DE102009032548A1 - New N,N,N',N'-tetrasubstituted amidinium salt obtained by reacting aliphatic or (hetero)aromatic mono-, di-, tri-, tetra-, penta- or hexahydroxy compounds with an amidinium salt in a solvent e.g. diethyl ether and dipropyl ether - Google Patents

Abstract

N,N,N',N'-Tetrasubstituted amidinium salt (Q). N,N,N',N'-Tetrasubstituted amidinium salt (Q) of formula (I) or (Ia). R 1>, R 2>optionally saturated up to 12C-alkyl, up to 12C-cycloalkyl, up to 12C-aromatically aliphatic residue, heterocyclic up to 12C-alkyl, up to 12C-(hetero)aryl or alkane-alpha , omega -diyl structure (in which a heteroatom of O, N or S is interrupted); R : 3-N'',N'',N''',N'''-tetraalkylamidinio-prop-1-in-1-yl, 2-alkoxy and/or 2-aryloxy and/or 2-alkylthio- and/or 2-arylthio- and/or 2-alkylamino- and/or 2-arylamino-3-N'',N'',N''',N'''-tetraalkylprop-1-en-1-yl, 3,3-bis(dialkylamino)-1-diorganomethylene-prop-1-en-1-yl, 1,3-dialkyl-6-dialkylamino-2-pyridon-4-yl, 5-alkoxycarbonyl-4-dialkylamino-2-furyl, 5-alkoxycarbonyl-4-dialkylamino-2-thienyl, 5-alkoxycarbonyl-4-dialkylamino-pyrrol-2-yl, 2,3-diorgano-5-N'',N'',N''',N'''-tetraalkyl-5-amidinio-bicyclo-[2.2.1]-hepta-2,5-dien-6-yl, 2,3-diorgano-5-N",N",N"',N'"-tetraalkylamidinio-7-oxa-bicyclo-[2.2.1]-hepta-2,5-dien-6-yl, 7-alkyl-2,3-diorgano-5-N'',N'',N''',N'''-tetraalkylamidinio-7-aza-bicyclo-[2.2.1]-hepta-2,5-dien-6-yl, 1-alkyl and/or 1-aryl-4-N'',N'',N''',N'''-tetraalkylamidinio-1,2,3-triazol-5-yl, 2-alkyl and/or 2-aryl-4-N'',N'',N''',N'''-tetraalkylamidinio isoxazol-5-yl, 3,5,6,7, 8-pentaorgano-2-N'',N'',N''',N'''-tetraalkylamidinio-indolizin-1-yl, 5,6,7,8-tetraorgano-3-N'',N'',N''',N'''-tetraalkylamidinio-4-hydroxychromon-2-yl, 5,6-diorgano-4-hydroxy-3-N'',N'',N''',N'''-tetraalkylamidinio-4H-pyran-2-yl-group, where the dialkylamino group in (I) contains X and Y 1>as anions; and X, Y1 : F ->, Cl ->, Br ->, I ->, ClO 4->, CF 3SO 3->, C 2F 5SO 3->, CF 3CO 2->, CO 3CO 2->, HCF 2CO 2->, C 4F 9SO 3->, (CF 3SO 2) 2N ->, B(C 6H 5) 4->, BF 4->, PF 6->, (C 6H 5) 2PF 4->, C 2H 5PF 5->, HSO 4->, SO 42>->, NO 3->, SbCl 6->, SbF 6->, SnCl 42>->, SnCl 62>->, TiCl 62>->, ZrCl 62>->, ZnCl 42>->, FeCl 4->or AlCl 4->. Independent claims are included for the preparations of (Q). [Image].

Description

N, N, N ', N'-peralkylated amidinium salts belong to the class of iminium salts which can be derived from carboxylic acids. They are valuable synthesis building blocks. So can be z. B. from N, N, N ', N'-tetramethylformamidinium salts 1 and alcohol-free alkoxides or Alkalidialkylamiden produce the extremely reactive orthoamide derivatives 2 and 3, which are also known as aminal esters or tris (dialkylamino) methanes. The compounds have been widely used because of their exceptional reactivity as formylating agents for CH- and NH-acidic compounds. [ Review article: DJ Pearson, Comprehensive Organic Functional Group Transformations, Vol. 6 (Ed., TL Gilchrist), Pergamon, Oxford, New York, Tokyo, 1995, p ].

N, N, N ', N'-peralkylated Amidinium salts 4, which are derived from carboxylic acids, the α-constant to the carboxyl group still have at least one CH bond, react under such conditions the most versatile usable ketenaminalen 5, the class of electron-rich Belong to olefins.

It It is therefore not surprising that a variety of synthetic methods have been developed for N, N, N ', N'-peralkylated amidinium salts, mostly of the N, N-dialkylamide or thioamide of the corresponding Carboxylic acid is assumed. This is how z. N, N, N ', N'-tetramethylformamidinium chloride (1a) Heating N, N-dimethylformamide chloride with N, N-dimethylcarbamoyl chloride.

For the preparation of iminium salts, which can be derived from aldehydes or ketones, cleavage reactions of O, N-acetals or aminals (N, N-acetals) with electrophilic reagents (carboxylic acid chlorides, alkylating agents, halogens, etc.) play an important role. Abstract: H. Böhme, M. Haake in H. Böhme, HG Viehe (eds.): Iminium Salts in Organic Chemistry, Adv. Org. Chem. 9/1, p. 123, Wiley & Sons, New York, London, Sidney, Toronto (1976) ]. To create z. B. in the reaction of bis (dialkylamino) methanes with benzoyl chloride Dialkylaminomethyleniminiumchloride 6. Accordingly obtained from 1,1,2,2-tetrakis (dialkylamino) ethane and acetyl bromide, the di-iminium salts 7 L. Citerio, ML Saccarello, R. Stradi, Synthesis 1979, 594-596 ].

These Synthetic methods have been developed because the necessary Aminals often directly from secondary amines and aldehydes or suitable ketones are accessible. Although some lead to iminium salts cleavage reaction known on orthoamide derivatives of carboxylic acids, so arise z. B. in the treatment of Aminalestern 2 or Dimethylformamidacetalen 8 with acyl cyanides bis (dimethylamino) acetonitrile (1c) or the weak dissociated alkoxy-dimethylamino-acetonitriles 9, but these are Synthesis methods are generally not significant because of the Cleavage produced iminium salts mostly the starting materials for the production of the orthoamides are.

Only in cases where the orthoamide derivatives are easily accessible, the method has found application [ W. Kantlehner, R. Bauer, H. Bredereck, Liebigs Ann. Chem. 1980, 538; W. Kantlehner, H. Lehmann, Th. Stahl, W. Kaim, Chemiker Ztg. 1991, 115, 183 ]. So z. B. the less reactive tris (N-methyl-anilino) methane 10 from orthoformic acid esters or fluorodichloromethane and N-methylaniline in the presence of sodium hydride or potassium tert-butoxide available. Cleavage of 10 with benzoyl chloride is expected to yield the corresponding formamidinium salt 11 [ DH Clemens, WD Emmons, J. Am. Chem. Soc. 1961, 83, 2588; DH Clemens, EY Shropshire, WD Emmons, J. Org. Chem. 1962, 27, 3664 ].

More recently, simple synthetic methods have been developed for the synthesis of orthoamide derivatives of aromatic and heteroaromatic carboxylic acids 16 and of alkynecarboxylic acids 14 derived from ortho-carbonic acid derivatives 12 [ H. Weingarten, Tetrahedron, 1968, 24, 2767-2771 ] and 13 [ W. Kantlehner, R. Kreß. J. Mezger, S. Ladendorf, Z. Naturforsch. [B], 2005, 60, 227 ] or of guanidinium salts such. B. 15 go out.

The bis-orthoamide XIV of the acetylenedicarboxylic acid could thus also be obtained [ W. Kantlehner, P. Speh, H. Lehmann, H.-J. Brauner, E. Haug, WW Mergen, chemist Ztg. 1990, 114, 176-178 ].

Cleavage of orthoamides 14 and 16 with benzoyl chloride (17) leads to the corresponding amidinium salts 18 and 19 [ R. Stieglitz, Dissertation University of Stuttgart 1993; W. Kantlehner, H. Lehmann, Th. Stahl, W. Kaim, Chemiker Ztg. 1991, 115, 183-186 ].

Of considerable preparative importance is the process for the preparation of amidinium salts 18, since these were not accessible by the methods known hitherto. For the preparation of carboximidinium salts, the aminolysis of N, N-dialkyl-alkoxymethyleneiminium salts 20 is frequently used [ W. Kantlehner, Iminium Salts in Org. Chemistry (Adv. Org. Chem. 1979, 9, 321-329 ; W. Kantlehner in Comprehensive Organic Synthesis Vol. 6 (Ed. E. Winterfeldt), Pergamon Press, Oxford, New York, Seoul, Tokyo, 1991, p. 485 ; G. Simchen in Methods of Organic Chemistry (Houben-Weyl) Vol. 5/1 Ed. J. Falbe, Thieme, Stuttgart 1985, p. 1 ].

Although a number of N, N-dialkyl-alkoxy-alkynylmethyleniminiumsalzen such. B. 21 accessible by alkylation of corresponding Alkincarbonsäureamiden [ J. Arient, J. Podstata, Coll. Czech. Chem. Commun. 39, 3117 (1974) ; HG Viehe, JS Tree, Chimia, 29, 300 (1975) ; JS Baum, HG Viehe, J. Org. Chem. 41, 183-187 (1976) ], but nucleophilic reagents with 21 do not react primarily with substitution of the ethoxy group but with addition to the polarized triple bond (Michael analogue addition).

Therefore is the standard method for producing amidinium salts mentioned above Type 18 from the compounds 21 unsuitable.

The literature describes the cleavage of thioorthoamide derivatives 22, 24 of acetylenedicarboxylic acid or butadiyindicarboxylic acid with perchloric acid in acetic anhydride. The bis (dithiolium) salts 23, 25 were recovered [ H. Awaji, T. Sugimoto, Z. Yoshida, J. Phys. Org Chem 1 (1988) 47-51 ].

Overall, only a few types of bis-iminium salts are described in the literature, of which the very stable N, N, N ', N', N ", N", N ", N"'oxamidinium salts 26 are the best known should be. The compounds are very readily available from tetrakis (dialkylamino) ethylenes and oxidants. [ Review article: E. Haug, W. Kantlehner, Methods of Organic Chemistry (Houben-Weyl) Vol. E15 / 3 (Ed. H. Kropf, E. Schaumann, Thieme Verlag Stuttgart-New York 1993, p ; W. Kantlehner Amidinium Salts in Iminium Salt in Organic Chemistry, Vol. 2 (Ed. H. Böhme, HG Viehe) Wiley, New York, London, Sidney, Toronto 1979, p. 321 ].

The Existence of di-iminium salts of type 7 has already been mentioned.

Other bis-amidinium salts, such as 28, 30, and 32, were obtained by oxidation of ketene-derived amines such as 27, 29 [ H. Weingarten, JS Wager, Tetrahedron Lett. 1969, 19, 3267-3268; H. Weingarten, JS Wager, J. Org. Chem. 1970, 35, 1750-1753 ] and tetrakis (dimethylamino) all (31) [ R. Gompper, J. Schelble, CS Schneider, Tetrahedron Lett. 1978, 19, 3896-3900 ] produced.

Bis-orthoamides of acetylenedicarboxylic acid on heating with elemental sulfur react to form "quadrupoles" 33, which upon reaction with alkylating agents give 2,3-bis (alkylthio) -but-2-en-diamidinium salts 34 [ W. Kantlehner, M. Hauber, M. Vettel, J. Prakt. Chem. 1996, 338, 403-413 ].

Bis-iminium salts 35, 36 are also obtained by double alkylation of dicarboxylic acid amides with dimethyl sulfate [ P. Schlack, W. Richter, Chem. Ber. 1970, 103, 3729-3732 ] or triethyloxonium tetrafluoroborate [ H. Bredereck, W. Kantlehner, D. Schweizer, Chem. Ber. 1971, 104, 3475-3485 ] accessible when the amide functions are separated by at least four or two carbon units.

The alkylation of ketene amines such as 29 [ CF Hobbs, H. Weingarten, J. Org. Chem. 1974, 39, 918-921 ], 38 [ U. Grusek, M. Heuschmann, Chem. Ber. 1987, 120, 2053-2064 ] 40 [ R. Schwesinger, M. Missfeldt, K. Peters, HG von Schnering, Angew. Chem. 1987, 99, 1210-1212, Angew. Chem. Int. Ed. Engl. 1987, 26, 1165-1167 ], with α, ω-dihaloalkanes the bisamidinium salts 37, 39, 41.

By N-alkylation of imidazoles and benzimidazoles bis-imidazolium salts such as 42 [ J.-C. Xiao, JM Shreeve, J. Org. Chem. 2005, 70, 3072-3078 ], 43 [ DJ Williams, D. Vanderveer, RL Jones, DS Menaldino, Inorg. Chim. Acta 1989, 165, 173-178 ] 44 [ WA Herrmann, M. Elison, J. Fischer, C. Koecher, GRJ Arthur, Chem. Eur. J. 1996, 2, 772-780 ] 45 [ K. Nagata, T. Itoh, M. Okada, A. Kohsawa, Tetrahedron 1996, 52, 6569-6580 ] 46 [ Z. Shi, H.G., L.-L. Lue, synth. Commun. 1996, 26, 3175-3178 ], 47 [ Y. Guo, Z. Shi, Synth. Commun. 2004, 34, 3183-3189 ] receive.

Analogously, bis-tetrahydropyrimidinium salts 48 can be obtained [ Alici, I., Oezdemir, N. Guerbuez, E. Cetinkaya, B. Cetinkaya, Heterocycles 2005, 65, 1439-1445 ].

Orthoamide derivatives of acetylenedicarboxylic acid such as XIV have been known for some time. Both XIVa [ W. Kantlehner, P. Speh, H. Lehmann, H.-J. Brauner, E. Haug, WW Mergen, chemist Ztg. 1990, 114, 176-178 ] as well as XIVb [ W. Kantlehner, M. Hauber, M. Vettel, J. Prakt. Chem. 1996, 338, 403-413 ] were prepared by thermolysis of 49a, b.

The orthoamides XIVa, b are also formed on the action of the guanidinium salts 51a, b on sodium hydride and acetylene in THF or on a mixture of sodium acetylide and sodium hydride in THF. The orthoamides XIVb-e are particularly advantageously obtained by transamination of the orthoamide XIVa with the corresponding sec. Amines. [ W. Kantlehner, M. Hauber, M. Vettel, J. Prakt. Chem. 1996, 338, 403-413 ]

Orthoamide derivatives of acetylenedicarboxylic acid having an aminal ester structure, such as. B. 52 arise uniformly in the reaction of methyl formate or N, N-dimethylformamide dimethyl acetal with XIVa M. Vettel, Dissertation University of Stuttgart 1995 ].

The aminal cleavage of the orthoamide derivatives XIV and 52 with benzoyl chloride should be analogous to comparable reactions - such as the cleavage of 1,1,1-tris (dimethylamino-3-phenyl-2-propene to bis-amidini umsalzen the acetylenedicarboxylic Ia1 lead.

Attempts to obtain bis-amidinium salts Ia1 by the action of acid chlorides or trimethylchlorosilane on the orthoamide XIVa have failed. In the reaction of XIVa with dimethylcarbamic acid chloride, only N, N, N ', N'-tetramethylurea and the guanidinium salt 51a could be obtained as reaction products. The bisketene-terminal 54 was obtained by the action of trimethylsilyl cyanide on the orthoamide XIVa [ W. Kantlehner, H. Lehmann, T. Stahl, W. Kaim, Chemiker Ztg. 1991, 115, 183-186 ].

It was therefore surprising that the implementation of XIVa with Trifluoroacetic anhydride in tetrahydrofuran at -50 ° C under dry nitrogen, the extremely hygroscopic bis-amidinium trifluoroacetate Ia2 delivers. The example of Ia2 with sodium tetrafluoroborate performed in dry methanol anion exchange results the air-stable bis (amidinium) tetrafluoroborate Ia3.

The Constitution of compound Ia3 is by a crystal structure analysis secured, which shows that the two levels in which the amidinium units lie, are mutually orthogonal.

The Bis (amidinium) salts Ia show extreme reactivity towards classical nucleophiles as well as dienes and dipoles.

For example, carboxylic acids are converted to anhydrides in the presence of catalytic amounts of organic bases. The formation of phthalic acid or acetic acid by the action of Ia3 in the presence of small amounts of triethylamine, phthalic anhydride or acetic anhydride in addition to the N, N, N ', N', N '', N '', N '' - octamethyl-2-hydroxy -2-butenamidinium bis (tetrafluoroborate) XVIII. Especially easy it is to isolate the little hygroscopic deprotonation of XVIII when Monoamidiniumtetraphenylborat XVIIIa when working with excess triethylamine and the BF ₄ ^- ion is replaced.

aromatic Alcohols add to the compounds Ia resulting in 2-aryloxy-2-butenedicarboxamidinium salts IIa leads. By way of example, the salts IIa1-IIa4 called, which are obtained with almost quantitative yield, if you have phenol, salicylic acid methyl ester, 1-naphthol and also 2-naphthol to act on Ia3 in acetonitrile. In the presence of Bases such as B. sodium carbonate cyclize the adducts of aromatic 2-hydroxycarboxylic acid esters and Ia3 type IIa2 extremely easy to fused γ-pyrone-2,3-bis (carboxamidinium) salts IIa2A. This is how z. B. from IIa2 already on prolonged standing chromium-2,3-bis (carboxamidinium bis-tetrafluoroborate IIa2A1.

Remarkably, The addition reactions also proceed with polyvalent aromatic Alcohols, to polycationic organic compounds (Polylektrolyte).

The Salt IIa5, which contains a sixfold charged cation, arises z. As in the implementation of phloroglucin with Ia3.

Appropriate Additions take place when salts Ia with thiols, primary and secondary aliphatic and aromatic amines as well Hydrazine derivatives reacts. Leave in such reactions z. For example, from Ia3 the amidinium salts IIb1, IIc1-IIc6 win. The compounds obtainable from hydrazine derivatives and Ia3, such as B. IIc6 convert extremely easily into stable Pyrazolcarboxamidiniumsalze such. B. IId1 order.

at the reaction of the salts Ia with the CH-acidic compounds, which are usually also with orthoamide derivatives of carboxylic acids, alkynecarboxylic acids or convert the carbonic acid, arise in the presence of bases such as triethylamine, alkali carbonates or alkali alcoholates N, N-, N ', N'-tetraalkyl-2-alkylidene-4,4-bis (dialkylamino) - (but-3-en) amidinium salts. For example, the amidinium salts IIIa, b were made from the bis (amidinium) salt Ia3 and malononitrile or ethyl cyanoacetate in Acetonitrile obtained in the presence of sodium carbonate.

Compounds containing CH ₂ - and NH ₂ -acide groupings, such as. B. at N-Acetylcyanacet amides, reacts with Ia under comparable conditions also primarily to N, N, N ', N'-tetraalkyl-2-alkylidene-4,4-bis (dialkylamino) - (but-3-ene) -amidinium salts IIIc, easily into the Pyrroliminiumsalze such. B. IVa pass over. These iminium salts can react with a further equivalent of the CH ₂ , NH ₂ -acid compound again in the sense of a condensation, resulting in 5-oxo-1,5-dihydro-pyrrole derivatives 64.

you can isolate without the intermediates IIIe, IV directly to compounds 64 arrive. This is obtained by the action of 2 mmol Cyanacetamid or N-phenylcyanacetamide on Ia3 in acetonitrile in Presence of sodium carbonate practically quantitatively the 5-oxo-1,5-dihydro-pyrrole derivatives 64a, b.

bifunctional Compounds such as aminocarboxylic acids, mercaptocarboxylic acids, Hydroxycarboxylic acids are also for reaction with the Ia is able to produce bis (iminium) salts. To react z. B. the Methyl esters of glycine, sarcosine or mercaptoacetic acid with Ia3 in acetonitrile in the presence of sodium carbonate at room temperature quantitatively to the N, N, N ', N'-tetramethyl-4-dimethylamino-5-methoxycarbonylpyrrole-2-carboxamidinium tetrafluoroborates Vc1, Vc2 and thiophene-2-carboxamidinium tetrafluoroborate Vb1, respectively.

at the implementation of aromatic and heteroaromatic 1,2-diamines with the salts Ia becomes a 2-dialkylamino-3-bis (dialkylamino) vinyl-substituted 1,4-diazine ring (= pyridazine ring) constructed, d. H. it is heterocyclic substituted ketenaminals. By this scheme we obtain from Ia3 and o-phenylenediamine or 2,3-diaminonaphthalene the quinoxaline derivatives XIIa, b.

The Reactive triple bond of the salts Ia enables Diels-Alder reactions. The resulting cycloadducts contain the structural elements of N, N, N ', N', N '', N '', N '' ', N' '' - tetraalkyl (but-2-ene) bis (amidinium) salts. In many cases, the reactions are already at room temperature. The bis-amidinium salts VIa and VIb form z. B. if you have solutions of Ia3 in acetonitrile with cyclopentadiene or furan at room temperature let stand.

The Salts Ia are also capable of dipolar cycloadditions, which in turn lead to bis-amidinium salts or bis-Ketenaminalen. From Ia3 and benzyl azide, N-methyl-phenylnitrone, (1-pyridinio) -ethyl-2-acetate [(in situ from 1- (2-ethoxycarbonylmethyl) pyridinium bromide and sodium carbonate)], Salicylaldehyde, 2-hydroxy-1-naphthaldehyde and N-phenyl-salicylaldehyde imine Thus, the bis-amidinium salts VII, VIII, XI, X and XI or the bis-ketenaminal XIII are recovered.

The Examples described below are intended to cover the scope of application of the patent.

Example 1:

N, N, N ', N', N ", N", N "', N""- octamethyl (but-2-yn) bis (amidinium) tetrafluoroborate (Ia3). To a cooled to -60 ° C solution of 58 ml, 86.9 g (414 mmol) of trifluoroacetic anhydride in 140 ml of dry THF under dry nitrogen, a solution of 22 g (70.5 mmol) of 1,4-bis [trisdimethylamino)] but- 2-in (XIVa) was added dropwise in 30 ml of anhydrous THF. After stirring for one hour at -50 ° C., the mixture is allowed to reach room temperature, the crystalline precipitate is suctioned off under dry nitrogen and washed with dry THF under dry nitrogen. After drying in vacuo, 23 g (72.6%) of N, N, N ', N', N ", N", N ''',N''' - octamethyl (but-2-yne) are obtained. bis (amidinium) bis-trifluoroacetate (Ia2) as an off-white to pale yellow solid. The connection is immediately in the minimum amount of absolute. Dissolved methanol. The solution is added with stirring to a solution of 17 g (185.3 mmol) of NaBF ₄ in 800 ml of absolute. Given methanol. The precipitate formed is filtered off, several times with absolute. Methanol and dried. Y. 17 g (85%) of Ia3 in the form of a whitish to pale yellow solid. After recrystallization from a little acetonitrile, the bis (amidinium) salt Ia3 is obtained as colorless prisms with mp 179 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ = 3.34 [s, 24H, 4N (CH ₃ ) ₂ ];
¹³ C NMR (125 MHz, CD ₃ CN) δ = 151.40 [C (1) / C (4)], 88.85 [C (2) / C (3)], 44.54 [N (CH ₃ ) ₂ ].

Example 2:

N, N, N ', N'-tetramethyl- [4,4-bis (dimethylamino) -2-oxo-but-3-en] -amidinium tetraphenylborate (XVIIIa). To a solution of 400 mg (1 mmol) of the bis (amidinium) salt Ia3 in 3 ml of dry acetonitrile are added at room temperature with stirring first 0.5 ml - corresponding to 520 mg (8.7 mmol) of acetic acid and then 0.15 ml of triethylamine. The mixture is stirred at 20 ° C for 19 h. The volatiles are removed in vacuo and the residue is dissolved in dry acetonitrile, to which is added a solution of 0.7 g (2 mmol) of sodium tetraphenylborate in 3 ml of dry acetonitrile. The sodium tetrafluoroborate formed is filtered off and the filtrate is evaporated in vacuo. The residue is mixed with methanol. The crystalline substance is filtered off and recrystallized from methanol. Yield 190 mg (34%) XVIIIa, colorless crystals of mp 168 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ = 7.27 (broad s, 8H, BPh ₄ ^- , o-ArH), 6.99 (t, J = 7 Hz, 8H, BPh ₄ ^- , m-ArH), 6.84 (t, 4H, J = 7 Hz, BPh ₄ ^-, p-ArH), 4:51 (s, 1H, C (3) H), 3.12 (s, 12H, 2 amidinium N (CH _{3) 2,} 2.92 (s , 12H, C (4) N (CH _{3) 2);}
¹³ C NMR (125 MHz, CD ₃ CN) δ = 170.63 (C = O), 170.10 (C (1)), 168.60 (C (4)), 165.30, 164.90, 164.70, 164.10 (BPh ₄ ^- , C ( 1 ')), 136.70 (BPh ₄ ^- , C (2')), 126.50 (BPh ₄ ^- , C (3 ')), 122.70 (BPh ₄ ^- , C (4')), 85.30 (C (3) ), 43.05 (C (1) - (NCH ₃ ) ₂ ) ₂ ), 41.59 (C (4) -N (CH ₃ ) ₂ ) ₂ .

Example 3:

(2,3-E) -N, N, N ', N', N '', N '', N '', N '' '- octamethyl-2-phenoxy-1,4-bis (amidinium) -2-butene-bistetrafluoroborat (IIa1). To a solution of 400 mg (1 mmol) of the bis (amidinium) salt Ia3 in 2 ml of dry acetonitrile are added with stirring 100 mg ultrafine powdered, anhydrous sodium carbonate and a Solution of 100 mg (1 mmol) of phenol in 2 ml of dry acetonitrile.

After stirring for 12 hours, the mixture is filtered. The filtrate is in Vak. evaporated and the solid residue from absolute. Recrystallized ethanol. Y. 390 mg (79%) IIa1, colorless crystals with mp 144-146 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ = 7.52 (t, J = 7Hz, 8H, m-ArH), 7.37 (t, 1H, J = 8Hz, p-ArH), 7.13 (d, 2H , J = 8Hz, o-ArH), 6.30 (s, 1H, C (3)), 3.25 (broad s, 6H, C (1) N (CH ₃ ) ₂ ), 3.18 (s, 12H, 2C ( 4) N (CH ₃ ) ₂ ), 3.01 (broad s, 6H, C (1) N (CH ₃ ) ₂ );
¹³ C NMR (125 MHz, CD ₃ CN) δ = 162.68, 162.55 (C (1), C (4)), 153.62 (ArC (1 ')), 150.31 (C (2)), 131.89 (ArC (3 ')), 127.70 (ArC (4')), 118.79 (ArC (2 ')), 111.96 (C (3)), 44.11 (C (1) amidinium N (CH ₃ ) ₂ ), 43.50 (C ( 4) amidinium N (CH ₃ ) ₂ ).

Example 4:

N, N, N ', N', N '', N '', N ''',N''' - octamethylchromen-2,3-bis (carboxamidinium) bis-tetrafluoroborate (IIa2A1). 100 mg (1 mmol) of finely powdered anhydrous sodium carbonate and 170 mg (1.1 mmol) of methyl salicylate are added with stirring to a solution of 400 mg (1 mmol) of the amidinium salt Ia3 in 3 ml of dry acetonitrile. After stirring for 24 hours at room temp. is filtered. The filtrate is evaporated in vacuo, the residue treated with dry methanol and heated to reflux. When cooling to room temp. precipitated product is filtered off with suction, washed several times with dry methanol and dried. Y. 320 mg (58%) IIa2, colorless crystals of mp 270-272 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ = 8.25 (d, J = 8Hz, 1H, C (5) H), 8.03 (t, J = 8Hz, 1H, C (7) H), 7.78 (d, J = 8Hz, 1H, C (8)), 7.72 (t, J = 8Hz, 1H, C (6) H), 3.47, 3.42, 3.22, 3.10 (4s, 4 x 6H, 4N (CH ₃ ) ₂ ).

Example 5:

N, N, N ', N', N '', N '', N '', N '''- octamethyl-2- (naphthalen-1-yloxy) -2-buten-1,4-bis ( amidinium) -bis-tetrafluoroborate (IIa3). 160 mg (1.1 mol) of 1-naphthol are added with stirring to 400 mg (1 mmol) of the bis (amidinium) salt Ia3 in 3 ml of dry acetonitrile. The yellow colored mixture is stirred for 12 h. The volatiles are removed in vacuo and the solid residue recrystallized from dry ethanol. Y. 220 mg (40%) IIa3, yellow crystals with mp 182-1840 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ = 8.30 (m, 1H, C (5 ') H), 8.02 (m, 1H, C (8') H), 7.86 (d, J = 8.3 Hz, 1H, C (4 ') H), 7.68 (m, 2H, C (6') H + C (7 ') H), 7.53 (t, J = 8 Hz, C (3') H), 6.90 ( d, J = 7.7 Hz, C (2 ') H), 6.51 (s, 1H, C (2) H), 3.24 (broad s, 6H, 1N (CH ₃ ) ₂ ), 3.18 (s, 12H, 2N (CH ₃ ) ₂ ), 3.06 (broad s, 6H, 1N (CH ₃ ) ₂ ).

Example 6:

N, N, N ', N', N '', N '', N '', N '''- octamethyl-2- (naphthalen-2-yloxy) -2-buten-1,4-bis ( amidinium) -bis-tetrafluoroborate (IIa4). To (400 mg, 1 mmol) of the bis (amidinium) salt Ia3 in 3 ml of dry acetonitrile is added with stirring 150 mg (1 mmol) of 2-naphthol. After 12 hours of stirring at room temperature, the volatiles are removed in vacuo. The solid residue is recrystallized from dry ethanol. Y. 510 mg (93%) IIa4, yellow crystals of mp 178-180 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ = 8.06 (d, J = 9 Hz, 1H), 7.99 (broad s, 1H), 7.97 (broad s, 1H), 7.67-7.53 (m, 3H), 7:32, 7:31 (2 d, J = 9 Hz, 1H), 6:38 (s, 1H, C (2) H), 3:34 (broad s, 6H, 1 N (CH _{3) 2),} 3.20 (s, 12H, 2N (CH ₃ ) ₂ ), 2.98 (br, s, 6H, 1N (CH ₃ ) ₂ ).

Example 7:

2- (1,3,5-Benzoltrioxytris) - [N, N, N ', N', N '', N '', N '', N '''- octamethyl (buten-2-ene) -1,4-bis (amidinium) hexakis tetrafluoroborate (IIa5). 60 mg (0.48 mol) of phloroglucin are added with stirring to 500 mg (1.25 mmol) of the bis (amidinium) salt Ia3 in 3 ml of dry acetonitrile. The batch is stirred for 48 h at room temperature. The volatiles are removed in vacuo and the residue treated with dry methanol. After standing for 24 hours, the solid is filtered off with suction, washed several times with dry methanol and dried. Y. 490 mg (78%) IIa5, yellowish powder of mp 248-250 ° C (Zers).
¹ H NMR (500 MHz, CD ₃ CN) δ = 6.53 (s, 2H), 6.45 (s, 2H), 6.39 (s, 2H), 3.32-3.17 (m, 72H, 12N (CH ₃ ) ₂ ).

Example 8:

(2,3-E) -N, N, N ', N', N '', N '', N '', N '''- octamethyl-2- (furan-2-yl) methylsulfanyl) - 2-butene-1,4-bis (amidinium) bis-tetraphenylborate (IIb1). To the solution of 400 mg of 1 mmol) of the bis (amidinium) salt Ia3 in 3 ml of dry acetonitrile is added with stirring 0.11 ml corresponding to 124 mg (1.08 mmol) of 2-furyl-methanethiol. The yellow reaction mixture is stirred for 2 h at room temp. stirred and treated with a solution of 0.7 g (2 mmol) of sodium tetraphenylborate in 5 ml of dry acetonitrile. The mixture is filtered and the filtrate in Vak. evaporated. The crystalline residue is digested twice with hot methanol, filtered off with suction and washed several times with dry methanol and dried. Y. 0.91 g (93%) IIb1, white-yellow solid with mp 192 ° C (dec.).
¹ H NMR (500 MHz, CD ₃ CN) δ = 7.40 (s, 1H, C (3) H), 7.28 (broad s, 8H, BPh ₄ ^- , o-ArH), 6.99 (t, J = 7.6 Hz , 8H, BPh ₄ ^- , m-ArH), 6.84 (t, 4H, J = 7.6 Hz, BPh ₄ ^- , p-ArH), 6.43-6.38 (m, furan C (3 ') H, C (4' ) H, C (5 ') H), 4.02 (s, CH ₂ S), 3.24 broad s, 6H, C (1) N (CH ₃ ) ₂ , 3.02 (s, 12H, C (4) -2N ( CH ₃ ) ₂ ), 3.00 (broad s, C (1) -N (CH ₃ ) ₂ );
¹³ C NMR (125 MHz, CD ₃ CN) δ = 165.34, 164.95, 164.56, 164.17 (BPh ₄ ^- , C (1 ')), 163.60, 163.53 (C (1)), 148.59 (C (2), 145.20 (C (3)), 144.95 (furan C (2 ')), 136.71 (BPh ₄ ^- , C (2')), 126.57 (BPh ₄ ^- , C (3 ')), 125.56 (furan C (5') ), 122.76 (BPh ₄ ^- , C (4 ')), 112.37 (furan C (4')), 111.14 (furan C (3 ')), 44.62, 43.97, 43.28 (amidinium (NCH ₃ ) ₂ ), 29.70 (CH ₂ S).

Example 9:

(2,3-E / Z) -N, N, N ', N', N '', N '', N '', N '''- octamethyl-2-dimethylamino-2-butene-1, 4-bis (amidinium) bis-tetraphenylborate (IIc1). A mixture of 400 mg (1 mmol) of the bis (amidinium salt Ia3, 170 mg (2.1 mmol) of dimethylamine hydrochloride and 150 mg (1.4 mmol) of sodium carbonate is stirred in 3 ml of dry acetonitrile for 3 hours at room temperature and then filtered The resulting sodium tetrafluoroborate is filtered off with suction and the filtrate is concentrated under reduced pressure, the residue is combined with methanol and heated under reflux for a few minutes at room temperature, the crystalline product is filtered off with suction and washed several times with Methanol: 840 mg (92%) of a stereoisomer mixture of (2,3-E) -IIc1 and (2,3-Z) -IIc1 in the ratio 3: 2 as yellow crystals with mp 260 ° C. (dec. ).
(2.3-Z) -IIc1: ¹ H NMR (500 MHz, CD ₃ CN) δ 7.27 (broad s, 8H BPh ₄ ^-, o-ArH)., 6.99 (t, J = 7.3 Hz, 8H, BPh ₄ ^- , m-ArH), 6.84 (t, 4H, J = 7.3 Hz. BPh ₄ ^- , p-ArH), 4.81 (s, 1H, C (3) H), 3.24 (s, 6H, 1 amidinium N (CH ₃ ) ₂ ), 3.10-2.90 (18H m, 3 amidinium N (CH ₃ ) ₂ ), 2.87 (s, 6H, C (2) -N (CH ₃ ) ₂ );
¹³ C NMR (125 MHz, CD 3 CN) δ = 166.88 (C (4)), 165.34, 164.95, 164.56, 164.17 (BPh ₄ ^- , C (1 ')), 162.11 (C (2)), 150.68 (C ( J)), 136.70 (BPh ₄ ^- , C (2 ')). 126.50 (BPh ₄ ^- , C (3 ')), 122.70 (BPh ₄ ^- , C (4')), 92.52 (C (3)), 44.29, 44.01, 43.39, 41.41 (amidinium N (CH ₃ ) ₂ ) ,
(2,3-E) -IIc 1b: ¹ H NMR (500 MHz, CD ₃ CN) δ = 7.27 (broad s, 8H, BPh ₄ ^- , o-ArH), 6.99 (t, J = 7.3 Hz 8H, BPh ₄ ^-, m-ArH), 6.84 (t, 4H, J = 7.3 Hz, BPh ₄ ^-, p-ArH), 4.61 (s, 1H, C (3) H), 3.20 (s, 6H, amidinium N ( CH ₃ ) ₂ ), 3.10-2.90 (m, 18H, 3 amidinium N (CH ₃ ) ₂ ). 2.85 (broad s, 3H, C (2) -NCH ₃ ), 2.72 (broad s, 3H, C (2) -NCH ₃ );
¹³ C NMR (125 MHz, CD ₃ CN) δ = 166.77 (C (4)), 165.34, 164.95, 164.56, 164.17 (BPh ₄ ^- , C (1 ')), 162.11 (C (2)), 150.26 ( C (1)), 136.70 (BPh ₄ ^- , C (2 ')), 126.50 (BPh ₄ ^- , C (3')), 122.70 (BPh ₄ ^- , C (4 ')), 90.56 (C (3 )), 44.21, 43.77, 42.99, 41.16 (amidinium N (CH ₃ ) ₂ ).

Example 10:

N, N, N ', N', N '', N '', N '', N '''- octamethyl-2- (morpholin-4-yl) 2-butene-1,4-bis (amidinium ) bis- (tetrafluoroborate) (IIc2). To a solution of 400 mg (1 mmol) of the bis (amidinium) salt Ia3 in 1.5 ml of dry acetonitrile, a solution of 180 mg (2 mmol) of morpholine in 1.5 ml of dry acetonitrile is added at room temperature with stirring. After stirring at room temperature for 18 hours, the volatile components are removed in vacuo. The residual foamy solid is washed twice with boiling THF and then suspended in diethyl ether. The whitish to pale yellow solid is filtered off and washed several times with diethyl ether and dried. Y. 480 mg (98%) IIc2, whitish to pale yellow crystals (isomer mixtures of (2,3-E) -IIc and (2,3-Z) -IIc in the ratio 6: 1) with mp 232-234 ° C.
(2.3-Z) -IIc2: ¹ H NMR (500 MHz, CD ₃ CN) δ = 5.29 (s, 1H, C (3) H), 3.81 (m, 4H, CH ₂ OCH _2), 3.45- 3.0 (m, 28H, 4-amidinium N (CH ₃ ) ₂ + -CH ₂ NCH ₂ -);
¹³ C NMR (125 MHz, CD ₃ CN) δ = 166.4 (C (4)), 162.2 (C (2)), 150.3 (C (1)), 97.5 (C (3)), 66.5 (-CH ₂ OCH ₂ -), 49.6 (-CH ₂ NCH ₂ -), 44.65, 44.40, 43.43 (amidinium N (CH ₃ ) ₂ ).
(2,3-E) -IIc2: ¹ H NMR (500 MHz, CD ₃ CN) δ = 4.90 (s, 1H, C (3) H), 3.12 (t, J = 5 Hz, 4H, CH ₂ OCH ₂ ), 3.45-3.0 (m, 28H, 4 amidinium N (CH ₃ ) ₂ + -CH ₂ NCH ₂ -);
¹³ C NMR (125 MHz, CD ₃ CN) δ = 166.3 (C (4)), 165.1 (C (2)), 148.8 (C (1)), 92.9 (C (3)), 66.5 (-CH ₂ OCH ₂ -), 49.6 (-CH ₂ NCH ₂ -), 44.25, 44.0, 43.2 (amidinium N (CH ₃ ) ₂ ).

Example 11:

N, N, N ', N', N '', N '', N '', N '''- octamethyl-2-cyanmethylamino-2-butene-1,4-bis (amidinium) bis-tetrafluoroborate (IIc3). A mixture of 400 mg (1 mmol) of the bis (amidinium) salt Ia3, 110 mg (1.2 mmol) of aminoacetonitrile hydrochloride, 150 mg (1.4 mmol) of sodium carbonate and 1.3 ml of acetonitrile is stirred for 1 h at room temperature and then filtered. The filtrate is evaporated in vacuo and the residue treated with dry methanol. The product formed is filtered off, washed several times with dry methanol and dried. Y. 260 mg (57%) IIc3 (2,3-E / Z isomer mixtures in the ratio 3: 2) pale violet crystals with mp. 168-170 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ = 6.67 and 6.07 (2 broad s, 0.4H + 0.6H, NH), 5.26 and 5.12 (2 broad s, 0.4H + 0.6H, C (3) H) , 4.35 and 4.16 (2 broad s, 0.8H + 1.2H, NCH ₂ CN), 3.36, 3.93, 3.19 (3 broad s, 9H, 3NCH ₃ ), 3.14 (broad s, 15H, 5NCH ₃ ).

Example 12:

(2,3-E) -N, N, N ', N', N '', N '', N '', N '''- octamethyl-2-phenylamino-2-butene-1,4- bis (amidinium) bis-tetrafluoroborate (IIc4). A solution of 400 mg (1 mmol) of the bis (amidinium) salt Ia3 in 1.5 ml of dry acetonitrile is added at room temperature while stirring with a solution of 200 mg (2 mmol) of aniline in 1.5 ml of dry acetonitrile. After 18 hours of stirring, the volatiles are removed in vacuo. The residual yellow oil is digested twice with boiling THF. The remaining residue is suspended at room temperature in dry diethyl ether. The resulting solid was filtered off with suction, washed several times with dry ether and dried. Y. 470 mg (95%) IIc4, yellow solid with m.p. 218 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ = 7.88 (s, 1H, NH), 7.44 (t, 2H, J = 7.8 Hz, m-ArH), 7.26 (t, 1H, J = 7.6 Hz, p -ArH), 7.00 (d, 2H, J = 7.6 Hz, o-ArH), 5.31 (s, 1H, C (3)), 3.35-2.70 (m, 24H, 4-amidinium N (CH ₃ ) ₂ );
¹³ C NMR (125 MHz, CD ₃ CN) δ = 165.64, 165.20 (C (1) and C (4)), 142.40 (C (2)), 138.80 (ArC (1 ')), 130.95 (ArC (3 ')), 126.85 (ArC (4')), 121.09 (ArC (2 ')), 98.02 (C (3)), 44.24, 43.75, 42.82 (amidinium N (CH ₃ ) ₂ ).

Example 13:

N, N, N ', N', N ", N", N ''',N''' - octamethyl-2- (4-chlorobenzoyl) -5-dimethylamino-2H-pyrazole-3-carboxamidinium tetraphenylborate (IID1). 170 mg (1 mmol) of 4-chlorobenzoylhydrazide are added with stirring to a solution of 400 mg (1 mmol) of the bis (amidinium) salt Ia3 in 3 ml of dry acetonitrile. The mixture is stirred at 50 ° C until a clear solution is formed and then stirred for 19 h at room temperature. Thereafter, it is filtered. The filtrate is treated with a solution of 0.7 g (2 mmol) of sodium tetraphenylborate in 5 ml of dry acetonitrile. The mixture is filtered and the filtrate evaporated in vacuo. The residue is mixed with methanol, the crystalline product is filtered off with suction and washed several times with methanol and dried. Y. 290 mg (40%) IIcb yellow crystals, which are recrystallized from acetonitrile, mp 258-260 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ = 7.90 (d, J = 8.6 Hz, 2H, acyl-o-ArH), 7.55 (d, J = 8.6 Hz, 2H, acyl-m-ArH), 7.27 (broad s, 8H, BPh ₄ ^-, o-ArH), 6.99 (t, J = 7.4 Hz, 8H, BPh ₄ ^-, m-ArH), 6.83 (t, 4H, J = 7.3 Hz, BPh ₄ ^-, p-ArH), 5.95 (s, 1H, C (4) H) 3.12 (broad s, 12H, 2-amidinium N (CH ₃ ) ₂ ), 2.90 (s, 6H, C (5) N (CH ₃ ) ₂ ).

Example 14:

N, N, N ', N'-Tetramethyl-2- (2', 2'-bis (dimethylamino) vinyl] -3,3-dicyano-acrylamidinium tetrafluoroborate (IIIa) To a solution of 400 mg (1 mmol) of the 100 mg (1.5 mmol) of malononitrile in 1.5 ml of dry acetonitrile and 100 mg (1 mmol) of sodium carbonate are added, with stirring, to (amidinium) salt Ia3 in 1.5 ml of dry acetonitrile and the mixture is stirred for a further 20 hours at room temperature The residue is largely dissolved in boiling, dry ethanol, the hot solution is filtered, and the product precipitates in crystalline form on cooling to room temperature, is filtered off with suction, washed several times with dry ethanol, and dried. 320 mg (84%) IIIa, yellow needles with mp 158-162 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ = 4.73 (s, 1H, C (1 ') H), 3.21 (broad s, 12H, 2C (1) N (CH ₃ ) ₂ ), 3.11 (s, 12H, C (2 ') N (CH _{3) 2).}
¹³ C NMR (125 MHz, CD ₃ CN) δ = 168.96 (C (2 ')), 167.53 (C (1)), 147.62 (C (2)), 119.57, 119.36 (2CN), 118.96 (C (3 )), 95.12 (C (1 ')), 44.25, 43.13. 42.33 (N (CH ₃ ) ₂ at C (1) and C (2 ')).

Example 15:

N, N, N ', N'-tetramethyl-2- (2', 2'-bis (dimethylamino) vinyl] -3-cyano-3-ethoxycarbonyl-acrylamidinium tetraphenylborate (IIIb) Solution of 400 mg (1 mmol) of the bis (amidinium) salt Ia3 in 1.5 ml of dry acetonitrile in solution of 220 mg (1.9 mmol) of ethyl cyanoacetate in 1.5 ml of dry acetonitrile and 100 mg (1 mmol) of sodium carbonate After 24 h Stirring at room temperature, the mixture is diluted with 2 ml of dry acetonitrile and filtered.With a solution of 360 mg (1 mmol) of sodium tetraphenylborate in about 3 ml of dry acetonitrile is added to the yellow-orange colored filtrate.The mixture is filtered and the filtrate in The residue is dissolved in boiling, dry methanol and the product which precipitates on cooling is filtered off with suction, washed several times with dry methanol and dried, yielding 580 mg (88%) of IIIb, yellow needles of mp 184-196 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ = 7.27 (broad s, 8H, BPh ₄ ^- , o-ArH), 6.99 (t, J = 7.4 Hz, 8H, BPh ₄ ^- , m-ArH), 6.84 (t, 4H, J = 7.3 Hz, BPh ₄ ^-, p-ArH), 4:55 (s, 1H, C (1 ') H), 4:07 (q, J = 7 Hz, 2H, COOCH ₂ CH _3), 3.20-2.90 (m, 24H: 12H, 2C (1) N (CH ₃ ) ₂ ) and broad s, at 3.06, 12H, C (2 ') N (CH ₃ ) ₂ ), 1.21 (t, J = 7 Hz, COOCH ₂ CH ₃ ).
¹³ C NMR (125 MHz, CD ₃ CN) δ = 173.12 (C (2)), 168.12 (C (2 '), 167.51 (C = O), 165.34, 164.95, 164.56, 164.17 (BPh ₄ ^- , C ( 1 ')), 148.27 (C (3)), 136.71 (BPh ₄ ^- , C (2')), 126.56 (BPh ₄ ^- , C (3 ')), 122.76 (BPh ₄ ^- , C (4') ), 121.12 (CN), 95.65 (C (1 '), 60.71 (COOCH ₂ CH ₃ ), 43.97, 43.02 (N (CH ₃ ) ₂ at C (1)), 42.28 (N (CH ₃ ) ₂ at C (2 ')), 14.95 (COOCH ₂ CH ₃ ).

Example 16:

2- {3- [2,2-bis (dimethylamino) vinyl] -4-cyano-5-oxo-1,5-dihydro-pyrrol-2-ylidenes -cyanacetamide (64a). A mixture of 400 mg (1 mmol) of the bis (amidinium) salt Ia3, 330 mg (3.9 mmol) of cyanoacetamide, 0.5 ml of triethylamine and 4 ml of dry acetonitrile is stirred at room temperature for 18 h and then heated to 80 ° C after 3 h. The volatiles are removed in vacuo. The residue is dissolved in dry chloroform and purified by flash chromatography (silica gel, elution first with CHCl ₃ , then with CHCl ₃ / acetone 1: 1). The eluate is evaporated in vacuo to give 64a as a deep purple solid. Recrystallization from dry methanol gives 300 mg (99%) of 64a with mp 202-204 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ = 10.76 (s, 1H, N (1) H), 7.74, 7.50 (2 s, 2H, CONH ₂ ), 6.07 (s, 1H, -CH = (N (Me) ₂ ) ₂ ), 3.10 (s, 12H, 4N (CH ₃ ) ₂ ).
¹³ C NMR (125 MHz, CD ₃ CN) δ = 168.44 (aminal C), 166.86, 166.54 (2C = O), 157.50 (C (2)), 148.49 (C (3)), 118.41, 118.17 (2CN) , 90.93 (-CH = (N (Me) ₂ ) ₂ ), 74.64 (NH ₂ COC =), 65.72 (C (4)), 41.52 (N (CH ₃ ) ₂ ).

Example 17:

N-phenyl-2- (3- [2,2-bis (dimethylamino) vinyl] -4-cyano-5-oxo-1-phenyl-1,5-dihydro-pyrrol-2-ylidenes-cyanoacetamide ( 64b) A mixture of 400 mg (1 mmol) of the bis (amidinium) salt Ia3, 500 mg (3.1 mmol) of N-phenylcyanacetamide, 200 mg (1.9 mmol) of sodium carbonate and 6 ml of acetonitrile is heated at 60 ° C. for 1.5 h After cooling to room temperature, it is filtered, and the resulting solid is washed several times with acetonitrile, methanol and water, and dried to give 360 mg (79%) of 64b, deep violet crystals which are recrystallized from acetonitrile Tetrafluoroborate: A solution of 64b in acetonitrile is acidified with 50% HBF ₄ and evaporated to dryness in vacuo and the residue is treated with methanol The tetrafluoroborate (64b · HBF ₄ ) crystallizes out, is filtered off with suction and recrystallized from acetonitrile, mp 180-182 ° C ,
64b · IIBF _4: ¹ H NMR (500 MHz, CD ₃ CN) δ = 7.60-6.90 (m, 12H), 3.16 (s, 12H), 2.98 (s, 2H).

Example 18:

N, N, N ', N'-tetramethyl-4-dimethylamino-5-methoxycarbonyl-pyrrole-2-carboxamidinium tetraphenylbo rat (Vc1). While stirring, 150 mg (1.2 mmol) of glycine methyl ester hydrochloride and 150 mg (1.4 mmol) of sodium carbonate are added to a solution of 400 mg (1 mmol) of the bis (amidinium) salt Ia3 in 3 ml of dry acetonitrile at room temperature. After stirring for 24 hours at 20 ° C and 1 hour of stirring at 80 ° C, the mixture is diluted with dry acetonitrile and filtered. The filtrate is treated with a solution of 360 mg (1 mmol) of sodium tetraphenylborate in 3 ml of dry acetonitrile. The reaction mixture is filtered and the filtrate evaporated in vacuo. The residue is dissolved in dry hot ethanol. After cooling to room temperature, the crystalline product is filtered off with suction, washed several times with dry ethanol and dried. Y. 455 mg (77%) Vc1, yellow crystals with mp 196-198 ° C (decomp.)
¹ H NMR (500 MHz, CD ₃ CN) δ = 10.9-8.9 (broad s, 1H, NH), 7.27 (broad s, 8H, BPh ₄ ^- . O-ArH), 6.98 (t, J = 7.3 Hz, 8H, BPh ₄ ^-, m-ArH), 6.83 (t, 4H, J = 7.3 Hz, BPh ₄ ^-, p-ArH), 6:38 (s, 1H, C (3) H), 3.81 (s, 3H, COOCH ₃ ), 3.25-2.85 (broad s, 12H, 2-amidinium N (CH ₃ ) ₂ ), 2.78 (s, 6H, N (CH ₃ ) ₂ );
¹³ C NMR (125 MHz, CD ₃ CN) δ = 165.34, 164.95, 164.56, 164.17 (BPh ₄ ^- C (1 ')) 162.1 (amidinium C), 160.4 (C = O), 148.1 (C (4)) , 136.7 (BPh ₄ ^- , C (2 ')), 126.5 (BPh ₄ ^- , C (3')), 122.7 (BPh ₄ ^- , C (4 ')), 120.0, 115.8 (C (2), C (5)), 108.9 (C (3)), 52.1 (COOCH ₃ ), 44.4 (C (4) -N (CH ₃ ) ₂ ), 43.6 (amidinium N (CH ₃ ) ₂ ).

Example 19:

N, N, N ', N'-tetramethyl-4-dimethylamino-5-methoxycarbonyl-N-methylpyrrole-2-carboxamidinium tetraphenylborate (Vc2). 170 mg (1.2 mmol) of N-methyl-glycine methyl ester hydrochloride and 150 mg (1.4 mmol) of sodium carbonate are added at room temperature to a solution of 400 mg (1 mmol) of the bis (amidinium) salt Ia3 in 30 ml of dry acetonitrile. The mixture is stirred for 24 h at room temperature and for 1 h at 80 ° C, then diluted with acetonitrile and filtered. The filtrate is treated with a solution of 360 mg (1 mmol) of sodium tetraphenylborate in 3 ml of dry acketonitrile. The mixture is filtered and the filtrate evaporated in vacuo. The residue is dissolved in hot methanol and then cooled to 5 ° C. The product is filtered off with suction and washed several times with methanol. Y. 250 mg (41%) Vc2, thin yellow plates with mp 174-176 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ = 7.27 (broad s, 8H, BPh ₄ ^- o-ArH), 6.98 (t, J = 7.5 Hz, 8H, BPh ₄ ^- m-ArH), 6.83 (t , 4H, J = 7.3 Hz, BPh ₄ ^-, p-ArH), 6:32 (s, 1H, C (3) H), 3.84 (s, 3H, COOCH _3), 3.61 (s, 3H, N (1) CH ₃ ), 3.19 and 2.85 (2 s, 12H, 2 amidinium N (CH ₃ ) ₂ ), 2.69 (C (4) N (CH ₃ ) ₂ );
¹³ C NMR (125 MHz, CD ₃ CN) δ = 165.34, 164.95, 164.56, 164.17 (BPh ₄ ^- , C (1 ')) 161.79 (amidinium C), 161.67 (C = O), 148.63 (C (4) ), 136.71 (BPh ₄ ^- , C (2 ')), 126.55 (BPh ₄ ^- , C (3')), 124.15 (C (2)), 122.74 (BPh ₄ ^- , C (4 ')), 118.52 C (5)), 106.97 (C (3)), 51.96 _(COOCH3), 44.96 (C (4) -N (CH _{3) 2),} 43.51 and 43.38 (amidinium N (CH _{3) 2),} 35.58 ( N (1) CH ₃ ).

Example 20:

N, N, N ', N'-tetramethyl-3-dimethylamino-5-methoxycarbonylthiophene-2-carboxamidinium tetraphenylborate (Vb1). A solution of 150 mg (1.41 mmol) of methyl thioglycolate in 1.5 ml of dry acetonitrile and 150 mg (1.4 mmol) is added to a solution of 550 mg (1.4 mmol) of the bis (amidinium) salt Ia3 in 3 ml of dry acetonitrile with stirring at room temperature. Sodium. After stirring at room temperature for 24 hours, the reaction is diluted with dry acetonitrile and filtered. The yellow filtrate is treated with a solution of 480 mg of m (1.4 mmol) of sodium tetraphenylborate in 3 ml of dry acetonitrile, the mixture is filtered and the filtrate is evaporated in vacuo. The residue is dissolved in boiling methanol. The product which separates on cooling to room temperature is filtered off with suction and washed several times with methanol and dried. Y. 510 mg (61%) Vb1, thin yellow plates with mp 174-176 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ = 7.27 (broad s, 8H, BPh ₄ ^- o-ArH), 7.18 (s, 1H, C (3) H), 6.98 (t, J = 7.3 Hz, 8H, BPh ₄ ^- m-ArH), 6.83 (t, 4H, J = 7.3 Hz, BPh ₄ ^-, p-ArH), 3.78 (s, 3H, COOCH _3), 3:08 (broad s, 12H, 2 amidinium N (CH ₃ ) ₂ ), 2.97 (C (4) N (CH ₃ ) ₂ );
¹³ C NMR (125 MHz, CD ₃ CN) δ = 165.35, 164.96, 164.57, 164.21 (BPh ₄ ^- , C (1 ')) 164.19 (amidinium C), 162.20 (C = O), 157.46 (C (4) , 136.71 (BPh ₄ ^- , C (2 ')), 131.71 (C (2)), 128.84 (C (3)), 126.5 (BPh ₄ ^- , C (3')), 122.73 (BPh ₄ ^- , C (4 ')), 111.1 C (5)), 52.58 (COOCH ₃ ), 44.26 (C (4) -N (CH ₃ ) ₂ ), 44.20 (amidinium N (CH ₃ ) ₂ ).

Example 21:

2 [2,2-bis (dimethylamino) vinyl] -3-dimethylaminoquinoxaline (XIIa) and N, N, N ', N'-tetramethyl-2- (3-dimethylammonioquinoxalin-2-yl) -acetamidinium bis-tetrafluoroborate. To a solution of 400 mg (1 mmol) of Ia3 in 3 ml of dry acetonitrile is added 120 mg (1.1 mmol) of o-phenylenediamine and stirred for 15 h at room temperature. Thereafter, water is added and the mixture is made alkaline by the addition of sodium carbonate and extracted twice with chloroform. The organic phase is washed with water, dried over sodium sulfate and filtered. The filtrate is evaporated in vacuo to give 220 mg (90%) of XIIa as a bright yellow, glassy solid. Bis-tetrafluoroborate: A solution of 290 mg (1.2 mol) of the ketenamine XIIa in methanol is acidified with 50% tetrafluoroboric acid. The batch is evaporated in vacuo. The residue is dried by dissolving three times in dry ethanol and then evaporating. The residue is treated with dry methanol and allowed to stand at 5 ° C for 18 h. The crystalline product is filtered off with suction, washed with ice-cold methanol and dried. Y. 210 mg (49%) of XIIa.2HBF ₄ , yellow crystals with mp 260-264 ° C. (dec.)
¹ H NMR (500 MHz, CD ₃ CN) δ = 7.58 (d, J = 8 Hz, 1H, C (5) H), 7.52 (d, J = 8 Hz, 1H, C (8) H), 7.30 (t, J = 7.6Hz, 1H, C (7) H), 7.24 (t, J = 7.6Hz, 1H, C (6) H), 4.65 (s, 1H, = CH-), 2.94 (s, 6 H, C (3) N (CH ₃ ) ₂ ), 2.82 (s, 12H, 2N (CH ₃ ) ₂ .
¹³ C NMR (125 MHz, CD ₃ CN) δ = 164.30 (= CH (N (CH ₃ ) ₂ ) ₂ ), 156.34 (C (3)), 149.98 (C (2)), 140.61, 137.87 (quinoxaline quatern C), 127.15 (C (5)), 127.02 (C (8)), 126.23 (C (/)), 125.34 (C (6)), 83.81 (= CH-), 41.41 (C (3) N (CH ₃ ) ₂ ), 40.81 (N (CH ₃ ) ₂ ).

Example 22:

2- [2,2-bis (dimethylamino) vinyl] -3-dimethylamino-benzo [g] quinoxalin-2-yl) -ethene (XIIb) and N, N, N ', N'-tetramethyl-2- (3 -dimethylammonioquinoxalin-2-yl) -acetamidinium-bis-tetrafluoroborate (XIIb.2HBF ₄ ). To a solution of 460 mg (1.1 mmol) of the bis (amidinium) salt Ia3 in 3 ml of dry acetonitrile is added with stirring at room temperature 160 mg (1 mmol) of 2,3-diamino-naphthalene in 4 ml of dry acetonitrile. After stirring for 18 h at room temperature, the solvent is removed in vacuo. The residue is dissolved in methylene chloride. The solution is washed first with an aqueous potassium carbonate solution and then with water. The organic phase is dried over sodium sulfate and then evaporated in vacuo. This gives 220 mg (75%) of XIIb as an orange-glossy glassy solid. Bis-tetrafluoroborate: A solution of 110 mg (0.38 mmol) of XIIb in 3 ml of acetonitrile is acidified with 50% tetrafluoroboric acid. The volatiles are removed in vacuo. The residue is dried by dissolving 3 times in dry acetonitrile and the acetonitrile is evaporated in vacuo. The residue is mixed with methanol and allowed to stand for several hours at room temperature. The crystals formed are filtered off with suction, washed with cold methanol and dried. Y. 110 mg (62%) XIIb.2HBF ₄ , orange crystals of mp 248-252 ° C (dec.).

The ¹ H NMR spectrum of the salt XIIb.2HBF ₄ in CD ₃ CN shows that a tautor mixture is present.
XIIb2 (tautomer a): ¹ H NMR (500 MHz, CD ₃ CN) δ = 7.96 (broad s, 1H, C (9)), 7.91-7.78 (m, 2H, C (5) H) + C (8 ) H, 7.68 (broad s, 1H, C (4) H), 7.55-7.42 (m, 2H, C (6) H + C (7) H), 5.55 (s, 1H, C (2 ') H (1)), 4.59 (s, 1H, C (2 ') H (2)), 3.22 (broad s, 6H, C (3) N (CH ₃ ) ₂ ), 3.21 (s, 12H, 2 N (CH ₃ ) ₂ ).
XIIb2 (tautomer b): ¹ H NMR (500 MHz, CD ₃ CN) δ = 8.55 (broad s, 2H), 8.33 (s, 1H), 8.12 (t, J = 9 Hz, 2H), 7.77-7.61 ( m, 2H), 3.62 (s, 6H, 1N (CH ₃ ) ₂ ), 3.50 (s, 12H, 2N (CH ₃ ) ₂ ).

Example 23:

N, N, N ', N', N '', N '', N '', N '''- octamethyl-bicyclo [2.2.1] hepta-2,5-diene-2,3-bis ( carboxamidinium) bis-tetrafluoroborate (VIa). A mixture of 860 mg (2.2 mmol) of the bis (amidinium) salt Ia3, 2 ml corresponding to 1.62 g (24.5 mmol) of freshly distilled cyclopentadiene and 5 ml of dry acetonitrile is stirred for 15 h at room temperature. After removal of the volatiles in vacuo, the residue is treated with dry methanol and the crystalline solid is filtered off with suction, washed several times with dry methanol and dried. Y. 970 mg (97%) of VIa, colorless crystals of mp> 240 ° C (dec.).
¹ H NMR (500 MHz, CD ₃ CN) δ = 7.09 (t, J = 2 Hz, 2H, C (5) H and C (6) H), 4.12 (m, 2H, C (1) H and C (4) H), 3.40-3.00 (m, 18H, 3N (CH ₃ ) ₂ ), 2.72 (broad s, 6H, 1N (CH ₃ ) ₂ ), 2.64 and 2.37 (2 d, J = 8 Hz, C (7) H ₂ ).
¹³ C NMR (125 MHz, CD ₃ CN) δ = 163.49 (2 amidinium C), 158.68 (C (2) + C (3)), 142.51 (C (5) + C (6)), 74.68 (C ( 7)), 56.82 (C (1) + C (4)), 44.01, 42.98 (NCH ₃ ).

Example 24:

N, N, N ', N', N '', N '', N '', N '''- octamethyl-7-oxa-bicyclo [2.2.1] hepta-2,5-dien-2, 3-bis (carboxamidinium) bis-tetrafluoroborate (VIb). A mixture of 1.5 g (3.8 mmol) of the bis (amidinium) salt Ia3, 8 g (118 mmol) of freshly distilled furan and 15 ml of dry acetonitrile is allowed to stand at room temperature for 17 days. The volatiles are removed in vacuo and the residue treated with dry methanol. The crystalline solid is filtered off, washed several times with dry methanol, optionally recrystallized again from dry methanol and dried. Y. 1.0 g (57%) VIb, colorless crystals with mp 140 ° C (dec.).
¹ H NMR (500 MHz, CD ₃ CN) δ = 7.41 (t, J = 1 Hz, 2H, C (5) H and C (6) H), 5.91 (t, J = 1 Hz, 2H, C ( 1) H and C (4) H), 3.55-2.95 (m, 18H, 3N (CH ₃ ) ₂ ), 2.74 (broad s, 6H, 1N (CH ₃ ) ₂ ).
¹³ C NMR (125 MHz, CD ₃ CN) δ = 161.39 (2 amidinium C), 159.69 (C (2) + C (3)), 143.27 (C (5) + C (6)), 87.20 (C ( 1) + C (4)), 44.00, 42.88 (NCH ₃ ).

Example 25:

N, N, N ', N', N '', N '', N '', N '''- octamethyl-1-benzyl-1H- [1,2,3] triazole-4,5-bis (carboxamidinium) bis-tetrafluoroborate (VII). To 400 mg (1 mmol) of the bis (amidinium) salt Ia3 in 3 ml of dry acetonitrile are added 505 mg (3.8 mmol) of benzyl azide. The mixture is stirred for 48 h at 65 ° C. The volatiles are removed in vacuo. The crystalline residue is mixed with dry methanol and heated briefly under reflux. After standing for several hours at room temperature, the crystals are filtered off with suction, washed several times with methanol and dried. Y. 450 mg (75%) of VII, colorless crystals of mp 272-274 ° C (dec.).
¹ H NMR (500 MHz, CD ₃ CN) δ = 7.47 (m, 3H, m + p-ArH), 7.43 (m, 2H, o-ArH), 5.75 (s, 2H, CH ₂ ), 3.5- 2.90 (m, 18H, incl. S, at 3.39, 3N (CH ₃ ) ₂ ), 2.81 (s, 6H, 1N (CH ₃ ) ₂ );
¹³ C NMR (125 MHz, CD ₃ CN) δ = 158.20, 154.72 (2 amidinium C), 139.80 (C (4)), 133.17 (C (5)), 130.69, 130.48 (m- and p-Ar (C ), 129.87 (quaternary Ar (C)), 129.75 (o-Ar (C)), 56.04 (CH ₂ ), 44.67, 44.24, 43.85 (NCH ₃ ).

Example 26:

N, N, N ', N', N '', N '', N '', N '''- octamethyl-2-methyl-3-phenyl-2,3-dihydro-isoxazole-4,5- bis (carboxamidinium) bis-tetrafluoroborate (VIII). To 400 mg (1 mmol) of the bis (amidinium) salt Ia3 in 3 ml of dry acetonitrile are added 160 mg (1.18 mmol) of N- (benzylidene) methylamine-N-oxide and stirred for 18 h at room temperature. The residue remaining in vacuo after removal of the volatiles is treated with dry methanol. After standing for several hours at 5 ° C, the crystals formed are filtered off with suction, washed several times with dry, cold methanol and dried. Y. 410 mg (76%) VIII, orange crystals with mp 142 ° C (dec.).
¹ H NMR (500 MHz, CD ₃ CN) δ = 7.52-7.41 (m, 5H, ArH), 5.57 (s, 1H, C (3)), 3.36, 3.32, 3.28, 3.25 (4 s, 4NCH ₃ ) , 3.19 (s, N (2) CH _3), 3.13 3.12 3.07 2.72 (4 s, 4 N (CH _3).
¹³ C NMR (125 MHz, CD ₃ CN) δ = 160.37, 155.39 (2 amidinium C), 150.61 (C (5)), 137.05 (quaternary, ArC), 130.76, 130.56 (m and p-ArC), 127.56 (o-ArC), 116.57 (C (4)), 77.04 (C (3)), 46.94 (N (2) CH ₃ ), 44.87, 44.20, 44.05, 43.91, 43.86, 43.55, 43.06, 42.92 (8NCH ₃ ).

Example 27:

N, N, N ', N', N '', N '', N '', N '''- octamethyl-3-ethoxycarbonyl-indolizine-1,2-bis (carbox) amidinium) bis-tetrafluoroborate (IX). A mixture of 400 mg (1 mmol) of the bis (amidinium) salt Ia3, 300 mg (1.2 mmol) of 1-pyridinio-ethoxycarbonylmethanide 100 mg (1 mmol) of sodium carbonate and 3 ml of dry acetonitrile are stirred for 24 h at room temperature. The mixture is diluted with about 5 ml of dry acetonitrile, filtered and the filtrate evaporated in vacuo. The residue is mixed with a little dry methanol and heated under reflux for 1-2 minutes. After standing for several hours at room temperature, the crystalline product is filtered off with suction, washed with methanol and dried and recrystallized again from dry methanol. Y. 200 mg (35%) with m.p. 174-176 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ = 9.60 (t, J = 6.8 Hz, 1H, C (5)), 7.70 (t, J = 8 Hz, 1H, C (7)), 7.64 (i.e. , J = 8.6 Hz, 1H, C (8)), 7.40 (t, J = 6.8 Hz, 1H, C (6)), 4.48 (q, J = 7 Hz, 2H, COOCH ₂ CH ₃ ), 7.52- 73.43 (s, 6H, 1 N (CH _{3) 2),} 3:37 (s, 6H, 1 N (CH _{3) 2),} 2.97 (s, 12H, 2 N (CH _{3) 2),} 1:40 (t, J = 7 Hz, COOCH ₂ CH ₃ ).
¹³ C NMR (125 MHz, CD ₃ CN) δ = 163.45, 162.14 (2 amidinium C), 160.06 (C = O), 139.63 (C (9)), 130.33, 130.28 (C (5) + C (7) ), 123.34 (C (3)), 119.52 (C (8)), 118.55 (C (6)), 102.63, 102.59 (C (1) + C (2)), 63.53 (COOCH ₂ CH ₃ ), 44.65 , 43.92, 43.79 (N (CH ₃ ) ₂ ), 14.76 (COOCH ₂ CH ₃ ).

Example 28:

N, N, N ', N', N ", N", N ''',N''' - octamethyl-4H-chromen-4-ol-2,3-bis (carboxamidinium) -bistetrafluoroborate (X ). A mixture of 400 mg (1 mmol) of the bis (amidinium) salt Ia3, 150 mg (1.2 mmol) of salicylaldehyde, 150 mg (1.4 mmol) of sodium carbonate and 3 ml of dry acetonitrile are stirred at room temperature for 48 h. The mixture is diluted with about 6 ml of acetonitrile, heated briefly under reflux and filtered hot. The filtrate is evaporated in vacuo. The residue is mixed with a little dry methanol and heated under reflux for 1-2 minutes. After several standing at room temperature, the crystalline product is filtered off with suction, washed with methanol and dried. Y. 460 mg (88%) X, colorless solid of mp 232-234 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ = 7.62 (d, J = 7.7 Hz, 1H, C (3) H), 7.53 (t, J = 7.7 Hz, 1H, C (7) H), 7.43 (t, J = 7.7Hz, 1H, C (6) H), 7.30 (d, J = 8Hz, 1H, C (8) H), 5.69 (s, 1H, C (4) H), 5.04 ( br. s, 1H, OH), 3.44, 3.37, 3.34, 3.33, 3.28, 3.24, 3.23, 3.16 (8 s, 4N (CH ₃ ) ₂ ).

Example 29:

N, N, N ', N', N '', N '', N '', N '''- octamethyl-1H-benzo [f] chromen-1-ol-2,3-bis (carboxamidinium) bis-tetrafluoroborate (XI). The mixture of 400 mg (1 mmol) of the bis (amidinium) salt Ia3, 0.9 g (5.2 mmol) of 2-hydroxy-naphthalene-1-carbaldehyde and 4.4 ml of dry acetonitrile is stirred for 24 h at room temperature. The volatiles are removed in vacuo. The residue is mixed with dry THF. The solid is filtered off, washed several times with dry THF and recrystallized from dry methanol. Y. 380 g (66%) XI, colorless solid of mp 252-254 ° C.
¹ H NMR (500 MHz, CD ₃ CN) δ 8.34 (d, J = 8 Hz, 1H, C (10)), 8.08 (d, J = 9 Hz, 1H, C (6) H), 8.03 (i.e. , J = 8Hz, 1H, C (7) H,) 7.74 (m, 1H, C (8) H), 7.64 (m, 1H, C (9) H), 6.23 (s, 1H, C (1 ) H, 4.95 (broad s, 1H, OH), 3.48, 3.44, 3.39, 3.37, 3.35, 3.34, 3.30, 3.14 (8 s, 4N (CH ₃ ) ₂ ).

Example 30:

2,3-bis [bis (dimethylamino) methylene] -4-phenylimino-chroman (XIII). A mixture of 400 mg (1 mmol) of the bis (amidinium) salt Ia3, 250 mg (1.27 mmol) of N-salicylidene-aniline, 150 mg (1.4 mmol) of sodium carbonate and 3 ml of dry acetonitrile are stirred at room temperature for 40 h. The mixture is diluted with about 5 ml of acetonitrile and then filtered. The filtrate is evaporated in vacuo and the residue is treated with methanol. The solid product is filtered off with suction and washed several times with methanol and dried. Y. 125 mg (30%) XIII, bright orange solid, mp 268-270 ° C (dec.).
¹ H NMR (500 MHz, CD ₃ CN) δ = 7.67 (t, J = 7.9 Hz, 1H, C (8) H), 7.54 (d, J = 8.4 Hz, 1H, (C (5 ')) 7.44 (t, J = 7.2 Hz, 2H, C (5 ') + C (3')), 7.21 (t, J = 7.65 Hz, 1H, (C (4 ')), 7.15-7.08 (m, 2H , C (7) + C (9)), 6.95 (d, J = 7.65 Hz, 2H, C (2 ') + C (6')), 3.44, 3.37, 3.30, 3.24 (4N (CH ₃ ) ₂ );
¹³ C NMR (125 MHz, CD ₃ CN) δ 163.63, 159.05 (= C (NMe ₂ ) ₂ ), 154.91 (C (10)), 151.26 (C (7 ')), 149.24 (C (4)), 148.32 (C (5)), 135.25 (C (7)), 130.86 (C (5 ') + C (3')), 128.65, 127.06 (C (8) + C (6)), 125.34 (C ( 4 ')), 120.23 (C (5)), 121.86, 119.15 (C (2) + C (3)), 118.68 (C (2') + C (6 ')), 44.67, 44.50, 44.21, 43.58 (4N (CH ₃ ) ₂ ).

QUOTES INCLUDE IN THE DESCRIPTION

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Claims (37)

N, N, N ', N'-tetrasubstituted amidinium salts of the general formula I in which R ¹ and R ^{2 represent} saturated or unsaturated alkyl radicals, cycloalkyl groups, aromatic aliphatic radicals, heterocyclic alkyl groups and also aromatic and heteroaromatic radicals, each of up to 12 Carbon atoms, where R ¹ and R ² are different but also identical, but may also be an alkane-α, ω-diyl structure in which, optionally, C, C chain heteroatoms such as O, S, N are inserted and the radical R for 3-N '', N '', N ''',N''' - Tetraalkylamidinio-prop-1-yn-1-yl, 2-alkoxy and 2-aryloxy or 2-alkylthio or 2-arylthio or 2-alkylamino or 2-arylamino-3-N '', N '', N ''',N''' - tetraalkylprop-1-en-1 -yl, 3,3-bis (dialkylamino) -1-diorganomethylene) -prop-1-en-1-yl, 1,3-dialkyl-6-dialkylamino-2-pyridone-4-yl, 5 Alkoxycarbonyl-4-dialkylamino-2-furyl, 5-alkoxycarbonyl-4-dialkylamino-2-thienyl, 5-alkoxycarbonyl-4-dialkylamino-pyrrol-2-yl, 2,3- Diorgano-5-N '', N '', N ''',N''' - tetraalkyl-5-amidinio-bicyclo [2.2.1] hepta-2,5-dien-6-yl, 2 , 3-diorgano-5-N '', N '', N '', N '''- tetraalkylamidinio-7-oxa-bicyclo [2.2.1] hepta-2,5-dien-6-yl , 7-alkyl-2,3-diorgano-5-N ", N", N "', N"' - tetraalkylamidinio-7-aza-bicyclo [2.2.1] hepta-2, 5-dien-6-yl, 1-alkyl or 1-aryl-4-N ", N", N "', N"' - tetraalkylamidinio-1,2,3-triazole-5 -yl, 2-alkyl- or 2-aryl-4-N '', N '', N ''',N''' - tetraalkylamidinio-isoxazol-5-yl, 3,5,6,7, 8-pentaorgano-2-N '', N '', N ''',N''' - tetraalkylamidinioindolizin-1-yl, 5,6,7,8-tetraorgano-3-N '', N '', N ''',N''' - tetraalkylamidinio-4-hydroxychromon-2-yl, 5,6-diorgano-4-hydroxy-3-N '', N '', N ''', N '''-Tetraalkylamidinio-4H-pyran-2-yl groupings in which the dialkylamino groups match those present in the amidinium function (in formula I) and act as anions X and Y, wherein X and Y are identical but may differ from each other and in detail stand for: F ^- , Cl ^- , Br ^- , I ^- , ClO ₄ ^- , CF ₃ SO ₃ ^- , C ₂ F ₅ SO ₃ ^- CF ₃ CO ₂ ^- , CO ₃ CO ₂ ^- , HCF ₂ CO ₂ ^- , C ₄ F ₉ SO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- , B (C ₆ H ₅ ) ₄ ^- , BF ₄ ^- , PF ₆ ^- , (C ₆ H ₅ ) ₂ PF ₄ ^- , C ₂ H ₅ PF ₅ ^- , HSO ₄ ^- , SO ₄ ^2- , NO ₃ ^- , SbCl ₆ ^- , SbF ₆ ^- , SnCl ₄ ^2- , SnCl ₆ ^2- , TiCl ₆ ^2- , ZrCl ₆ ^2- , ZnCl ₄ ^2- , FeCl ₄ ^- , AlCl ₄ ^- .

Compounds according to claim 1, characterized in that the anions, X, Y are defined as Cl ^-, Br ^-, I ^-, CF ₃ SO ^-, CCl ₃ SO ₃ ^-, CF3CO ₂ ^-, CCl ₃ CO ₂ ^-, ClO ₄ ^- , BF ₄ ^- , B (C ₆ H ₅ ) ₄ ^- , PF ₆ ^- and the substituents R ¹ and R ² correspond to R ¹ = R ² = CH ₃ , C ₂ H ₅ , C ₃ H ₇ , (CH ₃ ) ₂ CH, C ₄ H ₉ , C ₂ H ₅ -CH-CH ₃ , (CH ₃ ) ₂ CH-CH ₂ , C ₅ H 14 ₁₁ , C ₆ H ₁₃ , C ₇ H ₁₅ , C ₈ H ₁₇ , C ₉ H ₁₇ , C ₁₀ , H ₂₁ , C ₁₁ H ₂₃ , C ₁₂ H ₂₅ , C ₁₃ H ₂₇ , C ₁₄ H ₂₉ , C ₁₅ H ₃₁ , C ₁₆ H ₃₃ , C ₁₇ H ₃₅ , C ₁₈ H ₃₇ , cC ₃ H ₅ cC ₄ H ₇ , cC ₅ H ₉ , cC ₆ H ₁₁ , cC ₇ H ₁₃ , C ₆ H ₅ , 4-Cl-C ₆ H ₄ , 4-CH ₃ OC ₆ H ₄ or are different, where R ¹ = CH ₃ in combination with R ² = C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , C ₅ H ₁₁ , C ₁₂ H ₂₅ , C ₁₄ H ₂₉ , C ₁₆ H ₃₃ , C ₁₇ H ₃₅ , cC ₄ H ₇ , cC ₅ H ₉ , cC ₆ H ₁₁ , cC ₇ H ₁₃ , C ₆ H ₅ , 4-Cl-C ₆ H _4, and R ¹ = C ₂ H ₅ in combination with R ² = C ₃ H ₇ , C ₄ H ₉ , C ₅ H ₁₁ , C ₆ H ₁₃ , C ₁₂ H ₂₅ , C ₁₄ H ₂₉ , C ₁₆ H ₃₃ , C ₁₇ H ₃₅ , cC ₄ H ₇ , cC ₅ H ₉ , cC ₆ H ₅ , C ₆ H ₅ , 4-CH ₃ -C ₅ H ₄ , 4-Cl-C ₆ H ₄ , 4-CH ₃ OC ₆ H is ₄ , or a linkage of R ¹ to R ² in which R ¹ -R ^{2 is} (CH ₂ ) ₂ , (CH ₂ ) ₃ , (CH ₂ ) ₄ , (CH ₂ ) ₅ , (CH ₂ ) ₆ , (CH ₂ ) ₂ -O- (CH ₂ ) ₂ , (CH ₂ ) ₂ -N (CH ₃ ) - (CH ₂ ) ₂ . Compounds according to claim 2, characterized in that they are (2-butyne) bisamidinium salts of general formula Ia

Compounds according to claim 2, characterized in that they are N, N, N ', N', N ", N", N ''',N''' - hexaalkyl-2-organoalkyl- (but-2 -en) -bis (amidinium) salts of the general formula II, where Z can be oxygen (amidinium salts IIa), sulfur (amidinium salts IIb) and organoamino groups NR ³ (amidinium salts IIc), in which R ^{3 is} the following radicals C ₆ H ₅ , 4-Cl-C ₆ H ₄ , 2-CH ₃ O ₂ CC ₆ H ₄ ,

-NH-CH ₃ , -NH-C ₂ H ₅ , -NH-C ₆ H ₅ , -N (CH ₃ ) ₂ , -N (C ₂ H ₅ ) ₂ , -N (CH ₃ ) -C ₆ H ₅ , -N (C ₆ H ₅ ) ₂ , -OH, OCH ₃ , OC ₆ H ₅ , OC ₂ H ₅ , CH ₂ CN, CH ₂ CO ₂ C ₂ H ₅ , and R for the following one to six-membered radicals: CH ₃ , C ₂ H ₅ , C ₃ H ₇ , (CH ₃ ) ₂ CH, C ₄ H ₉ , (CH ₃ ) ₂ CH-CH ₂ , CH ₃ -CH ₂ -CH-CH ₃ , C ₅ H _11, C ₈ H _17, C ₁₆ H _33, C ₁₈ H _37, cC ₆ H _13, cC ₆ H _13,

IIa: Z = O, IIb: Z = S, IIc: Z = NR ³ 4a. Compounds according to Claim 2, characterized in that they are N, N, N ', N'-tetraalkylpyrazole-2-carboxamidinium salts of the general formula IId and the radicals R, R ¹ and R ^{2 are} as defined in Claim 4 to match.

Compounds according to claim 2, characterized in that they are N, N, N ', N'-tetraalkyl-2-alkylidene-4,4-bis (dialkylamino) - (but-3-ene) amidinium salts of general formula III where R ³ and R ^{4 are} independently CN, CO ₂ CH ₃ , CO ₂ C ₂ H ₅ , CONH ₂ , CONHCH ₃ , CONHC ₆ H ₅ , CON (CH ₃ ) ₂ , NO ₂ , O ₂ NC ₆ H ₄ , CH ₃ CO ₃ C ₂ H ₅ CO ₃ C ₆ H ₅ CO,

and R ³ linked to R ^4, the two-membered radicals

but R ³ can also stand for H, CH ₃ , C ₂ H ₅ , C ₆ H ₅ , if R ⁴ = NO ₂ or

means.

Compounds according to claim 2, characterized in that they are 1-alkyl or aryl-2-dialkylamino-3 - [(2,2-bis (dialkylamino) vinyl] -4-acyl or 4-alkoxycarbonyl or 4-cyano- or 4-nitro-5-oxo-pyrrolium salts of the general formula IV where R ⁴ , CO ₂ C ₂ H ₅ , CONH ₂ , CONCH ₃ , CONHC ₆ H ₅ , CON (CH ₃ ) ₂ , CH ₃ CO, C ₆ H ₅ CO, 4-Cl-C ₆ H ₅ CO ₃ , NO ₂ and R ^{3 are} the radicals H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₆ H ₅ , 2 -Cl-C ₆ H ₄ , 3-Cl-C ₆ H ₄ , 4-Cl-C ₆ H ₄ .

Compounds according to Claim 2, characterized in that they are N, N, N ', N'-tetraalkyl-5-alkoxycarbonyl-4-dialkylamino-2-carboxamidinium salts of pyrrole, thiophene and furan of the general formula V where R ³ is CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , C ₆ H ₅ and each Z is O, S and NR ⁴ where R ^{4 is} H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₆ H ₅ stands.

a: Z = O, b: Z = S, c: Z = NR ⁴ Compounds according to claim 2, characterized in that they are N, N, N ', N', N '', N '', N ''',N''' - octaalkyl-bicyclo- [2.2.1] - hepta-2,5-diene-bis-endo-5,6-dicarboxamidinium salts of the general formula VI wherein Z is CH ₂ , O and NR ⁵ where R ⁵ = H, CH ₃ , C ₂ H ₅ , C ₆ H ₅ and R ³ and R ^{4 are} independently H, CH ₃ , C ₂ H ₅ , OCH ₃ , N (CH ₃ ) ₂ , C ₆ H ₅ .

a: Z = CH ₂ , b: Z = 0, c: Z = NR ⁵ Compounds according to claim 2, characterized in that they are N ", N ''',N''' - octaalkyl-1-alkyl and 1-aryl-1,2,3-triazole-4,5-dicarboxamidinium salts of general formula VII wherein R is CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₆ H ₅ , C ₆ H ₅ -CH ₂ , Cl-C ₆ H ₄ -, CH ₃ OC ₆ H ₄ ,

Compounds according to claim 2, characterized in that they are N, N, N ', N', N ", N", N ''',N''' - octaalkyl-2-alkyl and 2-aryl, respectively -isoxazole-4,5-dicarboxamidinium salts of the general formula VIII wherein R ^{3 is} CH ₃ , C ₂ H ₅ , (CH ₃ ) ₂ CH, C ₆ H ₅ and R ^{4 is} H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , (CH ₃ ) ₂ CH, C ₆ H ₅ -CH ₂ , C ₆ H ₅ , Cl-C ₆ H ₄ ,

Compounds according to claim 2, characterized in that they are N, N, N ', N', N '', N '', N ''',N''' - octaalkyl-indolizine-3-EA-substituted 1 , 2-dicarboxamidinium salts of the general Formula IX is where EA is CN, CO ₂ CH ₃ , CO ₂ C ₂ H ₅ , CON (CH ₃ ) ₂ , CON- (CH ₃ ) -C ₆ H ₅ , HCO, CH ₃ CO ₃ C ₆ H ₅ CO ₃ NO ₂ , O ₂ NC ₆ H ₄ , CH ₃ SO ₂ , C ₆ H ₅ SO ₂ , (CH ₃ O) ₂ PO-, (C ₂ H ₅ O) ₂ PO, (NC) ₂ C = CH , (CN) (C ₂ H ₅ OCO) = CH and R ³ , R ^{4 are} independently CH ₃ , C ₂ H ₅ , C ₆ H ₅ , C ₁ -C ₄ H ₄ , OCH ₃ , CN, COCH ₃ , N (CH ₃ ) ₂ .

Compounds according to Claim 2, characterized in that they are N, N, N ', N', N '', N '', N ''',N''' - octaalkyl-4-hydroxy-chromen-2, 3-dicarboxamidinium salts of the general formula X, where R ³ , R ⁴ , R ⁵ , R ⁶ independently of one another are H, CH ₃ , C ₂ H ₅ , C ₆ H ₅ , Cl, OCH ₃ .

Compounds according to Claim 2, characterized in that they are N, N, N ', N', N '', N '', N ''',N''' - octaalkyl-4-hydroxy-4H-pyrane 2,3-dicarboxamidinium salts of the general formula XI, wherein AB is a 5-7 membered unsubstituted or substituted isocyclic or heterocyclic saturated, unsaturated or aromatic ring in which as heteroatoms in AB, the elements N, O and S can act.

Compounds according to Claim 2, characterized in that they are 2,2-bis (2,2-dialkylamino-vinyl) -3-dialkylamino-benzo-fused pyrazines of the general formula XII, where YR ⁴ = ZR ⁵ = CH, and the structural element

for the following radicals:

when R ³ = R ⁶ = H.

Compounds according to claim 2, characterized in that they are benzo or heterocyclic fused 2,3-bis [bis (dialkylaminomethylene) -4-imino-2,3-dihydro-4H-pyrans of the general formula XIII, where R ³ for CH ₃ , (CH ₃ ) ₃ C, C ₆ H ₅ , 4-Cl-C ₆ H ₄ and the cyclic AB AB bond for

with R = CH ₃ , C ₆ H ₅ .

A process for the preparation of N, N, N ', N', N '', N '', N ''',N''' - tetrasubstituted (2-butyne) -bis-amidinium salts (bis-amidinium salts of acetylenedicarboxylic acid) of general formula Ia according to claim 3, characterized in that reacting bis (orthoamide) derivatives of acetylenedicarboxylic XIV at temperatures between -90 ° C and + 20 ° C in a solvent or a solvent mixture with cleavage reagents of the general formula XV, wherein in the general formula XY for carboxylic anhydrides

Anhydrides of dicarboxylic acids

symmetrical or mixed sulfonic anhydrides (X = R ³ SO ₃ , Y = R ⁴ SO ₂ ), disulfonic anhydrides

Carbonsäuresulfonsäureanhydride

Carboxylic acids (X = R ³ COO, Y = H and sulfonic acids (R ³ = SO ₃ H, R ⁴ = H) are, and the radicals R ³ and R ⁴ in XY may be the same or different and for aliphatic, saturated, or unsaturated, mono- or polyhalogenated alkyl groups, or optionally halogenated arylalkyl or aryl radicals, which In the case of anhydrides of dicarboxylic acids and sulfonic acids, the symbol A stands for α, ω-alkanediyl structures in which the C, C chain is optionally interrupted by heteroatoms such as O, N, S is preferred, with multi-halogenated alkanediyl units having up to 12 carbon atoms, in which the halogens are each in α-position to the carbonyl or sulfonyl groups, are preferred, however, A may also be alicyclic, optionally halogenated and for aromatic and heteroaromatic radicals having up to 12 carbon atoms, which are substituted in the 1,2-position by the oxydicarbonyl or Oxidisulfonyl- or Carbonyloxysulfonylgruppe.

A method according to claim 16, characterized characterized in that the solvent selected is from diethyl ether, dipropyl ether, dibutyl ether, methyl propyl ether, Methyl-butyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, Dimethoxymethane, diethoxymethane, 1,1-dimethoxyethane, 1,1-diethoxyethane, Anisole, ethyl phenyl ether, pentane, hexane, cyclohexane, methylcyclohexane, Heptane, petroleum ether, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, Acetone, ethyl methyl ketone, diethyl ketone, methyl propyl ketone, acetophenone, Acetonitrile, propionitrile, butyronitrile, methoxyacetonitrile, ethoxyacetonitrile, Benzonitrile, nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, Nitrobenzene, dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N, N ', N'-tetramethylurea, N, N-diethyl-N', N'-dimethylurea, N, N-dimethyl-N ', N'-dipropylurea, N, N, N', N'-tetraethylurea, N, N, N ', N'-tetrabutylurea, Dimethyl sulfoxide, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, Ethyl butyrate, methyl benzoate, ethyl benzoate, water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, Glycol, methyl glycol, ethyl glycol, propyl glycol, glycerol, 2-methoxyethanol, 2-ethoxyethanol, 2-propyloxyethanol, 2-butyloxethanol or mixtures this. Process according to Claim 16, characterized in that the radicals R ³ and R ⁴ are fluorinated and chlorinated alkyl groups. A method according to claim 17, characterized characterized in that with the following acids or their anhydrides at temperatures between -50 and + 20 ° C, especially preferably between -40 and -10 ° C, reacted are: trifluoroacetic acid, trichloroacetic acid, Difluoroacetic acid, dichloroacetic acid, 2,2-difluoropropionic acid, 2,2-dichloropropionic acid, trifluoromethanesulfonic acid. A process for the preparation of N, N, N ', N', N '', N '', N ''',N''' - tetrasubstituted 2-butyne bis (amidinium) salts of the general formulas Ia 'and Ia''according to Claim 3, characterized in that in the bis (amidinium) salts Ia a partial or complete anion exchange is carried out by reacting the salts Ia or Ia 'in solvents according to claim 17 at temperatures between -60 and + 60 ° C; preferably between -20 ° C and + 20 ° C with the alkali metal salts of fluorinated sulfonic acids such as trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, bis (perfluoroalkanesulfonyl) imides such as sodium or potassium bis (trifluoromethanesulfonyl) imide, complex acids such as sodium tetraphenylborate, sodium tetrafluoroborate, sodium tetracyanoborate , Sodium hexafluorophosphate, sodium ethylpentafluorophosphate, potassium diphenyltetrafluorophosphat and separates the resulting liquid or solid products, or by salts Ia and Ia 'with silver or thallium (I) salts of carboxylic acids, sulfonic acids, sulfuric acid, nitric acid, Tetrafluoroboric in solvents according to claim 17 are reacted and after separation of the silver or thallium salts AgX or TlX by evaporation of the solvent or the solvent, the salts Ia 'or Ia''receives, or by the salts Ia or Ia 'with Lewis acids such as BF ₃ , BCl ₃ , SbF ₅ , SbCl ₅ , SnCl ₂ , SnCl ₄ , TiCl ₄ , ZrCl ₄ , ZnCl ₂ , FeCl ₃ , AlCl ₃ in solvents according to claim 17, and the precipitating salts Ia 'or Ia'', now complex anions such as. B. BF4, SbCl ₆ , isolated, or by using the salts Ia or Ia 'with strong acids (Ho> 10) such as fluorosulfonic acid, conc. Sulfuric acid, perchloric acid, trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, tetrafluoroboric acid, bis (trifluoromethanesulfonyl) imide and 2-hydroxonium-5-bora-1,4,6,9-tetraoxa-2,3,7,9-tetraoxo-spiro [2,2] nonane-5-id in solvents according to claim 17 at temperatures between -40 and + 40 ° C, preferably between -5 and + 10 ° C and the resulting liquid or solid salts Ia 'or Ia''by decantation, suction or Evaporation isolated, or by the salts Ia or Ia 'without solvent or in solvents according to claim 17 at temperatures between -10 and + 150 ° C, preferably between +20 and + 100 ° C with alkylating agents such. B. alkyl chlorides, alkyl bromides, dialkyl sulfates, alkyl sulfonates such as methyl methanesulfonate or ethyl, Trifluormethansulfonsäurealkylmethyl- or ethyl ester, Perfluorbutansulfonsäuremethyl- or ethyl ester, arene sulfone acid alkyl esters such as p-toluenesulfonic acid methyl ester or ethyl, Trialkyloxoniumsalzen such as trimethyl or triethyl-oxoniumfluoroborat, hexachloroantimonat, -tetrachloroferrat, -Tetrrachlorozinkat, -hexachlorostannat etc. reacted under alkylation of the anions X, the volatile compounds - optionally in vacuo - distilled off and the remaining salts Ia 'and Ia''isolated.

Process for the preparation of carboxylic anhydrides and N, N, N ', N', N '', N '', N ''',N''' - hexaalkyl-2-aryloxy- (but-2-ene) -bis ( amidinium) salts of the general formula XVIII, characterized in that carboxylic acids or dicarboxylic acids, if appropriate in the presence of catalytic amounts of bases without solvent or in solvents according to claim 17 with bis (amidinium) salts of the general formula Ia according to claim 3 between +20 and +100 ° C to the reaction and the resulting anhydrides after separation of the salts XVIII by distillation or extraction and recrystallization isolated.

A method according to claim 21, characterized characterized in that the base is selected from trimethylamine, Triethylamine, tripropylamine, tributylamine, methyldiethylamine, methyldipropylamine, Methyl-dibutylamine, ethyl-propylamine, ethyl-butylamine, trimethylsilyldimethlamine, Trimethylsilyldiethylamine, trimethylsilylpropylamine, trimethylsilylpyrrolidine, Trimethylsilylpiperidine, trimethylsilylmorpholine, bis (trimethylsilyl) methylamine, propylamine, N, N, N ', N'-tetramethylethylenediamine or propylenediamine or butylenediamine, N, N-dimethylaniline, N, N-diethylaniline, methyl-dicyclohexylamine, Ethyl dicyclohexylamine, methyl diisopropylamine, ethyl diisopropylamine, Pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-dimethylaminopyridine, N-methylpiperidine, N-methylmorpholine, N-methylpyrrolidine, 1,4-dimethylpiperazine, Quinoline, isoquinoline, N, N, N ', N'-tetramethyl-ethylenediamine or -propylenediamine or -butylenediamine, sodium or potassium or calcium or magnesium methoxide, Sodium or potassium or calcium or magnesium ethanolate, sodium or potassium or calcium or magnesium propiolate, sodium or Potassium or calcium or magnesium butanolate, sodium or potassium or calcium carbonate or magnesium carbonate, sodium hydride, potassium hydride, Sodium or potassium amide, sodium or potassium bis-trimethylsilylimide, Guanidine carbonate, guanidine, N, N, N ', N'-tetramethylguanidine, N, N-diethylguanidine, N, N-dipropylguanidine, N, N-dibutylguanidine, N- (amino-imino-methyl) -pyrrolidine, N- (aminoimino-methyl) -pipradine, N- (amino-imino-methyl) -morpholine, N, N'-bis (amino-iminomethyl) -piperazine, ethylene-diguanidine, Propylene endiguanidine, butylene denduanidine, N, N'-dimethyl-ethylenediguanidine or mixtures of these. Process for the preparation of N, N, N ', N', N '', N '', N ''',N''' - hexaalkyl-2-organooxy- (but-2-ene) -bis (amidinium) salts of general formula IIa according to claim 4, characterized in that aliphatic, aromatic or heteroaromatic mono-, di-, tri-, tetra-, penta- or hexahydroxy compounds in which the aliphatic, aromatic or heteroaromatic radicals z. B. by alkoxycarbonyl groups, halogens, alkoxy groups, alkyl or aryl radicals may be substituted with salts of general formula Ia in solvents as in claim 17, optionally in the presence of bases according to claim 22, wherein per hydroxy group of the oligohydroxy an equivalent of corresponding salt Ia is used.

Process for the preparation of N, N, N ', N', N '', N '', N ''',N''' - hexaalkyl-2-organothio (but-2-ene) -bis (amidinium) salts of general formula IIb according to claim 4, characterized in that aliphatic, aromatic or heteroaromatic mono-, di-, tri-, tetra-, penta- or Hexathiohydroxy (or "mercapto") - compounds in which the aliphatic, aromatic or heteroaromatic radicals R z. B. by alkoxycarbonyl groups, halogens, alkoxy groups, alkyl or aryl radicals may be substituted with salts of general formula Ia in solvents according to claim 17, optionally in the presence of bases, as set forth in claim 22.

A process for the preparation of N, N, N ', N', N ", N", N ''',N''' - hexaalkyl-2-organoamino or 2-diorganoamino (but-2-ene ) -bis (amidinium) salts of the general formula IIc and N, N, N ', N'-tetraalkyl-3-dialkylamino-2-organo-pyrazole-2-carboxamidinium salts of the general formula IId characterized in that primary or secondary aliphatic , aromatic or heteroaromatic mono-, di-, tri-, tetra-, penta- or hexaamino compounds in which the aliphatic, aromatic or heteroaromatic radicals R z. B. by alkoxycarbonyl groups, halogens, alkoxy groups, alkyl or aryl radicals may be substituted with salts of the general formula Ia in solvents, as mentioned in claim 15, optionally in the presence of bases as in claim 16, reacted.

A process for the preparation of N, N, N ', N'-tetraalkyl-2-alkylidene-4,4-bis (dialkylamino) - (but-3-ene) -amidinium salts of the general formula III according to claim 5, characterized in that CH ₂ -acid compounds CH ₂ R ³ R ⁴ , wherein R ³ and R ^{4 are} independently CN, CO ₂ CH ₃ , CO ₂ C ₂ H ₅ , CONH ₂ , CONHCH ₃ , CONHC ₆ H ₅ , CON (CH ₃ ) ₂ , NO ₂ , O ₂ NC ₆ H ₄ , CH ₃ CO ₃ C ₂ H ₅ CO ₃ C ₆ H ₅ CO,

and R ³ linked to R ^4, the two-membered radicals

but R ³ can also stand for H, CH ₃ , C ₂ H ₅ , C ₆ H ₅ , if R ⁴ = NO ₂ or

means, with salts of the general formula Ia in the presence of bases according to claim 22, in solvents, which are mentioned in claim 17, brings to reaction and the products III z. B. by suction or - optionally after prior separation of the salts formed - isolated by evaporation of the solvent.

A process for the preparation of 1-alkyl or 1-aryl-2-dialkylamino-3- [2,2-bis (dialkylamino) vinyl] -4-acyl or 4-alkoxycarbonyl or 4-cyano or 4 -nitro-5-oxo-pyrroliumsalze of the general formula IV according to claim 6, characterized in that amidinium salts of the general formula III - wherein R ³ is an aliphatic, aromatic or heterocyclic radical, heated, and with ring closure the dialkylamine HNR ¹ R ^{2 is} split off.

A process for the preparation of 1-alkyl or 1-aryl-2-dialkylamino-3- [2,2-bis (dialkylamino) vinyl] -4-acyl or 4-alkoxycarbonyl or 4-cyano or 4 nitro-5-oxo-pyrrolium salts and 1-alkyl- or 1-aryl-2- (alkylamino-organo-methylene) -3- [bis (dialkylamino) vinyl] -4-organo-5-oxo-2H, 5H -pyrroles of general formula IV or 64 according to claim 5, characterized in that CH ₂ -acide compounds CH ₂ R ³ R ⁴ , in which R ^{3 is} an organoaminocarbonyl, with compounds of general formula Ia in the molar ratio 1: 1 or 2: 1 in the presence of bases according to claim 22, optionally in solvents according to claim 17, are reacted and the resulting condensation products without isolation of compounds of formula III by heating, directly into the amidinium IV or Ketenaminale 64 converted.

Process for the preparation of N, N, N ', N'-tetraalkyl-4-dialkylamino-5-alkoxycarbonylpyrrole-2-carboxamidinium salts and N, N, N', N'-tetraalkyl-4-dialkylamino-5-alkoxycarbonylthiophene-2 carboxamidinium salts and N, N, N ', N', N ", N" -tetraalkyl-4-dialkylamino-5-alkoxycarbonyl-furan-2-carboxamidinium salts of the general formula NEN Formulas Va, Vb, Vc according to claim 7, characterized in that bis (amidinium) salts of the general formula Ia with α-hydroxycarboxylic acids, α-mercaptocarboxylic acids or α-amino, α-N-alkyl or α-N -Arylamino- or heteroarylaminocarboxylic acids, in solvents according to claim 17 in the presence of bases according to claim 22, between -20 ° C and + 100 ° C, preferably between 0 ° C and + 60 ° C.

Va: Z = O Vb: Z = S Vc: Z = NR ⁴ Process for the preparation of N, N, N ', N', N ", N", N "', N"' - octaalkylbicyclo [2.2.1] hepta-2,5-diene bis -Nendo-5,6-dicarboxamidinium salts, N, N, N ', N', N ", N", N "', N"' - octaalkyl-7-oxa, and 7-aza-bicyclo, respectively [2.2.1] hepta-2,5-diene-bis-endo-5,6-dicarboxamidinium salts of the general formula VIa-c according to Claim 8, characterized in that cyclopentadiene, 2-substituted or 2,3-disubstituted cyclopentadienes, Furan, 2-substituted or 2,3-disubstituted furans, pyrrole, 1-substituted, 2-substituted or 2,3-disubstituted pyrroles with bis (amidinium salts of the general formula Ia in solvents as listed in claim 17, between 0 and 160 ° C, preferably between +10 and + 80 ° C without pressure or under pressure (1-200 bar, more preferably between 1 and 20 bar) are reacted.

VIa: Z = CH ₂ VIb: Z = O VIc: Z = NH, NR ⁵ Process for the preparation of N, N, N ', N', N '', N '', N ''',N''' - octaalkyl-1-alkyl- or 1-aryl-1,2,3- Benzotriazole-4,5-dicarboxamidinium salts of the general formula VII according to claim 9, characterized in that salts of the general formula Ia in a dipolar aprotic solvent selected from acetone, ethyl methyl ketone, diethyl ketone, methyl propyl ketone, acetophenone, acetonitrile, propionitrile, butyronitrile, methoxyacetonitrile, Ethoxyacetonitrile, benzonitrile, nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, nitrobenzene, dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N, N ', N'-tetramethylurea, N, N-diethyl-N ', N'-dimethylurea, N, N-dimethyl-N', N'-dipropylurea, N, N, N ', N'-tetraethylurea, N, N, N', N'- Tetrabutylurea, dimethyl sulfoxide, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl benzoate, ethyl benzoate o which reacts a mixture of these, between 0 and 100 ° C, preferably between 20 and 60 ° C, with aliphatic or aromatic azides.

Process for the preparation of N, N, N ', N', N '', N '', N ''',N''' - octaalkyl-2-alkyl or 2-aryl-3-aryl-isoxazole 4,5-dicarboxamidinium salts of the general formula VIII according to claim 10, characterized in that bis (amidinium) salts of the general formula Ia with nitrones

in solvents, as specified in claim 17, between -10 and + 100 ° C, preferably between 0 and + 40 ° C are reacted.

A process for the preparation of N, N, N ', N', N ", N", N ''',N''' - octaalkyl-indolizine-3-EA-substituted, 1,2-dicarboxamidinium salts of the general Formula IX according to claim 11, characterized in that bis (amidinium) salts of the general formula Ia with pyridinium salts or pyridine-derived salts of the general formula XIX in the presence of atmospheric oxygen and bases, which are mentioned in claim 22, in solvents according to claim 17 , between -10 and + 100 ° C, preferably between 0 and + 40 ° C are reacted.

A process for the preparation of N, N, N ', N', N '', N '', N ''',N''' - octaalkyl-4-hydroxy-chromen-2,3-dicarboxamidinium salts of the general formula X according to Claim 12 and 5,6-heterocyclic "benzo analogue" condensed N, N, N ', N', N ", N", N ''',N''' - octaalkyl-4-hydroxy-4H- pyran-2,3-dicarboxamidiniumsalze of the general formula XI according to claim 13, characterized in that aromatic or heteroaromatic α-hydroxy aldehydes with bis (amidinium) salts of the general formula Ia in solvents, as mentioned in claim 17, optionally in the presence of bases , according to claim 22, between -10 and + 100 ° C, preferably between +10 and + 50 ° C are reacted.

Process for the preparation of 2- [2,2-bis (dialkylamino) vinyl] -3-dialkylamino-benzo-fused pyrazine derivatives of general formula XII according to claim 14, characterized in that bis (amidinium) salts of general formula Ia with 1,2- diamino-substituted aromatics such as. As 1,2-diaminobenzene or nucleus-substituted 1,2-diaminobenzenes, 1,2-diaminonaphthalenes or nucleus-substituted 1,2-diaminonaphthalenes, and α, β-diaminosubstituierten heterocyclic compounds without solvents or solvents - according to claim 17, optionally in Gegenart of bases - According to claim 22 - be implemented.

A process for the preparation of ketenamines of general formula XIII (benzo or heterocyclic fused 2,3-bis [bis (dialkylaminomethylene)] - 4-imino-2,3-dihydro-4H-pyrane]) according to claim 15, characterized in that that bis (amidinium) salts of general formula Ia with imines of α-hydroxyaldehydes of general formula XX in solvents according to claim 17, in the presence of bases according to claim 22, between -10 ° C and + 100 ° C, preferably between + 10 ° C and + 50 ° C are reacted.

Process according to the claims 21-36, characterized in that instead of the pure Salts Ia the solutions of bis (amidinium) salts of acetylenedicarboxylic acid Ia, from the bis-orthoamides XIV and the cleavage reagents XV according to claims 16 to 19, or by anion exchange reactions according to claim 20, immediately without further purification for the corresponding reactions used.