Use of quaternised compounds in dyeing paper.

The invention relates to compounds of general formula I.<chemistry id="chem0001" num="0001"><img file="EP0013751A2_D0001.tif" /></chemistry>in the<ul id="ul0001" list-style="none"><li>A¹ and A² the rest of a quaternized methylene active compound and</li><li>B are a pontic.</li></ul>

The residues of the methylene-active compounds are quaternized heterocyclic residues whose methylene-active group is CH- or CH₂ is. They originate predominantly from the optionally fused pyridinium or pyrylium series or from quaternized benzthiazoles, benzimidazoles, indolenines, quinoxalones or pyrimidones.

The following are examples of the compounds of the formulas A¹H₂ or A²H₂ cited:

<chemistry id="chem0002" num="0002"><img file="EP0013751A2_D0002.tif" /></chemistry><chemistry id="chem0003" num="0003"><img file="EP0013751A2_D0003.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP0013751A2_D0004.tif" /></chemistry><chemistry id="chem0005" num="0005"><img file="EP0013751A2_D0005.tif" /></chemistry><chemistry id="chem0006" num="0006"><img file="EP0013751A2_D0006.tif" /></chemistry><chemistry id="chem0007" num="0007"><img file="EP0013751A2_D0007.tif" /></chemistry><chemistry id="chem0008" num="0008"><img file="EP0013751A2_D0008.tif" /></chemistry><chemistry id="chem0009" num="0009"><img file="EP0013751A2_D0009.tif" /></chemistry>

The bridge members B come from aromatic or heterocyclic bisaldehydes, predominantly the benzene series, which still have common substituents, such as chlorine, methyl, methox^y or can wear ethoxy. Individual residues B are, for example:<chemistry id="chem0010" num="0010"><img file="EP0013751A2_D0010.tif" /></chemistry><chemistry id="chem0011" num="0011"><img file="EP0013751A2_D0011.tif" /></chemistry><chemistry id="chem0012" num="0012"><img file="EP0013751A2_D0012.tif" /></chemistry><chemistry id="chem0013" num="0013"><img file="EP0013751A2_D0013.tif" /></chemistry><chemistry id="chem0014" num="0014"><img file="EP0013751A2_D0014.tif" /></chemistry><chemistry id="chem0015" num="0015"><img file="EP0013751A2_D0015.tif" /></chemistry><chemistry id="chem0016" num="0016"><img file="EP0013751A2_D0016.tif" /></chemistry><chemistry id="chem0017" num="0017"><img file="EP0013751A2_D0017.tif" /></chemistry><chemistry id="chem0018" num="0018"><img file="EP0013751A2_D0018.tif" /></chemistry>and<chemistry id="chem0019" num="0019"><img file="EP0013751A2_D0019.tif" /></chemistry>where RC₁- to C₄-Alkyl, ß-hydroxyethyl, ß-C yanäthyl means or benzyl.

To prepare the compounds of the formula I, compounds of the formula A¹H₂ and A²H₂, which can be the same or different, with bisaldehydes of the formula<chemistry id="chem0020" num="0020"><img file="EP0013751A2_D0020.tif" /></chemistry>implement in a known manner.

Details of the reactions can be found in the examples in which parts and percentages are by weight unless otherwise noted.

The compounds of the formula I are particularly suitable for dyeing sized and unsized papers in bulk, the affinities both for lignin-containing (wood pulp-containing) and lignin-free paper stocks being high. The dyes are largely substantive, the waste water after coloring is colorless to almost colorless. The nuances that can be achieved are between yellow and blue.

Compounds of the formula I in which A¹ and / or A² come from the quinolinium, y -picolinium, indolinium, benzthiazolium and quinoxalonium series and the radicals B correspond to the formulas<chemistry id="chem0021" num="0021"><img file="EP0013751A2_D0021.tif" /></chemistry>correspond, where B¹ represents an alkylene or aralkylene radical and R has the meaning given.

Preferred residues B¹ are for example - (CH₂)_2-6 or<chemistry id="chem0022" num="0022"><img file="EP0013751A2_D0022.tif" /></chemistry>

example 1

<chemistry id="chem0023" num="0023"><img file="EP0013751A2_D0023.tif" /></chemistry>

14.7 parts of diphenylpiperazine dialdehyde and 22 parts of 1,4-dimethylpyridinium methyl sulfate are refluxed in 100 parts of ethylene glycol monomethyl ether in the presence of two parts of piperidine for two hours. After cooling, it is suctioned off and washed with methanol.

Yield: 12 parts

The dye colors paper in the mass orange. The color strength, the brilliance and the very low wastewater color of bleached fabrics are to be emphasized.

Dyes with similarly good properties are obtained with the following methylene-active components. The hue again refers to bleached fabrics.<chemistry id="chem0024" num="0024"><img file="EP0013751A2_D0024.tif" /></chemistry><chemistry id="chem0025" num="0025"><img file="EP0013751A2_D0025.tif" /></chemistry><chemistry id="chem0026" num="0026"><img file="EP0013751A2_D0026.tif" /></chemistry><chemistry id="chem0027" num="0027"><img file="EP0013751A2_D0027.tif" /></chemistry><chemistry id="chem0028" num="0028"><img file="EP0013751A2_D0028.tif" /></chemistry><chemistry id="chem0029" num="0029"><img file="EP0013751A2_D0029.tif" /></chemistry>

Example 2.

<chemistry id="chem0030" num="0030"><img file="EP0013751A2_D0030.tif" /></chemistry>7.5 parts of the aldehyde of the formula<chemistry id="chem0031" num="0031"><img file="EP0013751A2_D0031.tif" /></chemistry>and 3.5 parts of 1,3,3-trimethyl-2-methylene indolenine are heated in 50 parts of 30 percent acetic acid at 100 ° C for one hour. It is diluted with water and precipitated with sodium chloride solution. Yield: 12 parts.

Woody and bleached fabrics are dyed red. Wastewater staining is low.

The above aldehyde is produced as follows: 96 parts of N-ethyl-N-β-dimethylaminoethylaniline are dissolved in 150 parts of acetone, and 44 parts of p-xylylene dichloride, dissolved in acetone, are added dropwise. After refluxing for eight hours, the product is suctioned off in the cold and dried. Yield: 123 parts, mp 220-222 ° C.

56 Parts of the doubled aniline derivative thus obtained are dissolved in 100 parts of dimethylformamide. 31 parts of phosphorus oxychloride are then added dropwise so that a temperature of 70 ° C. is not exceeded. The reaction is completed by heating to 90 ° C. The mixture is worked up by pouring it into water. The cationic bisaldehyde is precipitated with sodium zinc chloride solution. Yield: 46 parts, mp 158-160 ° C.

Good paper dyes are also obtained by using the following heterocyclic methylene bases:<chemistry id="chem0032" num="0032"><img file="EP0013751A2_D0032.tif" /></chemistry><chemistry id="chem0033" num="0033"><img file="EP0013751A2_D0033.tif" /></chemistry><chemistry id="chem0034" num="0034"><img file="EP0013751A2_D0034.tif" /></chemistry><chemistry id="chem0035" num="0035"><img file="EP0013751A2_D0035.tif" /></chemistry><chemistry id="chem0036" num="0036"><img file="EP0013751A2_D0036.tif" /></chemistry><chemistry id="chem0037" num="0037"><img file="EP0013751A2_D0037.tif" /></chemistry><chemistry id="chem0038" num="0038"><img file="EP0013751A2_D0038.tif" /></chemistry>

The quaternization of N-ethyl-N-ß-dimethylaminoethylaniline was also carried out with the following bishalogen compounds:<chemistry id="chem0039" num="0039"><img file="EP0013751A2_D0039.tif" /></chemistry><chemistry id="chem0040" num="0040"><img file="EP0013751A2_D0040.tif" /></chemistry>and<chemistry id="chem0041" num="0041"><img file="EP0013751A2_D0041.tif" /></chemistry>

The dyes made from these intermediates behave similarly to those already described.

This also applies to the products obtained when the N-ethyl-N-ß-dimethylethyl-aniline used was replaced by the following aniline derivatives:<chemistry id="chem0042" num="0042"><img file="EP0013751A2_D0042.tif" /></chemistry><chemistry id="chem0043" num="0043"><img file="EP0013751A2_D0043.tif" /></chemistry><chemistry id="chem0044" num="0044"><img file="EP0013751A2_D0044.tif" /></chemistry><chemistry id="chem0045" num="0045"><img file="EP0013751A2_D0045.tif" /></chemistry><chemistry id="chem0046" num="0046"><img file="EP0013751A2_D0046.tif" /></chemistry>

Example 3

<chemistry id="chem0047" num="0047"><img file="EP0013751A2_D0047.tif" /></chemistry>

5.2 parts of 4,4'-diphenyldialdehyde and 13.8 parts of 2,3-dimethylbenzthiazolium methyl sulfate are kept in 50 parts of ethanol with the addition of one ml of piperidine at 80 ° C. for two hours. You cool down and suction. Yield: 9 parts.

Woody and bleached fabrics are dyed bright golden yellow. Only four or two percent of the dye used remains in the wastewater. The dye is very strong in color.

The corresponding dyes were also obtained with the following components:<chemistry id="chem0048" num="0048"><img file="EP0013751A2_D0048.tif" /></chemistry><chemistry id="chem0049" num="0049"><img file="EP0013751A2_D0049.tif" /></chemistry><chemistry id="chem0050" num="0050"><img file="EP0013751A2_D0050.tif" /></chemistry><chemistry id="chem0051" num="0051"><img file="EP0013751A2_D0051.tif" /></chemistry><chemistry id="chem0052" num="0052"><img file="EP0013751A2_D0052.tif" /></chemistry>

Example 4

<chemistry id="chem0053" num="0053"><img file="EP0013751A2_D0053.tif" /></chemistry>

10.9 parts of 1,4-dimethylpyridinium methyl sulfate and 11.2 parts of the aldehyde of the formula<chemistry id="chem0054" num="0054"><img file="EP0013751A2_D0054.tif" /></chemistry>are boiled for two hours in 100 parts of alcohol in the presence of 0.5 part of piperidine. It is diluted with water and the dye is precipitated by adding zinc chloride. Yield: 19 parts.

Papers containing wood are colored reddish yellow with good wastewater behavior.

The following methylene-active heterocycles were also used:<chemistry id="chem0055" num="0055"><img file="EP0013751A2_D0055.tif" /></chemistry><chemistry id="chem0056" num="0056"><img file="EP0013751A2_D0056.tif" /></chemistry><chemistry id="chem0057" num="0057"><img file="EP0013751A2_D0057.tif" /></chemistry><chemistry id="chem0058" num="0058"><img file="EP0013751A2_D0058.tif" /></chemistry>The following aldehydes were used with similar results: (anion C1 ° in each case)<chemistry id="chem0059" num="0059"><img file="EP0013751A2_D0059.tif" /></chemistry><chemistry id="chem0060" num="0060"><img file="EP0013751A2_D0060.tif" /></chemistry><chemistry id="chem0061" num="0061"><img file="EP0013751A2_D0061.tif" /></chemistry><chemistry id="chem0062" num="0062"><img file="EP0013751A2_D0062.tif" /></chemistry><chemistry id="chem0063" num="0063"><img file="EP0013751A2_D0063.tif" /></chemistry><chemistry id="chem0064" num="0064"><img file="EP0013751A2_D0064.tif" /></chemistry><chemistry id="chem0065" num="0065"><img file="EP0013751A2_D0065.tif" /></chemistry><chemistry id="chem0066" num="0066"><img file="EP0013751A2_D0066.tif" /></chemistry><chemistry id="chem0067" num="0067"><img file="EP0013751A2_D0067.tif" /></chemistry><chemistry id="chem0068" num="0068"><img file="EP0013751A2_D0068.tif" /></chemistry>and<chemistry id="chem0069" num="0069"><img file="EP0013751A2_D0069.tif" /></chemistry>

Example 5

<chemistry id="chem0070" num="0070"><img file="EP0013751A2_D0070.tif" /></chemistry>20 Parts of the aldehyde of the formula<chemistry id="chem0071" num="0071"><img file="EP0013751A2_D0071.tif" /></chemistry>and 31 parts of 1,4-dimethylpyridinium methyl sulfate are stirred in 50 parts of methyl glycol under piperidine catalysis at 120 ° C. for two hours. It is diluted with alcohol and suctioned off.

Yield: 28 parts.

Woody and lignin-free fabrics are dyed orange if the bathroom is well exhausted.

The dyes also provide practically colorless waste water from the following methylene-active components:

<chemistry id="chem0072" num="0072"><img file="EP0013751A2_D0072.tif" /></chemistry><chemistry id="chem0073" num="0073"><img file="EP0013751A2_D0073.tif" /></chemistry><chemistry id="chem0074" num="0074"><img file="EP0013751A2_D0074.tif" /></chemistry><chemistry id="chem0075" num="0075"><img file="EP0013751A2_D0075.tif" /></chemistry><chemistry id="chem0076" num="0076"><img file="EP0013751A2_D0076.tif" /></chemistry><chemistry id="chem0077" num="0077"><img file="EP0013751A2_D0077.tif" /></chemistry><chemistry id="chem0078" num="0078"><img file="EP0013751A2_D0078.tif" /></chemistry><chemistry id="chem0079" num="0079"><img file="EP0013751A2_D0079.tif" /></chemistry><chemistry id="chem0080" num="0080"><img file="EP0013751A2_D0080.tif" /></chemistry><chemistry id="chem0081" num="0081"><img file="EP0013751A2_D0081.tif" /></chemistry><chemistry id="chem0082" num="0082"><img file="EP0013751A2_D0082.tif" /></chemistry><chemistry id="chem0083" num="0083"><img file="EP0013751A2_D0083.tif" /></chemistry><chemistry id="chem0084" num="0084"><img file="EP0013751A2_D0084.tif" /></chemistry><chemistry id="chem0085" num="0085"><img file="EP0013751A2_D0085.tif" /></chemistry><chemistry id="chem0086" num="0086"><img file="EP0013751A2_D0086.tif" /></chemistry><chemistry id="chem0087" num="0087"><img file="EP0013751A2_D0087.tif" /></chemistry><chemistry id="chem0088" num="0088"><img file="EP0013751A2_D0088.tif" /></chemistry><chemistry id="chem0089" num="0089"><img file="EP0013751A2_D0089.tif" /></chemistry><chemistry id="chem0090" num="0090"><img file="EP0013751A2_D0090.tif" /></chemistry>

Also very good wastewater-resistant paper dyes with high brilliance are obtained with the following aldehydes:<chemistry id="chem0091" num="0091"><img file="EP0013751A2_D0091.tif" /></chemistry><chemistry id="chem0092" num="0092"><img file="EP0013751A2_D0092.tif" /></chemistry><chemistry id="chem0093" num="0093"><img file="EP0013751A2_D0093.tif" /></chemistry><chemistry id="chem0094" num="0094"><img file="EP0013751A2_D0094.tif" /></chemistry><chemistry id="chem0095" num="0095"><img file="EP0013751A2_D0095.tif" /></chemistry><chemistry id="chem0096" num="0096"><img file="EP0013751A2_D0096.tif" /></chemistry><chemistry id="chem0097" num="0097"><img file="EP0013751A2_D0097.tif" /></chemistry>and<chemistry id="chem0098" num="0098"><img file="EP0013751A2_D0098.tif" /></chemistry>