA)

The preparation of the compound was carried out analogously to previously reported synthesis instructions ^[9,10] .

To 10.3 g (60 mmol) of N, N, N ', N'-tetramethyl-chloroformamidinium chloride (16) in 63 mL of dry acetonitrile are added with stirring at max. 10-20 ° C, a mixture of 4.5 g (60 mmol) of 2-methylaminoethanol and 7.3 g (72 mmol) of triethylamine added dropwise. The mixture is heated under reflux for 1 h, the acetonitrile distilled off and the residue is added with stirring with a cold solution of 2.4 g (60 mmol) of NaOH in 7.2 mL of water, with triethylamine is released. The residue obtained by evaporation (in vacuo in a rotary evaporator and then under oil pump vacuum) is treated with 70 ml of dry acetonitrile and the mixture is heated to 80 ° C. The precipitated sodium chloride is filtered off, the filtrate from the solvent and triethylamine first on a rotary evaporator, then freed in an oil pump vacuum. The viscous brown guanidinium chloride thus obtained is washed at max. 100 ° C in oil pump vacuum again dried. N, N, N ', N', N ", N" -hexamethylguanidinium hexachloroantimonate (1aC)

1.85 g (10.3 mmol) of N, N, N'N ', N ", N" -hexamethylguanidinium chloride (1aB) and 3.15 g (10.5 mmol) of antimony pentachloride are each dissolved in 11 mL of dry dichloromethane. The clear, optionally previously filtered solutions are mixed with stirring, wherein the salt 1aC precipitates. After cooling to room temperature, 20 mL of dry diethyl ether are added with stirring to complete the precipitation. The yellow guanidinium salt 1aC is filtered off with suction and recrystallized from 1,2-dichloroethane - mp. 272 ° C (dec.). ¹ H NMR (250 MHz, CD ₃ CN): δ = 2.88 (s, 18H, NCH ₃ ). ¹³ C-NMR (126 MHz, CD ₃ CN): δ = 39.0 (NCH ₃ ), 162.2 ( ⁺ CN ₃ ). C ₇ H ₁₈ C ₆ N ₃ Sb (478.71) calc .: C 18.37, H 3.96, N 9.18, Cl 23.23; Found: C 18.69, H 3.93, N 9.17, CI 22.76. N, N-diallyl-N ', N'-didecyl-N ", N" -diethylguanidinium hexachloroantimonate (1aE)

5.1 g (9.9 mmol) of N, N-diallyl-N ', N'-didecyl-N ", N" -diethylguanidinium chloride (1aD) and 3.0 g (10.0 mmol) of antimony pentachloride are each dissolved in 15 mL of dichloromethane. The clear, optionally previously filtered solutions are mixed with stirring. The reaction mixture is evaporated in a rotary evaporator in vacuo. The remaining brown viscous mass is dissolved in 20 ml of dichloromethane and precipitated by adding dry diethyl ether. The product is dried under oil pump vacuum at 100 ° C. N, N, N ', N', N ", N" -hexamethylguanidinium trichloroplumbate (1aF)

0.82 g (4.56 mmol) of (1aB) and 1.18 g (4.24 mmol) of lead (II) chloride are each dissolved in 20 mL of dimethylsulfoxide (DMSO). The clear, optionally previously filtered solutions are mixed with stirring. After the addition of chloroform, the salt (1aF) (colorless crystals) precipitates, mp. 292 ° C. C ₇ H ₁₈ Cl ₃ N ₃ Pb (457.80) calc .: C 18.37, H 3.96, N 9.18, Cl 23.23; Found: C 18.69, H 3.93, N 9.17, CI 22.76. N, N, N ', N', N ", N" -hexamethylguanidinium tetrachlorobismutate-acetonitrile solvate (1aG)

The clear, optionally filtered solutions of 3.63 g (20.2 mmol) of 1aB in 40 mL and 6.48 g (20.6 mmol) of bismuth (III) chloride in 62 mL of dry acetonitrile are slowly mixed with stirring. After a few minutes separates 1aG. The crystals are filtered off, washed with cold, dry acetonitrile and recrystallized from dry acetonitrile. Concentration of the mother liquor gives further product. Drying takes place in an oil pump vacuum at max. 100 ° C. Yield: 8.3 g (83%) of colorless crystals with Mp. 195 ° C. ¹ H-NMR (500 MHz, [D ₆ ] DMSO, TMS): δ = 2.08 (s, 1.5H, CH ₃ -CN), 2.88 (s, 18H, NCH ₃ ). ¹³ C-NMR (125.7 MHz, [D ₆ ] DMSO, TMS): δ = 1.06 (CH ₃ CN), 37.8 (NCH ₃ , obscured by the solvent), 161.1 (CN), 161.1 ( ⁺ CN ₃ ). C ₇ H ₁₈ BiCl ₄ N ₃ .0.5 CH ₃ CN (515.66) calc .: C, 18.64; H, 3.81; N, 9.51; Cl, 27.51; Found .: C 18.86, H 3.80, N 9.20, CI 27.16. N-butyl-N-ethyl-N ', N'-dihexyl-N'',N'-dimethylguanidinium tetrachlorobismutate (1aI)

0.815 g (2.17 mmol) of N-butyl-N-ethyl-N ', N'-dihexyl-N ", N" -dimethylguanidinium chloride (1aH) and 0.719 g (2.28 mmol) of bismuth (III) chloride are respectively in the 15th mL of dry acetonitrile. The clear, optionally previously filtered solutions are mixed with stirring. After approx. 10 min. the batch is freed from the solvent in a rotary evaporator. The remaining, yellow-brown viscous liquid is dissolved in tetrahydrofuran. The product is precipitated by the addition of diethyl ether as a thick yellow-brown mass. C ₂₁ H ₄₆ BiCl ₄ N ₃ (691.40) calc .: C 36.48, H 6.71, N 6.08, Cl 20.51; Found: C 36.61, H 6.59, N 5.29, Cl 20.60. 1-butyl-3-methylimidazolium hexachloroantimonate (11b)

4.0 g (22.9 mmol) of 1-butyl-3-methylimidazolium chloride (11a) and 7.0 g (23.4 mmol) of antimony pentachloride are each dissolved in 15 mL of dry dichloromethane. The clear, optionally previously filtered solutions are mixed with stirring. The resulting yellow solution of 11b is filtered and the filtrate is freed from the solvent in a rotary evaporator. The residue is dissolved in approx. 30 mL dichloromethane. Upon addition of 30 mL of dry diethyl ether, the salt 11b separates out as a yellow solid, which is dried at 100 ° C. in an oil pump vacuum. Yield: 8.6 g (80%), mp. 107-108 ° C. 1-butyl-3-methylimidazolium trichloroplumbate (11c)

1,158 g (6.63 mmol) of 11a and 1,843 g (6.63 mmol) of lead (II) chloride are each dissolved in 20 mL of DMSO with gentle heating. The clear, optionally previously filtered solutions are mixed with stirring. The yellow colored solution is mixed with THF, whereby viscous yellow droplets are deposited. The viscous precipitate solidifies to colorless crystals, which are filtered off, washed with THF and diethyl ether. The product is dried in an oil pump vacuum at 100 ° C, mp. 105 ° C. - C ₈ H ₁₅ Cl ₃ N ₂ Pb (452.78) calc .: C 21.22, H 3.34, N 6.19, Cl 23.49; Found: C 21.34, H 3.34, N 6.11, Cl 23.20. 1-butyl-3-methylimidazolium tetrachlorobismuthate (11d)

6.48 g (37.1 mmol) of 11a and 10.64 g (33.7 mmol) of bismuth (III) chloride are dissolved in 50 mL or 80 mL of dry acetonitrile. The clear, optionally previously filtered solutions are mixed with stirring. The resulting yellow solution is filtered and the filtrate is concentrated in a rotary evaporator to about 20 mL. After the addition of dichloromethane, 11d separates out as a viscous liquid. The solvents are decanted and the residue first in a rotary evaporator in vacuo and then in an oil pump vacuum at max. 100 ° C freed of solvent residues. Yield: 14.3 g (87%), mp. 59 ° C. C ₈ H ₁₆ BiCl ₄ N ₂ (490.01) calc .: C, 19.61, H, 3.09, N, 5.72, Cl, 28.94; Found: C 20.46, H 3.21, N 5.52, Cl 28.08.

literature

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Claims (6)

Compounds 1a to 8 which contain complex anions M (Y _P Z _q ) ⁴ , where M is Cu, Ag, Au, Cd, Hg, Tl, Pb, Sn, Sb, Bi, Hf, Ta, W, Pd, Pt, Y and Z are halogen (where Y = Z can also be), and are oxygen, where Y and Z may be bonded to M directly or in the form of divalent radicals, as in the case of oxalic acid, malonic acid, salicylic acid, Pyrocatechol, nitrilotriacetic acid, ethylenediaminetetraacetic acid or oxydiacetic acid is the case,

where the radicals R ¹ to R ^{6 may be the} same or different and are hydrogen, branched and unbranched aliphatic alkyl, substituted and unsubstituted Alicyclyl-, aryl, aralkyl, alkylaryl, heteroalkyl radicals, optionally substituted by hydroxy, metal oxy - (metals with molar mass> 32 g / mol), cyano, nitro, halogen, alkoxycarbonyl, hydroxycarbonyl, metalloxycarbonyl (metals with molar mass> 32 g / mol) and aminocarbonyl groups may be substituted, or the radicals R ¹ -R ² or R ³ -R ⁴ and R ⁵ -R ^{6 may} be connected to each other and form cyclic structures or the radicals R ¹ and R ⁵ and R ⁴ and R ^{6 may} be linked together, ie form a chain or R ¹ and R ³ and simultaneously R ⁴ and R ⁵ or R ¹ and R ³ and at the same time R ² and R ^{5 are} connected, whereby bi- and tricyclic cations of the type 1, 2, 3 or 7 are formed, in the general formulas 4, 5, 6 R ¹ also for alkoxy and aryloxy groups and Al kylthio- and arylthio groups, in the formulas of the cations of the salts 4 and 5 Y for hydrogen and the same organic radicals as defined for the substituents R ¹ to R ⁵ , organo-oxysulfonyl R-OSO ₂ -, amino and Organoaminosulfonyl R ₂ N-SO ₂ -, organosulfonyl R-SO ₂ -, dihalophosphinoyl Hal ₂ P (O) -, diorganooxyphosphinoyl (RO) ₂ P (P) -, haloorganooxyphosphinoyl HalP (O) OR-, halo-organophosphinoyl RP (O) Halo, dihalophosphino Hal ₂ P-, halo-triorgano-phosphoranyl R ₃ P (Cl) -, acyl R-CO, wherein the definition of the radicals R corresponds to the definition which has been made for the radicals R ¹ to R ⁵ , or zwitterionic adducts of the general formulas 4 and 5, which consist of carboxylic acid amides, ureas, and their thio, seleno and Telluroanaloga and Lewis acids selected from halides (X) of boron (BX ₃ ), aluminum (AlX ₃ ), thallium (TlHal ₃ ), antimony (SbX ₃ , SbX ₅ ), bismuth (BiX ₃ ), tin (SnX ₂ , Sn) ₄ ), zinc (ZnX ₂ ), E form (FeX ₃ ), titanium (TiX ₄ ), zirconium (ZrX ₄ ), hafnium (HfX ₄ ), niobium (NbX ₅ ), tantalum (TaX ₅ ), molybdenum (MoX ₆ ), tungsten (WX ₆ ) Compounds of formula 1a which contain the anion PtCl _b ^2- with (R ¹ = R ² = R ³ = R ⁴ = R ⁵ = R ⁶ = CH ₃ ) and R ¹ = R ² = R ⁵ = CH ₃ and R ² = R ⁴ = R ⁶ = C ₂ H ₅ ^[8] , compounds 3 with (R ¹ = R ² = R ³ = CH ₃ , X = SbCl ₆ ^[7] and compounds (6a: R ¹ = H, R ² = R ³ = CH _3, Hal = Cl, X = SbCl ₆ ^[11]; 7a-d: X = SbCl ₆ ^- , R ¹ = R ² = R ³ = R ⁴ = CH ₃ , R ¹ -R ² = R ³ = R ⁴ = (CH ₂ ) ₄ , (CH ₂ ) ₃ , CH ₂ CH ₂ O-CH ₂ CH ₂ ^{[12] are} excluded. Compounds 9-15 with complex anions M (Y _P Zq) ^n- in which M is Ag, Au, Cd, Hg, Tl, Pb, Sb, Bi, Hf, Ta, W, Pd, Pt and Y and Z is Halogen (where Y = Z may also be) and are oxygen, wherein Y and Z may be bonded to M directly or in the form of organic divalent radicals, such as in oxalic acid, malonic acid, salicylic acid, catechol, nitrilotriacetic acid, ethylenediaminetetraacetic acid or oxydiacetic acid the case is,

where the radicals R ¹ to R ^{4 may be} identical or different and are hydrogen, branched and unbranched aliphatic alkyl, substituted and unsubstituted Alicyclyl-, aryl, aralkyl, alkylaryl, heteroalkyl radicals, which may be substituted by hydroxy, metal oxy - (metals with molar mass> 32 g / mol), cyano, nitro, halogen, alkoxycarbonyl, hydroxycarbonyl, metalloxycarbonyl (metals with molar mass> 32 g / mol) and aminocarbonyl groups may be substituted, or the radicals R ¹ -R ² or R ³ -R ^{4 may} be joined together and cyclic structures. Process for the preparation of iminium iodides 1a-8 (X = I) from iminium chlorides 1a-8 (X = Cl) hydriodic acid and / or alkali or ammonium iodides and salts 1a to 15 with complex anions of the general formula (MYpZq) ^n- from iminium salts 1a to 15 [X = Cl, BF ₄ , ClO ₄ , B (C ₆ H ₅ ) ₄ ] and complex acids HnMpZq or their alkali metal or ammonium salts, characterized in that reacting the starting materials in the stoichiometric or superstoichiometric ratio without or with solvents, and the reaction products, optionally after removal of the solvents, isolated by suction or by phase separation and, if necessary, purified by recrystallization or reprecipitation from organic solvents,

where the radicals R ¹ to R ^{6 may be the} same or different and are hydrogen, branched and unbranched aliphatic alkyl, substituted and unsubstituted Alicyclyl-, aryl, aralkyl, alkylaryl, heteroalkyl radicals, optionally substituted by hydroxy, metal oxy - (metals with molar mass> 32 g / mol), cyano, nitro, halogen, alkoxycarbonyl, hydroxycarbonyl, metalloxycarbonyl (metals with molar mass> 32 g / mol) and aminocarbonyl groups may be substituted, or the radicals R ¹ -R ² or R ³ -R ⁴ and R ⁵ -R ^{6 may} be connected to each other and form cyclic structures or the radicals R ¹ and R ⁵ and R ⁴ and R ^{6 may} be linked together, ie form a chain or R ¹ and R ³ and simultaneously R ⁴ and R ⁵ or R ¹ and R ³ and at the same time R ² and R ^{5 are} connected, whereby bi- and tricyclic cations of the type 1, 2, 3 or 7 are formed, in the general formulas 4, 5, 6 R ¹ also for alkoxy and aryloxy groups and Al kylthio- and arylthio groups, in the formulas of the cations of the salts 4 and 5 Y for hydrogen and the same organic radicals as defined for the substituents R ¹ to R ⁵ , organo-oxysulfonyl R-OSP ₂ -, amino and Organoaminosulfonyl R ₂ N-SO ₂ -, organosulfonyl R-SO ₂ -, dihalophosphinoyl Hal ₂ P (O) -, diorganooxyphosphinoyl (RO) ₂ P (P) -, haloorganooxyphosphinoyl HalP (O) OR-, halo-organophosphinoyl RP (O) Halo, dihalophosphino Hal ₂ P-, halo-triorgano-phosphoranyl R ₃ P (Cl) -, acyl R-CO, wherein the definition of the radicals R corresponds to the definition which has been made for the radicals R ¹ to R ⁵ , or zwitterionic adducts of the general formulas 4 and 5, which consist of carboxylic acid amides, ureas, and their thio, seleno and Telluro analogs and Lewis acids selected from halides (X) of boron (BX ₃ ), aluminum (AlX ₃ ), thallium (TlHal ₃ ), antimony (SbX ₃ , SbX ₅ ), bismuth (BiX ₃ ), tin (SnX ₂ , SnX ₄ ), zinc (ZnX ₂ ), iron (FeX ₃ ), titanium (TiX ₄ ), zirconium (ZrX ₄ ), hafnium (HfX ₄ ), niobium (NbX ₅ ), tantalum (TaX ₅ ), molybdenum (MoX ₆ ) To form tungsten (WX ₆ ). A process as claimed in claim 3 for the preparation of iminium iodides 1a to 8 (X =I) from iminium chlorides 1a-8 (X =Cl) and alkali iodides, characterized in that the reactants are reacted with one another directly without solvents or in dipolar protonic or aprotic solvents such as alcohols, ether alcohols ( such as 2-ethoxyethanol), ester alcohols, lower chlorinated hydrocarbons (such as 1,2-dichloroethane, dichloromethane, trichloromethane, etc.), nitroalkanes, dialkyl ketones, alkylnitriles, N, N-dialkylated carboxylic acid amides. Urethanes or N, N'-peralkylated ureas are reacted, the precipitated alkali chloride separated and the remaining residue is optionally evaporated and optionally the product thus obtained by recrystallization or reprecipitation from organic solvents, optionally with the addition of water, is further purified. Process according to Claim 3 for the preparation of salts 1a to 15 with complex anions of the general formula (MY _p Z _q ) ^n- from iminium salts 1a-15 [X =Cl, BF ₄ , ClO ₄ , B (C ₆ H ₅ ) ₄ ] and complex acids H _n MY _p Z _q or their alkali metal or ammonium salts, characterized in that the starting materials in stoichiometric ratio or with excess acids H _n MY _p Z _q or their salts without solvent (preferably, if the starting materials 1a to 15 are liquid) or in water or in mixtures of water and dipolar aprotic or protonic solvents, but also in pure dipolar aprotic and protonic solvents or mixtures of these solvents selected from alkyl nitriles, nitroalkanes, chlorinated hydrocarbons such as 1,2-dichloroethane, Methylene chloride, chloroform, dialkyl ketones, N, N-disubstituted carboxylic acid amides, urethanes and N, N-peralkylated ureas, mono- and polyhydric alcohols, ether alcohols, ether or ester alcohols and converting the precipitated alkali metal salts [X = Cl, BF _4, ClO _4, B (C ₆ H _{5) 4]} is separated, the remaining reaction mixture, if appropriate, evaporated, the products thus obtained by recrystallization or precipitation from organic solvents - optionally with the addition of Water "in the complex anions M (Y _p Z _q ) ^{n -M} for Cu, Ag, Au, Cd, Hg, Tl, Pb, Sn, Sb, Bi, Hf, Ta, W, Pd, Pt, Y and Z may be halogen (where Y = Z may also be) and also oxygen, where Y and Z may be bonded to M directly or in the form of organic double-bonded radicals, as for example with oxalic acid, malonic acid, salicylic acid, pyrocatechol, nitrilotriacetic acid , Ethylenediaminetetraacetic acid or oxydiacetic acid is the case. Process according to claim 3 for the preparation of salts 1a-15 with complex organic anions (MY _p Z _q ) ^n- from halides 1a-15 (X = F, Cl, Br, I) and metal halides MY _p-1 Z _q or MY _p Z _q-1, characterized in that the reactants are reacted in a stoichiometric ratio or more than stoichiometric, in solution or without solvent, wherein the defined in claim 5 definition ranges for M, Y and Z and the solvents apply.