MXPA98010234A - Use of triazine-based grapes to be used as neutralizers in processes for elaboration ofpa - Google Patents
Use of triazine-based grapes to be used as neutralizers in processes for elaboration ofpaInfo
- Publication number
- MXPA98010234A MXPA98010234A MXPA/A/1998/010234A MX9810234A MXPA98010234A MX PA98010234 A MXPA98010234 A MX PA98010234A MX 9810234 A MX9810234 A MX 9810234A MX PA98010234 A MXPA98010234 A MX PA98010234A
- Authority
- MX
- Mexico
- Prior art keywords
- formula
- compound
- optionally substituted
- carbon atoms
- process according
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 32
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- 241000219094 Vitaceae Species 0.000 title 1
- 235000021021 grapes Nutrition 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 86
- -1 triazine compound Chemical class 0.000 claims abstract description 39
- 239000006081 fluorescent whitening agent Substances 0.000 claims abstract description 13
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- 230000000694 effects Effects 0.000 claims abstract description 7
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- 230000002401 inhibitory effect Effects 0.000 claims abstract description 3
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- 239000001257 hydrogen Substances 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
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- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000000539 amino acid group Chemical group 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical group 0.000 claims description 13
- XOAAWQZATWQOTB-UHFFFAOYSA-N Taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims description 12
- 230000003472 neutralizing Effects 0.000 claims description 12
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- HBDWQSHEVMSFGY-UHFFFAOYSA-N 2-azaniumyl-4,5-dihydroxy-5-oxopentanoate Chemical compound OC(=O)C(N)CC(O)C(O)=O HBDWQSHEVMSFGY-UHFFFAOYSA-N 0.000 claims description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
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- QIVBCDIJIAJPQS-SECBINFHSA-N D-tryptophane Chemical compound C1=CC=C2C(C[C@@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-SECBINFHSA-N 0.000 claims description 2
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- NYPYHUZRZVSYKL-ZETCQYMHSA-N Diiodotyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC(I)=C(O)C(I)=C1 NYPYHUZRZVSYKL-ZETCQYMHSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- SNDPXSYFESPGGJ-BYPYZUCNSA-N L-2-aminopentanoic acid zwitterion Chemical compound CCC[C@H](N)C(O)=O SNDPXSYFESPGGJ-BYPYZUCNSA-N 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 2
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 2
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- AHLPHDHHMVZTML-BYPYZUCNSA-N L-ornithine Chemical compound NCCC[C@H](N)C(O)=O AHLPHDHHMVZTML-BYPYZUCNSA-N 0.000 claims description 2
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 2
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 2
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims description 2
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- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
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- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
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- 230000001264 neutralization Effects 0.000 abstract description 5
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- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000005227 red mallee Nutrition 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- PMMYEEVYMWASQN-DMTCNVIQSA-N trans-L-hydroxyproline Chemical compound O[C@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-DMTCNVIQSA-N 0.000 description 1
- 229940029612 triethanolamine Drugs 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon(0) Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to: providing a method for the inhibition (neutralization) of the effect of anionic fluorescent whitening agents on a substrate, which comprises treating the substrate with a UVA triazine compound, some of which are new compounds
Description
USE OF TRIAZINE-BASED GRAPES FOR USING AS NEUTRALIZERS IN PROCESSES FOR PROCESSING PAPER The present invention relates to a process- to inhibit (neutralize) the effect of fluorescent whitening agents on substrates, especially on fiber materials, when treating substrates. with certain ultra-violet absorption agents based on triazine (UVAs) -some of which are novel compounds. The fluorescent whitening effect exerted by the fluorescent whitening agents in the fiber materials treated with said agents, provides an aesthetically pleasing and valuable bleaching improvement in the appearance of the fiber materials thus treated. Particularly in the paper itry, however, there are situations in which the fluorescent whitening effect exerted by the agents can lead to problems. For example, many paper producing machines are required to produce, alternatively, bleached and unbleached paper. Problems arise when after the machine has been used to produce bleached paper, it is subsequently required for the production of unbleached paper. Under these circumstances, residual fluorescent whitening agent from the production of bleached agent remains in the machine parts and contaminates the paper obtained in the subsequent production of unbleached paper.
It is possible, of course, to completely clean the
'paper machine and its associated recycling systems every. once it has been used to produce bleached paper and then it will immediately be used to produce unbleached paper. This complete cleaning is expensive, however it deteriorates the production capacity. It has already been proposed in DE-A-2 448 293 to apply a neutralizing compound to paper material, which is not bleached before or after the formation of the sheets. These neutralizing compounds have been suggested to add to bleached waste paper from which unbleached paper is going to be produced. The neutralizing compounds used in DE-A-2 448 293 are water-soluble acid addition salts or quaternary ammonium salts of the compounds containing a group of the formula:
wherein the substituents on the phenyl nucleus are in the m- or p- position among themselves. Most of the processes for modern paper production, however, are operated under neutral pH conditions and the compounds of DE-A-2 448 293 are unsatisfactory for this use, since they only partially absorb in the fiber under neutral application conditions. . As a consequence, a non-absorbent neutralizing compound is undesirably-discharged into the waste water. Still further, the compounds of DE-A-448 293 tend to flocculate, which is disadvantageous for use in the "wet end" (paper forming) part of the papermaking process. Surprisingly, it has been found that ultra-violet triazine-based absorbers (UVAs), when used as neutralizers in paper production processes, provide better absorption in the fiber, less pollution of waste water and less influence on stability of dispersion (less tendency to flocculate) with respect to the compounds of DE-A-2 448 293. Accordingly, the present invention provides a method for inhibition
(neutralization) of the effect of anionic fluorescent whitening agents on a substrate, which comprises treating the substrate with a triazine UVA compound. A preferred class of triazine UV absorbers is one that has the formula:
where at least one of Rl? R2 and R3 is a radical of the formula
wherein R 4, R 5 and R 6 independently are hydrogen, alkoxy with 1 to 12 carbon atoms; hydroxy; -0-CH2-CO-NH-CH2OH; S03 wherein M is hydrogen, sodium, potassium, ammonium, mono-, di-, tri- or tetra-alkyl having 1 to 4 carbon-ammonium atoms, mono-, di- or tri-hydroxyalkyl with 1 to 4 carbon atoms; carbon-ammonium or ammonium which is di- or tri-substituted by a mixture of alkyl groups with 1 to 4 carbon atoms or hydroxyalkyl with 1 to 4 carbon atoms; or
-O- (CH2) n-N - Y2,? X where n is an integer of 2
to 6 and preferably 2 or 3; Yt and Y2 independently are alkyl with 1 to 4 carbon atoms optionally substituted by halogen, cyano, hydroxy or alkoxy with 1 to 4 carbon atoms, or Yx and Y2 together with the nitrogen atom to which they are bound form a heterocyclic ring of 5 to 7 members, preferably a ring morpholine, pyrrolidine, piperidine or hexamethyleneimine, - Y3 is hydrogen, alkenyl with 3 to 4 carbon atoms or alkyl with 1 to 4 carbon atoms optionally substituted by cyano, hydroxy or alkoxy with 1 to 4 carbon atoms or Y1 (Y2 and Y3 joined with the nitrogen atom to which they connect, form a pyridine or picoline ring, and X1 ~ is a colorless anion, preferably CH3OSO3"or C2HsOS03 -" and the substituent (s) R.sup.1, R.sup.2 and R.sup.3 are independently halogen, preferably chlorine, alkoxy with 1 to 12 carbon atoms or phenyl, the phenyl substituent is optionally substituted by one or more of hydroxy, alkoxy with 1 to 12 carbon atoms, -0- CH2- CO-NH-C H2OH, S03M where M has its previous meanings. In the compounds of the formula (1), the alkyl groups with 1 to 4 carbon atoms, Yl7 Y2 and Y3 can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertbutyl, methyl and ethyl are preferred . Alkoxy groups with 1 to 12 carbon atoms Rl t R2, R3,
R4, Rs and R6 may for example be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-amyloxy, n-hexoxy, n-heptoxy, n-octoxy, isooctoxy, n-nonoxy , n-decoxy, n-undecoxy or n-dodecoxy, methoxy and ethoxy are preferred. Alkyl radicals in the mono-, di-, tri- or tetra-alkyl groups with 1 to 4 carbon atoms-ammonium M are preferably methyl. Mono-, di- or tri-hydroxyalkyl groups with 1 to 4 carbon atoms-monium M, preferably those derived from ethanolamine, di-ethanolamine or tri-ethanolamine. When M is ammonium it is di-, or tri-substituted by a mixture of alkyl groups with 1 to 4 carbon atoms or hydroxyalkyl with 1 to 4 carbon atoms, preferably it is N-methyl-N-ethanolamine or N, N -dimethyl-N-ethanolamine. M preferably, however, is hydrogen or sodium. Preferred compounds of formula (1) are those having the formulas:
) 2 The compounds of the formula (1) are known and can be prepared, for example, by the method described in the U.S. Pat. Nos. 3118887 and 5197991. A second preferred class of triazine UVAs is one that has the formula: halogen
wherein M has its previous meaning and R7 and R8 are alkoxy with 1 to 12 carbon atoms or S03M wherein M has its previous meaning. Preferably, halogen is chlorine. Alkoxy groups with 1 to 12 carbon atoms, RT and R8 can be for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-amyloxy, n-hexoxy, n-heptoxy, n -octoxy, isooctoxy, n-nonoxy, n-decoxy, n-undecoxy or n-dodecoxy, methoxy and ethoxy are preferred. A preferred compound of the formula (2) is that which has the formula:
The compounds of the formula (2) are known and can be prepared, for example, by the method described in U.S. Pat. Nos. 3118887 and 5197991. A third preferred class of triazine UVAs is one that has the formula:
where M has the previous meaning; ? and n2 independently are O or l, provided that if x is 0, n2 is 0;
R9 is optionally substituted aryl or a group having the formula:
wherein Rn is optionally substituted alkyl or optionally substituted aryl; or when n2 is 0, R9 can also be a group having one of the formulas:
where Rn has the previous meaning;
wherein R12 is M, optionally substituted alkyl or optionally substituted aryl;
where R12 has the previous meaning, -
wherein R13 is hydrogen, optionally substituted alkyl or optionally substituted aryl, - and R10 is hydrogen, halogen, preferably chloro, optionally substituted alkyl, optionally substituted aryl, / \ -N O, -OH,
-NH2, -N (CH2CH2OH) 2, -N [CH2CH (OH) CH3] 2, -NH-R12, -N (R12) 2 or -OR12 wherein R12 has the prior meaning, or R10 is an amino acid residue from which a hydrogen atom in the amino group has been removed.
When one or more of R10 / u, R12 and R13 is optionally substituted alkyl, preferred optionally substituted alkyl groups R10, Rn / R12 and Ri3 are alkyl groups with
1 to 12 carbon atoms, especially 1 to 4 carbon atoms. The alkyl groups may be branched or unbranched and may be optionally substituted, for example by halogen such as fluorine, chlorine or bromine, by alkoxy with 1 to 4 carbon atoms, such as methoxy or ethoxy, by phenyl or carboxyl, by alkoxycarbonyl with 1 to 4 carbon atoms, such as acetyl, for a mono- or di-alkylated amino group with 1 to 4 carbon atoms or for -S03M, wherein M has the previous meaning. When one or more of R10, Ru, Ri2 and 33 are optionally substituted aryl, preferably they are a phenyl or naphthyl group which may be substituted by alkyl with 1 to 4 carbon aromos, for example by methyl, ethyl, propyl, isopropyl , butyl, isobutyl, sec-butyl or tert-butyl, by alkoxy with 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy or tert-butoxy, by halogen such as fluorine , chlorine or bromine, by alkanoylamino with 2 to 5 carbon atoms such as acetylamino, propionylamino or butyrylamino, by nitro, sulfo or by amino di-alkyl with 1 to 4 carbon atoms. Preferably, each of the amino acid residues R10 is the same. Examples of preferred amino acid residues R10 include those having the formula -NH-CH (C02H) -R14, wherein R14 is hydrogen or a group 'having the formula -CHR15R16 wherein R15 and R6 are independently hydrogen or alkyl with 1 to 4 carbon atoms, optionally substituted by one or two substituents selected from hydroxy, thio, methylthio, amino, carboxy, sulfo, phenyl, 4-hydroxyphenyl, 3,5, iodo-4-hydroxyphenyl, β-indolyl, β -imidazolyl and NH = C (NH2) NH-. Specific examples of amino acids from which these preferred Rio amino acid residues are derived, include glycine, alanine, sarcosine, serine, cysteine, phenylalanine, tyrosine (4-hydroxyphenylalanine), diiodotyrosine, tryptophan (β-indolilalanine), histidine (β -imidazolylalanine), α-aminobutyric acid, methionine, valine (aminoisovaleric acid), norvaline, leucine (c-amino-n-caproic acid), arginine, ornithine (a, delta-diaminovaleric acid), lysine (acid, e- diaminocaproic), aspartic acid (aminosuccinic acid), glutamic acid (α-aminoglutaric acid), threonine, hydroxyglutamic acid and taurine, as well as mixtures and optical isomers thereof. Of these amino acids from which the preferred amino acid residues R10 is derived, glutamic acid and aspartic acid are particularly preferred. A further preferred example of an amino acid from which an amino acid residue R10 can be derived is iminodiacetic acid.
Other less preferred examples of amino acids from which the amino acid residues R10 - can be derived include cysteine, lanthionine, proline and hydroxyproline. "In each of the compounds of the formula (3) it is preferred that it be used in a neutral form, to say that M is different from hydrogen, preferably a cation formed of an alkali metal, in particular sodium or an amine In the compounds of the formula (3), preferably Rg is phenyl, methylphenyl, dimethylphenyl or a group of the formula:
wherein R1X has the above meaning and is preferably alkyl having 1 to 4 carbon atoms, especially methyl or ethyl, - and preferably R10 is phenyl, tnenylphenyl, dimethylphenyl, / / \, -NH2, Cl, N0 \ /
N (CH2CH2OH) 2 or -N [CH2CH (OH) CH3] 2. Preferred compounds of formula (3) are those having the formula:
The compounds of the formula (3) can be produced by reacting, under known reaction conditions, cyanuric chloride, successively in any desired sequence with each of aminoestilbenesulfonic acid, an amino compound capable of introducing a group R9 and a compound capable of introducing a group R10, wherein R9 and R10 each have their previous meanings. Asymmetric compounds of the formula (3) that is to say those where n2 is zero, can be produced by the method described in GB-A-2, 298, 22. The starting materials are known compounds that are readily available. The majority of the compounds of the formula (3) are known. Those compounds of the formula (3), however, wherein R9 is optionally substituted aryl and R10, M, t and n2 have their prior meaning, are considered new compounds and as such form a further aspect of the present invention. The new compounds of the formula (3) can be produced from cyanuric chloride, as described above, but are preferably produced by using the appropriate intermediate selected from 2-chloro-4,6-diphenyl-1,3,5- triazine [produced according to the method of A. Ostrogovich; Chemi er Ztg. 36 (1912) 739], 2-amino-4-chloro-6-phenyl-1,3,5-triazine [produced according to the method described by HK Reimschuessel, NTMcDevitt, - J. Am. Chem. Soc. 82 (1960) 3756-3762] or the novel intermediate 2-chloro-4-N-orpholino-6-phenyl-1,3,5-triazine. This latter novel intermediate can be obtained by reacting 2,4-dichloro-6-phenyl-1,3,5-triazine with morpholine under known reaction conditions.
The ultra-violet triazine-based absorbent agents used as neutralizing compounds according to the process of the present invention, are preferably used in an amount in the range of 0.5 to 50 times the amount of fluorescent whitening agent present in the substrate to try. The following Examples are further illustrated in the present invention. Examples 1 to 5 5 G of dry sulphite pulp, consisting of a 1: 1 mixture of bleached berry wood fibers and bleached spruce fibers (Schopper-Riegler), are suspended in 150 ml of water, 5% a calcium carbonate filler is then added to the fiber suspension, followed by 0.2% active substance, each based on fiber weight, of the fluorescent whitening agent having the formula:
(like the salt diethanolamine). The mixture is then stirred at room temperature for 15 minutes. 25 ml of a solution, in a mixture of dimethylsulfoxide / water (20:80) of one of the following neutralizer test compounds are then added to give respective pulp suspensions containing .0.2% by weight, based on the weight of pulp, of the test neutralizing compound:
The respective test neutralizing compounds are then stirred for an additional 15 minutes at room temperature to allow them to exert their effect. Sheets of paper are then formed from the respective suspensions (diluted to a consistency of 0.2% with 10 ° German hardness water) using a Rapid-Kothen apparatus. After drying the finished paper sheet for 15 minutes, a dry paper sheet has a weight per unit area of 160 g / m2. For the purpose of comparison, a sheet of paper is produced in the same manner from the basic pulp suspension containing the fluorescent whitening agent but without the test neutralizing compound.
24 Hours after the production of paper sheets? respectively, Ganz whiteness and fluorescence (ISO) were determined using the Spektaflash device. The Ganz method is described in detail in Ciba-Geigy Review 1973/1, and also the article "Whiteness Measurement", ISCC Conference on Fluorescence and Fluorescence Materials Colorimetry, illiamsburg, February 1972, published in the Journal of Color and Appearance (Magazine of Color and Appearance), 1, No. 5 (1972). The results obtained are established in the following Table. Table
The results in the Table indicate the significant reduction in whiteness and fluorescence of paper treated with a compound according to the present invention.
In emplo 6
4. 32 g of 4,4'-diaminostilben-2, 2'-disulfonic acid are stirred in 200 ml of dimethylformamide and heated to 55 ° C. Then 4.32 g 'of 2-chloro-4,6-diphenyl-1,3,5-triazine [produced according to the method of A. Ostrogovich;
Chemiker Ztg. 36 (1912) 739] and 2.27 g of sodium carbonate and the resulting mixture is heated at 105-110 ° C for 28 hours.
After cooling, the yellow suspension thus obtained is rotated, boiled with 150 ml of a mixture of methanol / methylethyl ketone / water, allowed to cool and filtered. After drying under vacuum, 5.45 g of a yellow powder of the formula are obtained
(106) characterized as follows: lambdamax 370 nm / e 54000 (DMF): ^ -RMN (DMSO-d6): d (in ppm) = 10.42 (s, 2H, NH-), 8.75 (d, 2H, aromatic) , 8.65 (d, 8H, aromatic), 8.14 (s, 2H, -CH = CH-),
7. 89 (dd, 2H, aromatic), 7.71 (d, 2H, aromatic), 7.68-7.56
(m, 12H, aromatic). Example 7 Using a procedure analogous to that described in
Example 6, the compound of the formula (107) is obtained and characterized as follows: lambdamax 370 nm / e 52900 (DMF): ^ -RMN (DMS0-d6): d (in ppm) = 10.42 (s, 2H, NH-), 8.76 (d, 2H, aromatic), 8.55 (d, 8H, aromatic), 8.14 (s, 2H, -CH = CH-), 7.85 (dd, 2H, aromatic), 7.70 (d, 2H, aromatic), 7.43 (d, 8H, aromatic), 2.45 (s, 12H, -CH3). Example 8
Using a procedure analogous to that described in Example 6, the compound of formula (108) is obtained and characterized as follows: lambdamax 364 nm / e 52900 (DMF): aH-NMR (DMSO-d6). : d (in ppm) = 10.31 (s, 2H, NH-) ", 8.33 id, 2H, aromatic), 8.O8 (s, 2H, -CH = CH-)," 8.02 (d, 4H, aromatic) , 7.90 (dd, 2H, aromatic), 7.63 (d, 2H, aromatic), 7.21 (d, 4H, aromatic), 7.18 (s, 4H, aromatic). 2.66 (s, 12H, -CH3), 2.36 (s, 12H, -CH3). Example 9
A) 15.82 g of 2,4-dichloro-6-phenyl-1,3,5-triazine are stirred at 20 ° C in 200 ml of acetone and treated with 6.2 ml of morpholine and 9.4 ml of collidine. The mixture is stirred for 6 hours, constitutes up to 1000 ml with cold water and acidified with concentrated HCl. After stirring for 20 minutes, the suspension is filtered with suction, washed with deionized water and dried over phosphorus pentoxide. In this manner, 18.21 g of a beige powder having the formula (109A) are obtained and characterized as follows: XH-NMR (acetone-dg); d (in ppm) = 8.41 (d, 2H, aromatic), 7.62 (t, 1H, aromatic, 7.52 (t, 2H, aromatic), 4.05 (t, 2H, -CH2-), 3.87 (t, 2H, - CH2-), 3.80-3.72 (m, 4H, -CH2-).
B) Using a procedure analogous to that described in Example 6, the compound of the formula (109A) is reacted with 4,4'-diaminostilben-2, 2'-disulfonic acid and the compound of the formula (103) is obtained and it is characterized as follows: lambdamax 363 nm / e 55557 (DMF / water): '? -RMN (D20): d (in ppm) = 8.56 (s, 2H, aromatic), 8.27 (d, 4H, aromatic), 7.84 (s, 2H, -CH = CH-), 7.73 (d, 2H, aromatic), 7.63 (t, 2H, aromatic), 7.59-7.48 (m, 6H, aromatic), 3.89 (s, 8H, -CH2- ), 3.80 (s, 8H, -CH2-). 10
Using a procedure analogous to that described in
Example 6, 2-amino-4-chloro-6-phenyl-1,3,5-triazine [produced according to the method described by H. K. Reimschuessel, N. T.
McDevitt; A. Am. Chem. Soc. 82 (1960) 3756-3762] is reacted with 4,4'-diaminostilben-2, 2'-disulfonic acid and the compound of the formula (110) is obtained and characterized as follows : lambdamax 360 nm / e 45366 (DMF / water): XH-NMR (MeOH-d4) ^: d (in ppm) = 8.65 (s, 2H, aromatic), 8.47 (d, 4H, aromatic), 8.17 (s) , 2H, -CH = CH-), 7.96 (d, 2H, aromatic), 7.85 (dd, 2H, aromatic), 7.63-7.52 (m, 6H, aromatic). Example 11
1. 2 g of 4-aminoacetophenone are dissolved in 30 ml of methyl cellosolve. To this solution, 3.3 g of the compound (91% purity) having the formula are added:
The reaction mixture is heated to 130 ° C, in an oil bath and kept at this temperature for 4 hours.
After a short time, the free acid version of the salt compound (111) crystallizes. After filtration with suction, the filter cake, dissolved in methanol, is converted into the disodium salt of the formula (111) using sodium methylate. After filtration with suction, washing with water and drying, 4.0 g (91% theory) of the disodium salt of the formula (111) are obtained. Elemental analysis of the compound that has the formula
(111) and that has the empirical formula C48H38N12Na208S2. 11.0 H20 gives: Req. % C 47.29; H 4.96; N 13.78; S 5.26; H20 16.24.
Found: C 47.05; H 4.96; N 13.87; S 5.28; H20 15.99.
Example 12 18.81 g of cyanuric chloride (98% purity) are dissolved in 95 ml of acetone and added to 100 g of a mixture of ice and water. For 30 minutes, a solution of 18.5 g of diaminostylben-di-sulfonic acid (100% pure) per drop is added in 320 g of a mixture of ice and water at a temperature in the range of -5 ° C to 0 ° C. C. Finally, for 15 minutes, 50 ml of a 1 molar solution of soda are added dropwise at this temperature and everything is stirred for an additional 1 hour. 13.5 g of 4-aminoacetophenone are added and the mixture is heated at 50CC for 90 minutes. During this procedure, the pH of the reaction mixture is maintained at 7-8 by the addition of sodium carbonate. In order to complete the reaction, the acetone is distilled off until the temperature of the reaction mixture has reached 66 ° C. The precipitated deposit is filtered with suction, washed with dilute aqueous sodium chloride (2%) and then with 300 ml of cold water. After "drying," there remain 44.8 g (88% theory) of the compound of the formula (101). Elemental analysis of the compound having the formula (101) and having the empirical formula C36H26N10O8Cl2S2Na2. 6.0 H20 gives: Req. % C 42.57; H 3.77; N 13.79. Found: C 42.59; H 3.85; N 13.74. Example 13
g of the compound of the formula (101) obtained from Example 12 is suspended in 100 ml of water. 1.3 g of taurine are added and the reaction mixture is heated to 90 ° C, and the pH is maintained at 9-10 using sodium carbonate. The reagents are allowed to react more at this pH and temperature for 15 hours. Finally, the reaction mixture is concentrated and the compound (113) is precipitated with acetone. After filtration with suction, washing with acetone and drying, 5.9 g (81% theory) of the compound (113) remain.
Elemental analysis of the compound having the formula (101) and having the "empirical formula C40H36N12Na4014S4 0.66 NaCl 16.5 H2O gives: Req.% C 32.8; H 4.74;? 11.47; S 8.75; Cl 1.60;? To 7.32 Found : C 32.7; H 4.7;? 12.5; S 9.1; Cl 1.6;? A 7.4.Example 14
Using a procedure analogous to that described in
Example 13, compound (114) is produced by reacting compound (101) with 0.9 g of sarcosine instead of taurine. The reaction is complete after 6 hours and the yield of the compound (114) is 93% theory. Elemental analysis of the compound that has the formula
(114) and having the empirical formula C42H36? 12? A012S2 15 H20 gives: Req. % C 38.02; H 5.01; ? 12.66. Found: C 38.10; H 4.87; ? 12.65. Example 15 Using a procedure analogous to that described in
Example 13, compound (115) is produced by reacting compound
(101) with N-methyl-ethanolamine instead of taurine. The reaction is complete after 6.5 hours and the yield of the compound (115) is 81% theory. The material analyzed was partially present as the N-methyl-ethanolamine salt. Elemental analysis of the compound having the formula (115) and having the empirical formula C42H42N12Na2O10S2. 0.6 N-methyl-ethanolamine. 5 H20 gives: Req. % C 47.0; H 5.02; N 15.78; S 5.73. Found: C 46.75; H 4.92; N 15.46; S 5.71. Example 16 10 g of the compound of the formula (101) are reacted with 5.8 g of L-glutamic acid in a 6: 9 by weight mixture of water and methyl cellosolve at 120 ° C. In an oil bath, the pH is maintained at 8-9 by the addition of sodium carbonate. After 6 hours, the reaction is complete. The reaction mixture is added dropwise in acetone acidified with HCl, whereby the compound of formula (116) precipitates as the free acid. After filtration with suction and washing with acetone-water, the filter cake is converted to the corresponding hexa-sodium salt by adding the calculated amount of aqueous sodium hydroxide and evaporating to dryness. The yield is 90% theory. Elemental analysis of the compound having the formula (116) and having the empirical formula C46H38N12Na6O10S2. 0.3 NaCl. 17 H20 gives: Req. % C 35.9; H 4.71; N 10.92; S 4.16.
Found: C 36.0; H 4.7; N 10.9; S 4.1 Example 17
The compound of formula (117) is obtained in a 87% yield of the theory by using the procedure described in Example 16, except that L-glutamic acid is replaced by iminodiacetic acid. Elemental analysis of the compound having the formula (117) and having the empirical formula C44H34N12Naa016S2. 0.8 NaCl. 15 H20 gives: Req. % C 35.1; H 4.28; N 11.16; S 4.26. Found: C 35.0; H 4.3; N 11.2; S 4.4. Examples 18 to 26 The activity of neutralizers of various triazine-based UVAs used in accordance with the present invention is investigated as follows. The fiber suspension employed is an industrially produced suspension consisting predominantly of eucalyptus pulp taken from the pulp circulating in a papermaking machine. Since the suspension of test fibers contains only a minor amount of fluorescent whitening agent, 0.1 wt.% Of active substance of a fluorescent whitening agent is added to the fiber suspension commercial paper based on a tetrasulphoestilbene substitute. 24 hr more, to allow the added fluorescent whitening agent to exert its effect, the neutralizing compound is added > test at a level of 0.8% by weight of active substance, to the fiber suspension in a consistency of 1% by weight. After 15 minutes of depletion time, a sheet of paper is formed using the Rapid Kothen system and the sheet is dried. The dried leaf is then exposed to xenon light (Spektraflash SF 500) and the fluorescence of the sheet is determined, first using a UV light barrier filter (420 nm) and then without the use of a UV light barrier filter. The difference between the two measurements at 440 nm is designated as the fluorescence (F 440). The test neutralizing compounds have the formula:
The test results obtained used in the compounds having various substituents R, are set forth in the following Table. Table Example t RF 440 control (without neutralizer) 31 18 NH 2 (compound 104) 9 19 anilino (NH-phenyl) (compound 111) 10 20 NH- (CH 2) 2-0CH 3 9 21 0- (CH 2) 2 -CH 3 18 22 NH- (CH 2) 5 -COOH 12 23 N (CH 3) (CH 2 COOH) (compound 114) 11 24 NH- (CH 2) 2 -SO 3 H (compound 113) 12 N (CH 3) - (CH 2) 2 -OH ( compound 115) 10 26 N (2H5) - (CH2) 2-OH 11 Since the higher the value of F 440, the greater the fluorescence, it will be noted that the test compounds significantly reduce (neutralize) the fluorescence with respect to the experiment of control .
Claims (31)
- CLAIMS 1. A process for al-inhibiting (neutralizing) the effect of anionic fluorescent whitening agents on a substrate, characterized in that it comprises treating the substrate as a triazine UVA compound.
- 2. A process according to claim 1, characterized in that the triazine UVA compound is a compound having the formula:where at least one of • R1; R2 and R3 is a radical of the formula:wherein R 4, R 5 and R 6, independently are hydrogen; C 1 -C 12 alkoxy, -hydroxy; -0-CH2-CO-NH-CH2OH; S03M wherein M is hydrogen, sodium, potassium, ammonium, mono-, di-, tri- or tetra-alkyl having 1 to 4 carbon atoms ammonium, mono-, di- or tri-hydroxyalkyl with 1 to 4 carbon atoms ammonium or ammonium which is di- or tri-substituted by "a mixture of alkyl groups with 1 to 4 carbon atoms or hydroxyalkyl with 1 to 4 carbon atoms, - orO (CH) n- + A- < Y2 Xi where n is an integer from 2 to 6, - \ Y.Y x and Y 2 are independently C 1 -C 4 -alkyl optionally substituted by halogen, cyano, hydroxy or alkoxy with 1 to 4 carbon atoms or Y x and Y 2 together with the nitrogen atom to which they are bound, each forming a 5-7 membered heterocyclic ring; Y3 is hydrogen, alkenyl with3 to 4 carbon atoms or alkyl with 1 to 4 carbon atoms optionally substituted by cyano, hydroxy or alkoxy with 1 to4 carbon atoms or Y1; Y2 and Y3, together with the nitrogen atom to which they are bound form a pyridine or picoline ring; and Xx ~ is a colorless anion, - and the substituent (s) Rx, R2 and R3 are independently halogen, alkoxy with 1 to 2 carbon atoms or phenyl, the phenyl substituent is optionally substituted by one or more of hydroxy, alkoxy with 1 to 12 carbon atoms, -0-CH2-CO-NH-CH2-OH, S03M where M has the previous meaning.
- 3. A process according to claim 2, characterized in that n is 2 or 3.
- 4. A process according to claim 3, characterized in that Y-, e Y2, together with the nitrogen atom to which they are connected form a ring morpholine, pyrrolidine, piperidine or hexamethyleneimine.
- 5. A process according to any of claims 2 to 4, characterized in that Xx "is CH3OS03" or C2H5OS03. "
- 6. A process according to any of claims 2 to 4, characterized in that the remaining substituents Rx, R2 and R3 are each independently chloro
- 7. A process according to claim 2, characterized in that the compound of the formula (1) has the formula:s) 2
- 8. A process according to claim 1, characterized in that the UVA triazine compound is a compound having the formula: halogenwherein M is as defined in claim 2, and R7 and R8 are alkoxy with 1 to 12 carbon atoms or S03M wherein M is as defined in claim 2.
- 9. A process according to claim 8, characterized in that halogen is chlorine.
- 10. A process according to any of claims 8 or 9, characterized in that a compound of the formula (2) has the formula:
- 11. A process according to claim 1, characterized in that the UVA triazine compound is a compound having the formula: wherein M is as defined in claim 2, - nx and n2 independently are. O or l, provided that if nx is 0, n2 is 0; R9 is optionally substituted aryl or a group having the formula:wherein Rxx is optionally substituted alkyl or optionally substituted aryl; or when n2 is 0, R9 can also be a group having one of the formulas:wherein RX1 is optionally substituted alkyl or optionally substituted aryl, -wherein R x 2 is M, optionally substituted alkyl or optionally substituted aryl; -..-where Rx2 has the previous meaning, -wherein R x 3 is hydrogen, optionally substituted alkyl or optionally substituted aryl; and R x0 is hydrogen, halogen, optionally substituted alkenyl or optionally substituted aryl;-DO NOT . -OH,-NH ,, -N (CH2CH2OH) 2, -N [CH2CH (OH) CH3] 2, -NH-R12, -N (R12) 2 or -OR12, wherein R12 has its previous meaning, or R10 is a residue amino acid from which a hydrogen atom in the amino group is removed.
- 12. A process according to claim 11, characterized in that Rxo is an amino acid residue having the formula -NH-CH (C02H) -RX4 wherein R14 is hydrogen or a group having the formula -CHR15R16 wherein R15 and RX6 are independently hydrogen or alkyl having 1 to 4 carbon atoms, optionally substituted by one or two substituents selected from hydroxy, thio, methylthio, amino, carboxy, sulfo, phenyl, 4-hydroxyphenyl, 3,5-diiodo-4-hydroxyphenyl, β- imidazolyl and NH = C (NH2) NH-.
- 13. A process according to claim 11, characterized in that Rx0 is an amino acid residue derived from glycine, alanine, sarcosine, serine, cysteine, phenylalanine, tyrosine (4-hydroxyphenylalanine), diiodotyrosine, tryptophan (β-indolilalanine), histidine ( (β-imidazolylalanine), α-aminobutyric acid, methionine, valine (α-aminoisovaleric acid), norvaline, leucine (c-aminoisocaproic acid), isoleucine (β-amino-β-methylvaleric acid), norleucine (α-amino acid) -caproic), arginine, ornithine (x, d-diaminovaleric acid), lysine, (a, e-diaminocaproic acid), aspartic acid (aminosuccinic acid), glutamic acid (a-aminoglutaric acid), threonine, hydroxy-glutamic acid or taurine, or an isomer mixture thereof, of these amino acids from which amino acid residues R10 are derived, glutamic acid and aspartic acid are particularly preferred.
- 14. A process according to claim 11, characterized in that R10 is an amino acid residue derived from iminodiacetic acid.
- 15. A method according to claim 11, characterized in that Rxo is an amino acid residue derived from taurine, sarcosine, glutamic acid or iminodiacetic acid.
- 16. A process according to claim 11, characterized in that Rxo is chloro, amino, phenyl, methylphenyl, dimethylphenyl, morpholino or an amino acid residue from which a hydrogen atom in the amino group has been removed.
- 17. A process according to claim 11, characterized in that R9 is phenyl, methylphenyl, dimethylphenyl or a group of the formula.wherein RX1 is as defined in claim 11; and Rxo is phenyl, methylpentyl, dimethylphenyl, -NH2, Cl, -N (CH2CH2OH) 2, -N [CH2CH (OH) CH3] 2• N P 'or an amino acid residue from which a des-hydrogen atom has been removed in the amino group.
- 18. A process according to claim 17, characterized in that R1X is alkyl with 1 to 4 carbon atoms 19. A process according to claim 17, characterized in that Rxx is methyl or ethyl. with claim 11, characterized in that the compound of the formula (3) has the formula:
- 10
- , > .-_. - * "
- 21. A method according to any of the preceding claims, characterized in that the triazine-based ultraviolet absorbing agent used-as a neutralizing compound, is used in an amount in the range of 0.5 to 50 times the amount of agent fluorescent whitening agent present in the substrate to be treated
- 22. A substrate when treated according to a method according to any of the preceding claims.>
- 23. A compound having the formula:wherein M is as defined in claim 2; nx and n2 independently are O or l, provided that if nx is 0, n2 is 0; R9 is optionally substituted aryl; and R10 is hydrogen, halogen, optionally substituted alkyl, optionally substituted aryl,-DO NOT'-OH, -NH2, -N (CH2CH20H) 2, -N [CH2CH (OH) CH3] 2, -NH-R13, -N (R13) 2 or -0RX3, wherein R13 is as defined in claim 11
- 24. A compound according to claim 23, characterized in that nx and n2 'each are 1;R9 is phenyl, methylphenyl or dimethylphenyl, and R10 is chloro, amino, phenyl, methylphenyl or dimethylphenyl, / \ -N-O '\ / -OH, -NH2, -N (CH2CH2OH) 2, -N [CH2CH ( OH) CH3] 2, -NH-RX3, -N (RX3) 2 or -0R13, wherein R13 is as defined in claim 11.
- 25. The compound having the formula:
- 26. The compound that has the formula:
- 27. The compound that has the formula:
- 28. The compound that has the formula:
- 29. The compound having the formula:
- 30. The compound having the formula:
- 31. The compound having the formula:
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9611614.0 | 1996-06-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
MXPA98010234A true MXPA98010234A (en) | 1999-04-27 |
Family
ID=
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