WO1985001940A1

WO1985001940A1 - Derivatives of 1,4-dihydropyridine, preparation thereof and pharmaceutical compositions containing them

Info

Publication number: WO1985001940A1
Application number: PCT/CH1984/000170
Authority: WO
Inventors: Arnold Vogel; Gerhard Bormann
Original assignee: Sandoz Ag
Priority date: 1983-11-01
Filing date: 1984-10-23
Publication date: 1985-05-09
Also published as: FR2554109A1; SE8405450L; GB2148895A; IT1199214B; IT8449079A1; BE900874A; AU3486884A; IT8449079A0; DE3438884A1; LU85621A1; NL8403302A; IL73363A0; DK517484D0; SE8405450D0; DK517484A; GB8427443D0

Abstract

Compounds having the formula (I), wherein R1 is hydrogen, cycloalkyl with 3 to 7 atoms of carbon, optionally substituted alkyl with 1 to 6 atoms of carbon; R2 and R4, independently from each other, represent hydrogen or alkyl with 1 to 6 atoms of carbon; R3 is hydrogen, alkyl with 1 to 25 atoms of carbon, nitro, trifluoromethyl, cyan, -COOR5, - COR6 or -S(O)nR7; Q is a completely insaturated ring system with at least 2 different ring hetero atoms of aromatic character. The derivatives are used as calcium antagonists.

Description

1,4-DIHYDRQPYRIDINE DERIVATIVES, THEIR PRODUCTION AND THE PHARMACEUTICAL PREPARATIONS CONTAINING THE SAME

The present invention relates to 1,4-dihydropyridine derivatives, their preparation and pharmaceutical preparations containing them.

The invention relates to the compounds of formula I.

wherein

R _{1 is} hydrogen; Cycloalkyl of 3 to 7 carbon atoms; or optionally substituted alkyl having 1 to 6 carbon atoms;

R ₂ and R _{4 are} independently hydrogen or alkyl of 1 to 6 carbon atoms;

R ₃ means: hydrogen; Alkyl of 1 to 25 carbon atoms; Nitro; Trifluoromethyl; Cyan; -COOR ₅ ; -COR ₆ ; or -S (O) _n R ₇ ; wherein

-COOR _{5 represents} carboxyl or an ester group; R ₆ means; Alkyl of 1 to 25 carbon atoms; Hydroxyalkyl of 2 to 24 carbon atoms, wherein the hydroxy portion is separated from the group to which R _{6 is} attached by at least 2 carbon atoms; Alkoxyalkyl with 1 to 24 carbon atoms in the alkoxy part and with 2 to 24

Carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R _{6 is} bonded by at least 2 carbon atoms; Alkenyl having 3 to 25 carbon atoms, the double bond being separated from the group to which R _{6 is} bonded by at least 1 carbon atom not involved in the double bond; Alkynyl having 3 to 25 carbon atoms, the triple bond being separated from the group to which R _{6 is} bonded by at least 1 carbon atom which is not involved in the triple bond; Cycloalkyl of 3 to 7 carbon atoms; Cycloalkylalky1 with 3 to 7 carbon atoms in the cycloalkyl part and with 1 to 24 carbon atoms in the alkyl part; Hydroxyalkoxyalkyl having 2 to 24 carbon atoms in the hydroxyalkoxy part and having 2 to 24 carbon atoms in the alkylene part, the hydroxyalkoxy part being separated from the group to which R _{6 is} attached by at least 2 carbon atoms and the hydroxy part being separated from the oxygen atom of the alkoxy part by at least 2 carbon atoms is; Phenyl, phenylalkyl with 7 to 30 carbon atoms or bis-phenylalkyl with 13 to 36 carbon atoms, the three last-mentioned substituents optionally being mono- or identical or differently di- or identical or differently trisubstituted by phenyl rings through alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxy or halogen with an atomic number from 9 to 53; a 5-membered heteroaryl radical with 1 heteroatom from the series nitrogen, oxygen and sulfur or 2 heteroatoms from the series nitrogen and either nitrogen, oxygen or sulfur, or one-membered heteroaryl radical with 1 to 4 nitrogen atoms, where; the latter two substituents are optionally connected to the rest of the molecule via an alkylene radical having 1 to 24 carbon atoms; -AOCOR ₈ ; -ANR ₉ R ₁₀ ; or -AN Ⓑ; wherein R ₈ is; Alkyl of 1 to 25 carbon atoms; Phenyl, phenylalkyl having 7 to 30 carbon atoms or bisphenylalkyl having 13 to 36 carbon atoms, the three last-mentioned substituents optionally being mono- or identical or different di- or identical or different trisubstituted in the phenyl rings by

Alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, hydroxy or halogen with an atomic number of 9 to 53; a 5-membered heteroaryl radical with 1 heteroatom from the series nitrogen, oxygen, sulfur or 2 heteroatoms from the series nitrogen and either nitrogen, oxygen or sulfur, or a 6-membered heteroaryl radical with 1 to 4 nitrogen atoms; Hydroxyalkyl having 2 to 24 carbon atoms, the hydroxy part being separate from the group to which

R _{8 is} bound by at least 2 carbon atoms;

Alkoxyalkyl having 1 to 24 carbon atoms in the alkoxy part and having 2 to 24 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R _{8 is} bonded by at least 2 carbon atoms; Alkenyl having 3 to 25 carbon atoms, the double bond being separated from the group to which R _{8 is} bonded, by at least 1 carbon atom not involved in the double bond; Alkynyl of 3 to 25 carbon atoms. wherein the triple bond is separated from the group to which R _{8 is} bonded by at least 1 carbon atom not involved in the triple bond; Cycloalkyl of 3 to 7 carbon atoms; Cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and with 1 to 24

Carbon atoms in the alkyl part; Hydroxyalkoxyalkyl having 2 to 24 carbon atoms in the hydroxyalkoxy part and having 2 to 24 carbon atoms in the alkyl part, the hydroxyalkoxy part being separated from the group to which R _{8 is} attached by at least 2 carbon atoms and the hydroxy part being separated from the oxygen atom of the alkoxy part by at least 2 carbon atoms ; Aminoalkyl having 2 to 24 carbon atoms, the nitrogen atom being separated from the group to which R _{8 is} bonded, by at least 2 carbon atoms and the amino part optionally being mono- or identical or differently disubstituted by alkyl having 1 to 6 carbon atoms, phenyl, phenylalkyl with 7 to 12 carbon atoms or bis-phenylalkyl with 13 to 18 carbon atoms, the three last-mentioned substituents optionally being mono or identical or different di- or identical or different trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 Carbon atoms, hydroxy or halogen with an atomic number of 9 to 53;

R _{9 represents} hydrogen or has the meaning given above for R ₈ ;

R _{10 is} either hydrogen or has the meaning given above for R ₈ or represents -COR ₁₁ , where R _{11 has} the meaning given above for R ₈ ; -N-Ⓑ means; a 5-, 6- or 7-membered saturated heterocyclic ring which, if it is 6- or 7-membered, may optionally contain a further hetero member from the series consisting of oxygen, sulfur and = NR ₁₂ , wherein

R _{12 is} either hydrogen or has the meaning given above for R ₈ and

A represents alkylene of 2 to 24 carbon atoms, which separates the group to which R _{6 is} attached by at least 2 carbon atoms;

R ₇ mutatis mutandis has the meaning given above for R ₆ , n stands for 0, 1 or 2;

Q represents a fused, completely unsaturated ring system with at least 2 different ring heteroatoms in total and with an aromatic character; and their ammonium salts in which R _{3 is} one of the tertiary amino groups defined above for R ₃ and is quaternized with a group of the formula alky, in which alk is alkyl having 1 to 4 carbon atoms and Y is the rest of an acid.

These compounds are hereinafter referred to briefly as "the compounds according to the invention".

Some of the compounds according to the invention fall under the very general disclosure of Bayer EP 71 819.

However, none of the compounds specifically disclosed in the above-mentioned European publication falls within the scope of the present invention. Another disclosure relating to compounds which are analogous to the compounds according to the invention is, for example, Bayer EP 2 208.

The publications mentioned above do not suggest any specific compounds similar to the compounds according to the invention. The compounds according to the invention have a particularly interesting pharmacological profile.

The compounds according to the invention are preferably in unquaternized form.

R ₅ preferably has mutatis mutandis the meaning given above for R ₆ .

R ₁ is preferably hydrogen. If it is not hydrogen, it preferably has one of the meanings given for R ₁ ^a , in particular unsubstituted alkyl, cycloalkylalkyl, optionally substituted phenylalkyl, alkoxyalkyl or morpholino; preferably unsubstituted alkyl or alkoxyalkyl; especially unsubstituted alkyl. If it means alkoxyalkyl, its alkoxy part is preferably separated from the nitrogen atom by at least 2 carbon atoms. R ₂ and R _{4 are} preferably alkyl, especially methyl. R ₃ is preferably nitro, trifluoromethyl, -COOR ₅ or -COR ₆ , in particular -COOR ₅ , R ₅ and / or R _{7 are} preferably alkyl, hydroxyalkyl, alkoxyalkyl, -AOCOR ₈ , -ANR ₉ R ₁₀ or -ANⒷ , in particular -ANR ₉ R ₁₀ or -ANⒷ. R ₆ preferably has the meaning given above for R ₅ and / or R ₇ or preferably represents a 5-membered heteroaryl radical with 2 nitrogen heteroatoms. R ₈ preferably denotes alkyl, or optionally substituted phenyl, phenylalkyl or bisphenylalkyl, in particular phenyl. R ₉ and R ₁₀ are preferably represents hydrogen or alkyl or optionally substituted phenyl, phenylalkyl or bis-phenylalkyl, preferably either both R ₉ and R _{10 are} hydrogen or one of R ₉ and R ₁₀ is alkyl and the other is alkyl, optionally substituted phenylalkyl or optionally substituted bis -phenylalkyl.-NⒷ preferably represents a 6-membered saturated heterocyclic ring which contains a further hetero member. R ₁₁ preferably represents alkyl, optionally substituted phenyl, optionally substituted phenylalkyl or optionally substituted bis-phenylalkyl,

R ₁₂ preferably does not represent hydrogen, it preferably means alkyl, optionally substituted phenylalkyl or optionally substituted bis-phenylalkyl. A preferably contains 2 carbon atoms or 7 to 24 carbon atoms, in particular 9 to 18 carbon atoms, in particular 9 to 14 carbon atoms, in particular 10 carbon atoms. It is preferably unbranched. n is preferably the number 1 or 2. Q preferably has at least 3 heteroatoms in total, in particular 3 heteroatoms. It is preferably a bicyclic system. Preferred groups Q are 2,1,3-benzoxadiazolyl and 2,1,3-benzothiadiazolyl, in particular 2,1,3-benzoxadiazolyl. If Q stands for a ring system which contains a benzene ring component, the 1,4-dihydropyridinyl radical is preferably bound to this benzene ring component, preferably in a position of the benzene ring component which is adjacent to other ring components. Alk preferably means methyl, Y preferably stands for the remainder of an inorganic acid, for example mesyl or halogen, in particular iodine.

Cycloalkyl with 3 to 7 carbon atoms preferably contains 3, 5 or 6, in particular 5 carbon atoms. Optionally substituted alkyl with 1 to 6 carbon atoms preferably has with the exception of hydrogen one of the meanings given below for R ^a ₁ , it stands in particular for methyl, alkyl having 1 to 5 carbon atoms preferably contains 1 to 4 carbon atoms, it means in particular methyl. Alkyl with 1 to 25 carbon atoms preferably contains 1 to 6 carbon atoms, it then preferably means methyl, ethyl or isooropvl, or 9 to 19 carbon atoms; especially 9 to 19 carbon atoms, especially 10 carbon atoms. Hydroxyalkyl with 2 to 24 carbon atoms preferably contains 2 to 6 or 9 to 18 carbon atoms, in particular 9 to 18 carbon atoms, alkoxyalkyl with 1 to 24 carbon atoms in the alkoxy part and with 2 to 24 carbon atoms in the alkylene part preferably contains 1 to 6 or 9 to 19, in particular 9 to 19 carbon atoms in the alkoxy part and preferably 2 to 6 or 9 to 18, in particular 9 to 18 carbon atoms in the alkylene part. Alkenyl with 3 to 25 carbon atoms and / or alkynyl with 3 to 25 carbon atoms preferably contain 3 or 7 to 25 carbon atoms, in particular 9 to 18 carbon atoms. Cycloalkyl with 3 to 7 carbon atoms and the cycloalkyl part of cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part preferably contain 3, 5 or 6, in particular 5 or 6, carbon atoms. The alkylene part of cycloalkylalkyl having 1 to 24 carbon atoms in the alkylene part preferably contains 1 carbon atom or 7 to 24, in particular 9 to 13 carbon atoms. The hydroxyalkoxy part of hydroxyalkoxyalkyl having 2 to 24 carbon atoms in the hydroxyalkoxy part preferably contains 2

Carbon atoms or 7 to 24, especially 9 to 18 carbon atoms. The alkylene part of hydroxyalkoxyalkyl having 2 to 24 carbon atoms in the alkylene part preferably contains 2 carbon atoms or 7 to 24, in particular 9 to 18 carbon atoms. The alkylene part of phenylalkyl having 7 to 30 carbon atoms or bis-phenylalkyl having 13 to 36 carbon atoms preferably contains wise 1 or 2 carbon atoms or 7 to 24, especially 9 to 18 carbon atoms, alkyl with 1 to 4 carbon atoms and / or alkoxy with 1 to 4 carbon atoms preferably contain 1 or 2, in particular 1 carbon atom (s). Halogen with an atomic number from 9 to 53 preferably represents fluorine or bromine, in particular bromine. Halogen with an atomic number of 9 to 35 preferably means fluorine or chlorine, in particular fluorine. A heteroaryl radical as defined above is preferably 5-membered, it preferably contains 1 or 2 nitrogen heteroatoms, in particular 2 and in particular means imidazolyl, in particular 1H-imidazol-1-yl, if it is 6-membered it preferably contains 1 or 2 nitrogen heteroatoms and means in particular pyridinyl. The alkylene radical having 1 to 24 carbon atoms, which optionally connects a heteroaryl radical to the rest of the molecule, preferably contains 1 carbon atom or 7 to 24, in particular 9 to 18, carbon atoms. The alkylene part of aminoalkyl having 2 to 24 carbon atoms preferably contains 2 carbon atoms or 7 to 24, in particular 9 to 18 carbon atoms. The amino part of aminoalkyl is preferably substituted, in particular disubstituted. Preferred substituents of the amino part of aminoalkyl are alkyl and / or optionally substituted phenylalkyl. The amino part of aminoalkyl is preferably disubstituted by alkyl and optionally substituted phenylalkyl. A 5-, 6- or 7-membered saturated heterocyclic ring as defined above is preferably 6-membered. It preferably means 1-piperazinyl. If it is 6 or 7-membered, it preferably contains a further hetero-link = NR ₁₂ .

The hydroxy portion of hydroxyalkyl and / or of hydroxyalkoxyalkyl and / or the amino portion of aminoalkyl are preferably attached to the most distant, end-chain carbon atom. If one Phenyl ring occurs in a substituent, it is preferably unsubstituted. If it is substituted, it is preferably monosubstituted, preferably in the para position. If it is disubstituted, it is preferably substituted in the ortho or meta and in the para position. If it is trisubstituted, it is preferably substituted in the meta, meta and para positions. Alkoxy and / or halogen are preferred substituents of a phenyl ring substituent. If a phenyl ring is polysubstituted, the substituents are preferably identical. In bis-phenylalkyl both phenyl rings are preferably attached to the same carbon atom. Bis-phenylalkyl preferably means bis-phenylmethyl.

A group of compounds according to the invention consists of the compounds of the formula Ia

wherein R ₂ and R _{4 have} the meaning given above,

R ^a ₁ means: hydrogen; Alkyl of 1 to 6 carbon atoms; Alkenyl having 3 to 6 carbon atoms, the double bond being separated from the nitrogen atom by at least 1 carbon atom not involved in the double bond; Alkynyl having 3 to 6 carbon atoms, the triple bond being separated from the nitrogen atom by at least 1 carbon atom not involved in the triple bond; Cycloalkyl of 3 to 7 carbon atoms; Cycloalkylalkyl of 4 to 8 carbon atoms; Hydroxyalkyl with 2 to 6 carbon atoms, the hydroxy part being separated from the nitrogen atom by at least 2 carbon atoms; Alkoxyalkyl of 2 to 6 carbon atoms; or phenylalkyl with 7 to 9 carbon atoms or phenylalkenyl with 9 to 12 carbon atoms, the double bond being separated from the nitrogen atom by at least 1 carbon atom not involved in the double bond, the latter two substituents optionally being mono- or identical or differently di- or identical or differently trisubstituted are in the phenyl ring independently of one another alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogen with an atomic number of 9 to 35 or hydroxy; Alkylcarbonyloxyalkyl having 2 to 6 carbon atoms in the alkylcarbonyl and in the alkylene part and wherein oxygen is separated from the nitrogen atom by at least 2 carbon atoms; Dialkylaminoalkyl with independently 1 to 6 carbon atoms in the alkyl parts and with 2 to 6 carbon atoms in the alkyl part and the amino group being separated from the nitrogen atom by at least 2 carbon atoms; or morpholinoalkyl having 2 to 6 carbon atoms in the alkylene part and the morpholino part being separated from the nitrogen atom by at least 2 carbon atoms;

stands for: hydrogen; Alkyl of 1 to 6 carbon atoms; Nitro; Trifluoromethyl; Cyan; -COOR ^a ₅ ; -COR ₆ ^a; , or -S (O) _n R ^a ₇ ; wherein

R _a5 means: hydrogen; Alkyl of 1 to 6 carbon atoms; Hydroxyalkyl with 2 to 6 carbon atoms, the hydroxy part being separated from the group to which R ^a ₅ is bound by at least 2 carbon atoms; Alkoxyalkyl having 1 to 6 carbon atoms in the alkoxy part and having 2 to 6 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ^a _{5 is} bonded by at least 2 carbon atoms;

Alkenyl having 3 to 6 carbon atoms, the double bond being separated from the group to which R ^a _{5 is} bonded, by at least 1 carbon atom not involved in the double bond; Alkynyl having 3 to 6 carbon atoms, the triple bond being separated from the group to which R ^a _{5 is} bonded, by at least 1 carbon atom not involved in the triple bond; Cycloalkyl of 3 to 7 carbon atoms; Cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and with 1 to 6 carbon atoms in the alkylene part; Hydroxyalkoxyalkyl with 2 to 6 carbon atoms in the alkoxy part and with 2 to 6 carbon atoms in the alkylene part, the hydroxyalkoxy part being separated from the group to which R ^a _{5 is} bonded by at least 2 carbon atoms and the hydroxy part being separated from the oxygen atom of the alkoxy part by at least 2 Carbon atoms; Phenyl, phenylalkyl with 7 to 12 carbon atoms or bis-phenylalkyl with 13 to 18 carbon atoms, the three last-mentioned substituents optionally being mono- or identical or different di- or identical or different trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxy or halogen with an atomic number of 9 to 53; a 5-membered heteroaryl radical with 1 heteroatom from the series nitrogen, oxygen and sulfur or 2 heteroatoms from the series nitrogen and either nitrogen, oxygen or sulfur, or a 6-membered heteroaryl radical with 1 to 4 nitrogen atoms, the latter 2 substituents optionally being bonded to the rest of the molecule via an alkylene radical having 1 to 6 carbon atoms; -A ^a OCOR ^a ₈ ; -A ^a NR ^a ₉ R ^a ₁₀ ; or A ^a NⒷ ^a ; wherein R ^{a is} ₈ : alkyl of 1 to 6 carbon atoms; Phenyl, phenylalkyl with 7 to 12 carbon atoms or bisphenylalkyl with 13 to 18 carbon atoms, the three last-mentioned substituents optionally being mono or identical or different di- or identical or different trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 Carbon atoms, hydroxy or halogen with an atomic number of 9 to 53; airien 5-membered heteroaryl radical with 1 heteroatom from the series nitrogen, oxygen and sulfur or 2 heteroatoms from the series

Nitrogen and either nitrogen, oxygen or sulfur, or a 6-membered heteroaryl radical having 1 to 4 nitrogen atoms; Hydroxyalkyl with 2 to 6 carbon atoms, the hydroxy part being separated from the group to which R ^a _{8 is} bonded by at least 2

Carbon atoms; Alkoxyalkyl having 1 to 6 carbon atoms in the alkoxy part and having 2 to 6 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ^a _{8 is} bonded by at least 2 carbon atoms; Alkenyl having 3 to 6 carbon atoms, the double bond being separated from the group to which R ^a _{8 is} bonded, by at least 1 carbon atom not involved in the double bond; Alkynyl having 3 to 6 carbon atoms, the triple bond being separated from the group to which R ^a _{8 is} bonded, by at least 1 carbon atom not involved in the triple bond; Cycloalkyl with 3 to 7 carbon atoms; Cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and with 1 to 6 carbon atoms in the alkylene part; Hydroxyalkoxyalkyl having 2 to 6 carbon atoms in the hydroxyalkoxy part and having 2 to 6 carbon atoms in the alkylene part, the

The hydroxyalkoxy part is separated from the group to which R ₈ ^{a is} bonded by at least 2 carbon atoms and the hydroxy part is separated from the oxygen atom of the alkoxy part by at least 2 carbon atoms; Aminoalkyl having 2 to 6 carbon atoms, the

Nitrogen atom is separated from the group to which R ₈ ^{a is} bonded by at least 2 carbon atoms and the amino part is optionally mono- or identical or differently disubstituted by alkyl having 1 to 6 carbon atoms, phenyl, phenylalkyl having 7 to 12 carbon atoms or bis- phenylalkyl having 13 to 18 carbon atoms, the three last-mentioned substituents optionally being mono- or identical or different di or identical or different tri-substituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, hydroxy or halogen with an atomic number of 9 to 53;

R ₉ ^{a represents} hydrogen or has the meaning given above for R ₈ ^a ; R ^a _{10 is} either hydrogen or has the meaning given above for R ₈ ^a or -COR ^a ₁₁ , where R ^a _{11 has} the meaning given above for R ₈ ^a ; NⒷ ^a stands for: a 5-, 6- or 7-membered saturated heterocyclic ring which, if it is 6- or 7-membered, can optionally contain a further hetero member from the series consisting of oxygen, sulfur and NR ^a ₁₂ , wherein R ^a _{12 is} either hydrogen or has the meaning given above for R ₈ ^a ; and

A ^{a represents} alkylene having 2 to 6 carbon atoms, which separates the group to which R ₅ ^{a is} bonded by at least 2 carbon atoms;

R ₆ ^a and R ₇ ^a with the exception of hydrogen have the meaning given above for R ₅ ^a ; and n has the meaning given above;

X represents oxygen or sulfur; and

R means: hydrogen; Alkyl of 1 to 4 carbon atoms; Alkoxy of 1 to 4 carbon atoms; Alkylthio of 1 to 4 carbon atoms; Alkylsulfonyl of 1 to 4 carbon atoms; Halogen with an atomic number from 9 to 35; Trifluoromethyl; Nitro; or hydroxy;

and their ammonium salts in which R ₃ ^{a is} one of the tertiary amino groups defined above for R ₃ ^a and is quaternized with a group of the formula alky, in which alk is alkyl having 1 to 4 carbon atoms and Y is the residue of an acid.

X preferably represents oxygen. R is preferably hydrogen. The rest

is preferably bound with its 4-position to the 4-position of the 1,4-dihydropyridinyl radical. Another group of compounds according to the invention consists of the compounds of the formula Iaa

wherein R, R ₂ , R ₄ and X have the meaning given above, R ₁ ^{aa represents} hydrogen or alkyl having 1 to 6 carbon atoms and R ^a ₃ ^a means: hydrogen; Alkyl of 1 to 6 carbon atoms; Nitro; Trifluoromethyl; Cyan; -COOR ₅ ^aa ; -COR ₆ ^aa ; or -S (O) _n R ₇ ^aa ; wherein R _{5 represents} ^aa : hydrogen; Alkyl of 1 to 6 carbon atoms; Hydroxyalkyl with 2 to 6 carbon atoms, the hydroxy part being separated from the group to which R ₅ ^{aa is} bonded by at least 2 carbon atoms; Alkoxyalkyl having 1 to 6 carbon atoms in the alkoxy part and having 2 to 6 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₅ ^{aa is} bonded by at least 2 carbon atoms; a 5-membered heteroaryl radical with 1 heteroatom from the series nitrogen, oxygen and sulfur or with 2 heteroatoms from the series nitrogen and either embroidery material, oxygen or sulfur, or a 6-membered

Heteroaryl radical with 1 to 4 nitrogen atoms; -A ^aa OCOR ₈ ^aa ; -A ^aa NR ₉ ^aa R ₁ ^a ₀ ^a ; or A ^aa NⒷ ^aa ; wherein R ₈ ^aa means: alkyl having 1 to 6 carbon atoms; Phenyl, phenylalkyl with 7 to 12 carbon atoms or bis-phenylalkyl with 13 to 18 carbon atoms, the three last-mentioned substituents optionally being mono- or identical or different di- or identical or different trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxy or halogen with an atomic number of 9 to 53; Hydroxyalkyl with 2 to 6 carbon atoms, the hydroxy part being separated from the group to which R ₈ ^{aa is} bonded by at least 2 carbon atoms; Alkoxyalky! with 1 to 6 carbon atoms in the alkoxy part and with 2 to 6 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₈ ^{aa is} bonded by at least 2 carbon atoms; R ₉ ^{aa is} hydrogen or has the meaning given above for R ₈ ^aa ; R ₁ ^a ₀ ^{a is} either hydrogen or has the meaning given above for R ₈ ^aa or represents -COR ^a 1 ^a 1, in which R ^a ₁₁ ^{a has} the meaning given above for R ^a ₈ ^a ;

-NⒷ ^aa stands for: a 5-, 6- or 7-membered saturated heterocyclic ring, which, if it is 6- or 7-membered, can optionally contain a further hetero member from the series oxygen, sulfur and NR ^a ₁₂ ^a , wherein R _a12 ^{a is} either hydrogen or has the meaning given above for ^R ₈ ^aa ; and A ^{aa represents} alkylene with 2 to 6 carbon atoms, which separates the group to which R ₅ ^{aa is} bonded by at least 2 carbon atoms; R ₆ ^aa and R ₇ ^aa with the exception of hydrogen have the meaning given above for R ₅ ^aa and n has the meaning indicated above;

and their ammonium salts, in which R ₃ ^{aa represents} one of the tertiary amino groups defined above for R ₃ ^aa and is quaternized with a group of the formula Alky, in which Alk is alkyl having 1 to 4 carbon atoms and Y is the residue of an acid.

Another group of compounds according to the invention consists of the compounds of the form! Iaaa

wherein R ₂ , R ₄ and X have the meaning given above and

Ra ₃ aa stands for: hydrogen; Nitro; Trifluoromethyl; Cyan; -COOR ^{a aa} 5 ^a ; or -COR ₆ ^aa ; wherein R ₅ and R ₆ ^{aa have} the meaning given above, and their ammonium salts, in which R ₃ ^{aaa represents} one of the tertiary amino groups defined above for R ₃ ^aaa and is quaternized with a group of the formula Alky as defined above.

In a subgroup of compounds of the formulas Iaa or Iaaa and their corresponding ammonium salts, R ₁ ^{aa represents} hydrogen.

In a further subgroup, R ₂ and R _{4 are} methyl. In another subgroup, X stands for oxygen. In another subgroup, X means sulfur. In a further subgroup, R ₃ ^{aaa represents} -COOR ₅ ^aa , in which R ₅ ^{aa has} the meaning given above. In a subgroup of compounds of the formula Iaa and their corresponding ammonium salts, R represents hydrogen.

A preferred group of compounds according to the invention consists of the compounds of the formula Ib

wherein R, R ₁ ^a , R ₂ , R ₄ and X have the meaning given above and R ₃ ^b means: hydrogen; Alkyl of 7 to 25 carbon atoms; Nitro; Trifluoromethyl; Cyan; -COOR ₅ ^b ; -COR ₆ ^b ; or -S (O) _n R ₇ ^b ; wherein R ₅ ^b means: hydrogen, alkyl having 7 to 25 carbon atoms; Hydroxyalkyl with 7 to 24 carbon atoms, the hydroxy part being separated from the group to which R ₅ ^{b is} bonded by at least 2 carbon atoms; Alkoxyalkyl having 1 to 24 carbon atoms in the alkoxy part and 2 to 24 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₅ ^{b is} bonded by at least 2 carbon atoms, with the proviso that at least one of the alkoxy and / or contains alkylene parts at least 7 carbon atoms; Alkenyl having 7 to 25 carbon atoms, the double bond being separated from the group to which R ^b _{5 is} bonded, by at least 1 carbon atom not involved in the double bond; Alkynyl having 7 to 25 carbon atoms, the triple bond being separated from the group to which R ₅ ^{b is} bonded, by at least 1 carbon atom not involved in the double bond; Cycloalkyl of 3 to 7 carbon atoms; Cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and with 7 to 24 carbon atoms in the alkylene part; Hydroxyalkoxyalkyl with 2 to 24 carbon atoms in the hydroxyalkoxy part and with 2 to 24 carbon atoms in the alkylene part, the hydroxyalkoxy part being separated from the group to which R ₅ ^{b is} bonded by at least 2 carbon atoms and the hydroxy part being separated from the oxygen atom of the alkoxy part by at least 2 Carbon atoms with which

Provided that at least one of the hydroxyalkoxy and / or alkylene parts contains at least 7 carbon atoms; Phenyl, phenylalkyl with 13 to 30 carbon atoms or bis-phenylalkyl with 19 to 36 carbon atoms, the three last-mentioned substituents optionally being mono- or identical or different di- or identical or different trisubstituted in the phenyl rings by Alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, hydroxy or halogen with an atomic number of 9 to 53; a 5-membered heteroaryl radical with 1 heteroatom from the series nitrogen, oxygen and sulfur or 2 heteroatoms from the series nitrogen and either nitrogen, oxygen or sulfur, or one

6-membered heteroaryl radical having 1 to 4 nitrogen atoms, the two latter substituents optionally being connected to the rest of the molecule via an alkylene radical having 7 to 24 carbon atoms; -A ^b OCOR ₈ ^b ;

-A ^b NR ₉ ^b R ^b ₁₀ ; or -A ^b NⒷ ^b ; wherein R ₈ ^b is: alkyl of 1 to 25 carbon atoms, with the proviso that if A ^{b contains} less than 7 carbon atoms, it contains 7 to 25 carbon atoms; Phenyl, phenylalkyl with 7 to 30 carbon atoms with the proviso that it contains 13 to 30 carbon atoms if A ^{b contains} less than 7 carbon atoms, or bis-phenylalkyl with 13 to 36 carbon atoms with the proviso that it contains 19 to 36 carbon atoms, if A ^{b contains} less than 7 carbon atoms, the three last-mentioned substituents optionally being mono- or identical or different di- or identical or different trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, hydroxyl or halogen with an atomic number from 9 to 53; one

5-membered heteroaryl radical with 1 heteroatom from the series nitrogen, oxygen and sulfur or 2 heteroatoms from the series nitrogen and either nitrogen, oxygen or sulfur, or a 6-membered heteroaryl radical with 1 to 4 nitrogen atoms; Hydroxyalkyl with 2 to 24 carbon atoms wherein the Hydroxy portion is separated from the group to which R ₈ ^{b is} attached by at least 2 carbon atoms, provided that it contains 7 to 24 carbon atoms if A ^{b contains} less than 7 carbon atoms; Alkoxyalkyl having 1 to 24 carbon atoms in the alkoxy part and having 2 to 24 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₈ ^{b is} bonded by at least 2 carbon atoms, with the proviso that if A ^{b is} less than Contains 7 carbon atoms, then at least one of the alkoxy and / or alkylene parts contains at least 7 carbon atoms; Alkenyl having 3 to 25 carbon atoms, the double bond being separated from the group to which R ₈ ^{b is} bonded, by at least 1 carbon atom not involved in the double bond, with the proviso that

Contains 7 to 25 carbon atoms if A ^{b contains} less than 7 carbon atoms; Alkynyl having 3 to 25 carbon atoms, the triple bond being separated from the group to which R ₈ ^{b is} bonded, by at least 1 carbon atom not involved in the triple bond, with the proviso that it contains 7 to 25 carbon atoms if A ^{b is} less than Contains 7 carbon atoms; Cycloalkyl of 3 to 7 carbon atoms; Cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl part and having 1 to 24 carbon atoms in the alkylene part, with the proviso that if A contains less than 7 carbon atoms it contains 7 to 24 carbon atoms in the alkylene part; Hydroxyalkoxyalkyl with 2 to 24 carbon atoms in the hydroxyalkoxy part and with 2 to 24 carbon atoms in the alkylene part, the hydroxyalkoxy part being separated from the group to which R ₈ ^{b is} bonded, by at least 2 carbon atoms and the hydroxy part being separated from the oxygen atom of the AlkoxyteiIs by at least 2 carbon atoms, with the proviso that if A ^{b contains} less than 7 carbon atoms, then at least one of the hydroxyalkoxy and / or alkylene parts contains at least 7 carbon atoms; Aminoalkyl having 2 to 24 carbon atoms, with the proviso that if A ^{b contains} less than 7 carbon atoms, it contains 7 to 24 carbon atoms, the nitrogen atom being separated from the group to which R ₈ ^{b is} bonded by at least 2 carbon atoms and the amino part is optionally mono or the same or differently disubstituted by alkyl having 1 to 6 carbon atoms, phenyl, phenylalkyl having 7 to 12 carbon atoms or bisphenylalkyl having 13 to 18 carbon atoms, the three last-mentioned substituents optionally being mono- or identical or different or are identical or different trisubstituted in the phenyl rings by alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxy or halogen with an atomic number from 9 to 53;

R ₉ ^{b represents} hydrogen or has the meaning given above for R ₈ ^b ; R ^b _{10 is} either hydrogen or has the meaning given above for R ₈ ^b or represents -COR ^b ₁₁ , in which Rb _{11 has} the meaning given above for R ₈ ^b ; -NⒷ ^b means: a 5-, 6- or 7-membered saturated heterocyclic ring, which may optionally contain, if it is 6- or 7-membered, a further hetero member from the series oxygen, sulfur and NR ^b ₁₂ , wherein R ^b _{12 is} either hydrogen or has the meaning given above for R ₈ ^b ; and

A ^{b represents} alkylene with 2 to 24 carbon atoms, which separates the group to which R ₅ ^{b is} bonded by at least 2 carbon atoms,

R ₆ ^b and R ₇ ^b with the exception of hydrogen have the meaning given above for R ₅ ^b ; and n has the meaning given above;

and their ammonium salts in which R ₃ ^{b represents} one of the tertiary amino groups defined above for R ₃ ^b and is quaternized with a group of the formula alky, in which alk is alkyl having 1 to 4 carbon atoms and Y is the residue of an acid.

Another preferred group of compounds according to the invention consists of the compounds of the formula Iba

wherein R, R ₁ ^aa , R ₂ , R ₄ and X have the meaning given above and R ₃ ^ba means: alkyl having 7 to 25 carbon atoms; -COOR ₅ ^ba ; -COR ₆ ^ba ; or -S (O) _n R ₇ ^ba ; wherein R ₅ ^ba means: alkyl having 7 to 25 carbon atoms; Hydroxyalkyl of 7 to 24 carbon atoms, the hydroxy part being separated from the group to which R ₅ ^{ba is} bonded by at least 2 carbon atoms; Alkoxyalkyl having 1 to 24 carbon atoms in the alkoxy part and 2 to 24 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₅ ^{ba is} bonded by at least 2 carbon atoms, with the proviso that at least one of the alkoxy and / or contains alkylene parts at least 7 carbon atoms; Alkenyl having 7 to 25 carbon atoms, the double bond being separated from the group to which R ₅ ^{ba is} bonded by at least 1 carbon atom which is not involved in the double bond; Alkynyl having 7 to 25 carbon atoms, the triple bond being separated from the group to which R ₅ ^{ba is} bonded by at least one carbon atom not involved in the triple bond; Cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and with 7 to 24 carbon atoms in the alkylene part; Hydroxyalkoxyalkyl with 2 to 24 carbon atoms in the hydroxyalkoxy part and with 2 to 24 carbon atoms in the alkylene part, the

The hydroxyalkoxy part is separated from the group to which R ₅ ^{ba is} bonded by at least 2 carbon atoms and the hydroxy part is separated from the oxygen atom of the alkoxy part by at least 2 carbon atoms, with the proviso that at least one of the hydroxyalkoxy and / or alkylene parts has at least 7 carbon atoms contains; Phenylalkyl with 13 to 30 carbon atoms or bis-phenylalkyl with 19 to 36 carbon atoms, the two latter substituents optionally being mono- or identical or differently di- or identical or differently trisubstituted in the phenyl rings by alkyl with

1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxy or halogen with an atomic number from 9 to 53; a 5-membered heteroaryl radical with 1 heteroatom from the series nitrogen, oxygen and sulfur or 2 heteroatoms from the series nitrogen and either nitrogen, oxygen or sulfur, or a 6-membered heteroaryl radical with 1 to 4 nitrogen atoms, the two substituents mentioned with the remaining part of the molecule is connected via an alkylene radical having 7 to 24 carbon atoms; -A ^ba -OCOR ₈ ^ba ; -A ^ba NR ₉ ^ba R ^b ₁₀ ^a ; or -A ^ba NⒷ ^ba ; wherein R ₈ ^ba means: alkyl of 1 to 25 carbon atoms, with the proviso that if A ^{ba contains} less than 7 carbon atoms it contains 7 to 25 carbon atoms; Phenyl, phenylalkyl having 7 to 30 carbon atoms, with the proviso that it contains 13 to 30 carbon atoms if A ^{ba contains} less than 7 carbon atoms, or bis-phenylalkyl with 13 to 36 carbon atoms, with the proviso that it contains 19 to 36 carbon atoms contains, if A contains less than 7 carbon atoms, the three latter substituents optionally being mono- or identical or different di- or identical or different trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, hydroxy or Halogen with one

Atomic number from 9 to 53; a 5-membered heteroaryl residue with 1 hetero atom from the series nitrogen, oxygen and sulfur or 2 hetero atoms from the series nitrogen and either nitrogen, oxygen or sulfur, or a δ-membered heteroaryl residue with 1 to 4 nitrogen atoms; Hydroxyalkyl with 2 to 24

Carbon atoms, the hydroxy part being separated from the group to which R ₈ ^{ba is} attached by at least 2 carbon atoms, with the proviso that it contains 7 to 24 carbon atoms if A ^{ba contains} less than 7 carbon atoms; Alkoxyalkyl with 1 to 24 carbon atoms in the alkoxy part and with 2 to 24 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₈ ^{ba is} bonded by at least

2 carbon atoms, with the measure that if A ^{ba contains} less than 7 carbon atoms, then at least one of the alkoxy and / or alkylene parts contains at least 7 carbon atoms; Alkenyl of 3 to 25 carbon atoms, the double bond being separated from the group to which R ₈ ^{ba is} bonded, by at least 1 carbon atom not involved in the double bond, with the proviso that it contains 7 to 25 carbon atoms if A ^{ba is} less than Contains 7 carbon atoms; Alkynyl having 3 to 25 carbon atoms, the triple bond being separated from the group to which R ₈ ^{ba is} bonded by at least 1 carbon atom which is not involved in the triple bond, with the proviso that it contains 7 to 25 carbon atoms if A ^{ba is} less than 7 Contains carbon atoms; Cycloalkyl of 3 to 7 carbon atoms; Cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and with 1 to 24

Carbon atoms in the alkylene part, with the proviso that there are - - - - - 7 to 24 carbon atoms in the alkylene contains part if A ^{ba contains} less than 7 carbon atoms; Hydroxyalkoxyalkyl with 2 to 24 carbon atoms in the hydroxyalkoxy part and with 2 to 24 carbon atoms in the alkylene part, the hydroxyalkoxy part being separated from the group to which R ₈ ^{ba is} bonded by at least 2 carbon atoms and the hydroxy part being separated from the oxygen atom of the alkoxy part by at least 2 Carbon atoms, with the proviso that if A ^{ba contains} less than 7 carbon atoms then at least one of the hydroxyalkoxy and / or alkylene parts contains at least 7 carbon atoms; Aminoalkyl of 2 to 24 carbon atoms, with the proviso that if A ^{ba contains} less than 7 carbon atoms, it contains 7 to 24 carbon atoms, the oxygen atom being separated from the group to which R ₈ ^{ba is} bonded by at least 2 carbon atoms and the amino part is optionally mono- or identical or differently disubstituted by alkyl having 1 to 6 carbon atoms, phenyl, phenylalkyl having 7 to 12 carbon atoms or bis-phenylalkyl having 13 to 18 carbon atoms, the three last-mentioned substituents optionally being mono- or identical or different or di - or are identical or different trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, hydroxy or

Halogen with an atomic number from 9 to 53; R ₉ ^{ba represents} hydrogen or has the meaning given above for R ₈ ^ba ; R ₁ ^b ₀ ^{a is} either hydrogen and has the meaning given above for R ₈ ^ba or -COR ^b ₁₁ ^a , in which _R1 ^ba _{1 has} the meaning given above for R ₈ ^ba ; -NⒷ ^ba means: a 5-, 6- or 7-membered saturated heterocyclic ring which, if it is 6- or 7-membered, may contain a further hetero-member from the series oxygen, sulfur and NR ^b ₁ ^a ₂ where R ₁ ^ba _{2 is} either hydrogen or has the meaning given above for R ₈ ^ba ; and

A ^{ba represents} alkylene with 2 to 24 carbon atoms, which separates the group to which R ₉ ^{ba is} bonded by at least 2 carbon atoms; R ₆ ^ba and R ₇ ^ba with the exception of hydrogen have the meaning given above for R ₅ ^ba ; and n has the meaning given above;

and their ammonium salts, in which R ₃ ^{ba stands} for one of the tertiary amino groups defined above for R ₃ ^ba and is quaternized with a group of the formula Alky, in which Alk is alkyl with 1 to 4 carbon atoms and Y is the residue of an acid.

Another preferred group of compounds according to the invention consists of the compounds of the formula Ibaa

wherein R ₂ , R ₄ and X have the meaning given above and R ₃ ^baa stands for: -COOR ₅ ^baa or -COR ₆ ^baa ; wherein R _{5 is} ^baa : alkyl of 9 to 19 carbon atoms; Hydroxyalkyl with 9 to 18 carbon atoms, the hydroxy part being separated from the group to which R ₅ ^{baa is} bonded by at least 2 carbon atoms; Alkoxyalkyl with

1 to 18 carbon atoms in the alkoxy part and 2 to 18 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₅ ^{baa is} bonded by at least 2 carbon atoms, with the proviso that at least one of the alkoxy and / or alkylene parts contains at least 9 carbon atoms; Hydroxyalkoxyalkyl with

2 to 18 carbon atoms in the hydroxyalkoxy part and with 2 to 18 carbon atoms in the alkyl part, the hydroxyalkoxy part being separated from the group to which R ₅ ^{baa is} bonded by at least 2 carbon atoms and the hydroxy part being separated from the oxygen atom of the alkoxy part by at least 2 carbon atoms, with the proviso that at least one of the hydroxyalkoxy and / or alkylene parts contains at least 9 carbon atoms; -A ^baa OCOR ₈ ^baa ;

-A ^baa NR ^b 9 ^aa R ^b 10 ^aa ; or -A ^baa N Ⓑ ^baa ; wherein

R ₈ ^baa means: alkyl having 1 to 19 carbon atoms, with the proviso that if A ^{baa contains} less than 9 carbon atoms it contains 9 to 19 carbon atoms; Phenyl, phenylalkyl with 7 to

24 carbon atoms, with the proviso that it contains 15 to 24 carbon atoms if A ^{baa contains} less than 9 carbon atoms, or bisphenylalkyl with 13 to 30 carbon atoms, with the proviso that it contains 21 to 30 carbon atoms if A ^baa less than 9 carbon atoms contains, the three latter substituents optionally mono- or identical or different di- or identical or different trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, hydroxy or halogen with an atomic number of 9 to 53 ; Hydroxyalkyl with 2 to 18 carbon atoms, the hydroxy part being separated from the group to which R ₈ ^ba _{a is} bonded by at least 2 carbon atoms, with the proviso that there are 9 to

Contains 18 carbon atoms if A ^{baa contains} less than 9 carbon atoms; Alkoxyalkyl having 1 to 18 carbon atoms in the alkoxy part and having 2 to 18 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₈ ^ba _{a is} bonded by at least 2 carbon atoms;

R ₉ ^ba _{a is} hydrogen or has the meaning given above for R ₈ ^ba _a ;

_R ^b ₁₀ ^{aa is} either hydrogen or has the meaning given above for R ₈ ^ba _a or -COR ^b ₁₁ ^aa , wherein R ^b ₁₁ ^{aa has} the meaning given above for R ₈ ^ba _a ;

-N Ⓑ ^baa means: a 5-, 6- or 7-membered saturated heterocyclic ring which, if it is 6- or 7-membered, can optionally contain a further hetero member from the series oxygen, sulfur and NR ^b ₁₂ ^aa , wherein R ^b ₁₂ ^{aa is} either hydrogen or has the meaning given above for R ₈ ^ba _a ; and A ^{baa represents} alkylene having 2 to 18 carbon atoms, which separates the group to which R ₅ ^ba _{a is} bonded by at least 2 carbon atoms;

R ₆ ^ba _a with the exception of hydrogen, the ^ba has _a meaning given above for R _5; and n has the meaning given above;

and their ammonium salts, in which R ₃ ^ba _{a represents} one of the tertiary amino groups defined above for R ₃ ^ba _a and is quaternized with a group of the formula Alky, in which Alk is alkyl having 1 to 4 carbon atoms and Y is the residue of an acid.

Another group of compounds according to the invention consists of the compounds of the formula Ic

wherein R, R ₁ ^a , R ₂ , R ₄ and X have the meaning given above and R ₃ ^c represents: hydrogen, nitro; Trifluoromethyl; Cyan; -COOR ₅ ^c ; -COR ₆ ^c ; or -S (O) _n R ₇ ^c ; wherein R ₅ ^c means: hydrogen, cycloalkyl having 3 to 7 carbon atoms; optionally by alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxy or halogen with an atomic number from 9 to 53 mono- or identical or different di- or identical or different trisubstituted phenyl; a 5-membered heteroaryl radical with 1 heteroatom from the series nitrogen, oxygen and sulfur or 2 heteroatoms from the series nitrogen and either nitrogen, oxygen or sulfur, or a 6-membered heteroaryl radical with 1 to 4 nitrogen atoms;

R ₆ ^c and R ₇ ^c with the exception of hydrogen have the meaning given above for R ₅ ^c ; and

n has the meaning given above.

Another group of compounds according to the invention consists of the compounds of the formula Ica

wherein R ₂ , R ₄ and X have the meaning given above and R ₃ ^ca stands for: hydrogen; Nitro; Trifluoromethyl; Cyan; -COOR ₅ ^ca ; or -CO R ₆ ^ca ; wherein

R ₅ ^ca means: hydrogen or a 5-membered heteroaryl radical with 1 hetero atom from the series nitrogen, oxygen and sulfur or 2 hetero atoms from the series nitrogen and either nitrogen, oxygen or sulfur; and

R ₆ ^ca with the exception of hydrogen has the meaning given above for R ₅ ^ca.

Another group of compounds according to the invention consists of the compounds of the formula Id

wherein R ₁ ^d to R ₄ ^d and Q ^{d have} the ^meaning given above for R ₁ to R ₄ and Q, with the proviso that the substituents in the 2- and 6-positions and / or in the 3- and 5 Positions of the 1,4-dihydropyridinyl radical are different,

and their ammonium salts in which R ₃ ^{d is} one of the tertiary amino groups defined above for R ₃ ^d and is quaternized with a group of the formula AlkY as defined above.

Another group of compounds according to the invention consists of the compounds of the formula Ie

wherein R ₁ ^e to R ₄ ^e and Q ^{e have} the meaning given above for R ₁ to R ₄ and Q, with the proviso that the substituents in the 2- and 6-positions and / or in the 3- and 5 Positions of the 1,4-dihydropyridinyl radical are different,

and their ammonium salts, in which R ₃ ^{e represents} one of the tertiary amino groups defined above for R ₃ ^e and is quaternized with a group of the formula AlkY as defined above.

In subgroups of compounds of the formulas Id and le and their corresponding ammonium salts, the substituents have corresponding meanings given above for the compounds of the formulas Ia, Iaa, Iaaa, Ib, Iba, Ibaa, Ic and Ica.

Another group of compounds according to the invention consists of the compounds of the formula Ip

wherein -COOR ₅ ^{p represents} an ester group.

Further groups of compounds according to the invention consist of the compounds of the formula Ip, in which R ₅ denotes ^p : a) cycloalkyl having 4 to 6 carbon atoms; b) alkyl having 1 to 12 carbon atoms or alkoxyalkyl having 1 to 10 carbon atoms in the alkoxy part and having 2 to 11 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₅ ^{p is} bonded by at least 2 carbon atoms and with the Provided that the alkoxy and alkylene parts together contain fewer than 13 carbon atoms; and

c) -A ^P NR ₉ ^p R ^p ₁₀ ; or A ^P NⒷ ^P ; wherein

R ₉ ^p stands for: hydrogen; Alkyl of 1 to 4 carbon atoms; Phenyl, phenylalkyl with 7 to 10 carbon atoms or bisphenylalkyl with 13 to 16 carbon atoms, the three latter substituents in the phenyl rings optionally being alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxy or halogen with an atomic number of 9 up to 53 are mono- or identical or different di- or identical or different trisubstituted; R ^p _{10 represents} hydrogen or alkyl of 1 to 4 carbon atoms;

-N-Ⓑ ^p stands for: a 5-, 6- or 7-membered saturated heterocyclic ring which may optionally contain, if it is 6- or 7-membered, another hetero member from the series oxygen, sulfur and NR ^p ₁₂ wherein R ^p _{12 has} the meaning given above for R ₉ ^p ; and A ^{p represents} straight-chain alkylene with 2 to 12 carbon atoms, which separates the group to which R ₅ ^{p is} bound by at least 2 carbon atoms.

In a subgroup from group a) of compounds of the formula I _p , R ₅ ^p denotes cyclopentyl or cyclohexyl. In a subgroup from group b) of compounds of the formula I _p , R ₅ ^{p represents} alkyl having 1 to 8 carbon atoms.

Another group of compounds according to the invention consists of the compounds of the formula Is

wherein X has the meaning given above; R ₂ ^s and R ₄ ^s independently represent alkyl of 1 to 4 carbon atoms and R ₃ ^s represents: hydrogen; Nitro; Trifluoromethyl; Cyan; -COOR ₅ ^s ; or -COR ₆ ^s ; wherein R ₅ ^s means: hydrogen; Alkyl of 1 to 12 carbon atoms; Hydroxyalkyl of 2 to 6 carbon atoms, the hydroxy part being separated from the group to which R ₅ ^{s is} bonded by at least 2 carbon atoms; -A ^s NR ₉ ^s R ₁ ^s _0; or -A ^s NⒷ ^s ; wherein R ₉ ^s and R ^s ₁₀ independently represent: hydrogen; Alkyl of 1 to 4 carbon atoms; optionally in the phenyl rings by alkoxy having 1 to 4 carbon atoms or halogen having an atomic number of 9 to 53 mono- or identically or differently disubstituted phenylalkyl having 7 to 10 carbon atoms;

-N-Ⓑ ^s means: piperidinyl or piperazinyl or piperidinyl or piperazinyl which is substituted in the 4-position by methyl, benzyl or bis-phenylmethyl, the two latter substituents optionally in the phenyl rings by alkoxy having 1 to 4 carbon atoms or halogen with an atomic number of 9 to 53 are disubstituted mono- or identical or different; and

A ^s means: alkylene with 2 to 14 carbon atoms, the group to which R ₅ ^{s is} bonded by at least 2

Separates carbon atoms; R ₆ ^{s represents} imidazolyl;

and their ammonium salts in which R ₃ ^{s is} one of the tertiary amino groups defined above for R ₃ ^s and is quaternized with a group of the formula AlkY as defined above.

Further groups of compounds according to the invention consist of the compounds of the formulas I, Ia, Iaa, Iaaa, Ib, Iba, Ibaa, Ic, Ica, Id, le and Is, where R ₃ , R ₃ ^a , R ₃ ^aa , R ₃ ^aa _a , R ₃ ^b , R ₃ ^ba , R ₃ ^ba _a , R ₃ ^c ,

R ₃ ^ca , R ₃ ^d , R ₃ ^e and R ₃ ^{s represent} ester groups as defined above under the corresponding formula, and optionally their corresponding ammonium salts as defined above. Further groups of compounds according to the invention consist of the compounds of the formulas Ia, Iaa, Iaaa, Ib, Iba, Ibaa, Ic, Ica and Is, in which X is sulfur, and, if appropriate, their corresponding ammonium salts as defined above.

The compounds according to the invention are obtained by a process which is characterized in that

a) corresponding compounds of formula II

where Q has the meaning given above, corresponding compounds of the formula III

wherein R ₂ and R _{3 have} the meaning given above, corresponding compounds of formula IV

wherein R. has the meaning given above, and corresponding compounds of formula V

wherein R _{1 has} the meaning given above, or their partial condensation products, advantageously condensed to 1,4-dihydropyridines, or

b) for the preparation of compounds of the formula I '

wherein R ₁ , R ₂ , R ₄ and Q have the meaning given above and R ^ is hydrogen, -COOR ₅ or -COR ₆ , wherein R ₅ and R _{6 have} the meaning given above.

corresponding compounds of formula VI

where R ₁ , R ₂ , R ₄ and Q have the above meaning and X represents a reactive group, appropriately converted.

The method according to the invention can be carried out analogously to known methods.

The choice of the most suitable process variant naturally depends on the nature of, for example, the substituents R _{1 and} R ₃ . Process variant a) can be carried out, for example, according to Hantzsch. The implementation can take place, for example, in solution. Suitable solvents are water, ethanol, dioxane, dimethylformamide, dimethyl sulfoxide, pyridine or glacial acetic acid.

Suitable reaction temperatures are about 20 to 160 ° C, preferably 60 to 120 ° C.

Process variant b) can also be carried out in a known manner. The choice of the most suitable reaction conditions depends, of course, primarily on the nature of the group R ₃ ^' . If R ₃ ^'is hydrogen, then X can be carboxyl, for example, and the conversion is decarboxylation. If R ₃ ^'is -COR ₆ , then X can represent carboxyl, for example, and the conversion is a substitution. If R ₃ ^'is carboxyl, then X means, for example, an easily cleavable ester group, such as an ammonium ester group, and the conversion is then hydrolysis.

If R ₃ ^'represents an ester group, then X means, for example, a group -COX', where X 'represents a reactive group suitable for producing an ester group.

The ester-resulting conversion can be, for example, an esterification. X 'is then expediently 1H-imidazol-1-yl. This process variant is suitable, for example, for conversion into a hydroxyalkyl; Amidoalkyl; Alkoxyalkyl; Acyloxyalkyl or substituted or unsubstituted aminoalkyl ester substituents. A corresponding compound of the formula VI, in which X is, for example, 1H-imidazol-1-yl-carbonyl, is thus reacted with a corresponding diol, amido / alcohol, ester / alcohol or amino alcohol. A suitable solvent is dioxane or a Excess of the reactant can be used. A further ester-yielding conversion can, for example, be an amination. This variant is suitable, for example, for conversion into an aminoalkyl ester substituent. A reactive group X represents, for example, a group -COOAX ", in which A has the meaning given above and X" represents chlorine, bromine or a group -R _z -SO ₂ -O-, in which R _{z is} phenyl, tolyl or lower alkylene _. means. X '' preferably means mesyloxy. The amination can be immediate, ie the reaction takes place directly with an amine which carries the substituent to be introduced, or indirectly, for example to introduce a primary amino group, by first converting it into a corresponding phthalimidoalkyl derivative, for example by reaction with sodium or potassium phthalimide, and then reacting the phthalimidoalkyl derivative thus obtained with hydrazine. The indirect method is preferred if the substituent to be introduced is a primary one

Represents aminoalkyl group. Another ester-yielding conversion is e.g. is an acylation of a primary or secondary amine. A reactive group X is then expediently the corresponding primary or secondary aminoalkoxycarbonyl group. A corresponding compound of formula VI is thus combined with a corresponding one

Acyl derivative, such as an N-hydroxysuccinimide ester implemented. A suitable solvent is, for example, dioxane. A further ester-yielding conversion can be, for example, an acylation of an alcohol. A reactive group X is then expediently the corresponding hydroxyalkoxycarbonyl group. A corresponding compound of formula VI is thus reacted with a corresponding acyl derivative, for example an acyl halide. The reaction is preferably carried out in the presence of a strong base, such as N-ethyldiisopropylamine. A suitable solvent is, for example, methylene chloride. Another ester-yielding conversion can be etherification, for example. A reactive group X is then expediently a group -COOAX ″, in which A and X ″ have the above meaning. The reaction is preferably carried out under strongly alkaline conditions. Quaternary ammonium salts can also be prepared analogously to known methods, for example by reaction with corresponding lower alkyl iodides. An alcohol such as methanol is suitable as a solvent.

If there are potentially reactive groups, such as hydroxyl or primary or secondary amino, it may be appropriate to carry out the process according to the invention with these groups in a protected form, e.g. for phenolic hydroxy in the form of a benzyloxy group, or for aliphatic hydroxy in the form of a tetrahydropyranyloxy group, or for amino in the form of a

Acylamino or phthalimido group, and then converting the protecting groups as such into the desired substituents, e.g. Benzyloxy in hydroxy, e.g. hydrogenolytic; Tetrahydropyranyloxy in hydroxy, e.g. by acid hydrolysis; and protected amino in unprotected amino, e.g. by acidic hydrolysis or hydrazinolysis.

The compounds according to the invention can be isolated and purified from the reaction mixture in a known manner.

The compounds according to the invention can be in free form or optionally in salt form. The free forms are normally neutral, unless there are ionizable substituents. Salt forms can exist, for example, if ionizable substituents, such as amino or phenolic hydroxy, are present. Salt forms can be obtained in a known manner from the compounds in free form and vice versa. Suitable acids for the formation of acid addition salts are, for example, hydrogen chloride, malone, p-toluenesulfonic acid and methanesulfonic acid. Suitable bases for the formation of anionic salts are, for example, sodium and potassium hydroxide. If the substituents in positions 2 and 6 and / or in positions 3 and 5 of the 1,4-dihydropyridinyl radical are different, the carbon atom in the 4-position is substituted asymmetrically. The corresponding compounds according to the invention can therefore occur in racemic form or in the form of the individual enantiomers.

The individual enantiomers can be obtained analogously to known methods, e.g. by fractional crystallization, e.g. of optically active diastereoisomeric salts, or by transesterification of optically pure esters which are substituted by easily cleavable, preferably basic ester groups, such as dimethylaminoethoxycarbonyl.

Insofar as the production of the required starting materials is not described, they are known or can be produced by methods known per se or analogously to the methods described here or analogously to methods known per se.

In the following examples, all temperatures are given in degrees Celsius without corrections.

Example 1: 4- (2,1,3-Benzoxadiazol-4-yl) -1,4-dihydro-2,6-dimethyl-5-nitro-pyridine-3-carboxylic acid ethyl ester

[Process variant a); Condensation of the condensation product of compounds of the formulas II and IV with the condensation product of compounds of the formulas III and V]

3.5 g of 1- (2,1,3-benzoxadiazol-4-yl) -2-nitro-l-buten-3-one and 1.95 g of ethyl 3-aminocrotonate are refluxed in 50 ml of dioxane for 6 hours heated. The mixture is then evaporated and the product chromatographed on silica gel using methylene chloride / ether as the eluent. The title binding (mp. 197 ° - from ether) is obtained.

The starting product is obtained by heating under reflux for 35 hours of a mixture of 44 g of 2,1,3-benzoxadiazole-4-carboxaldehyde, 30.6 g of nitroacetone, 1.26 g of piperidine and 1.78 g

Acetic acid in 700 ml of benzene. After subsequent chromatographic purification on silica gel using methylene chloride as the eluent, 1- (2,1,3-benzoxadiazol-4-yl) -2-nitro-1-buten-3-one (mp 105 °) is obtained from ether ).

Example 8: 4- (2,1,3-Benzoxadiazol-4-yl) -1, 4-dihydro-2,6-dimethyl-5-nitropyridine-3-carboxylic acid ethyl ester

[Process variant b); Imidazolide Conversion]

A mixture of 1.5 g of 4- (2,1,3-benzoxadiazol-4-yl) -1,4-dihydro-3- (1H-imidazol-1-ylcarbonyl) -2,6-dimethyl-5-nitropyridine and 30 ml of ethanol is heated to boiling temperature for 8 hours. The mixture is evaporated and the residue is chromatographed on silica gel using ether as the eluent. The title compound is obtained (mp. 195 ° - from ether).

The compounds according to the invention in free form or, if appropriate, in the form of their physiologically tolerable salts are distinguished by interesting pharmacological properties. they can be used as medicines.

They show typical effects for calcium antagonists. They have a pronounced muscle-relaxing effect, especially on smooth muscles, as can be seen from the determination of vasodilating and hypotensive activity in standard tests. For example, in the anesthetized cat they use "tracer microspheres" (R. Hof et al., Basic Res. Cardiol. 75 [1980] 747-756 and 76 [1981] 630-638 ^* , R. Hof et al., J. Cardiovasc.Pharmacol. 4 [1982] 352-362) coronary vasodilation, an increase in blood flow in the skeletal muscles and a decrease in blood pressure after intravenous administration from about 30 to about 1000 / µg kg, for example from about 100 to about 500 µg / kg.

A decrease in blood pressure is also seen in the awake, spontaneously hypertensive rat (method of Gerold and Tschirki, drug research 1S [1968] 1285) after administration of about 1 to about 10 mg / kg p.o. detected.

They are therefore suitable for use as calcium channel blockers

They also have a vasodilating effect on the capillary blood vessels in the carotid area, the vasoconstrictor effect of serotonin is suppressed and the associated disregulation is inhibited. They are therefore suitable for the prophylaxis and treatment of migraines and vascular headaches, such as "cluster headache", in particular for the interval treatment (prevention) of migraines. Preferred in this indication are those compounds which have a relatively low effect on blood pressure and peripheral blood vessels.

The compounds also have very little negative inotropic activity. They are therefore not cardio-depressive and even have a certain cardiosimulatory effect. It is therefore possible to use relatively high daily doses if desired, even in patients for whom the administration of calcium channel blockers is generally contraindicated, e.g. in patients with heart failure.

In those compounds which are asymmetrically substituted in the 4-position of the 1,4-dihydropyridinyl radical, this lack of cardiodepression can appear differently in one or the other enantiomeric form.

For the above-mentioned uses as medicaments, the dose to be used naturally varies depending on the substance used, the mode of administration and the desired treatment. In general, however, satisfactory results are achieved with a daily dose of approximately 10 mg to approximately 1600 mg; if necessary, it can be administered in 1 to 3 portions or as a slow-release form. Suitable dosage forms for, for example, oral or non-oral administration generally contain from about 2.5 mg to about 800 mg in addition to solid or liquid carriers.

The preferred indications are coronary insufficiency and cardiac insufficiency, especially ischemic heart failure.

Preferred for the prophylaxis and treatment of migraines and vascular headaches are those compounds in which Q represents a 2,1,3-benzothiadiazolyl radical.

The compounds according to the invention in free form or, if appropriate, in the form of their physiologically tolerable salts, preferably acid addition salts, can be administered alone or in a suitable dosage form. The invention also relates to pharmaceutical preparations which contain the compounds according to the invention in free form or, if appropriate, in the form of their physiologically tolerable salts, and to the preparation of these pharmaceutical preparations in a manner known per se. The auxiliaries and carriers customary in pharmacy can be used for their production. You can e.g. for use in enteral, preferably oral, administration e.g. as tablets, or in particular for sublingual administration, e.g. as buccal tablets, or for parenteral administration, e.g. as injectable solutions or suspensions. Sublingual administration is preferred.

Claims

1,4-DIHYOROPYRIDINE DERIVATIVES, THEIR PRODUCTION AND THEIR PHARMACEUTICAL PREPARATIONS CONTAINING THEM

1. The compounds of formula I.

wherein

R 1 and R. independently of one another represent hydrogen or alkyl having 1 to 6 carbon atoms;

R ₃ means: hydrogen; Alkyl of 1 to 25 carbon atoms; Nitro; Trifluoromethyl; Cyan; -COOR ₅ ; -COR ₆ ; or -S (O) _n R ₇ ; wherein -COOR _{5 represents} carboxyl or an ester group;

R ₆ means: alkyl with 1 bfs 25 carbon atoms; Hydroxyalkyl of 2 to 24 carbon atoms, wherein the hydroxy portion is separated from the group to which R _{6 is} attached by at least 2 carbon atoms; Alkoxyalkyl with

1 to 24 carbon atoms in the alkoxy part and with 2 to 24 carbon atoms in the alkylene part, the alkoxy part of the group to which R _{6 is} bonded by at least

2 carbon atoms is separated; Alkenyl having 3 to 25 carbon atoms, the double bond being separated from the group to which R _{6 is} bonded by at least 1 carbon atom not involved in the double bond; Alkynyl having 3 to 25 carbon atoms, the triple bond being separated from the group to which R _{6 is} bonded by at least 1 carbon atom which is not involved in the triple bond; Cycloalkyl of 3 to 7 carbon atoms; Cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and with 1 to 24 carbon atoms in the alkylene part; Hydroxyalkoxyalkyl having 2 to 24 carbon atoms in the hydroxyalkoxy part and having 2 to 24 carbon atoms in the alkylene part, the hydroxyalkoxy part being separated from the group to which R _{6 is} bonded by at least 2 carbon atoms and the hydroxy part being separated from the oxygen atom of the alkoxy part by at least 2 carbon atoms is; Phenyl, phenylalkyl with 7 to 30 carbon atoms or bisphenylalkyl with 13 to 36 carbon atoms, the three last-mentioned substituents optionally being mono- or identical or differently di- or identical or differently trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy having 1 up to 4 carbon atoms, hydroxy or halogen with an atomic number from 9 to 53; a 5-membered heteroaryl radical with 1 heteroatom from the series nitrogen, oxygen and sulfur or 2 heteroatoms from the series nitrogen and either nitrogen, oxygen or sulfur, or a 6-membered heteroaryl radical with 1 to 4 nitrogen atoms, the latter two substituents optionally also the remaining part of the molecule is connected via an alkylene radical having 1 to 24 carbon atoms; -AOCOR ₈ ; -ANR ₉ R ₁₀ ; or -ANⒷ; wherein R ₈ is: alkyl of 1 to 25 carbon atoms; Phenyl, phenylalkyl having 7 to 30 carbon atoms or bisphenylalkyl having 13 to 36 carbon atoms, the three latter substituents optionally being mono- or identical or differently di- or identical or differently trisubstituted in the phenyl rings by

Alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, hydroxy or halogen with an atomic number of 9 to 53; a 5-membered heteroaryl radical with 1 hetero atom from the series nitrogen, oxygen and sulfur or 2 hetero atoms from the series nitrogen and either Nitrogen, oxygen or sulfur, or one

6-membered heteroaryl radical with 1 to 4 nitrogen atoms; Hydroxyalkyl of 2 to 24 carbon atoms, the hydroxy part being separated from the group to which R _{8 is} attached by at least 2 carbon atoms;

Alkoxyalkyl having 1 to 24 carbon atoms in the alkoxy part and having 2 to 24 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R _{8 is} bonded by at least 2 carbon atoms; Alkenyl having 3 to 25 carbon atoms, the double bond being separated from the group to which R _{8 is} bonded, by at least 1 carbon atom not involved in the double bond; Alkynyl with 3 to 25 carbon atoms, wherein the triple bond is separated from the group to which R _{8 is} bonded by at least 1 carbon atom not involved in the triple bond; Cycloalkyl of 3 to 7 carbon atoms; Cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and with 1 to 24 carbon atoms in the alkyl part; Hydroxyalkoxyalkyl having 2 to 24 carbon atoms in the hydroxyalkoxy part and having 2 to 24 carbon atoms in the alkylene part, the hydroxyalkoxy part being separated from the group to which R _{8 is} attached by at least 2 carbon atoms and the hydroxy part being separated from the oxygen atom of the alkoxy part by at least 2 carbon atoms ; Aminoalkyl having 2 to 24 carbon atoms, the nitrogen atom being separated from the group to which R _{8 is} bonded by at least 2 carbon atoms and the amino part optionally being mono- or identical or differently disubstituted by alkyl having 1 to 6 carbon atoms, phenyl , Phenylalkyl with 7 to 12 carbon atoms or bis-phenylalkyl with 13 to 18 carbon atoms, the three latter substituents optionally being mono- or identical or different di- or identical or different trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxy or halogen with an atomic number of 9 to 53;

R _{9 represents} hydrogen or has the meaning given above for R ₈ ;

R _{10 is} either hydrogen or has the meaning given above for R ₈ or represents -CO R ₁₁ , wherein R _{11 has} the meaning given above for R ₈ ; -NⒷ means; a 5-, 6- or 7-membered saturated heterocyclic ring which, if it is 6- or 7-membered, may optionally contain a further hetero-member from the series oxygen, sulfur and = NR ₁₂ , in which

R _{12 is} either hydrogen or has the meaning given above for R ₈ and

R ₇ mutatis mutandis has the meaning given above for R ₆ ; n represents 0, 1 or 2;

Q is a fused-completely unsaturated ring system with at least 2 different ring heteroatoms in total and with an aromatic character;

and their ammonium salts, in which R _{3 is} one of the tertiary amino groups defined above for R ₃ and is quaternized with a group of the formula alky, in which alk is alkyl having 1 to 4 carbon atoms and Y is the rest of an acid, in free form or optionally in salt form,

2. Compounds according to claim 1 of formula Ia

wherein R ₂ and R _{4 have} the meaning given above; R _{1 represents} ^a ; Hydrogen; Alkyl of 1 to 6 carbon atoms; Alkenyl having 3 to 6 carbon atoms, the double bond being separated from the nitrogen atom by at least 1 carbon atom not involved in the double bond;

Alkynyl with 3 to 6 carbon atoms, the triple bond being separated from the nitrogen atom by at least

1 carbon atom not involved in the triple bond; Cycloalkyl of 3 to 7 carbon atoms; Cycloalkylalkyl of 4 to 8 carbon atoms; Hydroxyalkyl with 2 to 6 carbon atoms, the hydroxy part being separated from the nitrogen atom by at least 2 carbon atoms; Alkoxyalkyl with

2 to 6 carbon atoms; or phenylalkyl with 7 to 9 carbon atoms or phenylalkylene with 9 to 12 carbon atoms, the double bond being separated from the nitrogen atom by at least 1 carbon atom not involved in the double bond, the latter two substituents being optionally mono- or identical or differently di- or identical or differently trisubstituted are in the phenyl ring independently of one another alkyl having 1 to 4 carbon atoms,

Alkoxy of 1 to 4 carbon atoms, halogen with an atomic number of 9 to 35 or hydroxy; Alkylcarbonyloxyalkyl having 2 to 6 carbon atoms in the alkylcarbonyl and in the alkylene part and wherein oxygen is separated from the nitrogen atom by at least 2 carbon atoms; Dialkylaminoalkyl with independently 1 to 6 carbon atoms in the alkyl parts and with 2 to 6 carbon atoms in the alkyl part and the amino group being separated from the nitrogen atom by at least 2 carbon atoms; or morpholinoalkyl having 2 to 6 carbon atoms in the alkylene part and the morpholino part being separated from the nitrogen atom by at least 2 carbon atoms; R ₃ ^a stands for: hydrogen; Alkyl of 1 to 6 carbon atoms;

Nitro; Trifluoromethyl; Cyan; -COOR ^a 5; -COR ₆ ^a ; or -S (O) _n R ₇ ^a ; wherein R ^a ₅ means: hydrogen; Alkyl of 1 to 6 carbon atoms; Hydroxyalkyl with 2 to 6 carbon atoms, the hydroxy part being separated from the group to which R ₅ ^{a is} bonded by at least 2 carbon atoms; Alkoxyalkyl having 1 to 6 carbon atoms in the alkoxy part and having 2 to 6 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₅ ^{a is} bonded by at least 2 carbon atoms; Alkenyl having 3 to 6 carbon atoms, the double bond being separated from the group to which R ₅ ^{a is} bonded, by at least 1 carbon atom not involved in the double bond; Alkynyl having 3 to 6 carbon atoms, the triple bond being separated from the group to which R ₅ ^{a is} bonded, by at least 1 carbon atom which is not involved in the triple bond; Cycloalkyl of 3 to 7 carbon atoms; Cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and with 1 to 6 carbon atoms in the alkylene part; Hydroxyalkoxyalkyl with 2 to 6 carbon atoms in the alkoxy part and with 2 to 6 carbon atoms in the alkylene part, the hydroxyalkoxy part being separated from the group to which R ₅ ^{a is} bonded by at least 2 carbon atoms and the hydroxy part being separated from the oxygen atom of the alkoxy part by at least 2 Carbon atoms; Phenyl, phenylalkyl with 7 to 12 carbon atoms or bis-phenylalkyl with 13 to 18 carbon atoms, the three last-mentioned substituents optionally being mono- or identical or differently di- or identical or differently trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, Alkoxy with 1 to 4 carbon atoms, hydroxy or halogen with an atomic number from 9 to 53; one

5-membered heteroaryl radical with 1 heteroatom from the series nitrogen, oxygen and sulfur or 2 heteroatoms from the series nitrogen and either nitrogen,

Oxygen or sulfur, or a 6-membered heteroaryl radical having 1 to 4 nitrogen atoms, the latter 2 substituents optionally being bonded to the rest of the molecule via an alkylene radical having 1 to 6 carbon atoms; -A ^a OCOR ₈ ^a ; -A ^a NR ₉ ^a R ₁ ^a ₁ ; or

A ^a NⒷ ^a ; wherein R ₈ ^a is: alkyl of 1 to 6 carbon atoms; Phenyl, phenylalkyl with 7 to 12 carbon atoms or bisphenylalkyl with 13 to 18 carbon atoms, the three latter substituents optionally being mono- or identical or differently di- or identical or differently trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxy or halogen with an atomic number of 9 to 53; a 5-membered heteroaryl radical with 1 heteroatom from the series nitrogen, oxygen and sulfur or 2 heteroatoms from the series nitrogen and either nitrogen, oxygen or sulfur, or a 6-membered heteroaryl radical with 1 to 4 nitrogen atoms; Hydroxyalkyl with 2 to 6 carbon atoms, the hydroxy part being separated from the group to which R ₈ ^{a is} bonded by at least 2 carbon atoms; Alkoxyalkyl with 1 to 6 carbon atoms in the alkoxy part and with 2 to 6 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₈ ^{a is} bonded by at least 2 carbon atoms; Alkenyl having 3 to 6 carbon atoms, the double bond being separated from the group to which R ₈ ^{a is} bonded, by at least 1 carbon atom which is not involved in the double bond; Alkynyl with 3 to 6 carbon atoms, the

The triple bond is separated from the group to which R ₈ ^{a is} bonded by at least 1 carbon atom which is not involved in the triple bond; Cycloalkyl with

3 to 7 carbon atoms; Cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and with 1 to 6

Carbon atoms in the alkylene part; Hydroxyalkoxyalkyl with 2 to 6 carbon atoms in the hydroxyalkoxy part and with 2 to 6 carbon atoms in the alkylene part, the hydroxyalkoxy part being separated from the group to which R ₈ ^{a is} bonded by at least 2 carbon atoms and the hydroxy part being separated from the oxygen atom of the alkoxy part by at least 2 carbon atoms; Aminoalkyl having 2 to 6 carbon atoms, the nitrogen atom being separated from the group to which R ₈ ^{a is} bonded, by at least 2 carbon atoms and the amino part optionally being mono- or identical or different, which is disubstituted by alkyl having 1 to 6 carbon atoms, phenyl , Phenylalkyl with 7 to 12 carbon atoms or bis-phenylalkyl with 13 to 18 carbon atoms, the three last-mentioned substituents optionally being mono- or identical or different di or identical or different trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, hydroxy or halogen with an atomic number from 9 to 53; R ₉ ^{a represents} hydrogen or has the meaning given above for R ₈ ^a ; R ^a _{10 is} either hydrogen or has the meaning given above for R ₈ ^a or -COR ^a ₁₁ , where R ^a _{11 has} the meaning given above for R ₈ ^a ;

-NⒷ ^a stands for: a 5-, 6- or 7-membered saturated heterocyclic ring which, if it is 6- or 7-membered, can optionally contain a further hetero member from the series oxygen, sulfur and NR ^a ₁₂ , wherein R ^a _{12 is} either hydrogen or has the meaning given above for R ₈ ^a ; and

X represents oxygen or sulfur; and R represents: hydrogen; Alkyl of 1 to 4 carbon atoms; Alkoxy of 1 to 4 carbon atoms; Alkylthio of 1 to 4 carbon atoms; Alkylsulfonyl of 1 to 4 carbon atoms; Halogen with an atomic number from 9 to 35; Trifluoromethyl; Nitro; or hydroxy; and their ammonium salts, in which R ₃ ^{a is} one of the tertiary amino groups defined above for R ₃ ^a and is quaternized with a group of the formal AlkY, where Alk is alkyl with 1 to 4 carbon atoms and Y is the rest of an acid, in free form or optionally in salt form.

3. Compounds according to claim 1 of formula Iaa

wherein R, R ₂ , R ₄ and X have the meaning given above,

R ₁ ^{aa represents} hydrogen or alkyl having 1 to 6 carbon atoms and

R ₃ ^aa means: hydrogen; Alkyl of 1 to 6 carbon atoms; Nitro; Trifluoromethyl; Cyan; -COO R ₅ ^aa ; -CO R ₆ ^aa ; or -S (O) _n R ₇ ^aa ; wherein

R ₅ ^aa means: hydrogen; Alkyl of 1 to 6 carbon atoms; Hydroxyalkyl with 2 to 6 carbon atoms, the hydroxy part being separate from the group to which

R ₅ ^{aa is} bound by at least 2 carbon atoms; Alkoxyalkyl having 1 to 6 carbon atoms in the alkoxy part and having 2 to 6 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₅ ^{aa is} bonded by at least 2 carbon atoms; a 5-membered heteroaryl radical with 1 heteroatom from the series nitrogen, oxygen and sulfur or with 2 heteroatoms from the series nitrogen and either nitrogen, oxygen or sulfur, or a 6-membered heteroaryl radical with 1 to 4 nitrogen atoms; -A ^aa OCO R ₈ ^aa ;

-A ^aa NR ₉ ^aa R ^a ₁₀ ^a ; or A ^aa N Ⓑ ^aa ; wherein

R ₈ ^aa means: alkyl having 1 to 6 carbon atoms;

Phenyl, phenylalkyl with 7 to 12 carbon atoms or bis-phenylalkyl with 13 to 18 carbon atoms, the three latter substituents optionally being mono- or identical or different di- or identical or different trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxy or halogen with an atomic number of 9 to 53;

Hydroxyalkyl with 2 to 6 carbon atoms, the hydroxy part being separate from the group to which

R ₈ ^{aa is} bound by at least 2 carbon atoms; Alkoxyalkyl having 1 to 6 carbon atoms in the alkoxy part and having 2 to 6 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₈ ^{aa is} bonded by at least 2 carbon atoms;

R ₉ ^{aa is} hydrogen or has the meaning given above for R ₈ ^aa ;

R ^a ₁₀ ^{a is} either hydrogen or has the meaning given above for R ₈ ^aa or represents -COR ₁ ^a ₁ ^a , wherein R ₁ ^aa _{1 has} the meaning given above for R ₈ ^aa ; -NⒷ ^aa stands for: a 5-, 6- or 7-membered saturated heterocyclic ring which, if it is 6- or 7-membered, can optionally contain a further heteroglled from the series oxygen, sulfur and NR ^a ₁₂ ^a , wherein R ^a ₁₂ ^{a is} either hydrogen or the above for

R ₈ ^aa has the meaning given; and A ^{aa represents} alkylene of 2 to 6 carbon atoms, which separates the group to which R ₅ ^{aa is} bonded by at least 2 carbon atoms;

R ₆ ^aa and R ₇ ^aa with the exception of hydrogen have the meaning given above for R ₅ ^aa and n has the meaning indicated above;

and their ammonium salts, in which R ₃ ^{aa represents} one of the tertiary amino groups defined above for R ₃ ^aa and is quaternized with a group of the formula AlkY, in which Alk is alkyl with 1 to 4 carbon atoms and Y is the rest of an acid, in free form or optionally in salt form.

4. Compounds according to claim 1 of formula Ib

wherein R, R ₁ ^a , R ₂ , R ₄ and X have the meaning given above and R ₃ ^b means: hydrogen; Alkyl of 7 to 25 carbon atoms; Nitro; Trifluoromethyl; Cyan; -COOR ₅ ^b ; -COR ₆ ^b ; or -S (O) _n R ^b ₇ ; wherein R ₅ ^b is: hydrogen; Alkyl of 7 to 25 carbon atoms; Hydroxyalkyl with 7 to 24 carbon atoms, the hydroxy part being separated from the group to which R ₅ ^{b is} bonded by at least 2 carbon atoms; Alkoxyalkyl with 1 to 24 carbon atoms in the alkoxy part and 2 to 24 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₅ ^{b is} bonded by at least 2 carbon atoms, with the proviso that at least one of the alkoxy and / or contains alkylene parts at least 7 carbon atoms; Alkenyl from 7 to 25

Carbon atoms, the double bond being separated from the group to which R ₅ ^{b is} bonded by at least 1 carbon atom not involved in the double bond; Alkynyl having 7 to 25 carbon atoms, the triple bond being separated from the group to which R ₅ ^{b is} bonded, by at least 1 carbon atom not involved in the double bond; Cycloalkyl of 3 to 7 carbon atoms; Cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and with 7 to 24 carbon atoms in the alkylene part; Hydroxyalkoxyalkyl with 2 to 24 carbon atoms in the hydroxyalkoxy part and with 2 to 24 carbon atoms in the alkylene part, the hydroxyalkoxy part being separated from the group to which R ₅ ^{b is} bonded by at least 2 carbon atoms and the hydroxy part being separated from the oxygen atom of the alkoxy part by at least 2 Carbon atoms with which Provided that at least one of the hydroxyalkoxy and / or alkylene parts contains at least 7 carbon atoms; Phenyl, phenylalkyl with 13 to 30 carbon atoms or Bls-phenylalkyl with 19 to 36 carbon atoms, the three last-mentioned substituents optionally being mono- or identical or different di- or identical or different trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxy or halogen with an atomic number of 9 to 53; a 5-link

Heteroaryl radical with 1 hetero atom from the series nitrogen, oxygen and sulfur or 2 hetero atoms from the series nitrogen and either nitrogen, oxygen or sulfur, or a 6-membered heteroaryl radical with 1 to 4 nitrogen atoms, the latter two substituents optionally having the rest of the Molecule are connected via alkylene radical having 7 to 24 carbon atoms; -A ^b OCOR ₈ ^b ; -A ^b NR ₉ ^b R ₁ ^b ₀ ; or -A ^b NⒷ ^b ; wherein R ₈ ^b is: alkyl of 1 to 25 carbon atoms, with the proviso that if A ^{b contains} less than 7 carbon atoms, it contains 7 to 25 carbon atoms; Phenyl, phenylalkyl with 7 to 30 carbon atoms with the proviso that it contains 13 to 30 carbon atoms if A ^{b contains} less than 7 carbon atoms, or bis-phenylalkyl with 13 to 36 carbon atoms with the proviso that it contains 19 to 36 carbon atoms, if A contains less than 7 carbon atoms, the three latter substituents optionally being mono- or identical or different di- or identical or different trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxy or halogen with an atomic number of 9 to 53; one

5-membered heteroaryl radical with 1 heteroatom from the series nitrogen, oxygen and sulfur or 2 heteroatoms from the series nitrogen and either nitrogen, oxygen or sulfur, or a 6-membered heteroaryl radical with 1 to 4 nitrogen atoms; Hydroxyalkyl of 2 to 24 carbon atoms, the hydroxy portion being separated from the group to which R ₈ ^{b is} attached by at least 2 carbon atoms, with the proviso that if A ^{b contains} less than 7 carbon atoms it contains 7 to 24 carbon atoms; Alkoxyalkyl having 1 to 24 carbon atoms in the alkoxy part and having 2 to 24 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₈ ^{b is} bonded by at least 2 carbon atoms, with the proviso that if A is less than 7 Contains carbon atoms, then at least one of the alkoxy and / or alkylene parts contains at least 7 carbon atoms; Alkenyl having 3 to 25 carbon atoms, the

Double bond is separated from the group to which R ₈ ^{b is} bonded by at least 1 carbon atom not involved in the double bond, with the proviso that if A ^{b contains} less than 7 carbon atoms, it contains 7 to 25 carbon atoms; Alkynyl with 3 to 25

Carbon atoms, the triple bond being separated from the group to which R ₈ ^{b is} bonded by at least

1 carbon atom not involved in the triple bond, with the proviso that it contains 7 to 25 carbon atoms if A ^{b contains} less than 7 carbon atoms; Cycloalkyl of 3 to 7 carbon atoms; Cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl part and having 1 to 24 carbon atoms in the alkylene part, with the proviso that if A contains less than 7 carbon atoms it contains 7 to 24 carbon atoms in the alkylene part; Hydroxyalkoxyalkyl with 2 to 24 carbon atoms in the hydroxyalkoxy part and with 2 to 24 carbon atoms in the alkylene part, where the hydroxyalkoxy part! is separated from the group to which R ₈ ^{b is} attached by at least 2 carbon atoms and the hydroxy part is separated from the oxygen atom of the alkoxy part by at least 2 carbon atoms, with the proviso that if A ^{b contains} less than 7 carbon atoms, then at least one the hydroxyalkoxy and / or alkylene parts contain at least 7 carbon atoms; Aminoalkyl having 2 to 24 carbon atoms, with the proviso that if A ^{b contains} less than 7 carbon atoms, it contains 7 to 24 carbon atoms, the nitrogen atom being separated from the group to which R ₈ ^{b is} bonded by at least 2

Carbon atoms and the amino part optionally mono- or identical or differently disubstituted by alkyl having 1 to 6 carbon atoms, phenyl, phenylalkyl having 7 to 12 carbon atoms or bis-phenylalkyl having 13 to 18 carbon atoms, the three last-mentioned substituents optionally being mono- or identical or are differently di- or identical or differently trisubstituted in the phenyl rings by alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxy or halogen with an atomic number from 9 to 53; R ₉ ^{b represents} hydrogen or has the meaning given above for R ₈ ^b ; R ^b _{10 is} either hydrogen or has the meaning given above for R ₈ ^b or represents -COR ^b ₁₁ , wherein R ^b _{11 has} the meaning given above for R ₈ ^b ;

-NⒷ means ^b ; a 5-, 6- or 7-membered saturated heterocyclic ring, which may optionally contain, if it is 6- or 7-membered, another hetero member from the series oxygen, sulfur and NR ^b ₁₂ , wherein R ^b _{12 is} either hydrogen or has the meaning given above for R8 ^b ; and A ^{b represents} alkylene of 2 to 24 carbon atoms, which separates the group to which R ₅ ^{b is} attached by at least 2 carbon atoms; R ₆ ^b and R ₇ ^b with the exception of hydrogen have the meaning given above for R ₅ ^b ; and n has the meaning given above;

and their ammonium salts in which R ₃ ^{b represents} one of the tertiary amino groups defined above for R ₃ ^b and is quaternized with a group of the formula AlkY, in which Alk is alkyl with 1 to 4

Carbon atoms and Y represent the rest of an acid, in free form or optionally in salt form.

5. Compounds according to claim 1 of formula Iba

wherein R, R ₁ ^aa , R ₂ , R ₄ and X have the meaning given above and

R ₃ ^ba means: alkyl having 7 to 25 carbon atoms; -COO R ₅ ^ba ; -CO R ^b ₆ ^a ; or -S (O) _n R ₇ ^ba ; wherein

R ₅ ^ba means: alkyl having 7 to 25 carbon atoms; Hydroxyalkyl of 7 to 24 carbon atoms, the hydroxy part being separated from the group to which R ₅ ^{ba is} bonded by at least 2 carbon atoms; Alkoxyalkyl having 1 to 24 carbon atoms in the alkoxy part and 2 to 24 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₅ ^{ba is} bonded by at least 2 carbon atoms, with the proviso that at least one of the alkoxy and / or contains alkylene parts at least 7 carbon atoms; Alkenyl having 7 to 25 carbon atoms, the double bond being separated from the group to which R ₅ ^{ba is} bonded by at least 1 carbon atom which is not involved in the double bond; Alkynyl having 7 to 25 carbon atoms, the triple bond being separated from the group to which R ₅ ^{ba is} bonded, by at least 1 carbon atom not involved in the triple bond; Cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and with 7 to 24 Carbon atoms in the alkylene part; Hydroxyalkoxyalkyl having 2 to 24 carbon atoms in the hydroxyalkoxy part and having 2 to 24 carbon atoms in the alkylene part, the hydroxyalkoxy part being separate from the group to which

R ₅ ^{ba is} bonded by at least 2 carbon atoms and the hydroxy part is separated from the oxygen atom of the alkoxy part by at least 2 carbon atoms, with the proviso that at least one of the hydroxyalkoxy and / or alkylene parts contains at least 7 carbon atoms; Phenylalkyl with 13 to 30 carbon atoms or bis-phenylalkyl with 19 to 36 carbon atoms, the two latter substituents optionally being mono- or identical or differently di- or identical or differently trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy having 1 up to 4 carbon atoms,

Hydroxy or halogen with an atomic number of 9 to 53; a

5-membered heteroaryl radical with 1 heteroatom from the series nitrogen, oxygen and sulfur or 2 heteroatoms from the series nitrogen and either nitrogen, oxygen or sulfur, or a 6-membered heteroaryl radical with 1 to 4 nitrogen atoms, the latter two Substituents are connected to the rest of the molecule via an alkylene radical having 7 to 24 carbon atoms; -A ^ba OCO R ₈ ^ba ; -A ^ba NR ₉ ^ba R ^b ₁₀ ^a ; or -A ^ba NⒷ ^ba ; wherein

R ₈ means ^ba ; Alkyl of 1 to 25 carbon atoms, with the proviso that if A ^{ba contains} less than 7 carbon atoms, it contains 7 to 25 carbon atoms; Phenyl, phenylalkyl having 7 to 30 carbon atoms, with the proviso that it contains 13 to 30 carbon atoms if A ^{ba contains} less than 7 carbon atoms, or bis-phenylalkyl with 13 to 36 carbon atoms, with the proviso that it contains 19 contains up to 36 carbon atoms if A ^{ba contains} less than 7 carbon atoms, the three latter substituents optionally being mono- or identical or different dl- or identical or differently trisubstituted in the phenyl rings by

Alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, hydroxy or halogen with an atomic number of 9 to 53; a 5-membered heteroaryl radical with 1 hetero atom from the series nitrogen, oxygen and sulfur or 2 hetero atoms from the series

Nitrogen and either nitrogen, oxygen or sulfur, or a 6-membered heteroaryl radical

1 to 4 nitrogen atoms; Hydroxyalkyl with 2 to 24 carbon atoms, the hydroxy part being separated from the group to which R ₈ ^{ba is} bound by at least

2 carbon atoms, provided that A ^{ba contains} less than 7 carbon atoms, provided that it contains 7 to 24 carbon atoms; Alkoxyalkyl with 1 to 24 carbon atoms in the alkoxy part and with 2 to 24 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₈ ^{ba is} bonded by at least

2 carbon atoms, with the proviso that if A ^{ba contains} less than 7 carbon atoms then at least one of the alkoxy and / or alkylene parts contains at least 7 carbon atoms; Alkenyl of 3 to 25 carbon atoms, the double bond being separated from the group to which R ₈ ^{ba is} bonded, by at least 1 carbon atom not involved in the double bond, with the proviso that it contains 7 to 25 carbon atoms if A ^{ba is} less than Contains 7 carbon atoms;

Alkynyl with 3 to 25 carbon atoms, the triple bond being separate from the group to which R ₈ ^ba is bound by at least 1 carbon atom not involved in the triple bond, with the proviso that it contains 7 to 25 carbon atoms if A ^{ba contains} less than 7 carbon atoms; Cycloalkyl of 3 to 7 carbon atoms; Cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and with 1 to 24 carbon atoms in the alkylene part, with the proviso that there are - - - - - 7 to 24 carbon atoms in the

Contains alkylene if A ^{ba contains} less than 7 carbon atoms; Hydroxyalkoxyalkyl with 2 to 24

Carbon atoms in the hydroxyalkoxy part and with 2 to 24 carbon atoms in the alkylene part, the hydroxyalkoxy part! is separated from the group to which R ₈ ^{ba is} attached by at least 2 carbon atoms and the hydroxy part is separated from the oxygen atom of the alkoxy part by at least 2 carbon atoms, with the proviso that if A contains less than 7 carbon atoms, then at least one of the Hydroxyalkoxy and / or alkylene parts contains at least 7 carbon atoms; Aminoalkyl having 2 to 24 carbon atoms, with the proviso that if A ^{ba contains} less than 7 carbon atoms, it contains 7 to 24 carbon atoms, the oxygen atom being separated from the group to which R ₈ ^{ba is} bonded by at least 2 carbon atoms and the amino part is optionally mono- or identical or differently disubstituted by alkyl having 1 to 6 carbon atoms, phenyl, phenylalkyl having 7 to 12 carbon atoms or bis-phenylalkyl having 13 to 18 carbon atoms, the three last-mentioned substituents optionally being mono- or identical or different or di - or are identical or different trisubstituted in the phenyl rings by alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxy or halogen with an atomic number from 9 to 53; R ₉ ^{ba represents} hydrogen or has the meaning given above for R ₈ ^ba ; R ^b ₁ ^a ₀ either means hydrogen or has the meaning given above for R8 ₈ ^ba or -COR ^b ₁₁ ^a , wherein R ^b ₁₁ ^{a has} the meaning given above for R ₈ ^ba ;

-NⒷ ^ba means a 5-, 6- or 7-membered saturated heterocyclic ring which, if it is 6 or 7-membered, can optionally contain a further hetero-member from the series oxygen, sulfur and NR ₁ ^ba ₂ , in which R ^b ₁ ^a _{2 is} either hydrogen or has the meaning given above for R ^b ₈ ^a ; and A ^{ba represents} alkylene having 2 to 24 carbon atoms, which separates the group to which R ₅ ^{ba is} bonded by at least 2 carbon atoms;

R ₆ ^ba and R ₇ ^ba with the exception of hydrogen have the meaning given above for R ₅ ^ba ; and n has the meaning given above;

and their ammonium salts, in which R ₃ ^{ba stands} for one of the tertiary amino groups defined above for R ₃ ^ba and is quaternized with a group of the formula Alky, in which Alk is alkyl with 1 to 4 carbon atoms and Y is the residue of an acid, in free form or optionally in salt form.

7. Compounds according to claim 1 of formula Ibaa

2 to 18 carbon atoms in the hydroxyalkoxy part and with 2 to 18 carbon atoms in the alkyl part, the

Hydroxyalkoxytei! is separated from the group to which R ₅ ^{baa is} bonded by at least 2 carbon atoms and the ^{hydroxy part} is separated from the oxygen atom of the alkoxy part by at least 2 carbon atoms, with the proviso that at least one of the hydroxyalkoxy and / or alkylene parts contains at least 9 carbon atoms ; -A ^baa OCOR ₈ ^baa ; - A ^{ba a} NR ^b ₉ ^aa R ^b ₁₀ ^aa ; or -A ^baa N Ⓑ; wherein

R ₈ ^baa means: alkyl having 1 to 19 carbon atoms, with the proviso that if A ^{baa contains} less than 9 carbon atoms it contains 9 to 19 carbon atoms; Phenyl, phenylalkyl with 7 to 24 carbon atoms, with the proviso that it

Contains 15 to 24 carbon atoms if A ^{baa contains} less than 9 carbon atoms, or bisphenylalkyl with 13 to 30 carbon atoms, with the proviso that it contains 21 to 30 carbon atoms if A ^{baa contains} less than 9 carbon atoms, the latter three Substituents optionally mono- or identically or differently di- or identically or differently trisubstituted in the phenyl rings by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, hydroxyl or halogen with an atomic number from 9 to 53; Hydroxyalkyl with 2 to 18 carbon atoms, the hydroxy part being separated from the group to which R ₈ ^{baa is} bonded by at least 2 carbon atoms, with the measure that it is 9 to

Contains 18 carbon atoms if A ^{baa contains} less than 9 carbon atoms; Alkoxyalkyl having 1 to 18 carbon atoms in the alkoxy part and having 2 to 18 carbon atoms in the alkylene part, the alkoxy part being separated from the group to which R ₈ ^{baa is} bonded by at least 2 carbon atoms; R ₉ ^{baa is} hydrogen or has the meaning given above for R ₈ ^baa ; either means hydrogen or has the meaning given above for R ^b ₈ ^aa or means -COR ^b ₁ ^a ₁ ^a , wherein R ₁ ^b ₁ ^{aa has} the meaning given above for R ₈ ^b _aa ; -NⒷ ^baa means: a 5-,

6- or 7-membered saturated heterocyclic ring, which, if it is 6- or 7-membered, can optionally contain a further hetero-member from the series oxygen, sulfur and NR ^b ₁ ^a ₂ ^a , wherein R ^b ₁ ^a ₂ ^a either ^Is hydrogen or has the meaning given above for R ₈ ^baa ; and

A ^b _{aa represents} alkylene with 2 to 18 carbon atoms, which separates the group to which R ₈ ^{baa is} bonded by at least 2 carbon atoms;

R ₆ ^baa, with the exception of hydrogen, has the meaning given above for R ₅ ^baa ; and n has the meaning given above;

and their ammonium salts, in which R ₃ ^{baa represents} one of the tertiary amino groups defined above for R ₃ ^baa and is quaternized with a group of the formula alky, in which alk is alkyl having 1 to 4 carbon atoms and Y is the residue of an acid,

in free form or optionally in salt form.

7. The compounds defined in claim 1 in free form or, optionally, in the form of their physiologically tolerable salts, for use as medicaments.

8. A process for the preparation of compounds of the formula I as defined in claim 1 and their ammonium salts, in which R _{3 represents} one of the tertiary amino groups defined above for R ₃ and is quaternized with a group of the formula Alky, in which Alk is alkyl with 1 to 4 carbon atoms and Y represent the residue of an acid, in free form or optionally in salt form, characterized in that a) corresponding compounds of the formula II

where Q has the above meaning, corresponding compounds of the formula III

where R ₂ and R _{3 are as defined} above,

corresponding compounds of formula IV

where R _{4 has the} above meaning, and corresponding compounds of formula V

where R _{1 has the} above meaning,

or their partial condensation products, appropriately condensed to 1,4-dihydropyridines, or

b) for the preparation of compounds of the formula I '

in which R ₁ , R ₂ , R ₄ and Q have the above meaning and R ₃ ^'is hydrogen, -COOR ₅ or -COR ₆ , in which R ₅ and R _{6 have the} above meaning, corresponding compounds of the formula VI

where R ₁ , R ₂ , R ₄ and Q have the above meaning and X represents a reactive group, appropriately converted, and optionally the compounds thus obtained in which R _{3 represents} one of the tertiary amino groups defined above for R ₃ , in quaternary ammonium salt form with compounds of the formula alky, in which alk is alkyl having 1 to 4 carbon atoms and Y is the residue of an acid, and the compounds thus obtained are recovered in free form or optionally in salt form.

9. Use of the compounds defined in claim 1 in free form or optionally in the form of their physiologically tolerable salts as medicaments.

10. Pharmaceutical preparations containing the compounds defined in claim 1 in free form or optionally in the form of their physiologically tolerable salts.