DE1768962C3 - Triacylated hydroxylamines and their use as activators for inorganic per compounds - Google Patents

Description

Aqueous solutions of inorganic per compounds, in particular of hydrogen peroxide or perborates, have long been used as oxidizing and bleaching agents for a wide variety of materials mainly used for textiles. However, the active oxygen only becomes active at temperatures above 7OX 'and preferably in the range from 80 to 100 "C with at a speed sufficient for practical purposes, so that these oxidizing and bleaching liquids do not use on temperature-sensitive materials. Such is the case, however Inorganic percompounds and especially alkalis containing perborates are often used for bleaching of temperature-sensitive textiles at temperatures of, for example, 30 to 50 "C, i.e. one works thus under conditions in which the active oxygen present in the bleaches is not fully used Effect comes, but remains largely unused in the lye.

It is known. To activate per compounds by N-acyl compounds, in particular N-acetyl compounds. For example, the corresponding use of N-acetylacetihydroxamic acid (Ν, Ο-diacetylhydroxylamine) is described in French patent specification 11 55 228. According to the information in French patent specification 12 32 554, activators for per compounds that _{can be used are found under the N 1 N-diacylamines.} These can be derivatives of aromatic amines, e.g. B. to be the N-diacetyl-loludin; however, an acyl radical of the diacylamine can also be linked to the amine radical to form a heterocyclic; such compounds are e.g. B. the N, N'-diacelyl-dimethylhydantoin or the Ν, Ν'-diacetyl-barbitone, but the heterocyclic compounds according to the information in this patent have a lower activation capacity than the acylated aromatic amines.

Other heterocyclic N-acyl compounds which can be used as activators ^for per compounds are mentioned in Belgian patent specification 6 63 716 (N-acetyl-N'-phenylhydrazide) and in Swiss patent specification 4,07,387 (N-acetyl maleic acid hydrazide).

Finally, the N-diacyl compounds are also used as activators according to DAS 11 62 967 (N, N, N'N'-Tetraacetyl-methylendiamiri or -ethylenediamine) and the Ν, Ν'-diacyl derivatives of urea according to the Dutch Laid-Open Specification 65 04 416 should be mentioned; in the latter, the nitrogen bound hydrogen atoms partially or completely be replaced by other atoms or groups of atoms, but there is no information about what kind these atoms or groups of atoms can be.

The invention relates to the triacylated hydroxylamines

ON-diacetyl-Np-toluene.siilfony! Hydroxy la in in
O-propionyl-N, N-surxiny I-hydroxylamine
O-benzoyl-Ν, Ν-succiny I-hydroxylamine
Op-Methoxybenzoy IN, N-succiny I-hydroxylamine
Op-nitrobenzoyl-NN-succinyl-hydroxylamine
O, O'-Ma! Onyl- [bis- N ₁ N -succiny! -Hydroxylamine]
O, O'-Stieeinyl- [bis- N ₁ N -succiny I -hydroxylamine]

and their use as activators for inorganic per compounds, making them practical for a effective oxidation and / or bleaching necessary minimum temperature lowered and / or the oxidation process is accelerated.

The Ο, Ν.Ν-triacylated hydroxylamines can be obtained by reacting hydroxylamine or hydroxylamine hydrochloride with the corresponding carboxylic acid anhydrides, chlorides or esters. Mixed acylated hydroxylamines are obtained by acylating the corresponding N-acyl- or N ₁ N-diucyl-hydroxyluminc with the related acid anhydrides, chlorides or esters. The N-acyl- or N, N-dbeyl-hydmxyluininc on which this reaction is based can be prepared by known processes (compare, for example, Tier, German former Ges. 29 [1896], 1560; |. Amer. Formerly Soc. 86 [1964], 18 W).

The O-substituted N.N-Succinylhydroxylamines used as activators according to the invention are new Substances, as well as the Ο, Ν-diacetyl-N-p-toluenesulfonyl-hydroxylamine. Also the O-benzoyl-N.N-succinylhydroxyluiiiin must sound like a new substance. C. D. Hurd and co-workers (|. Org. Chemistry 19 [1954], 1140) by cyclization of Ν, Ν'-dibenzoxysuccinainide obtained with acetic anhydride a compound of melting point 116 "C, which it for O-benzoyl-N.N-suecinylhydroxylamine held, as a by-product they isolated a substance with a melting point of 155 to 1 36 "C, which they bezeii as 2-Benzoyltetrahyc! ro-O-isoxazine-3,6-dione hneed. When implementing N-Hydroxy-succininiicl with benzoyl chloride, however, a substance with a melting point of 137 to 139 ° C, which is a similar one Has a melting point like the isomeric 2-Hcnzoyl-ietrahydro-O-isoxazine-3,6-dione, but NMR, IR and mass spectra are similar to those of the other hydroxysuccinimide derivatives, whose structure is clearly secured, so that it can be assumed that this is the case is the O-benzoyl-N, N-hydroxylamine. For them substance protection is therefore claimed for new substances.

Among the inorganic.-n peroxides to be activated In practice, hydrogen peroxide plays the most important role. It can be as such, but also in the form of it mostly solid peroxohydrates or investment products in inorganic and organic compounds are used will. The latter include, for example

the addition products of hydrogen peroxide with urea or melamine; to the peroxohydrates belong e.g. B. the perborates, perortho-, perpyro-, perpolyphosphates, percarbonates and persilicates. the But activators according to the invention can also be used together with real peracids, such as, for example Caro's acid (peroxomonosulphuric acid H2SO5) or peroxodisulfuric acid (H) SjOb) or its salts can be used.

In general, each molecule of activator can add one active oxygen atom to the respective per compound activate; for a complete activation of the active oxygen used would therefore be theoretical Apply activator and per compound in equimolar amounts. In many cases the practice achieves one but also with significantly smaller amounts of activator satisfactory effects, while on the other hand can also use the activator in relatively large excesses; in general, the The amount of activator used is 0.1 to 3, preferably 0.25 to 2 mol per g-Aioin of active oxygen.

The acceleration of the bleaching or oxidation process shows up both at low temperatures lying in the range of 20 "C, as well as when they are exceeded this temperature limit, where you can go up to 95 C. The specialist has to depending on the solving problem the possibility of using the activators according to the invention either the treatment temperature to reduce and / or to shorten the treatment time while maintaining the same temperature. Finally, you can also do a deep and combine high temperature bleach in one operation. In such cases it can be an advantage be to use the activator in less than the amount; it will then only be a at lower temperatures Part of the existing active oxygen activated; the rest stands for the bleaching at elevated temperatures to disposal.

The conditions to be observed when working with the activators to be used according to the invention are, for example concentration of the peroxide, temperature. pll-Werl and duration of treatment, are essentially based on the substance to be oxidized or bleached, and possibly also on the substance to be oxidized or bleached Carrier material on or in which the substance to be bleached is located. The mostly aqueous oxidation resp. Bleaching liquids can contain 20 to 500, preferably 50 to 250 mg / l of active oxygen and one Have a pH in the range from 2 to 12, preferably 7 to 11.5 and in particular 8 to 10.5.

The activators to be used according to the invention can be used wherever previously Peroxo compounds, in particular hydrogen peroxide or perborates, as oxidizing agents or bleaching agents has used. This applies e.g. B. for bleaching oils, fats and waxes, in cosmetic iiaar and Skin treatment, when disinfecting or sterilizing, when passivating aluminum or others I. light metal surfaces and especially when bleaching of all types of fiber.

The desired pH value of the claimed agents is made by adding acidic, neutral or alkaline reacting substances, possibly adjusted by buffer mixtures, above all by such additives, which were previously used in corresponding, customary types of application.

These include, for example, water-soluble or water-insoluble stabilizers for per compounds,

serving to lower the surface tension of the aqueous oxidizing or bleaching liquids anionic, nonionic, cationic or zwitterionic surface-active substances, slightly acidic to alkaline reacting builder substances, including inorganic or organic complexing agents for the Water and heavy metal ions are to be counted, as well as inorganic or organic Colloidal substances, especially water-soluble organic high polymers.

Limit the use of these solid and especially powdery to granular oxidizing and bleaching agents the advantages of the activators to be used according to the invention do not relate solely to activation of the existing per-compounds. · In particular by adding activators with melting points above 100 "C, preferably above 120'C and In particular in the range from 130 to 200 ° C., the oxidizing and bleaching agents according to the invention remain good shelf-stable, d. H. they show only a very low loss of active oxygen even after prolonged storage and at the same time only a very small decrease in oxygen activation.

The solid activators can be used as powder or granules with the other components of the oxidation and mix bleach.

The liquid at room temperature, but also the solid particles in the oxidizing and bleaching agent to be incorporated activators can also with water-soluble or water-insoluble, preferably in Water swellable high molecular weight organic substances be encapsulated or encased. Suitable Capsule b / .w. Hüllsubslanzen are z. B. gelatin, methyl, oxethyl or carboxymethyl cellulose, starch and starch derivatives. Solid water-soluble polyglycol ethers can also be used for this purpose.

Of the inorganic per compounds, especially those in aqueous solution are neutral to alkaline Reactive compounds, especially the Pcrborate, of practical interest.

Among the various perborates, sodium perborate tetrahydrate (NaBo., · HjO .. ■ J H..O) great practical importance. In its place, partially or completely, i. H. until the approximate composition NaBO .. · H_> O_>, dehydrated perborate can be used. Finally are too Borates NaBO containing active oxygen. · HjO .. useful in which the ratio Na..O: tt.Oj is smaller is than 0.5: 1 and preferably in the range 0.4 to 0.15: I and in which the ratio H> Oj: Na im Range from 0.5 to 4: I. These products are in the German patent specification 9 01 287 or in the American see patent 24 91 789 described.

The perborate can be wholly or partly by others Inorganic per compounds, in particular by peroxohydrates, are replaced, such as, for example Peroxohydrates of ortho-, pyro- or polyphosphates and carbonates.

The oxidizing and bleaching agents according to the invention can be customary water-insoluble or water-soluble Contain stabilizers for per compounds in amounts of up to 10, preferably from 0.5 to 8 percent by weight.

The various magnesium silicates are suitable as water-insoluble perstabilizers. Usually it is here about precipitation products that occur when aqueous solutions of alkali silicates are combined with solutions from magnesium salts arise. The ratio MgO: SiO ,. can range from 4: 1 to 1: 4,

preferably from 2: 1 to 1: 2. Used many times you can get a product with a ratio MgO: SiO2 = 1: 1- These magnesium silicates can be replaced by the corresponding silicates of other alkaline earth metals, cadmium or tin. > Hydrous oxides of tin can also be used as stabilizers. These stabilizers are mostly in Amounts from 1 to 8, preferably from 2 to 7% of the weight of the total preparation are present.

The water-insoluble stabilizers can be quite n> or partially replaced by water-soluble ones. As such, those to be discussed later are suitable organic complexing agents, the amount used depending on the strength of the complexes formed in the Range from 0.25 to 5, preferably from 0.5 to 2.5 from ι ^ Weight of the entire remedy can be.

It is often important to maintain a certain pH value when using the agents according to the invention; therefore one sets this v ^; eleven times weakly acidic, neutral or alkaline reacting substances. i <> The pH value of a 1% solution will usually be in the range from 7 to! 2.

Examples of manufacture
of the activators according to the invention: s

Example H 1
ON-diacctyl-Np-toluenesulfonyl-hydro. ylamin

46.2 g (0.25 mol) of Np-toluenesulfonyl-hydroxylamine are mixed with 75.6 g (0.75 mol) of acetic anhydride with stirring, the temperature rising to 65 to 70 ^° C. within one hour. The mixture is stirred for a further 14 hours, the reaction solution is evaporated in vacuo and the remaining crude product is recrystallized from isopropanol; Bulge: 47.5 g (64% of theory) ON-diacetyl-Np-toluenesulfonylhydroxylamine; F. 65 to 67 ^c C.

Analysis for C,, HuNO, S (MG: 271.30):

Calculates: a <<

C48.70%, H 4.80%, N 5.17%, S 11.81%;

found:

C 48.53%, H 4.79%. N 5.54%, S 11.56%.

B e i s ρ i e I H 2

O-propionyl-NN-suceinyl hydroxylamine
(N-propionyloxy-succinimide)

The solution of 33 g (approx. 0.3 mol) of N-hydroxysuccinimide in 340 ml of propionic anhydride is ^{stirred at 80 °} C. for 4 hours. After the reaction solution has been evaporated in vacuo, the residue crystallizes through. After recrystallization once from isopropanol, 42.4 g (85.6% of theory) of N-propionyloxyss succinimide are obtained; 47 to 48 ° C.

Analysis WrC ₇ HqNO ₄ (MG: 171.15):

Calculated: (49.20%, H 5.26%, N 8.19%;

found: C 49.89%, H 5.40%, N 7.90%. <«>

Example H 3

O-benzoyl-N.N-succinyl-hydroxylamine

(N-Ben / oxy-succinimide) << \

To the suspension of 17.3 g (0.15 mol) of N-hydroxysuccinimide in 200 ml of ether and 60 ml of pyridine are added dropwise at 5 ° C with stirring within 15 minutes Solution of 17.5 ml (0.15 mol) of benzoyl chloride in 50 ml Ether to. The mixture is left to stir for a further 2 hours at room temperature, 200 ml of water are added and the suction is filtered colorless, crystalline product. After two recrystallizations from isopropanol, 19.8 g are obtained (60.2% of theory) analytically pure N-benzoxy-suecinimide; F. 137 to 139 C.

Analysis for C, ιHhNO ₄ (MG: 219.20):

Calculated: C 60.27%, H 4.14%, N 6.39%:
found: C 60.69%. H 3.76%, N 6.50%.

Example 114

Op-Methoxybenzoyl-NN-suceinyl-hydroxylamine
(Np-methoxybenzoxy-succinimide)

The representation of the p-methoxybenzoyl derivative takes place analogously to the information in Example 3 above.

From 46.0 g (0.4 mol) of N-hydroxysuccinimide and 68.24 {.> (0.4 mol) of p-methoxybenzoyl chloride is obtained after recrystallization from isopropanol 79.8 g (80% of Theory) N-p-methoxybenzoxy-succininiid; F. 142 to 14 5 ° C.

Analysis for C,> H _n NO -, (MW: 249.23):

Calculated: C "57.80%. H 4.45%. N 5.62%:
found: C "57.73%. 114.09%, N 5.55%.

Example 115

Op-Niirobenzoyl-NN-siiccinyl-hydroxylamine
(Np-nitrobcn / oxy-suecinimide)

By analogy with the procedure in Example 3, wins from 27.5 g (0.24 mol) of N-hydroxysuccinimide and 41.0 g (0.24 mol) of p-nitrobenzoyl chloride according to the Recrystallization from acetonitrile 28.0 g (44.4% of theory) of N-p-nitrobenzene / oxy-succinimide; F. 212 to 215 ° C.

Analysis for C ₁ , H "N>O" (MW: 264.20):

Calculated: C 50.00%, H 3.06%, N 10.60%;
found: C 50.52%, 112.72%. N 10.89%.

Example 116

O.O'-Malonyl-bis-fN.N-succinyl-hydroxylamine]
(N-malonyloxy-disuccinimide)

The suspension of 79.0 g (0.68 mol) of N-hydroxy-succinimide in 500 ml of dry benzene and 48.0 g (0.34 mol) of malonyl chloride is 15 hours at 40 to 45 ° C and then stirred for a further 2 hours at the boiling point until the evolution of HCl has ended. That Crude N-malonyloxy-disuccinimide which has precipitated in almost quantitative yield is filtered off with suction with ether washed and recrystallized once from acetonitrile; Yield: 66.7 g (65.7% of theory) analytically pure N-malonyloxy-disuccinimiu with a melting point of 244 ° C (Zcrs).

Analysis RIrCuHi ₁₁ NA (MG: 298.22):

Calculated: C 44.31%, H 3.38%. N 9.39%;
found: C 44.60%. 113.29%. N 9.72%.

Example H 7

Table for example V 2

O, O'-succinyl-bis- [N, N-succinyl-hydroxylamine]
(N-succinyloxy-disuccinimide)

The suspension of 115.0 g (I ₁ O mole) of N-hydroxysuccinimide in II of dry toluene and 77.5 g (0.5 mole) of succinyl chloride is boiled for 10 hours until the end of the HO-development under reflux. The precipitated product is filtered off with suction and washed with ether; Yield: 149 g (95.5% of theory) of N-succinyloxy-disuccinimide, melting point 279 to 283 ° C. (decomp.).

Analysis for C, ₂ H, ₂ N ₂ O ₈ (MW: 312.24):

Calculated: C 46.16%, H 3.87%, N 8.97%;
found: C 46.34%, H 3.93%, N 8.97%.

All compounds prepared were also identified by their IR, NMR and mass spectra clearly characterized.

Examples of the use according to the invention
of the products described as activators for inorganic per compounds.

Examples V1 to V4

The usefulness of the activators used according to the invention was demonstrated by the following experiments demonstrated:

Solutions containing 0.615 g NaBO ₂ · H ₂ O ₂ · 3 H ₂ O (4 mmol) and 2.5 g Na ₄ P ₂ O ₇ · 10H ₂ O per liter were heated to 45 ° or 45 ° after the addition of 4 mmol of activator . 60 ⁰ C heated and kept during the entire experiment with stirring at the specified temperature. 100 ml were pipetted off at certain time intervals, immediately added to a mixture of 250 g ice and 15 ml glacial acetic acid and then after adding approx.

035 g potassium iodide with 0.1 N sodium thiosulfate solution and strength titrated as an indicator.

Consumed under the specified conditions

with 100% activation of the peroxo compounds used, 8.0 ml of thiosulfate solution. In the Tables are both the thiosulphate consumption and the percentage of activated peroxo compound specified.

Table for example V 1

Activation of 'crborat with lir / ielte Vklivieriing O-I'ropionyl-N, N-suc %O cinyl-hydroxylamiri activated Pnihc- at 45 C ■ nahnie 80.0 after ml at W) ( 65.2 ν Minulei 0.1 n- activated 52.2 Na ₂ S ₂ O, ml 38.6 7.29 91.2 0.1 iv 19.8 7.23 90.5 Na ₂ S ₂ O, 7.6 Λ = 1 6.65 83.2 6.40 0 5 6.39 79.9 5.21 10 5.69 71.0 4.18 15th 4.95 61.8 3.09 30th 4.39 54.8 1.58 45 0.61 60 0

Table for example V 3

Activation of perborate with Ο, Ν-diacetyl-p-loluene sulfonyl hydroxylamine

sample limcllc activation at W) C %O took activated naeh at 45 C ml ν minutes 0.1 n- 34.4 ml %O Na ₂ S ₂ O ₁ 41.2 0.1 n- activated 2.75 25.4 Na ₃ S ₂ O ₃ 3.30 20.1 Λ = 1 2.08 26.0 2.03 0 5 4.14 51.7 1.61 0 10 4.62 57.7 0 0 15th 4.18 52.2 0 30th 2.01 25.2 0 45 0.65 8.1 60 0 0

Table for example V4

Activation of perborate with [Ν, Ν-succinyl-hydroxylamine]

0, O '- succinyl - bis

Activation of perboral with O-Benzoyl-N, N-succinyl- 50 Probe- Hrziclie activation hydroxylamine

sample Achieved activation %O at 60 C %O took activated activated after at 45 C ml A 'minutes 7.9 0, ln- 15.1 ml 15.6 Na ₂ S ₂ O ₃ 28.4 0, in- 25.6 1.21 38.9 Na ₃ S ₂ O ₃ 34.2 2.27 43.8 V = 1 0.63 49.1 3.11 42.5 5 1.25 51.7 3.51 21.0 10 2.05 42.5 3.40 10.0 15th 2J4 1.68 30th 3.92 0.80 45 4.13 60 3.40

would take

after

χ minutes

at 45 (. '

ml

0.1 n-Na ₂ S ₂ O ₃

% o activated

at 60 C

ml

0.1 n-Na ₂ S ₂ O ₃

%O

activated

■■ 1 3.72

5 5.60

10 6.51

15 6.42

30 6.22

45 5.63

60 5.46

46.5 70.0 81.4 80.0 77.9 70.4 68.3

4.45 6.81 6.13 5.66 4.25 2.94 2.03

55.6 85.2 76.7 71.0 53.2 36.8 25.4

As can be seen from the tables, the substances examined show good activation de

Perborates, although the course of activation differs from case to case. The compound O-propionyl-N, N-succinyl hydroxylamine (see Example V 2) shows both at 45 ° C and at 60 ⁰ C immediately after the start of the experiment, a maximum activation, which lasts especially at 45 ° C over time. The compound O-benzoyl-NN-succinyl-hydroxylamine (Example V 1) reaches its maximum activation at 45 ° C. only after about 45 minutes, in order to then maintain a relatively high degree of activation until the end of the experiment. At 60 ⁰ C the maximum activation occurs already after about 15 minutes, after then, the activation decreases faster than at 45 ° CON-diacetyl-p-toluolsulfonylhydroxylamin (Example V 3) activated at 45 ° C after 10 minutes most and then quickly diminishes in effect; at 60 ^° C. it is activated to a medium strength for about 15 minutes. O, O'-succinyl-bis- [N, N-succinyl-hydroxylamine] (Example V 4) shows an initially increasing and then only slightly decreasing ability to be activated both at 45 ° C. and at 60 ° C. This different behavior in the course of activation over time gives the person skilled in the art the possibility of choosing an activator whose effect is optimally adapted to the respective bleaching or oxidation process.

Example V5

Aqueous solutions containing _{10 to 200 g / l H 2} O ₂ are usually used for bleaching hair, for dyeing hair with the aid of oxidizing dyes and for oxidative post-treatment of hair after shaping under the action of reducing thio compounds (Kaltwell-Vei drive).

If this treatment is carried out after adding 20 to 500 g / l of one of the activators according to the invention, in particular one of the activators according to Examples V 1 to V 4, a considerable increase in the oxidizing effect of the H ₂ O ₂ can be observed, so that, if desired, can also work at lower H ₂ O ₂ concentrations.

Comparative example

To demonstrate the use of O, O'-succinyl-bis- [N, N-succinyl-hydroxylamine] in comparison to the known Aküvatoren N'O-diacetyl-hydroxylamine (French patent 11 55 228) and N-acetyl-N'-phenyl-hydantoin (Belgian patent 6 63 716) technical progress to be achieved the experiments described for Examples VI to V 4 using these three activators repeated. The results can be found in the following table:

sample % activated oxygen at 60 N, () - l) iacetyl- (hi I insal / took of the activator hydroxylamine after ν minutes O, () '- succinyl N-AtCIyI- his- | N, N-suc- 25.0 N'-phenyl- mono-hydroxyl 47.1 hydanloin amine) 48.2 Λ = I. 55.6 45.0 73.0 5 85.2 34.0 66.0 10 76.7 23.0 51.0 15th 71.0 38.8 30th 53.2 17.9 60 25.4 6th

As the results show, the activator according to the invention exceeds Ο, Ο'-succinyl-bis- [N, N-succinyl-hydroxylamine] the well-known activator N-acetyl-N'-phenyl-hydantoin in its rapid activating effect and thus offers a progressive alternative. Compared to the well-known activator Ν, Ο-diacetyl-hydroxylamine the activator according to the invention is particularly superior.

Claims (1)

Patent claims: l.O.N-diacetyl-N-p-toluenesulfonylhydroxylamine. 2.0-propionyl-Ν, Ν -succiny! -Hydroxylamine. 3. O-Benzoyl-N, N-suc: ynyl-hydroxylamine. 4. O-p-methoxybenzoyl-N.N-succinyl-hydroxylamine. 5.0-p-nitrobenzoyl-N.N-succinyl-hydroxylamine. 6.0.O'-malonyl-bis-fN.N-succinyl-hydroxylamine]. 7.0, O'-succinyl-bis- [N, N-succinyl-hydroxylamine]. 8. Use of triacylated hydroxylamines according to claim I to 7 as activators for inorganic per compounds in an amount of 0.1 to 3, preferably 0.25 to 2 mol of activator per g-atom of active oxygen. 9. Use of triacylated hydroxylamines according to claim I to 7 as Aklivatorcn for inorganic per compounds in oxidizing and bleaching fluids, the 20 to 500, preferably 50 Contains up to 250 mg / 1 active oxygen.