Use of heterocyclic compounds as bleach activators or optical lighteners in washing and cleaning agents.

The present invention relates to the use of heterocyclic compounds of the general formula I.<chemistry id="chem0001" num="0001"><img file="EP0502013B1_D0001.tif" /></chemistry> in which the variables have the following meaning<dl id="dl0001"><dt>X</dt><dd>0, S or the grouping N-R³, where R³ is hydrogen, C₁-C₂₅-alkyl; Is C₁-C₂₅ acyl or an aryl group with up to 12 C atoms,</dd><dt>Y</dt><dd>CH or N,</dd><dt>R¹</dt><dd>for X = S or N-R³ Hydrogen, a C₁-C₂₅-alkyl or C₂-C₂₅-alkene group or a phenyl radical, which is additionally substituted by one or two C₁-C₄-alkyl, C₁-C₄ alkoxy, hydroxyl, carboxyl, sulfo, amino , C₁-C₄ acylamino, nitro or cyano groups or chlorine or bromine atoms can be substituted, where two substituents can be the same or different,</dd><dt>R¹</dt><dd>for X = 0 Phenyl, o-, m- or p-tolyl, p-chlorophenyl, m-nitrophenyl, m-methoxyphenyl or m-methylsulfonylphenyl,</dd><dt>R²</dt><dd>for X = s or N-R³ Hydrogen, a C₁-C₄ alkyl, C₁-C₄ alkoxy, hydroxyl, carboxyl, sulfo, amino or C₁-C₄ acylamino group or a chlorine or bromine atom and</dd><dt>R²</dt><dd>for X = 0 hydrogen</dd></dl> as bleach activators or optical brighteners in washing and cleaning agents.

The invention also relates to detergents and cleaning agents which contain the compounds I.

In EP-B 099 197 (1) and EP-B 240 057 (2) the usual bleach activators for detergents and cleaning agents include acylated amines such as tetraacetylethylene diamine (TAED), acylated sugars such as pentaacetyl glucose, carboxylic acid esters such as sodium p- called acetoxybenzenesulfonate and a number of acylated heterocyclic compounds, namely hydantoins, cyclic hydrazides, triazoles, urazoles, imidazolines, glycolurils, piperazines and cyclic ureas.

US Pat. No. 3,822,114 (3) describes aldehyde and ketone compounds as bleach activators. Piperidine derivatives and tetrahydrothiopyranone and 4-oxacyclohexanone derivatives are cited as examples of heterocyclic ketones.

Literature J. Org. Chem. Vol. 14, pp. 967-981 (1949) (4) describes the preparation of benz- (4H) 1,3-oxazin-4-one and derivatives substituted in the 2-position described. Methyl, ethyl, n-propyl, phenyl, o- and p-tolyl, o- and p-chlorophenyl, o- and p-nitrophenyl and 3-pyridyl are mentioned as substituents. No statement is made about the application properties of these compounds.

EP-A 332 294 (5) relates to detergent compositions which contain, inter alia, benz- (4H) 1,3-oxazin-4-ones of the formula I (X = 0, Y = CH, R² = H) as bleach activators, where R¹ represents hydrogen, alkyl, alkaryl, aryl, aralkyl, alkoxyl, haloalkyl, amino, aminoalkyl, carboxyl or a carboxyl-containing group. In the description and the examples only those compounds are mentioned in which R¹ denotes alkyl, in particular methyl, amino, aminoalkyl, acyl, alkoxyl, haloalkyl, alkoxyalkylene ether groups or alkylene carboxylate groups.

The bleach activators of the prior art have proven to be in need of improvement. In particular, the amount of these agents that is necessary to achieve sufficient effectiveness in the detergents and cleaning agents is often too high.

It was therefore an object of the present invention to provide bleach activators which, when used in a smaller amount, have the same effect as the agents of the prior art.

We have found that this object is achieved by using the heterocyclic compounds I mentioned at the outset.

For the case Y = CH, the compounds I to be used according to the invention belong to the substance classes of the benz- (4H) 1,3-oxazin-4-one (X = O), benz- (4H) 1,3-thiazine-4- one (X = S) and (4H) 1,3-quinazolin-4-one (X = N-R³) or to the corresponding pyrido-fused compounds (Y = N).

In a preferred embodiment, benz (4H) 1,3-oxazin-4-one derivatives (Y = CH) are used in which R 1 has the meaning given for the case X = O. The use of 2- (p-tolyl) -, 2- (p-chlorophenyl) -, 2- (m-nitrophenyl) -, 2- (p-methylsulfonylphenyl) - and especially 2-phenyl-benz- (4H) 1,3-oxazin-4-one.

In a further preferred embodiment, benz- (4H) 1,3-thiazin-4-one (Y = CH) and (4H) 1,3-quinazolin-4-one (Y = CH) and their derivatives, in which R¹ and R² have the meanings given for the case X = S or N-R³.

The radicals R³ are C₁-C₂₅ alkyl groups, preferably C₁-C₁₀ alkyl groups, for example methyl, ethyl, n-propyl, n-butyl, 2-ethylhexyl or isononyl, C₁-C₂₅ acyl groups, preferably C₁-C₁₀ acyl groups, for example Formyl, acetyl, propionyl, butyryl or octanoyl, or an aryl group with up to 12 carbon atoms such as naphthyl, biphenyl, tolyl, xylyl or especially phenyl.

In the case of X = S or N-R³ in addition to hydrogen, the following R¹ are to be mentioned:<ul id="ul0001" list-style="dash"><li>C₁-C₂₅ alkyl groups, preferably C₁-C₁₀ alkyl groups, which may be straight-chain or branched, for example methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, 1-ethylpentyl, n-octyl, 2,4,4-trimethylpentyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-pentadecyl and n-heptadecyl</li><li>C₂-C₂₅ alkenyl groups, preferably C₂-C₆ and C₁₅-C₂₁ alkenyl groups, for example vinyl, 1-propenyl, 2-propenyl, heptadec-8-enyl, heptadeca-8,11-dienyl and heptadeca-8,11,14 -trienyl</li><li>a phenyl radical which can additionally carry one or two, preferably one, substituent, for example phenyl, o-, m- or p-tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3, 4- or 3.5 dimethylphenyl, o-, m- or p-ethylphenyl, m- or p-tert-butylphenyl, o-, m- or p-methoxyphenyl, 2,3-, 2,4-, 2, 5-, 2,6-, 3,4- or 3,5-dimethoxyphenyl, o-, m- or p-hydroxyphenyl, 3-hydroxy-4-methoxyphenyl, o-, m- or p-carboxyphenyl, o-, m- or p-sulfophenyl, o-, m- or p-aminophenyl, o-, m- or p-acetaminophenyl, o-, m- or p-nitrophenyl, o-, m- or p-cyanophenyl, o-, m- or p-chlorophenyl and o-, m- or p-bromophenyl.</li></ul>

In the case of X = S or N-R³, in addition to hydrogen, the radicals R² are a C₁-C₄alkyl group, for example methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, a C₁-C₄- Alkoxy group, for example methoxy, ethoxy, n-butoxy or tert-butoxy, a hydroxyl, carboxyl, sulfo, amino or C₁-C₄ acylamino group, for example acetamino, propionylamino or butyrylamino, and a chlorine or bromine atom . These substituents can be in the 5-, 6-, 7- or 8-positions.

Preferred radicals R² are hydrogen, a C₁-C₄-alkyl, C₁-C₄-alkoxy or a hydroxyl group.

The compounds I are outstandingly suitable as bleach activators or as optical brighteners for detergents and cleaning agents, in particular when washing household textiles at temperatures from 30 to 60 ° C. Usually only a third of the amount of I is required as a bleach activator, compared to the usual bleach activators, in order to achieve the same effect with the compounds I as with these.

The present invention furthermore relates to detergents and cleaning agents which contain 0.1 to 10% by weight, preferably 0.5 to 6% by weight, based on the total amount of the preparation, of one or more heterocyclic compounds I.

To improve the bleach activator effect, the detergents and cleaning agents can also contain other conventional bleach activators in the amounts customary for this.

The following are additional bleach activators:<ul id="ul0002" list-style="dash"><li>polyacylated sugars, for example pentaacetyl glucose;</li><li>Acyloxybenzenesulfonic acids and their alkali and alkaline earth metal salts, for example sodium p-isononanoyloxy-benzenesulfonate or sodium p-benzoyloxy-benzenesulfonate;</li><li>N-diacylated and N, N'-tetraacylated amines, for example N, N, N ', N'-tetraacetyl-methylenediamine and -ethylenediamine, N, N-diacetylaniline, N, N-diacetyl-p-toluidine or 1,3- diacylated hydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin;</li></ul>

In addition, there are also additional bleach activators:<ul id="ul0003" list-style="dash"><li>N-alkyl-N-sulfonyl-carbonamides, for example N-methyl-N-mesyl-acetamide or N-methyl-N-mesyl-benzamide;</li><li>N-acylated cyclic hydrazides, acylated triazoles or urazoles, for example monoacetyl-maleic acid hydrazide;</li><li>O, N, N-trisubstituted hydroxylamines, for example O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine or O, N, N-triacetylhydroxylamine;</li><li>N, N'-diacyl-sulfurylamide, for example N, N'-dimethyl-N, N'-diacetyl-sulfurylamide or N, N'-diethyl-N, N'-dipropionyl-sulfurylamide;</li><li>Triacyl cyanurates, for example triacetyl cyanurate or tribenzoyl cyanurate;</li><li>Carboxylic anhydrides, for example benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;</li><li>1,3-diacyl-4,5-diacyloxy-imidazolines, for example 1,3-diacetyl-4,5-diacetoxyimidazoline;</li><li>Tetraacetylglycoluril and tetrapropionylglycoluril;</li><li>diacylated 2,5-diketopiperazines, for example 1,4-diacetyl-2,5-diketopiperazine</li><li>Acylation products of propylene diurea and 2,2-dimethylpropylene diurea, for example tetraacetyl propylene diurea;</li><li>α-acyloxy-polyacyl-malonamides, for example α-acetoxy-N, N'-diacetylmalonamide;</li><li>Diacyl-dioxohexahydro-1,3,5-triazines, e.g. 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine.</li></ul>

Detergent and cleaning agent formulations with the compounds I and, if appropriate, further customary bleach activators generally contain, as additional constituents, based on the total weight of the formulation, 6 to 25% by weight of surfactants, 15 to 50% by weight of builder and, if appropriate, co-builder , 10 to 30% by weight of bleach and 5 to 30% by weight of auxiliaries such as enzymes, foam regulators, corrosion inhibitors, further optical brighteners, fragrances, Dyes or formulation aids such as sodium sulfate in the usual amounts for this. The exact specification of these constituents is known to the person skilled in the art and therefore need not be described in more detail here.

Examples

Use of benz- (4H) 1,3-oxazin-4-ones I as bleach activators in household detergents

Detergent preparations of the composition

<dl id="dl0002"><dt>6.25% by weight</dt><dd>Sodium dodecylbenzenesulfonate</dd><dt>4.7% by weight</dt><dd>ethoxylated C₁₃-C₁₅ oxo alcohol with 7 mol ethylene oxide</dd><dt>2.8% by weight</dt><dd>Tallow soap</dd><dt>1.0% by weight</dt><dd>Carboxymethyl cellulose</dd><dt>2.0% by weight</dt><dd>Copolymer of maleic acid and acrylic acid (weight ratio 30:70, average molecular weight 70,000)</dd><dt>4,5</dt><dd>% By weight sodium disilicate</dd><dt>1,0</dt><dd>% By weight magnesium silicate</dd><dt>25,0</dt><dd>% By weight of zeolite A</dd><dt>10,0</dt><dd>% By weight sodium perborate monohydrate</dd><dt>x% by weight</dt><dd>Bleach activator</dd><dt>(30.75-x) wt%</dt><dd>Sodium sulfate</dd></dl> were examined for their suitability for textile washing. The amount x and the type of bleach activator are given in the table.

8 g / l of wash liquor were used in each case from this test detergent.

The following washing conditions were used:

The Launder-O-meter from Atlas was used as the washing device.

The water hardness of the wash water was 16.8 ° d ≙ 3 mmol Ca²⁺ / 1 (ca²⁺: Mg²⁺ = 3: 1).

The washing time including heating-up time was 30 minutes in each case and the liquor ratio was 1: 12.5.

The following test fabrics were used:<ul id="ul0004" list-style="none"><li>A: Cotton fabric with immediate black as test soiling (test fabric EMPA 115)</li><li>B: Polyester fabric with carotene / cooking oil soiling</li></ul>

The degree of bleaching was determined on the basis of photometric measurement of the reflectance levels of the fabrics before and after washing in Elrepho (Datacolor) from Zeiss at a wavelength of 460 nm (barium white standard according to DIN 5033).

The following relationship applies to the calculation of the degree of bleaching:<maths id="math0001" num=""><math display="block"><mrow><mtext>BG = </mtext><mfrac><mrow><msub><mrow><mtext>F</mtext></mrow><mrow><mtext>v</mtext></mrow></msub><msub><mrow><mtext> - F</mtext></mrow><mrow><mtext>n</mtext></mrow></msub></mrow><mrow><msub><mrow><mtext>F</mtext></mrow><mrow><mtext>v</mtext></mrow></msub><msub><mrow><mtext> - F</mtext></mrow><mrow><mtext>O</mtext></mrow></msub></mrow></mfrac><mtext> x 100</mtext></mrow></math><img file="EP0502013B1_D0002.tif" /></maths> the Kubelka-Munk relationship applies to the color strength F (= dirtiness of the fabric):<maths id="math0002" num=""><math display="block"><mrow><mtext>F = </mtext><mfrac><mrow><mtext>(1-R) ​​²</mtext></mrow><mrow><mtext>2R</mtext></mrow></mfrac></mrow></math><img file="EP0502013B1_D0003.tif" /></maths> mean<dl id="dl0003"><dt>R:</dt><dd>Reflectance (measured variable)</dd><dt>v:</dt><dd>before washing the soiled test fabric</dd><dt>n:</dt><dd>after washing the soiled test fabric</dd><dt>O:</dt><dd>before soiling the fabric.</dd></dl>

The table shows the calculated degrees of bleaching of the test fabrics after a single wash at 20 ° C, 38 ° C or 60 ° C.<tables id="tabl0001" num="0001"><img file="EP0502013B1_D0004.tif" /></tables>