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WO1997030025A1 - Dicarbamoyl compounds - Google Patents

Dicarbamoyl compounds Download PDF

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Publication number
WO1997030025A1
WO1997030025A1 PCT/EP1997/000616 EP9700616W WO9730025A1 WO 1997030025 A1 WO1997030025 A1 WO 1997030025A1 EP 9700616 W EP9700616 W EP 9700616W WO 9730025 A1 WO9730025 A1 WO 9730025A1
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Prior art keywords
formula
compounds
alkyl
phenyl
radical
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German (de)
French (fr)
Inventor
Claus Marschner
Manfred Patsch
Ulrike Schlösser
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/51—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
    • C07C309/09—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton
    • C07C309/10—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
    • C07C309/15—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton the nitrogen atom of at least one of the amino groups being part of any of the groups, X being a hetero atom, Y being any atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/28—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
    • C07C317/38—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atom of at least one amino group being part of any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylaminosulfones
    • C07C317/40—Y being a hydrogen or a carbon atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group

Definitions

  • the invention relates to compounds of general formula I.
  • n 0, 1 or 2
  • W is optionally substituted by Ci to C4 alkyl, chlorine, bromine or phenyl substituted C 2 - to C 4 -alkylene, Cs-C 7 -cycloalkyl alkenylene or C 2 -C 4 alkenylene or optionally substituted by methyl, ethyl, methoxy , Ethoxy, hydroxy, chlorine, bromine, hydroxysulfonyl, nitro, amino, acetylamino or carboxyl-substituted phenylene,
  • C 2 is optionally substituted by ether oxygen, imino, imino or C Phenyl ⁇ -C 4 -alkylimino - ß alkylene or a radical of the For ⁇ to C mel
  • L 1 and L 2 independently of one another C -.- to C 4 -alkylene
  • Y is vinyl or a radical of the formula C 2 H 4 Q, where Q is
  • Ar phenyl or naphthyl where both radicals are mono- to triple by Cx to C 6 alkyl, C x to C 6 alkoxy, fluorine, chlorine, bromine, nitro, amino, hydroxy, hydroxysulfonyl, carboxyl, Ci to C 6 -alkoxycarbonyl, acetylamino, a radical of the formula
  • R 1 and R 2 are independently hydrogen or
  • Ci to C 6 alkyl and n, X and Y have the meaning given, mean
  • the object of the present invention was to provide new dicarbamoyl compounds.
  • the new compounds should be easily accessible and advantageously be suitable as intermediates for dyes.
  • the bridge member X is in particular optionally C 2 to C 8 alkylene interrupted simply by oxygen, imino, phenylimino or (C (-C 4 ) -alkylimino.
  • radicals X are, for example, CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 OCH 2 CH 2 , CH 2 CH 2 NHCH 2 CH 2 ,
  • the first three radicals being particularly preferred.
  • the rest Q stands for hydroxy or for a group which can be split off under alkaline reaction conditions.
  • groups are, for example, chlorine, bromine, C 1 -C 4 -alkylsulfonyl, phenylsulfonyl, OSO 3 H, SS0 3 H, OP (0) (OH) 2 , C 1 -C 4 -alkylsulfonyloxy, phenylsulfonyloxy, C ⁇ -C 4 -alka- noyloxy, -CC 4 -dialkylamino or a radical of the formula
  • L 1 , L 2 and L 3 independently of one another each have the meaning of C ⁇ -C 4 alkyl or benzyl and An each have the meaning of one equivalent of an anion.
  • Anions which may be used here are, for example, fluoride, chloride, bromide, iodide, mono-, di- or trichloroacetate, methanesulfonate, benzenesulfonate or 2- or 4-methylbenzenesulfonate.
  • the substituents for Ar are in particular fluorine, chlorine, bromine, methyl, hydroxy, methoxy, ethoxy, hydroxysulfonyl, carboxyl, carbamoyl, sulfamoyl, nitro, amino, acetylamino or radicals of the formulas
  • the compounds of the formula I are suitable, for example, as diazo components (Ar substituted by NH 2 ) or as coupling components (coupling point in the Ar radical) and are valuable intermediates for the preparation of reactive dyes.
  • Example 3 20 33 g of the aniline obtained in Example 3 were introduced into 98 g of oleum (24% strength) with ice cooling at 35-40 ° C. and stirred at 55 ° C. for about 6 hours.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Dicarbamoyl compounds of general formula (I) wherein: m is 1 or 2, n is 0, 1 or 2, W if necessary C2 to C4 alkylene is substituted by C1 to C4 alkyl, chlorine, bromine or phenyl or phenylene optionally substituted by methyl, ethyl, methoxy, ethoxy, hydroxy, chlorine, bromine, hydroxysulfonyl, nitro, amino, acetalamino, or carboxyl; X is C2-C8 alkylene interrupted one to three times, optionally substituted by ether oxygen, imino, phenylimino or C1 to C4 alkylamino or a residue of the formula (II); Z is a residue of formula (III) or (IV); R is hydrogen, C1 to C4 alkyl, phenyl, CH2CH2OH, CH2CH2OSO3H, CH2CH2SO3H or a residue of formula (V); L?1 and L2¿ are independently C¿1? to C4 alkylenes; Y is vinyl or a residue of the formula C2H4Q where Q means hydroxy or a residue separable under alkalic reaction conditions; and Ar means phenyl or naphthyl and both residues can be substituted one to three times by C1-C6 alkyl, C1-C6 alkoxy, fluorine, chlorine, bromine, nitro, amino, hydroxy, hydroxysulfonyl, carboxyl, C1 to C6 alkoxycarbonyl, acetylamino, a residue of formula (VI), (VII), SO2NH-X-S(O)n-Y or S(O)n-Y where R?1 and R2¿ are independently hydrogen or C¿1? to C6 alkyl and n, X and Y have the given meaning. The invention also relates to the use of these compounds for the preparation of fiber reactive dyes.

Description

DicarbamoylVerbindungenDicarbamoyl compounds

Beschreibungdescription

Die Erfindung betrifft Verbindungen der allgemeinen Formel IThe invention relates to compounds of general formula I.

Ar NHC- •W- I —z—x— S(0)nY I, mAr NHC- • W- I —z — x— S (0) n YI, m

in derin the

m 1 oder 2,m 1 or 2,

n 0, 1 oder 2,n 0, 1 or 2,

W gegebenenfalls durch Ci- bis C4-Alkyl, Chlor, Brom oder Phenyl substituiertes C2- bis C4-Alkylen, Cs-C7-Cyclo- alkenylen oder C2-C4-Alkenylen oder gegebenenfalls durch Methyl, Ethyl, Methoxy, Ethoxy, Hydroxy, Chlor, Brom, Hydroxysulfonyl, Nitro, Amino, Acetylamino oder Carboxyl substituiertes Phenylen,W is optionally substituted by Ci to C4 alkyl, chlorine, bromine or phenyl substituted C 2 - to C 4 -alkylene, Cs-C 7 -cycloalkyl alkenylene or C 2 -C 4 alkenylene or optionally substituted by methyl, ethyl, methoxy , Ethoxy, hydroxy, chlorine, bromine, hydroxysulfonyl, nitro, amino, acetylamino or carboxyl-substituted phenylene,

gegebenenfalls durch Ethersauerstoff, Imino, Phenyl¬ imino oder Ci- bis C4-Alkylimino ein- bis dreifach un¬ terbrochenes C2- bis Cß-Alkylen oder ein Rest der For¬ melmono- to trisubstituted un¬ terbrochenes C 2 is optionally substituted by ether oxygen, imino, imino or C Phenyl¬ -C 4 -alkylimino - ß alkylene or a radical of the For¬ to C mel

00

Ll* Z L2 L l * ZL 2

ein Rest der Formelna rest of the formulas

RR

ΓΛΓΛ

N- oder N NN- or N N

Wasserstoff , Ci * bis C4 -Alkyl , Phenyl , CH2CH2OH, CH2CH2OS03H , CH2CH2S03H oder ein Res t der Formel X S (0) nYHydrogen, Ci * to C 4 alkyl, phenyl, CH 2 CH 2 OH, CH 2 CH 2 OS0 3 H, CH 2 CH 2 S0 3 H or a radical of the formula XS (0) n Y

L1 und L2 unabhängig voneinander C-.- bis C4-Alkylen,L 1 and L 2 independently of one another C -.- to C 4 -alkylene,

Y Vinyl oder ein Rest der Formel C2H4Q, wobei Q fürY is vinyl or a radical of the formula C 2 H 4 Q, where Q is

Hydroxy oder eine unter alkalischen Reaktions- bedingungen abspaltbare Gruppe steht,Is hydroxy or a group which can be split off under alkaline reaction conditions,

Ar Phenyl oder Naphthyl, wobei beide Reste ein- bis drei¬ fach durch Cx- bis C6-Alkyl, Cx- bis C6-Alkoxy, Fluor, Chlor, Brom, Nitro, Amino, Hydroxy, Hydroxysulfonyl, Carboxyl, Ci- bis C6-Alkoxycarbonyl, Acetylamino, einen Rest der FormelAr phenyl or naphthyl, where both radicals are mono- to triple by Cx to C 6 alkyl, C x to C 6 alkoxy, fluorine, chlorine, bromine, nitro, amino, hydroxy, hydroxysulfonyl, carboxyl, Ci to C 6 -alkoxycarbonyl, acetylamino, a radical of the formula

R1 RlR 1 Rl

C02N S02N R2 R2C0 2 N S0 2 N R2 R2

S02NH X S(0)n Y oder S(0)n-S0 2 NH XS (0) n Y or S (0) n -

substituiert sein können, wobei R1 und R2 unabhängig voneinander für Wasserstoff odermay be substituted, wherein R 1 and R 2 are independently hydrogen or

Ci- bis C6-Alkyl stehen und n, X und Y die angegebene Bedeutung haben, bedeutenCi to C 6 alkyl and n, X and Y have the meaning given, mean

sowie ihre Verwendung zur Herstellung faserreaktiver Farbstoffe.as well as their use for the production of fiber-reactive dyes.

Aufgabe der vorliegenden Erfindung war es, neue DicarbamoylVer¬ bindungen bereitzustellen. Die neuen Verbindungen sollten leicht zugänglich sein und sich vorteilhaft als Zwischenprodukte für Farbstoffe eignen.The object of the present invention was to provide new dicarbamoyl compounds. The new compounds should be easily accessible and advantageously be suitable as intermediates for dyes.

Demgemäß wurden die eingangs näher bezeichneten Dicarbamoylver- bindungen der Formel I gefunden. Alle in den hier aufgeführten Formeln auftretenden Alkyl- und Alkylengruppen können sowohl geradkettig als auch verzweigt sein. Beispiele für Alkylgruppen sind Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, see-Bu¬ tyl, tert. -Butyl, Pentyl, Isopentyl, Neopentyl, Hexyl und Methyl pentyl. Die obigen Ausführungen zur Alkylgruppe gelten in ent¬ sprechender Weise für die Alkylgruppe in Alkoxy, Alkoxycarbonyl und Alkylimino. Einzelne Reste W sind z.B.:We have found that this object is achieved by the dicarbamoyl compounds of the formula I described at the outset. All alkyl and alkylene groups occurring in the formulas listed here can be both straight-chain and branched. Examples of alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, see-butyl, tert. -Butyl, pentyl, isopentyl, neopentyl, hexyl and methyl pentyl. The above statements on the alkyl group apply accordingly to the alkyl group in alkoxy, alkoxycarbonyl and alkylimino. Individual residues W are, for example:

CH3 C2H5 CH3 CH3 CH3 CH 3 C 2 H 5 CH 3 CH 3 CH 3

I I I I | CH2CH , CH2CH , CH CH , CH2 CH CH2 ,IIII | CH 2 CH, CH 2 CH, CH CH, CH 2 CH CH 2 ,

CH2CH2CH2CH2 , CH2

Figure imgf000005_0001
Cl Cl Cl Cl CH3 CH 2 CH 2 CH 2 CH 2 , CH 2
Figure imgf000005_0001
Cl Cl Cl Cl CH 3

CH2CH, CH2CH, CH= C CH= C und CH 2 CH, CH 2 CH, CH = C CH = C and

Br c6H5 BrBr c 6 H 5 Br

vorzugsweise CH2CH2, CH2CH2CH2, CH= CH,preferably CH 2 CH 2 , CH 2 CH 2 CH 2 , CH = CH,

Figure imgf000005_0002
Figure imgf000005_0002

Weiterhin sind als Reste W C6H3CH3, C6H3C1, C6H3Br, C6H2(CH3)2, C6H3N02, CgH3COOH und C6H3S03H zu nennen.Further residues are WC 6 H 3 CH 3 , C 6 H 3 C1, C 6 H 3 Br, C 6 H 2 (CH 3 ) 2 , C 6 H 3 N0 2 , CgH 3 COOH and C 6 H 3 S0 3 To call H.

Das Brückenglied X ist insbesondere gegebenenfalls einfach durch Sauerstoff, Imino, Phenylimino oder (Cχ-C4) -Alkylimino unterbro¬ chenes C2- bis Cs-Alkylen.The bridge member X is in particular optionally C 2 to C 8 alkylene interrupted simply by oxygen, imino, phenylimino or (C (-C 4 ) -alkylimino.

Einzelne Reste X sind beispielsweise CH2CH2, CH2CH2CH2, CH2CH2OCH2CH2, CH2CH2NHCH2CH2,Individual radicals X are, for example, CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 OCH 2 CH 2 , CH 2 CH 2 NHCH 2 CH 2 ,

CH3 CH 3

CH2CH2N CH2CH2 / CH 2 CH 2 N CH 2 CH 2 /

CH2CH2OCH2CH2OCH2CH2 , CH2CH2OCH2CH2OCH2CH2OCH2CH2 , CH2CH2NHCH2CH2NHCH2CH2 , C4H8 oder O 97/30025 PCΪ7EP97/00616CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 , CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 , CH 2 CH 2 NHCH 2 CH 2 NHCH 2 CH 2 , C 4 H 8 or O 97/30025 PCΪ7EP97 / 00616

CH2 C NH CH2CH2 ,CH 2 C NH CH 2 CH 2 ,

wobei die drei ersten Reste besonders bevorzugt sind.the first three radicals being particularly preferred.

Für R sind Methyl, Phenyl oder der Rest der Formel X-S(0)nY und insbesondere Wasserstoff bevorzugt.For R, methyl, phenyl or the rest of the formula XS (0) n Y and in particular hydrogen are preferred.

Der Rest Q steht für Hydroxy oder für eine unter alkalischen Re¬ aktionsbedingungen abspaltbare Gruppe. Solche Gruppen sind z.B. Chlor, Brom, Cι-C4-Alkylsulfonyl, Phenylsulfonyl, OSO3H, SS03H, OP(0) (OH)2, Cι-C4-Alkylsulfonyloxy, Phenylsulfonyloxy, Cχ-C4-Alka- noyloxy, Cι-C4-Dialkylamino oder ein Rest der FormelThe rest Q stands for hydroxy or for a group which can be split off under alkaline reaction conditions. Such groups are, for example, chlorine, bromine, C 1 -C 4 -alkylsulfonyl, phenylsulfonyl, OSO 3 H, SS0 3 H, OP (0) (OH) 2 , C 1 -C 4 -alkylsulfonyloxy, phenylsulfonyloxy, Cχ-C 4 -alka- noyloxy, -CC 4 -dialkylamino or a radical of the formula

0

Figure imgf000006_0001
0
Figure imgf000006_0001

wobei L1, L2 und L3 unabhängig voneinander jeweils die Bedeutung von Cχ-C4-Alkyl oder Benzyl und An jeweils die Bedeutung eines Äquivalents eines Anions besitzen. Als Anionen können dabei z.B. Fluorid, Chlorid, Bromid, Iodid, Mono-, Di- oder Trichloracetat, Methansulfonat, Benzolsulfonat oder 2- oder 4-Methylbenzol- sulfonat in Betracht kommen.where L 1 , L 2 and L 3 independently of one another each have the meaning of Cχ-C 4 alkyl or benzyl and An each have the meaning of one equivalent of an anion. Anions which may be used here are, for example, fluoride, chloride, bromide, iodide, mono-, di- or trichloroacetate, methanesulfonate, benzenesulfonate or 2- or 4-methylbenzenesulfonate.

Bevorzugt sind Dicarbamoylverbindungen der Formel I, in der n 0 oder 2, insbesondere 2, bedeutet.Dicarbamoyl compounds of the formula I in which n denotes 0 or 2, in particular 2, are preferred.

Y ist vorzugsweise CH=CH2, CH2CH2OH, CH2CH2OS03H, CH2CH2C1 oder CH2CH2OCOCH3.Y is preferably CH = CH 2 , CH 2 CH 2 OH, CH 2 CH 2 OS0 3 H, CH 2 CH 2 C1 or CH 2 CH 2 OCOCH 3 .

Als Substituenten für Ar sind insbesondere Fluor, Chlor, Brom, Methyl, Hydroxy, Methoxy, Ethoxy, Hydroxysulfonyl, Carboxyl, Carbamoyl, Sulfamoyl, Nitro, Amino, Acetylamino oder Reste der FormelnThe substituents for Ar are in particular fluorine, chlorine, bromine, methyl, hydroxy, methoxy, ethoxy, hydroxysulfonyl, carboxyl, carbamoyl, sulfamoyl, nitro, amino, acetylamino or radicals of the formulas

S02NH X — S (0) nY oder S {0) nY zu nennen, wobei n, X und Y die angegebene Bedeutung haben und Verbindungen mit 1 oder 2 Substituenten bei Phenyl und bis zu drei Substituenten bei Naphthyl für Ar bevorzugt sind.S0 2 NH X - S (0) n Y or S {0) n Y to name, where n, X and Y have the meaning given and compounds with 1 or 2 substituents for phenyl and up to three substituents for naphthyl for Ar are preferred.

Verbindungen der Formel I, in denen m für 1 steht, werden bevor¬ zugt.Compounds of the formula I in which m is 1 are preferred.

Die Verbindungen der Formel I eignen sich in Abhängigkeit von der Konstitution z.B. als Diazokomponenten (Ar durch NH2 substituiert) oder als Kupplungskomponenten (Kupplungsstelle im Ar-Rest) und sind wertvolle Zwischenprodukte zur Herstellung von Reaktivfarb¬ stoffen.Depending on their constitution, the compounds of the formula I are suitable, for example, as diazo components (Ar substituted by NH 2 ) or as coupling components (coupling point in the Ar radical) and are valuable intermediates for the preparation of reactive dyes.

Zur Herstellung der Verbindungen der Formel I kann man z.B. Verbindungen der FormelFor the preparation of the compounds of formula I, e.g. Compounds of the formula

Figure imgf000007_0001
m
Figure imgf000007_0001
m

mit Verbindungen der Formelwith compounds of the formula

HZ X S(0)n-HZ XS (0) n -

umsetzen, m, n, W, Ar, Z, X und Y haben dabei die angegebenen Be¬ deutungen.implement, m, n, W, Ar, Z, X and Y have the meanings given.

Einzelheiten der Umsetzungen können den Beispielen entnommen wor- den, in denen sich Angaben über Teile und Prozente, sofern nicht anders vermerkt, auf das Gewicht beziehen.Details of the implementations can be found in the examples, in which parts and percentages, unless stated otherwise, relate to the weight.

Beispiel 1example 1

Eine Mischung aus 220 g des Bernsteinsäureimids der Formel

Figure imgf000008_0001
A mixture of 220 g of the succinimide of the formula
Figure imgf000008_0001

und 133 g 2-Aminoethyl-2' -hydroxyethylsulfid wurde 3 Stunden auf 60-65°C erhitzt. Nach vollständigem Umsatz (DC-Kontrolle) wurde abgekühlt und die Produktsuspension mit 0,5 1 Ethanol verdünnt.and 133 g of 2-aminoethyl-2 '-hydroxyethyl sulfide was heated at 60-65 ° C for 3 hours. After conversion was complete (TLC control), the mixture was cooled and the product suspension was diluted with 0.5 l of ethanol.

Der Niederschlag wurde abgesaugt und getrocknet. Man isolierte 298 g der Verbindung der FormelThe precipitate was filtered off and dried. 298 g of the compound of the formula were isolated

Figure imgf000008_0002
Figure imgf000008_0002

iH-NMR [D6-DMSO] : δ 2.3-2,7 (M, 8H) , 3.2 (M, 2H) , 35 (M, 2H) , 4.7 (brS, OH), 7.6 (M, Aromaten-H) , 7.9 (M, Aromaten-H) , 8.1 (M, Aromaten-H) , 8.7 (S, NH) , 10.5 (S, NH) ppm. i H-NMR [D 6 -DMSO]: δ 2.3-2.7 (M, 8H), 3.2 (M, 2H), 35 (M, 2H), 4.7 (brS, OH), 7.6 (M, aromatics H), 7.9 (M, aromatics-H), 8.1 (M, aromatics-H), 8.7 (S, NH), 10.5 (S, NH) ppm.

Beispiel 2Example 2

Eine Mischung aus 220 g des Bernsteinsäureimids der FormelA mixture of 220 g of the succinimide of the formula

Figure imgf000008_0003
Figure imgf000008_0003

und 133 g 2-Aminoethyl-2'hydroxyethylsulfid wurde 3 Stunden auf 60-65°C erhitzt. Nach dem Abkühlen gab man 250 ml Wasser zu und stellte den pH-Wert mit konz. Salzsäure auf 5,0. Nach Zugabe von 1 g Wolframsäure wurden dann bei 65 bis 80°C 248 g 30 gew. -%iges wäßriges Wasserstoffperoxid innerhalb einer Stunde zugetropft. Nach dem Abkühlen wurde der Niederschlag abgesaugt und getrock¬ net. Man isolierte 325 g der Verbindung der Formeland 133 g of 2-aminoethyl-2'hydroxyethyl sulfide was heated at 60-65 ° C for 3 hours. After cooling, 250 ml of water were added and the pH was adjusted to conc. Hydrochloric acid to 5.0. After adding 1 g of tungstic acid, 248 g of 30 wt. Were then at 65 to 80 ° C. -% aqueous hydrogen peroxide added dropwise within an hour. After cooling, the precipitate was filtered off and dried. 325 g of the compound of the formula were isolated

Figure imgf000009_0001
Figure imgf000009_0001

l-H-NMR [D6-DMSO] : δ = 2.5 (M, 3H) , 2.6 (M, 2H) , 3.2 (M, 4H) , 1 H NMR [D 6 -DMSO]: δ = 2.5 (M, 3H), 2.6 (M, 2H), 3.2 (M, 4H),

3.5 (M, IH) , 3.8 (M, 2H) , 5.1 (brS, OH),3.5 (M, IH), 3.8 (M, 2H), 5.1 (brS, OH),

7.6 (M, IH, Aromaten-H) , 7.9 (M, 2H, Aroma- ten-H) , 8.2 (M, IH, Aromaten-H)7.6 (M, IH, aromatics-H), 7.9 (M, IH, aromatics-H), 8.2 (M, IH, aromatics-H)

8.7 (brS,NH), 10.5 (brS, NH) ppm.8.7 (brS, NH), 10.5 (brS, NH) ppm.

Beispiel 3:Example 3:

250 g des Produkts aus Beispiel 2 wurden in 1,5 Litern Äthanol/ THF-Gemisch (2/1) gelöst und in Gegenwart von 5 g eines Raney- Nickel-Katalysators bei 25-30°C unter Schütteln mit Wasserstoff begast. Nach beendeter Wasserstoffaufnähme wurde vom Katalysator abfiltriert und das Filtrat unter vermindertem Druck eingeengt. Man isolierte nach der Trocknung 228 g der Verbindung der Formel250 g of the product from Example 2 were dissolved in 1.5 liters of ethanol / THF mixture (2/1) and gassed with hydrogen in the presence of 5 g of a Raney nickel catalyst at 25-30 ° C. with shaking. After the hydrogen uptake had ended, the catalyst was filtered off and the filtrate was concentrated under reduced pressure. After drying, 228 g of the compound of the formula were isolated

Figure imgf000009_0002
Figure imgf000009_0002

Gehaltsbestimmung durch Diazotierung: 94 %Diazotization content determination: 94%

!H-NMR [D6-DMSO] : δ = 2.4 (M, 2H) , 2.5 (M, 2H) , 3.2 (M, 4H) , 3.4 (M, 2H) , 3.8 (M, 2H) , 5.0 (brS, NH2) , 5.1 (T, OH), 6.2 (M, IH, Aromaten-H) 6.6 (M, IH, Aromaten-H), 6.8 (M, 2H, Aromaten-H), 8.1 (brS, NH) 9.6 (brS, NH) ppm. ! H-NMR [D 6 -DMSO]: δ = 2.4 (M, 2H), 2.5 (M, 2H), 3.2 (M, 4H), 3.4 (M, 2H), 3.8 (M, 2H), 5.0 (brS , NH 2 ), 5.1 (T, OH), 6.2 (M, IH, aromatics-H) 6.6 (M, IH, aromatics-H), 6.8 (M, 2H, aromatics-H), 8.1 (brS, NH) 9.6 (brS, NH) ppm.

Beispiel 4:Example 4:

33 g der gemäß Beispiel 3 erhaltenen Verbindung wurden unter Eis- kühlung bei 35-40°C in 98 g Monohydrat (100 Gew. -%ige Schwefel- säure) eingetragen und ungefähr 12 Stunden bei Raumtemperatur ge¬ rührt. Nach vollständigem Umsatz (DC-Kontrolle) wurde die Mischung auf 300 g Eis gegossen, und anschließend durch Einstreuen von kalzi¬ nierter Soda unter Rühren und Kühlung auf pH-Wert 5 eingestellt.33 g of the compound obtained according to Example 3 were introduced into 98 g of monohydrate (100% by weight sulfuric acid) while cooling with ice at 35-40 ° C. and stirred for about 12 hours at room temperature. After complete conversion (TLC control), the mixture was poured onto 300 g of ice and then adjusted to pH 5 by sprinkling calcined soda with stirring and cooling.

5 Man erhält eine elektrolythaltige Lösung der Verbindung der For¬ mel5 An electrolyte-containing solution of the compound of the formula is obtained

Figure imgf000010_0001
Figure imgf000010_0001

15 die ohne weitere Reinigung zu Folgeumsetzungen, insbesondere FarbstoffSynthesen, verwendet werden kann.15 which can be used for subsequent reactions, in particular dye syntheses, without further purification.

Beispiel 5:Example 5:

20 33 g des in Beispiel 3 erhaltenen Anilins wurden unter Eiskühlung bei 35-40°C in 98 g Oleum (24 %ig) eingetragen und ungefähr 6 Stunden bei 55°C gerührt.20 33 g of the aniline obtained in Example 3 were introduced into 98 g of oleum (24% strength) with ice cooling at 35-40 ° C. and stirred at 55 ° C. for about 6 hours.

Nach vollständigem Umsatz (DC-Kontrolle) wurde die Mischung auf 25 300 g Eis gegossen und anschließend durch Einstreuen kalzinierter Soda unter Rühren und Kühlung auf pH-Wert 5 gebracht.After complete conversion (TLC control), the mixture was poured onto 25 300 g of ice and then brought to pH 5 by sprinkling calcined soda with stirring and cooling.

Durch Abkühlen auf 0 - 5°C unter Rühren fiel Natriumsulfat aus, das nach ungefähr einer Stunde durch Absaugen entfernt wurde.By cooling to 0-5 ° C. while stirring, sodium sulfate precipitated out, which was removed by suction after about an hour.

3030

Man erhält dann eine elektrolythaltige Lösung der Verbindung der FormelAn electrolyte-containing solution of the compound of the formula is then obtained

Figure imgf000010_0002
Figure imgf000010_0002

40 die ohne weitere Reinigung zu Folgeumsetzungen, insbesondere FarbstoffSynthesen verwendet werden kann.40 which can be used for subsequent reactions, in particular dye synthesis, without further purification.

45 45

Figure imgf000011_0002
Figure imgf000011_0002

Figure imgf000011_0001
Figure imgf000012_0001
11
Figure imgf000011_0001
Figure imgf000012_0001
11

Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001

Claims

Patentansprüche claims Dicarbamoylverbindungen der allgemeinen Formel IDicarbamoyl compounds of the general formula I
Figure imgf000017_0001
Figure imgf000017_0001
 in derin the m 1 oder 2,m 1 or 2, n 0, 1 oder 2,n 0, 1 or 2, w gegebenenfalls durch C.- bis C4-Alkyl, Chlor, Brom oder Phenyl substituiertes C2- bis C4-Alkylen, C5- bis C7-Cycloalkenylen oder C2- bis C4-Alkenylen oder gegebenenfalls durch Methyl, Ethyl, Methoxy, Ethoxy, Hydroxy, Chlor, Brom, Hydroxysulfonyl, Nitro, Amino, Acetylamino oder Carboxyl substi¬ tuiertes Phenylen,w is optionally substituted by C. - C 4 -C 4 alkyl, chlorine, bromine or phenyl substituted C 2 -C 4 alkylene, C 5 -C 7 cycloalkenylene or C 2 -C 4 alkenylene or optionally by methyl, ethyl, methoxy, ethoxy, Hydroxy, chlorine, bromine, hydroxysulfonyl, nitro, amino, acetylamino or carboxyl-substituted phenylene, X gegebenenfalls durch Ethersauerstoff, Imino, Phe¬ nylimino oder Ci- bis C4-Alkylimino ein- bis drei¬ fach unterbrochenes C2- bis C$-Alkylen oder ein Rest der FormelX is optionally substituted by ether oxygen, imino, Phe¬ nylimino or Ci- to C 4 alkylimino mono- to drei¬ times interrupted C 2 - to C $ alkylene or a radical of the formula L1 C Z L2L 1 CZ L2 ein Rest der Formelna rest of the formulas N- oder N N —N- or N N - R Wasserstoff, Ci- bis C4-Alkyl, Phenyl, CH2CH2OH, CH2CH2OSθ3H, CH2CH2SO3H oder ein Rest der Formel X S (0) nYR is hydrogen, Ci to C 4 alkyl, phenyl, CH 2 CH 2 OH, CH 2 CH 2 OSθ 3 H, CH 2 CH 2 SO 3 H or a radical of the formula XS (0) n Y L1 und L2 unabhängig voneinander C-_ - bis C4-Alkylen,L 1 and L 2 independently of one another are C 1 -C 4 -alkylene, Y Vinyl oder ein Rest der Formel C2H4Q, wobei Q für Hydroxy oder einen unter alkalischen Reaktions- bedingungen abspaltbaren Rest steht,Y is vinyl or a radical of the formula C 2 H 4 Q, where Q is hydroxyl or a radical which can be split off under alkaline reaction conditions, undand Ar Phenyl oder Naphthyl, wobei beide Reste ein- bis dreifach durch Ci- bis Ce-Alkyl, Ci- bis Ce-Alkoxy,Ar is phenyl or naphthyl, where both radicals are mono- to triple by Ci to Ce alkyl, Ci to Ce alkoxy, Fluor, Chlor, Brom, Nitro, Amino, Hydroxy, Hydroxysulfonyl, Carboxyl, C± - bis Cξ-Alkoxy¬ carbonyl, Acetylamino, einen Rest der FormelFluorine, chlorine, bromine, nitro, amino, hydroxy, hydroxysulfonyl, carboxyl, C ± to Cξ-alkoxy carbonyl, acetylamino, a radical of the formula ^- R1 ^R1 C°2N ^ R2 , S02N ^ R2 ^ - R 1 ^ R 1 C ° 2N ^ R2 , S0 2 N ^ R2 S02NH— X—S(0)n—Y oder S(0)n—yS0 2 NH-X-S (0) n -Y or S (0) n -y substituiert sein können, wobei R1 und R2 unabhän¬ gig voneinander für Wasserstoff oder Ci- bis Ce-Alkyl stehen und n, X und Y die angegebene Be¬ deutung haben, bedeuten.may be substituted, where R 1 and R 2 independently of one another are hydrogen or Ci to Ce alkyl and n, X and Y have the meaning given. 2. Verbindungen der Formel I nach Anspruch 1, wobei m 1 ist.2. Compounds of formula I according to claim 1, wherein m is 1. 3. Verbindungen der Formel I nach Anspruch 1, wobei n 2 ist.3. Compounds of formula I according to claim 1, wherein n is 2. 4. Verbindungen der Formel I nach Anspruch 1, wobei4. Compounds of formula I according to claim 1, wherein W CH2CH2, CH2CH2CH2, CH=CH,
Figure imgf000018_0001
W CH 2 CH 2 , CH 2 CH 2 CH 2 , CH = CH,
Figure imgf000018_0001
Figure imgf000018_0002
Figure imgf000018_0002
 5. Verbindungen der Formel I gemäß Anspruch 1, wobei X C2- bis CQ-Alkylen, das gegebenenfalls einfach durch Sauerstoff, Imino, Phenylimino oder Cι-C4-Alkylimino unterbrochen ist, be¬ deutet.5. Compounds of formula I according to claim 1, wherein XC 2 - to CQ-alkylene, which is optionally simply interrupted by oxygen, imino, phenylimino or -CC 4 -alkylimino, means. 6. Verbindungen der Formel I nach Anspruch 1, wobei6. Compounds of formula I according to claim 1, wherein R Wasserstoff, Methyl, Phenyl oder ein Rest der FormelR is hydrogen, methyl, phenyl or a radical of the formula X-S(0)nY ist und n, X und Y die angegebene Bedeutung ha- ben.XS (0) n is Y and n, X and Y have the meaning given. 7. Verbindungen der Formel I nach Anspruch 1, wobei7. Compounds of formula I according to claim 1, wherein Y CH=CH2, CH2CH20H, CH2CH20S03H, CH2CH2C1 oder CH2CH2OCOCH3 ist.Y is CH = CH 2 , CH 2 CH 2 0H, CH 2 CH 2 0S0 3 H, CH 2 CH 2 C1 or CH 2 CH 2 OCOCH 3 . 8. Verbindungen der Formel I nach Anspruch 1, wobei8. Compounds of formula I according to claim 1, wherein Ar Phenyl oder Naphthyl bedeutet, die jeweils ein- bis drei- fach durch Fluor, Chlor, Brom, Methyl, Hydroxy, Methoxy, Ethoxy, Hydroxysulfonyl, Carboxyl, Carbamoyl, Sulfamoyl, Nitro, Amino, Acetylamino oder einen Rest der Formel S02NH-X-S (0)nY oder S(0)n-Y substituiert sein können, wo¬ bei n, X und Y die angegebene Bedeutung haben.Ar means phenyl or naphthyl, each one to three times by fluorine, chlorine, bromine, methyl, hydroxy, methoxy, ethoxy, hydroxysulfonyl, carboxyl, carbamoyl, sulfamoyl, nitro, amino, acetylamino or a radical of the formula S0 2 NH -XS (0) n Y or S (0) n -Y may be substituted, where n, X and Y have the meaning given. Verwendung der Verbindungen gemäß Anspruch 1 zur Herstellung von faserreaktiven Farbstoffen. Use of the compounds according to claim 1 for the production of fiber-reactive dyes.
PCT/EP1997/000616 1996-02-15 1997-02-11 Dicarbamoyl compounds Ceased WO1997030025A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0174909A1 (en) * 1984-08-30 1986-03-19 Ciba-Geigy Ag Reactive dyes, their preparation and their use
EP0414637A1 (en) * 1989-08-23 1991-02-27 Ciba-Geigy Ag Process for the production of aromatic amines
EP0552605A1 (en) * 1992-01-23 1993-07-28 BASF Aktiengesellschaft Mixed oxalic acid diamides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0174909A1 (en) * 1984-08-30 1986-03-19 Ciba-Geigy Ag Reactive dyes, their preparation and their use
EP0414637A1 (en) * 1989-08-23 1991-02-27 Ciba-Geigy Ag Process for the production of aromatic amines
EP0552605A1 (en) * 1992-01-23 1993-07-28 BASF Aktiengesellschaft Mixed oxalic acid diamides

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