Phthalimidohexanperacid, process for preparing the same and use thereof
6 claims: 6 independent, 0 dependent
- 1A compound of the formula Composé de formule Verbindung der Formel
- 2A process for the preparation of the compound as claimed in claim 1, which comprises reacting phthalic anhydride with ω-aminocaproic acid and oxidizing the resulting imidocarboxylic acid using hydrogen peroxide in the presence of a strong acid. Procédé de préparation du composé selon la revendication 1, caractérisé en ce que l'on fait réagir l'anhydride d'acide phtalique avec l'acide ω-aminocaproïque et on oxyde l'acide imidocarboxylique obtenu avec du peroxyde d'hydrogène en présence d'un acide fort. Verfahren zur Herstellung der Verbindung gemäß Anspruch 1, dadurch gekennzeichnet, daß man Phthalsäureanhydrid mit ω-Aminocapronsäure umsetzt und die erhaltene Imidocarbonsäure mit Wasserstoffperoxid in Gegenwart einer starken Säure oxidiert.
- 3A process for the preparation of the compound as claimed in claim 1, which comprises reacting phthalic anhydride with caprolactam under pressure in the presence of water and oxidizing the resulting imidocarboxylic acid using hydrogen peroxide in the presence of a strong acid. Procédé pour la préparation du composé selon la revendication 1, caractérisé en ce que l'on fait réagir l'anhydride d'acide phtalique avec le caprolactame en présence de l'eau, sous pression, et on oxyde l'acide imidocarboxylique avec du peroxyde d'hydrogène en présence d'un acide fort. Verfahren zur Herstellung der Verbindung gemäß Anspruch 1, dadurch gekennzeichnet, daß man Phthalsäureanhydrid mit Caprolactam in Gegenwart von Wasser unter Druck umsetzt und die erhaltene Imidocarbonsäure mit Wasserstoffperoxid in Gegenwart einer starken Säure oxidiert.
- 4Procédé selon la revendication 3, caractérisé en ce que l'on effectue la réaction sous une surpression de 1 à 30 bar, de préférence de 2 à 5 bar. The process as claimed in claim 3, wherein the reaction is carried out at a gage pressure of from 1 to 30 bar, preferably from 2 to 5 bar. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß die Umsetzung bei einem Überdruck von 1 bis 30 bar, vorzugsweise 2 bis 5 bar erfolgt.
- 5Procédé selon la revendication 3 ou 4, caractérisé en ce que l'on effectue la réaction dans un intervalle de 2 à 20 heures, de préférence de 5 à 10 heures, à une température de 100 à 250°c, de préférence de 120 à 200 °C, sous une atmosphère de gaz inerte. The process as claimed in claim 3 or 4, wherein the reaction is carried out over a period of from 2 to 20 h, preferably from 5 to 10 h, at a temperature of from 100 to 250°C, preferably from 120 to 200°C, under an inert gas atmosphere. Verfahren nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß die Umsetzung über einen Zeitraum von 2 bis 20 h, vorzugsweise 5 bis 10 h, bei einer Temperatur von 100 bis 250°C, vorzugsweise 120 bis 200°C, unter Inertgasatmosphäre erfolgt.
- 6The use of the compound as claimed in claim 1 in bleaching, oxidizing and cleaning compositions. Utilisation du composé selon la revendication 1 dans les produits de blanchiment, d'oxydation et de nettoyage. Verwendung der Verbindung gemäß Anspruch 1 in Blech-, Oxidations- und Reinigungsmitteln.
Independent claims6
33 paragraphs, as filed
Inorganic persalts have long been known as bleach additives in detergents. However, since they only develop their optimal bleaching power at temperatures above 60 ° C, a number of organic compounds are described for their activation, which react with hydrogen peroxide during the washing process to release a peroxycarboxylic acid, which already has a bleaching effect at 40 - 60 ° C. An overview of numerous known perborate activators such as N-acyl compounds (tetraacetylethylenediamine, tetraacetylmethylene diamine, tetraacetylglycoluril) or activated esters (pentaacetylglucose, acetoxibenzenesulfonate sodium, benzoyloxibenzenesulfonate sodium) is given, for example, in US Pat. No. 4,248,928.
In addition, a number of organic peroxycarboxylic acids have recently been described as bleaching systems for detergents. In addition to commercially available peroxycarboxylic acids such as dodecanedipercarboxylic acid (EP 127 782) and monoperoxiphthalic acid (EP 27 693), succinic acid (DE 34 38 529), perglutaric acid (DE 35 39 036) and sulfoperbenzoic acid (EP 124 969) are described. However, the problem with these peroxycarboxylic acids is their low storage stability, which is only partially ensured by special physical or chemical stabilization. The production of magnesium salts (EP 105 689) or the addition of phosphine oxide / sodium sulfate (DE 33 20 497) has proven particularly useful here. According to EP 170 386, organic peroxycarboxylic acids are also stabilized by an additional amide group in the molecule. Examples include N-decanoyl-6-aminoperoxicaproic acid or 3- (N-nonyl-carbamoyl) perpropionic acid. The storage stability of these compounds can be increased further by conversion into the magnesium salt and by adding borates (US Pat. No. 4,686,063). However, the free peroxycarboxylic acids described so far show a clear decrease in active oxygen even under relatively mild storage conditions. This is also, as our own experiments show, in the case of J. Chem. Soc.<u>1982</u>, 3821 and Chem. Ind. <u>1961</u>, 469 described imidopercarboxylic acids the case. There is therefore still great interest in storage-stable organic peroxycarboxylic acids with high bleaching efficiency which are easily and safely accessible.
The invention relates to ω-phthalimidoperoxihexanoic acid of the formula<chemistry id="chem0001" num="0001"><img file="EP0349940B1_D0001.tif" /></chemistry>
This connection is established through the following steps:<ul id="ul0001" list-style="none" compact="compact"><li>-a- Synthesis of imidocarboxylic acid</li><li>-b- Oxidation to percarboxylic acid</li><li>-c- Isolation of imidoperoxy carboxylic acid.</li></ul>
The individual steps are explained in more detail below. The imidocarboxylic acid in step -a- can be prepared in a manner known per se by reacting phthalic anhydride with ω-aminocaproic acid (see Houben-Weyl, Methods of Organic Chemistry, XI / 2, p. 17).
The imidocarboxylic acid can also be produced particularly inexpensively from ε-caprolactam. For this purpose, the lactam is reacted with the anhydride in the presence of water under pressure for 2 to 20 h, preferably 5 to 10 h at a temperature of 100 to 250 ° C., preferably 120 to 200 ° C., under an inert gas atmosphere in a suitable reaction vessel. The excess pressure can be 1 to 30 bar, preferably 2 to 5 bar.
The conversion of the imidocarboxylic acid obtained in step -a- to imidopercarboxylic acid takes place by reaction with an oxidation mixture of hydrogen peroxide and a strong acid. Hydrogen peroxide is used as a 30 to 95 percent, preferably 35 to 50 percent aqueous solution. In addition to sulfuric acid, suitable acidic catalysts are methanesulfonic acid or an acidic ion exchanger. Sulfuric acid is used as a 50 to 96 percent, preferably 75 to 96 percent, aqueous solution.
Hydrogen peroxide is used in 1 to 20 times, preferably 1.5 to 4 times, molar excess. It has also proven to be advantageous to add the hydrogen peroxide in portions. In general, a 2- to 5-fold excess of sulfuric acid - based on the imidocarboxylic acid - is used. The reaction temperature is between 5 and 50 ° C, preferably between 15 and 45 ° C.
Since the claimed imidoperoxycarboxylic acid precipitates out of the reaction mixture, it can be isolated in a simple manner in step -c- by filtration or centrifugation. The precipitation process can be accelerated and completed by adding water. It is also possible to remove the imidoperoxycarboxylic acid by extraction with an organic solvent.
The imidoperoxycarboxylic acid according to the invention is solid, almost odorless, has a low vapor pressure and is of excellent thermal stability. It can be used as a solution, powder or in processed form alone or in combination with other substances for bleaching, oxidation or disinfection purposes.
It is preferably used as a bleaching agent in solid or liquid detergents and cleaning agents, since its bleaching and disinfecting effect is fully effective in a wide temperature range below 60 ° C.
It is particularly suitable for incorporation into powder detergents in granulated, extruded, tableted or agglomerated form. Aids known per se such as boric acid, sulfates, phosphates, carbonates, zeolites, carboxymethyl cellulose etc. and film-forming substances such as fatty acids, fatty acid amides or esters, fatty alcohol polyglycol ethers or polyethylene glycols are possible as additives in this processing mode.
The compound according to the invention proves to be superior in comparison to the known bleaching system perborate / TAED (tetraacetylethylene diamine). While bleaching systems based on perborate tend to fix the blood on the tissue in the case of blood stains and thus drastically reduce its washability, this antagonistic effect is not observed when using the peroxycarboxylic acid according to the invention described here.
When using equimolar amounts of active oxygen, the compound according to the invention is superior in bleaching efficiency to tea and red wine soils to the previously described peroxycarboxylic acids and dicarboxylic acids. A significant oil solubility of the compound described here is also advantageous, as a result of which, in particular, hydrophobic oil-containing soiling such as grill oil or spaghetti sauce is bleached well.
example
a) ω-phthalimidohexanoic acid
113.2 g (1 mol) of ε-caprolactam, 18 g of water and 148.1 g (1 mol) of phthalic anhydride are reacted in an autoclave for 5 hours at 160 ° C. and 3 bar nitrogen. The melt is then poured into a porcelain bowl.<ul id="ul0002" list-style="none" compact="compact"><li>Yield: 261 g (99.8%), white crystals</li><li>Mp: 104-105 ° C</li></ul>
b) ω-phthalimidoperoxyhexanoic acid
653.2 g (2.5 mol) of ω-phthalimidohexanoic acid are oxidized as follows:
The imidocarboxylic acid is dissolved in 2 to 2.5 times the amount of sulfuric acid and 2.5 equivalents of hydrogen peroxide (35-50 percent) are added dropwise with ice cooling 50 so that the internal temperature can be kept between 40 and 45 ° C. After the addition, the mixture is cooled to 25-30 ° C., diluted with water and the precipitated peracid is filtered off with suction. The filter cake is washed with water and dried in a vacuum drying cabinet at 35 ° C.<ul id="ul0003" list-style="none" compact="compact"><li>Yield: 636.6 g (91.8%), white crystals</li><li>Active oxygen content: 5.4% (93.6%)</li><li>Mp: 89-90 ° C</li></ul>
Washing attempts in the Launder-O-Meter
The tests were carried out at 40 and 60 ° C in the Launder-O-Meter using the test soils tea on WFK cotton, red wine on EMPA cotton and standard soiling on WFK cotton. The bleaching systems were metered in such a way that in each case 25 mg / l of active oxygen resulted in the wash liquor. 1.5 g / l IEC detergent were used as detergents. The washing time was 30 minutes. The bleaching effect was determined as an increase in reflectance on the various test fabrics. The evaluation is carried out in the usual way. <tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="7" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="22.50mm" /><colspec colnum="2" colname="col2" colwidth="22.50mm" /><colspec colnum="3" colname="col3" colwidth="22.50mm" /><colspec colnum="4" colname="col4" colwidth="22.50mm" /><colspec colnum="5" colname="col5" colwidth="22.50mm" /><colspec colnum="6" colname="col6" colwidth="22.50mm" /><colspec colnum="7" colname="col7" colwidth="22.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" rowsep="0" align="center">Bleaching system</entry><entry namest="col2" nameend="col7" align="center">Remission values</entry></row><row><entry namest="col1" nameend="col1" rowsep="0" /><entry namest="col2" nameend="col3" align="center">default</entry><entry namest="col4" nameend="col5" align="center">tea</entry><entry namest="col6" nameend="col7" align="center">red wine</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">40 ° C</entry><entry namest="col3" nameend="col3" align="center">60 ° C</entry><entry namest="col4" nameend="col4" align="center">40 ° C</entry><entry namest="col5" nameend="col5" align="center">60 ° C</entry><entry namest="col6" nameend="col6" align="center">40 ° C</entry><entry namest="col7" nameend="col7" align="center">60 ° C</entry></row></thead><tbody valign="top"><row rowsep="0"><entry namest="col1" nameend="col1" align="center">Perborate</entry><entry namest="col2" nameend="col2" align="char" char=",">49,5</entry><entry namest="col3" nameend="col3" align="char" char=",">59,4</entry><entry namest="col4" nameend="col4" align="char" char=",">58,4</entry><entry namest="col5" nameend="col5" align="char" char=",">62,8</entry><entry namest="col6" nameend="col6" align="char" char=",">55,5</entry><entry namest="col7" nameend="col7" align="char" char=",">56,9</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="center">Perborate / TAED</entry><entry namest="col2" nameend="col2" align="char" char=",">48,3</entry><entry namest="col3" nameend="col3" align="char" char=",">63,6</entry><entry namest="col4" nameend="col4" align="char" char=",">66,9</entry><entry namest="col5" nameend="col5" align="char" char=",">67,4</entry><entry namest="col6" nameend="col6" align="char" char=",">59,8</entry><entry namest="col7" nameend="col7" align="char" char=",">60,0</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">PAP</entry><entry namest="col2" nameend="col2" align="char" char=",">49,0</entry><entry namest="col3" nameend="col3" align="char" char=",">64,9</entry><entry namest="col4" nameend="col4" align="char" char=",">72,2</entry><entry namest="col5" nameend="col5" align="char" char=",">75,0</entry><entry namest="col6" nameend="col6" align="char" char=",">67,7</entry><entry namest="col7" nameend="col7" align="char" char=",">73,1</entry></row></tbody></tgroup></table></tables>
With equimolar use of the bleaching systems, the results show a significantly better bleaching performance of the peracid PAP (ω-phthalimidoperoxyhexanoic acid) according to the invention than the previously used bleaching system perborate / TAED (tetraacetylethylene diamine).
Washing attempts in the Launder-O-Meter
The tests were carried out analogously to that described above. The peroxycarboxylic acids DPDDA (diperoxidodecanedioic acid), PMP (monoperphthalic acid) and NAPSA (nonylmonoamido succinic acid) were tested against PAP as bleaching systems.<tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="5" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" rowsep="0" align="center">Peroxyacids</entry><entry namest="col2" nameend="col5" align="center">Remission values</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" rowsep="0" /><entry namest="col2" nameend="col3" align="center">tea</entry><entry namest="col4" nameend="col5" align="center">red wine</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">38 ° C</entry><entry namest="col3" nameend="col3" align="center">60 ° C</entry><entry namest="col4" nameend="col4" align="center">38 ° C</entry><entry namest="col5" nameend="col5" align="center">60 ° C</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="center">DPDDA</entry><entry namest="col2" nameend="col2" align="char" char=",">69,6</entry><entry namest="col3" nameend="col3" align="char" char=",">73,6</entry><entry namest="col4" nameend="col4" align="char" char=",">65,5</entry><entry namest="col5" nameend="col5" align="char" char=",">71,8</entry></row><row><entry namest="col1" nameend="col1" align="center">PMP</entry><entry namest="col2" nameend="col2" align="char" char=",">66,8</entry><entry namest="col3" nameend="col3" align="char" char=",">71,1</entry><entry namest="col4" nameend="col4" align="char" char=",">61,1</entry><entry namest="col5" nameend="col5" align="char" char=",">65,4</entry></row><row><entry namest="col1" nameend="col1" align="center">NAPSA</entry><entry namest="col2" nameend="col2" align="char" char=",">68,1</entry><entry namest="col3" nameend="col3" align="char" char=",">72,2</entry><entry namest="col4" nameend="col4" align="char" char=",">63,7</entry><entry namest="col5" nameend="col5" align="char" char=",">68,6</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">PAP</entry><entry namest="col2" nameend="col2" align="char" char=",">68,4</entry><entry namest="col3" nameend="col3" align="char" char=",">77,1</entry><entry namest="col4" nameend="col4" align="char" char=",">67,2</entry><entry namest="col5" nameend="col5" align="char" char=",">74,3</entry></row></tbody></tgroup></table></tables>
Attempted washing in the washing machine
The tests were carried out in a Miele washing machine (Automatic W432) with the 40 ° temperature program (main wash and step spin) using 2 kg of fiber. The bleaching effect was measured as an increase in reflectance on EMPA test strips (EMPA 103). In each case 4.5 g / l of detergent were used, which were produced by mixing IEC detergent with the respective bleaching system.<tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="left">laundry detergent</entry><entry namest="col2" nameend="col2" align="center">default</entry><entry namest="col3" nameend="col3" align="center">red wine</entry><entry namest="col4" nameend="col4" align="left">blood</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">IEC</entry><entry namest="col2" nameend="col2" align="char" char=",">24,7</entry><entry namest="col3" nameend="col3" align="char" char=",">54,8</entry><entry namest="col4" nameend="col4" align="char" char=",">65,5</entry></row><row><entry namest="col1" nameend="col1" align="left">IEC / 10% perborate</entry><entry namest="col2" nameend="col2" align="char" char=",">27,8</entry><entry namest="col3" nameend="col3" align="char" char=",">54,9</entry><entry namest="col4" nameend="col4" align="char" char=",">37,1</entry></row><row><entry namest="col1" nameend="col1" align="left">IEC / 10% perborate / 3% TAED</entry><entry namest="col2" nameend="col2" align="char" char=",">28,0</entry><entry namest="col3" nameend="col3" align="char" char=",">57,7</entry><entry namest="col4" nameend="col4" align="char" char=",">44,2</entry></row><row><entry namest="col1" nameend="col1" align="left">IEC / 3% PAP</entry><entry namest="col2" nameend="col2" align="char" char=",">32,2</entry><entry namest="col3" nameend="col3" align="char" char=",">57,8</entry><entry namest="col4" nameend="col4" align="char" char=",">68,5</entry></row><row><entry namest="col1" nameend="col1" align="left">IEC / 6% PAP</entry><entry namest="col2" nameend="col2" align="char" char=",">34,9</entry><entry namest="col3" nameend="col3" align="char" char=",">63,1</entry><entry namest="col4" nameend="col4" align="char" char=",">66,6</entry></row><row><entry namest="col1" nameend="col1" align="left">IEC / 9% PAP</entry><entry namest="col2" nameend="col2" align="char" char=",">34,4</entry><entry namest="col3" nameend="col3" align="char" char=",">66,6</entry><entry namest="col4" nameend="col4" align="char" char=",">65,5</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">IEC / 6% DSIPH</entry><entry namest="col2" nameend="col2" align="char" char=",">36,6</entry><entry namest="col3" nameend="col3" align="char" char=",">59,1</entry><entry namest="col4" nameend="col4" align="char" char=",">65,6</entry></row><row rowsep="1"><entry namest="col1" nameend="col4" align="justify">TAED = tetraacetylethylenediamine PAP = ω-phthalimidoperoxyhexanoic acid DSIPH = ω- [2-dodecylsuccinimido] peroxyhexanoic acid</entry></row></tbody></tgroup></table></tables>
The tests show a clear superiority of the imidoperoxy carboxylic acid according to the invention over known bleaching systems. In particular, when these peracids are used, no antagonistic effect on the washability of blood stains is observed.
Example 14
Determination of the oil solubility of bleaching systems
To determine the oil solubility of a bleaching system, the bleaching system was introduced at 20 ° C. into a mixture of 50% deionized water and 50% isopropyl myristate, the pH was adjusted to 9 and the mixture was stirred intensively for 10 minutes. After the phase separation, the proportion of peroxycarboxylic acid in the oil and water phases was determined titrimetrically.<tables id="tabl0004" num="0004"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Bleaching system</entry><entry namest="col2" nameend="col2" align="center">Oil solubility at pH 9</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Perborate / TAED</entry><entry namest="col2" nameend="col2" align="left">6 %</entry></row><row><entry namest="col1" nameend="col1" align="left">DPDDA</entry><entry namest="col2" nameend="col2" align="left">15 %</entry></row><row><entry namest="col1" nameend="col1" align="left">PAP</entry><entry namest="col2" nameend="col2" align="left">38 %</entry></row><row><entry namest="col1" nameend="col1" align="left">Perborate / Isonobs</entry><entry namest="col2" nameend="col2" align="left">54 %</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">DSIPH</entry><entry namest="col2" nameend="col2" align="left">86 %</entry></row></tbody></tgroup></table></tables>
Storage tests of free peroxycarboxylic acids
The tests were carried out in open vessels in the warming cabinet. The content of peroxycarboxylic acid was determined titrimetrically.<tables id="tabl0005" num="0005"><table frame="all"><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="center">Peroxy carboxylic acid</entry><entry namest="col2" nameend="col2" align="center">Storage time (weeks)</entry><entry namest="col3" nameend="col3" align="center">temperature</entry><entry namest="col4" nameend="col4" align="center">Active oxygen loss</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">PAP</entry><entry namest="col2" nameend="col2" align="right">4</entry><entry namest="col3" nameend="col3" align="right">25 ° C</entry><entry namest="col4" nameend="col4" align="left">1,4 %</entry></row><row><entry namest="col1" nameend="col1" align="left">NAPSA</entry><entry namest="col2" nameend="col2" align="right">4</entry><entry namest="col3" nameend="col3" align="right">25 ° C</entry><entry namest="col4" nameend="col4" align="left">14,6 %</entry></row><row><entry namest="col1" nameend="col1" align="left">PAP</entry><entry namest="col2" nameend="col2" align="right">4</entry><entry namest="col3" nameend="col3" align="right">40 ° C</entry><entry namest="col4" nameend="col4" align="left">2,0 %</entry></row><row><entry namest="col1" nameend="col1" align="left">NAPSA</entry><entry namest="col2" nameend="col2" align="right">4</entry><entry namest="col3" nameend="col3" align="right">40 ° C</entry><entry namest="col4" nameend="col4" align="left">29,3 %</entry></row><row><entry namest="col1" nameend="col1" align="left">PAP</entry><entry namest="col2" nameend="col2" align="right">4</entry><entry namest="col3" nameend="col3" align="right">50 ° C</entry><entry namest="col4" nameend="col4" align="left">12,0 %</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">NAPSA</entry><entry namest="col2" nameend="col2" align="right">2</entry><entry namest="col3" nameend="col3" align="right">50 ° C</entry><entry namest="col4" nameend="col4" align="left">100,0 %</entry></row></tbody></tgroup></table></tables>
4 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| WO2014183795A1 | Cited by | World Intellectual Property Organization (WIPO) | Applicant |
| WO2013178290A1 | Cited by | World Intellectual Property Organization (WIPO) | Applicant |
| US8093198B2 | Cited by | United States of America | Applicant |
| US7183247B2 | Cited by | United States of America | Applicant |
| US7179778B2 | Cited by | United States of America | Applicant |
| WO2013178289A1 | Cited by | World Intellectual Property Organization (WIPO) | Applicant |
| EP0325288A1 | Cites | European Patent Office (EPO) | Examiner |
| EP0325289A1 | Cites | European Patent Office (EPO) | Examiner |
| EP0170386A | Cites | European Patent Office (EPO) | – |
| EP0260134A | Cites | European Patent Office (EPO) | – |
| EP0325288A | Cites | European Patent Office (EPO) | – |
| EP0325289A | Cites | European Patent Office (EPO) | – |
26 members in 15 offices
Priority claims5
| Document | Office | Kind | Date |
|---|---|---|---|
| 3823172 | Germany | A | |
| 3823172 | Germany | A | |
| 3823172 | Germany | – | |
| 3823172 | – | – | – |
| DE19883823172 | – | – | – |
Members26
| Document | Office | Kind | |
|---|---|---|---|
| NO892834D0 | Norway | D0 | |
| NO892834L | Norway | L | |
| EP0349940A1 | European Patent Office (EPO) | A1 | |
| AU3793489A | Australia | A | |
| DE3823172A1 | Germany | A1 | |
| BR8903368A | Brazil | A | |
| KR900001652A | Republic of Korea | A | |
| JPH0276850A | Japan | A | |
| ZA895178B | South Africa | B | |
| US5061807A | United States of America | A | |
| AU624392B2 | Australia | B2 | |
| MX16730A | Mexico | A | |
| NO175204B | Norway | B | |
| AR246265A1 | Argentina | A1 | |
| NO175204C | Norway | C | |
| DE3823172C2 | Germany | C2 | |
| KR0135527B1 | Republic of Korea | B1 | |
| EP0349940B1This record | European Patent Office (EPO) | B1 | |
| AT166049T | Austria | T | |
| ATE166049T1 | Austria | T1 | |
| DE58909834D1 | Germany | D1 | |
| ES2118055T3 | Spain | T3 | |
| CA1340443C | Canada | C | |
| HK1009646A1 | Hong Kong, China | A1 | |
| US5994284A | United States of America | A | |
| JP3065322B2 | Japan | B2 |
65 legal events, as 5 offices reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | Office | |
|---|---|---|---|
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Announcement of lapse in spainLapsedFD2A | FD2A | ES | |
| Patent expired after termination of 20 yearsExpiredPE20 | PE20 | GB | |
| Notification of lapseLapsedST | ST | FR | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Change of name or company nameCD | CD | FR | |
| Appeal reference modifiedAppealORIGINAL CODE: EPIDOSCREFNOAPAH | APAH | EP | |
| Opposition rejectedOpposition27O | 27O | EP | |
| Opposition rejectedOppositionORIGINAL CODE: 0009273PLBN | PLBN | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: OPPOSITION REJECTEDSTAA | STAA | EP | |
| Nl: lapsed or anulled due to non-payment of the annual feeLapsedNLV4 | NLV4 | EP | |
| Patent ceasedCeasedPL | PL | CH | |
| Se: european patent has lapsedLapsedEUG | EUG | EP | |
| Appeal dossier modifiedAppealORIGINAL CODE: EPIDOS NOAPOAPAC | APAC | EP | |
| Nl: opposition has been filed with the epoOppositionNLR1 | NLR1 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Opposition filed (corrected)OppositionR26 | R26 | EP | |
| Opposition data, opponent's data or that of the opponent's representative modifiedOppositionORIGINAL CODE: 0009299OPPOPLAB | PLAB | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| European patent in force as of 2002-01-01IF02 | IF02 | GB | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Appeal dossier modifiedAppealORIGINAL CODE: EPIDOS NOAPOAPAC | APAC | EP | |
| Appeal reference modifiedAppealORIGINAL CODE: EPIDOS REFNOAPAE | APAE | EP | |
| Appeal dossier modifiedAppealORIGINAL CODE: EPIDOS NOAPOAPAC | APAC | EP | |
| Opposition rejectedOppositionORIGINAL CODE: EPIDOS REJOPLBO | PLBO | EP | |
| Reply of patent proprietor to notice(s) of oppositionOppositionORIGINAL CODE: EPIDOS OBSOPLBF | PLBF | EP | |
| Nl: opposition has been filed with the epoOppositionNLR1 | NLR1 | EP | |
| Nl: opposition has been filed with the epoOppositionNLR1 | NLR1 | EP | |
| Opposition filedOpposition26 | 26 | EP | |
| Opposition filedOpposition26 | 26 | EP | |
| Reply of patent proprietor to notice(s) of oppositionOppositionORIGINAL CODE: EPIDOS OBSOPLBF | PLBF | EP | |
| Opposition filedOppositionORIGINAL CODE: 0009260PLBI | PLBI | EP | |
| Unpublished change to opponent dataORIGINAL CODE: EPIDOS OPPOPLBQ | PLBQ | EP | |
| Fr: translation filedET | ET | EP | |
| Definitive protectionFG2A | FG2A | ES | |
| Gb: translation of ep patent filed (gb section 77(6)(a)/1977)GBT | GBT | EP | |
| It: translation for a ep patent filedITF | ITF | EP | |
| It: translation for a ep patent filedITF | ITF | EP | |
| Corresponds to:REF | REF | EP | |
| European patent takes effect as a national patent in ch/liEP | EP | CH | |
| Designated contracting statesAK | AK | EP | |
| Corresponds to:REF | REF | EP | |
| (expected) grantORIGINAL CODE: 0009210GRAA | GRAA | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOS IGRAGRAH | GRAH | EP | |
| Party data changed (applicant data changed or rights of an application transferred)RAP1 | RAP1 | EP | |
| Despatch of communication of intention to grantORIGINAL CODE: EPIDOS AGRAGRAG | GRAG | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOS IGRAGRAH | GRAH | EP | |
| Despatch of communication of intention to grantORIGINAL CODE: EPIDOS AGRAGRAG | GRAG | EP | |
| Despatch of communication of intention to grantORIGINAL CODE: EPIDOS AGRAGRAG | GRAG | EP | |
| First examination report despatched17Q | 17Q | EP | |
| Request for examination filed17P | 17P | EP | |
| Designated contracting statesAK | AK | EP | |
| Public reference made under article 153(3) epc to a published international application that has entered the european phaseORIGINAL CODE: 0009012PUAI | PUAI | EP |
Numbers
- Publication
- 0349940
- Publication, DOCDB
- 0349940
- Publication, EPODOC
- EP0349940
- Application
- 89112062
- Application, DOCDB
- 89112062
- Application, EPODOC
- EP19890112062
Titles3
- German
- Phthalimidoperoxihexansäure, Verfahren zu deren Herstellung und deren Verwendung
- English
- Phthalimidohexanperacid, process for preparing the same and use thereof
- French
- Phthalimidohexanpéracide, procédé pour sa préparation et son application
Classification
- CPC, 8
- C07D207/412
- C07D209/48
- C07D207/448
- C07D211/88
- C07D223/10
- C07D487/04
- C11D3/3945
- C07D209/58
- IPC, 15
- C07D207 40
- C07D207 404
- C07D207 412
- C07D207 44
- C07D207 448
- C07D207 452
- C07D209 48
- C07D211 40
- C07D211 88
- C07D223 10
- C07D487 04
- C11D3 39
- C11D3 395
- C11D7 54
- D06L3 02
Designated states11
- Contracting states, 11
- Austria
- Belgium
- Switzerland
- Germany
- Spain
- France
- United Kingdom
- Italy
- Liechtenstein
- Netherlands (Kingdom of the)
- Sweden
