US3825543A - N-acylated tetraaza-bicyclo-nonandiones and compositions for activating oxygen - Google Patents

Abstract

N-ACYLATED 2,4,6,8 - TETRAAZA-BICYCLO-(3,3,1)-NONAN-3,7DIONES OF THE FORMULA

2-R2,4-R4,6-R3,8-R1-2,4,6,8-TETRAAZABICYCLO(3.3.1)NONAN-

3,7-DIONE

WHEREIN AT LEAST TWO OF R1, R2, R3 AND R4 ARE ACYLS OF ORGANIC CARBOXYLIC ACIDS HAVING 2 TO 10 CARBON ATOMS AND THE REMAINDER OF R1, R2, R3 AND R4 ARE MEMBERS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND SAID ACYL OF ORGANIC CARBOXYLIC ACIDS HAVING 2 TO 10 CARBON ATOMS, AND R5 AND R6 ARE MEMBERS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND METHYL, AS WELL AS THE METHOD OF PRODUCING THE SAME AND COMPOSITIONS CONTAINING THE SAME FOR ACTIVATION OF PERCOMPOUNDS IN AQUEOUS SOLUTIONS AT TEMPERATURES BELOW 70* C.

Description

United States Patent ABSTRACT OF THE DISCLOSURE N-acylated 2,4,6,8 tetraaza-bicyclo-(3,3,1)-nonan-3,7- diones of the formula wherein at least two of R R R and R are acyls of organic carboxylic acids having 2 to carbon atoms and the remainder of R R R and R are members selected from the group consisting of hydrogen and said acyl of organic carboxylic acids having 2 to 10 carbon atoms, and R and R are members selected from the group consisting of hydrogen and methyl, as well as the method of producing the same and compositions containing the same for activation of percompounds in aqueous solutions at temperatures below 70 C.

THE PRIOR ART Aqueous solutions of inorganic percompounds, particularly peroxide or perborates, have long since been used as oxidation and bleaching agents for the most varied types of materials. Of course, the active oxygen becomes effective with a sufficient speed for practical purposes only at temperatures in excess of 70 C., preferably in the range between 80 C. and 100 C., so that these bleaching agents cannot be used with thermo-sensitive materials with which, taking into account the material to be bleached, work has to be carried out at relatively low temperatures.

It has already been proposed to add specific N-acyl compounds to the aqueous solutions of percompounds in order to activate the latter. According to German Published Application DAS 1,162,967, the compounds used for this purpose should contain at least two acyl groups attached to the same nitrogen atom, such as N,N,N'- triacetylmethylenediamine, N,N,N',N'-tetraacetylmethylenediamine and the like. According to German Published Application DAS 1,291,317, compounds of the general formula RCONR OCR serve this purpose, wherein R and R signify C alkyl residues, while R may constitute an optional organic radical which may be combined with R to form a ring, if desired substituted, such as caprolactam, N-acylated barbitone, phthalimide, anthranil, N-acylated hydantoin or saccharine rings.

Copending United States Patent Application Ser. No. 141,372, filed May 7, 1971, now Pat No. 3,715,184, describes the use of acylated glycolurils of the general formula 3,825,543 Patented July 23, 1974 wherein at least two of the residues R and R constitute acyl residues having 2 to 8 carbon atoms, while the other residues signify hydrogen atoms and/or alkyl or aryl residues having 1 to 8 carbon atoms and/or acyl residues having 2 to 8 carbon atoms, as activators for percom pounds. The acyl residues present in one molecule may be the same or diiferent. Preferably, tetraacylglycolurils having similar C acyl residues are used, particularly tetraacetylglycoluril.

OBJECTS OF THE INVENTION An object of the present invention is the obtaining of N-acylated 2,4,6,8-tetraaza-bicyclo (3,3,1) nonan-3,7- diones of the formula wherein at least two of R R R and R are acyls of organic carboxylic acids having 2 to 10 carbon atoms and the remainder of R R R and R are members selected from the group consisting of hydrogen and said acyl of organic carboxylic acids having 2 to 10 carbon atoms, and R and R are members selected from the group consisting of hydrogen and methyl.

Another object of the present invention is the development of a process for the production of the above N- acylated 2,4,6,8-tetraaza-bicyclo-(3,3,1)-nonan-3,7-diones.

A yet further object of the present invention is the development of a method of activating aqueous solutions of percompounds at temperatures below 70 C. by utilization of the above N-acylated 2,4,6,S-tetraaza-bicyclo- (3,3,1 )-nonan-3,7-diones.

These and other objects of the invention will become more apparent as the description thereof proceeds.

DESCRIPTION OF THE INVENTION The present invention relates to new chemical substances which may be used as activators for percompounds which produce H 0 in aqueous solution, said compounds being N-acylation products produced by acylating in a manner known per se a 2,4,6,8-tetraaza-bicyclo-(3,3,1)- nonane-3,7-dione of the general formula I:

H {I I in which R and R individually signify a methyl residue or a hydrogen atom. The new acylation products preferably contain at least two acyl residues attached to the nitrogen atoms of the general formula II:

When preferably four acyl residues are attached to the nitrogen atoms, the compounds correspond to the general formula III:

Rio 111 wherein R-,, R,, R, and R represent hydrocarbon residues, optionally substituted having 1 to 9 carbon atoms, and R and R represent methyl residues or hydrogen atoms.

The acyls and acyls and hydrogen of R to R or the residues R, to R may be the same or different. Since compounds having similar acyls R to R or similar residues R to R are simpler to produce, these compounds have greater practical importance. The acyls of R to R are preferably acyls of organic carboxylic acids having 2 to l carbon atoms selected from the group consisting of alkanoic acids having 2 to 4 carbon atoms, haloalkanoic acids having 2 to 4 carbon atoms, nitriloacetic acid, benzoic acid, alkylbenzoic acids having 8 to 10 carbon atoms, alkoxybenzoic acids having 8 to 10 carbon atoms, halobenzoic acids, nitrobenzoic acids, nitrilobenzoic acids, nitrotoluic acid, and halotoluic acid.

Among these acyls are acetyl, propionyl, butyryl, chloroacetyl, nitriloacetyl, benzoyl, toluoyl, p-methoxybenzoyl, mor p-chlorobenzoyl, mor p-nitrobenzoyl, nitrilobenzoyl, nitrotoluoyl and chlorotoluoyl. In formula III the group --COR corresponds to R of formula II where R is acyl. If the residues R to R are of aliphatic nature, they have preferably 1 to 3 carbon atoms. If aromatic residues are involved, they may contain up 'to 9 carbon atoms. Accordingly, the following are preferred as residue R to R methyl, ethyl, nor i-propyl, phenyl, toluyl or xylyl residues. Suitable substituted groups are C; alkoxy] groups, halogen atoms, nitroor nitrile groups; mor p-chloro-, or mor p-nitro-substituted residues may be mentioned as examples of chloroand/or nitro-substituted aromatic residues.

2,4,6,8-Tetraacetyl 2,4,6,8 tetraaza-bicyclo-(3,3,l)- nonan-3,7-dione and its 9,9-dimethyl derivatives are of particular practical importance. However, the tetrapropionyl, tetrabutyryl or tetrabenzoyl derivatives may be used instead, as well as mixed acylated compounds such as acetylpropionyl derivatives or acetyl-benzoyl derivatives.

Propylenedicarbamide serves as the raw material for producing these kinds of new compounds in which R and R represent hydrogen. The propylenedicarbamide is obtainable by condensation of urea with malonic dialdehyde 0r l,l,3,3-tetramethoxypropane [cf. Chemical Abstracts, Vol. 57 (1962), columns 13627i/l3628a or Vol. 58 (1963), column 4552c]. Starting materials in which R and R represent methyl residues are obtained in accordance with the data given in German Published Application DAS 1,212,978.

In a manner known per se, these starting materials are converted into the acylation products by acylation, for example, with the corresponding carboxylic acids and anhydrides thereof, carboxylic acid halides, or with ketenes. Sulfuric acid is suitable as the catalyst when acylating with carboxylic acid anhydrides. Advantageously, the process is carried out at a temperature of from 40 to 100 C. Mixed acylated products may be produced by converting the non-acylated starting material with a mixture of acylation agents; by acylation in stages using different acylating agents or by re-acylating a tetraacylated product with a different acylation agent.

The substances produced as technical raw products by this process are already usable in this state as activating agents for percompounds, but if importance is attached to their purity, they may be purified in a conventional manner by, for example, recrystallization or chromatographic processes.

Furthermore, the present invention relates to the use of the above-described N-acyl compounds as activators for H 0 or percompounds producing H 0 in water.

The percompounds to be activated in aqueous solution can be any type of inorganic or organic percompound which will release active oxygen in an aqueous solution. For economic reasons, the percompounds preferably utilized are inorganic peroxides, inorganic peracids, inorganic peroxyhydrates and products of the addition of hydrogen peroxide with inorganic and organic compounds.

Of the peroxides to be activated, hydrogen peroxide is of the greatest practical importance. It may be used as such, but may also be used in the form of its mostly solid peroxyhydrates or products of addition with inorganic and organic compounds. The latter include, for example, the products of addition of hydrogen peroxide to urea or melamine, and examples of the peroxyhydrates are the perborates, perortho-, perpyro-, and perpoly-phosphates, percarbonates and persilicates. The peroxyhyhydrates are preferably soluble in water and are ordinarily utilized in the form of their alkali metal salts, such as their sodium salts. The activators, according to the invention, however, may also be used together with true peracids, such as for example, Caros acid (peroxymonosulfuric acid, H 50 or peroxydisulfuric acid (11 8 0 or their salts.

Each acyl residue present in the acetylated 2,4,6,8- tetraaza-bicyclo-(3,3,1)nonan-3,7-dione activator is able to activate an active oxygen atom of the percompound used. Therefore, in theory, the activator and percompound should be used in equivalent amounts for complete activation of the active oxygen present. In practice, however, satisfactory effects are attained in many cases even with substantially smaller amounts of activator, while on the other hand, the activator may also be used in relatively large excess.

It is possible to obtain perceptibly improved bleaching and oxidation values if only 1% of the total oxygen present is activated. An excess of activator is also possible. Generally, the quantity of activator to be used lies in the range of 5% to 500%, preferably from 10% to 200%, of the quantity required theoretically, 100% corresponding to an acyl residue per atom of active oxygen. If the tetraacetyl derivative is used as an activator, 2.38 parts by weight tetraacetyl derivative are theoretically required for a 100% activation for each part by weight of H 0 and 0.51 parts by weight of the tetraacetyl derivative for one part by weight of The activation, in accordance with the invention, of the oxygen is most clearly perceptible at temperatures in the range of 20 C. to C., especially from 30 C. to 60 C. Nevertheless, it is possible to use higher temperatures up to 100 C. for example, particularly when using deficient quantities of activator, so that chemically activated oxygen is used at temperatures up to 70 C., and thermally activated oxygen at higher temperatures, particularly temperatures in excess of C. Depending upon the problem to be solved, it is possible for the technician, when using the activators according to the invention, either to reduce the temperature of treatment and/or to shorten the time of treatment, the temperature remaining the same. Finally, a low and a high temperature bleach can also be combined in one operation. In such cases it may be advantageous to add less than the theoretical amounts of activator; then at low temperatures only a part of the active oxygen present is activated, and the remainder is available for the bleaching at elevated temperatures.

The conditions to be maintained during operation with the activators according to the invention, such as for example, the concentration of the peroxide, temperature, pH value and time of treatment, depend substantially on the substance to be oxidized and/or bleached, and in some cases on the carrier material on or in which the substance to be bleached is present. The usually aqueous oxidizing or bleaching liquids may contain from 20mg. to 500 mg., preferably from 50 mg. to 250 mg., per liter of active oxygen and have a pH value of from 4 to 12, preferably from 7 to 11.5, and particularly from 8 to 11. It should be kept in mind that the activators act by way of the intermediately formed percarboxylic acids. Therefore, carboxylic acid is produced during the oxidation or bleaching process and this should be neutralized by an alkali if a shift in the pH valuev is not desired.

As indicated, aqueous solutions of percompounds and the N-acylated 2,4,6,8-tetraaza bicyclo (3,3,1) nonan- 3,7-diones, optionally with other ingredients as indicated below may be utilized. These aqueous solutions preferably contain sufficient percompounds to give a concentration of from 20 mg. to 500 mg., preferably 50 mg. to 250 mg. per liter of active oxygen and sufficient N-acylated 2,4,6,8-tetraaza-bieyelo-(3,3,1)-nonan-3,7-dione activator to provide from 0.05 to 5, preferably 0.1 to 2 acyls of the N-acylated activator per active oxygen atom.

The activators according to the invention may be used wherever percompounds, especially hydrogen peroxide or perborates, have previously been used as oxidizing and/ or bleaching agents. This applies, for example, to the bleaching of oils, fats and waxes, to cosmetic skin and hair treatment, in disinfection or sterilization, in passivation of aluminum or other light metal surfaces, and especially in the bleaching of fibrous substances of all kinds.

The desired pH value is adjusted by addition of acid, neutralor alkaline-reacting substances, possibly by buffer mixtures, and particularly by additives which have also been co-employed in a corresponding, formely customary treatment.

These frequently include the surface-active substances which serve to decrease the surface tension of the aqueous oxidizing or bleaching liquid, such as for example, soap or known synthetic detergents of anionic, non-ionic, amphoterie or cationic nature. When working in the alkaline range, alkaline substances may be added as well as inorganic or organic complex-forming compounds, especially complex-forming compounds suitable for binding the so-called hardness-producing substances in water or heavy metals which may possibly be present.

Furthermore, the invention relates to agents for producing aqueous oxidation baths effective in the cold, particularly alkaline bleaching and Washing solutions, effective in the cold, for textiles. The composition of such agents lies generally in the range of the following recipe:

1% to 90% by weight of acylation products, serving as activators for percompounds, of N-acylated 2,4,6,8- tetraaza-bicyclo-(3,3,l)-nonan-3,7-diones of formula II shown above,

99% to 10% by weight of other conventional constituents of aqueous oxidation liquids, particularly of alkaline bleaching or washing compositions for textiles.

The acylation products contain as activators in the products, in accordance with the invention, preferably at least two and particularly four acyl residues combined with nitrogen. The latter compounds correspond to formula III shown above.

In particular, the invention relates to solid oxidation compositions for bleaching and washing agents consisting essentially of from 5% to 90% by weight of an activator N-acylated 2,4,6,S-tetraaza-bicyclo-(3,3,1)-nonan-3,7- dione, from 95% to 10% by weight of at least one alkaline-reacting builder salt, from 0 to by weight of a surface-active compound selected from the group consisting of anionic surface-active compounds, non-ionic surface-active compounds and amphoteric surface-active compounds, and from 0 to 30% by weight of other customary bleaching composition additions selected from the group consisting of percompound stabilizers, heavy metal complexing agents, corrosion inhibitors and optical brighteners, as well as solid, powdery-to-granular oxidation compositions for bleaching and washing agents consisting essentially of a water-soluble solid inorganic percompound in the form of its alkali metal salt and an activator N-acylated 2,4,6,8 tetraaza bicyclo (3,3,1 )-nonan-3,7- dione, said activator being present in an amount sulficient that from 0.05 to 5 acyls in said N-acylated 2,4,6,8- tetraaza-bieyclo-(3,3,l)-nonan-3,7-dione are present per active oxygen atoms in said percompound.

The other conventional constituents of such agents of the above formulation include particularly those substances which are contained in bleaching, pre-washing or full washing agents, such as neutraland/or alkaline-re acting builders, percompounds yielding H 0 in aqueous solution, stabilizers for percompounds, complex formers, tensides or surface-active compounds, additives for increasing or reducing the foaming of the tensides, textile softeners, soil suspension agents, enzymes, optical brighteners, anti-corrosion agents, anti-microbial substances, perfumes, dyes, etc.

The activators may be coated or encased in any 0ptional manner in such agents, so that the activators do not come into direct contact with the other constituents of the mixture. Thus the keeping qualities of such mixtures are considerably improved.

The products of the invention can be employed in the most varied technical fields anywhere it is important to activate oxygen in order to oxidize. It performs its oxidizing effect already at temperatures of 20 C. to 70 C., preferably 30 to 60 C. Examples for such application fields are the cleaning of instruments, apparatus, pipe lines and vessels of wood, plastic, metal, ceramic, glass, etc., in the industry or in technical plants; the cleaning of furniture, walls, the dishwashing in the household; and particularly the bleaching or laundering of textiles of any kind in industry, in commercial laundries and in the household. The low temperature bleaching with the use of chemically actviated oxygen may also be combined with a high temperature bleaching in which the oxygen is activated thermally. There is, therefore, the possibility in the industry, in the commerce and in the household, dependent upon the problems to be solved, by the use of the activators of the invention either to lower the treatment temperature and/or to shorten the treatment at the same temperature, or as already mentioned, to combine a low temperature and a high temperature bleaching.

In addition to cotton, regenerated cellulose or linen, it is possible in commerce or in the home to wash and/or bleach the so-called easy wash textiles which are made from highly finished cotton or synthetic fibers, such as polyamide, polyester, polyacrylonitrile, polyurethane, polyvinylchloride or polyvinylidenechloride fibers, or which contain the latter mixed with other fibers. The textiles designated easy wash" and someties as non-iron also include fabrics made from a mixture of synthetic fibers and cotton which may be specifically finished.

Even if the activators to be used in accordance with the invention achieve their effect together with percompounds yielding H 0 in aqueous solution, the agents in accordance with the invention do not necessarily have to contain percompounds. Agents containing activators, and containing no percompounds, may be of interest in the textile industry or in commercial laundries where percompounds are frequently added to the wash liquor in the form of hydrogen peroxide. Also such agents may also be of value in the home, if they are used in common with activator-free bleaching washing agents. For such purposes, it is advisable to put these agents on the market in the form of tablets or apportioned in packages.

In addition to the activators and the other additives, such products frequently contain certain quantities of auxiliary washing agents and washings agents of conventional,

neutral and preferably alkaline-reacting builders, so that their composition is substantially in the range of the following formula:

% to 90%, preferably 7% to 70%, by weight of activator in accordance with the invention,

95% to 10%, preferably 93% to by weight of neutral or preferably alkaline-reacting builders customary in auxiliary and washing agents,

0 to 15%, preferably 0 to 10%, by weight, of tensides,

0 to preferably 0 to 10%, by weight of other conventional constituents of bleaching liquors, such as stabilizers for percompounds, complex formers for heavy metals, corrosion inhibitors, optical brighteners, etc.

With respect to their effects, the activators to be used in accordance with the invention are comparable to the best known products. Furthermore, they have the special advantage that all the acyl residues present are available for activating the oxygen. Thus, theoretically equivalent quantities of active oxygen and activator have to be used for completely activating the active oxygen present. In many cases in practice, it is sufficient to activate only a portion of the active oxygen. For example, it is possible to obtain perceptibly improved bleaching and oxidation values if only 1% of the total oxygen present is activated. A surplus of activator is also possible. In general, the quantity of the activator to be used is in the range from 5% to 500%, preferably from 10% to 200%, of the theoretically required quantity. 100% corresponds to one acyl residue for each atom of active oxygen. If the tetraacetyl derivative is used as an activator, 2.38 parts by weight of tetraacetyl derivative are required theoretically for 100% activation per part by Weight of H 0 and 0.51 parts by weight of tetraacetyl derivative are theoretically required for one part by weight of Thus in products which contain percompounds yielding H 0; in aqueous solution, as well as containing the activators in accordance with the invention, the quantitative proportion of active oxygen to activator should be in the above-mentioned range. The composition of such products is then substantially in the range of the following formula:

(1) 5% to 100%, preferably 10% to 90%, by weight of a bleaching component comprising 50% to 95% by weight of percompounds yielding H 0; in aqueous solution 50% to 5% by weight of activators in accordance with the invention, and (2) 95% to 0, preferably 90% to 10%, by weight of other conventional constituents of oxidation and bleaching agents, particularly of bleaching agents for textiles.

The activators in such products are preferably present in quantities such that the quantity of activator is from 5% to 500%, preferably 10% to 150%, of the theoretically required quantity, the theoretically required quantity (=100%) corresponding to one acyl residue for each active oxygen atom.

Such special products preferred for the textile industry or for commercial laundries contain preferably more than 40% by weight of percompounds and activators, while the bleaching, soaking, pre-washing and washing agents primarily used in the home generally contain no more than 40% by weight, preferably from 10% to 40%, particularly from 10% to by weight of percompounds and activators.

The composition preferred for the textile industry, or for special products intended for commercial laundries, lies generally in the range of the followig formula:

% to 100%, preferably to 80%, by weight of a bleaching component in accordance with the above definition,

60% to 0, preferably to 20%, by weight of neutral or preferably alkaline-reacting builders,

0 to 40% by weight of tensides and, if required, additives for increasing or reducing the foaming of the tensides,

0 to 30%, preferably 1% to 20%, by weight of other conventional constituents of bleaching agents such as complex formers, textile softeners, soil suspension agents, enzymes, optical brighteners, anti-corrosion agents, anti-microbial substances, perfumes, dyes, etc.

The combination, in accordance with the present invention, of activators and percompounds and, if required, stabilizers, anti-corrosion agents, and complex formers, may also be incorporated to advantage in the soaking agents to be used primarily in the home, usually at room temperature, particularly when the washing remains for a long period of time in, the soaking bath. Such soaking agents have substantially the following composition:

0 to 5% by weight of tensides,

% to 95% by weight, preferably 55% to 90% by weight, of preferably inorganic alkaline-reacting builders,

5% to 40%, preferably 10% to 40%, by weight of bleaching component in accordance with the above definition.

The composition of the prewashing, fine and full washing agents generally lies in the range of the following formula:

5% to 40% by weight of tensides,

5% to 80% by weight of neutral or preferably inorganic alkaline-reacting builders,

5% to 40% by weight, preferably 10% to 40%, by weight of bleaching component in accordance with the above definition,

0 to 20% by weight of other conventional constituents of such washing agents.

In such washing agents, the quantity of the neutral or preferably inorganic alkaline-reacting builder is usually at least equal to and preferably greater than the quantity of the tensides present.

The invention relates particularly to the use of the above-described activators in bleaching, soaking, prewashing and main washing agents whose composition lies generally in the range of the following formula:

(a) 2% to 40%, preferably 8% to 30%, by weight of tensides or combinations of tensides, comprising:

0 to 100%, preferably 25% to by weight of anionic surface-active compounds of the sulfonate and/or sulfate type with preferably 8 to 18 carbon atoms in the hydrophobic residue, 7

0 to 100%, preferably 5% to 40%, by weight of non-ionic surface-active compounds, f

0 to 100%, preferably"10%- to 50%, by weight of soap,

0 to 6%, preferably 0.5% to 3%, by weight of foam stabilizers, i

0 to 8%, preferably 0.5% to 5%, by weight of foam inhibitors.

(b) 10% to 82%, preferably 35% to by weight of complex-forming and/or non-complex-forming builders, at least a portion of these builders having an alkaline reaction and the quantity of the alkaline-to-neutral reacting builders being preferably 0.5 to 7 times, and particularly 1 to 5 times, the total tenside combination.

(c) 10% to 50%, preferably 10% to 45%, by weight of the combination, in accordance with the invention, of percompound, particularly perborate and activator and, if required, stabilizers for the percompounds, the quantity of this combination being preferably such that the content of active oxygen in the total washing agent amounts to 1% to 4%,-preferably 1.5% to 3.5%, by weight. a

(d) 0 to 20%, preferably 2% to 15%, by weight of other washing agent constituents such as corrosion inhibitors, soil suspension agents, anti-microbial substances, optical brighteners, enzymes, perfumes, dyes, water.

Of particular practical importance are the washing agents which are intended for use in washing machines, preferably in drum-type washing machines in which the tenside component generally amounts to 7% to 30% by weight. This component generally has the following composition:

8% to 95%, preferably 25% to 75%, by weight of tensides (anionic surface-active compounds) of sulfonate and/or sulfate type with preferably 8 to 18 carbon atoms in the hydrophobic residue,

to 80%, preferably 10% to 50%, by weight of soap,

insofar as when the soap is present, the quantitative proportion (sulfonatej-l-sulfate): soap preferably lies in the range between 10:1 to 1:10, particularly :1 to 1:2,

0 to 35% by weight of non-ionic tensides,

0 to 6%, preferably 0.5% to 3%, by weight of foam stabilizers,

0 to 8%, preferably 0.5% to 5%, by weight of nonsurface-active foam inhibitors, the foaming of the tenside component being reduced either by the simultaneous presence of tensides of the sulfonate and/or sulfate type and foam-inhibiting soap and/or by the presence of the non-surface-active inhibitors.

Sodium perborate tetrahydrate (NaBO -H O -3H O) has particular practical importance among the preferably inorganic percompounds yields H 0 in aqueous solution. Partially or completely dehydrated perborates, i.e., perborates dehydrated up to NaB0 -H O may be used instead of sodium perborate tetrahydrate. Alternatively, the borates NaBO -H 0 (as described in German Pat. No. 901,287 or in US. Pat. 2,491,789) may be in used in which the ratio Na O:B O is less than 0.5 :1 and preferably from 0.4 to 0.15:1, while the ratio H O :Na is from 0.5 to 4:1. All these perborates may be replaced entirely or partially by other inorganic percompounds, particularly by peroxyhydrates, for example, the peroxyhydrates of the ortho-, pyroor polyphosphates, particularly of tripolyphosphates, and of the carbonates. These peroxyhydrates are preferably soluble in water and are ordinarily utilized in the form of their alkali metal salts, such as the sodium salts.

It is advisable to incorporate quantities of from 0.25% to by weight of conventional water-soluble and/or water-insoluble stabilizers for stabilizing the percompounds in the products of the invention. The magnesium silicates of a ratio of MgO:SiO =4:1 to 1:4, preferably 2:1 to 1:2, and particularly 1:1, generally obtained by precipitation from aqueous solutions, are suitable as water-insoluble stabilizers for percompounds. These compounds, for example, amount to from 1% to 8%, preferably 2% to 7%, of the weight of the entire preparation. Other alkaline earth metal silicates, cadmium silicates or tin silicates of corresponding composition may be used instead of the magnesium silicates. Water-containing oxides of tin are also suitable as stabilizers. Stabilizers soluble in water, which may be present together with stabilizers insoluble in water, are the organic complex formers whose quantity can amount to 0.25% to 5% preferably 0.5% to 2.5% of the weight of the entire preparation.

The tensides contain in the molecule at least one hydrophobic residue of mostly 8 to 26, preferably 10 to 22 and especially 10 to 18 carobn atoms, and at least one anionic, nonionic or amphoteric water-solubilizing group. The preferably saturated hydrophobic residue is mostly aliphatic, but possibly also alicyclic in nature. It may be combined directly with the water-solubilizing groups or through intermediate members, such as through benzene rings, carboxylic-acid ester links, carbonamide links or sulfonic-acid amide links as well as through etheror ester-like residues of polyhydric alcohols.

Soaps, which are derived from natural or synthetic fatty acids, possibly also from resin acids or naphthenic acids, are utilizable as anionic detergent substances, especially if these acids have iodine values of not more than 30 and preferably less than 10.

Among'the synthetic anionic tensides, the sulfonates and sulfates possess particularly practical importance.

The sulfonates include, for example, alkylbenzenesul fonates with preferably straight-chain C especially C1044 alkyl residues, alkanesulfonates, obtainable from preferably saturated aliphatic C especially C1243 hydrocarbons by sulfochlorination or sulfoxidation, mixtures of alkenesulfonates, hydroxyalkanesulfonates and alkanedisulfonates, known under the name of olefinsulfonates," which are formed by acidic or alkaline hydrolysis of the sulfonation products which first result from terminal or non-terminal C and preferably C1248 olefins by sulfonation with sulfur trioxide. The sulfonates, uitlizable according to the invention, include also salts, preferably alkali metal salts of a-SLllfO fatty acids and salts of esters of these acids with mono or polyhydric alcohols with 1 to 4, and preferably 1 to 2 carbon atoms.

Further useful sulfonates are salts of fatty acid esters of hydroxyethanesulfonic acid or of dihydroxypropanesulfonic acid, the salts of the fatty alcohol esters of lower aliphatic or aromatic sulfomonoor dicarboxylic acids, containing 1 to 8 carbon atoms, the alkylglycerylether sulfonates and the salts of the amide-like condensation products of fatty acids or sulfonic acids with aminoethanesulfonic acid.

Tensides of the sulfate type include fatty alcohol sulfates, especially those derived from coconut fatty alco hols, tallow fatty alcohols or from oleyl alcohol, also sulfatized fatty acid alkylamides or fatty acid monoglycerides and sulfated alkoxylation products of alkylphenols (C alkyl), fatty alcohols, fatty acid amides, or fatty acid alkylolamides with 0.5 to 20, preferably 1 to 8, and particularly 2 to 4 ethylene and/or propyleneglycol residues in the molecule.

As anionic tensides of the carboxylate type, for example, the fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids, are suitable as well as the amidelike condensation products of fatty acids or sulfonic acids with aminocarboxylic acids, such as glycocoll, sarcosine or with protein hydrolysates.

The anionic tensides are mostly present as salts of the alkali metals, particularly of sodium, as well as the ammonium salts and salts of lower alkylamines or lower alkylolamines.

The nonionic tensides, for the sake of simplicity called hereafter Nonionics, include the polyethyleneglycol ethers, obtained by addition of from 4 to 100, preferably 6 to 40 and especially 8 to 20 mols of ethylene oxide to fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid amides or sulfonic acid amides, as well as the still water-soluble adducts of propylene oxide or butylene oxide to the above. Furthermore, products known by the trade name Pluronics or Tetronics belong to the Nonionics. These products are obtained from waterinsoluble polypropyleneglycols or from water-insoluble propoxylated lower aliphatic alcohols with l to 8, preferably 3 to 6 carbon atoms, or from water-insoluble propoxylated lower alkylenediamines, by ethoxylation until water-soluble. Finally, the partly water-soluble reaction products of the above-named aliphatic alcohols with propylene oxide, known as Ucon-Fluid can also be used as Nonionics.

Further useful Nonionics are fatty acid alkylolamides or sulfonic acid alkylolamides, derived, for example, from monoor diethanolamine, from dihydroxypropyl amine or other polyhydroxyalkyl amines, such as the glycamines. Also the oxides of higher tertiary amines with a hydro phobic alkyl residue and two shorter alkyl and/or alkylol residues, with up to 4 carbon atoms each, can be considered as Nonionics.

Amphoteric tensides contain in the molecule both acidic groups, such as carboxyl, sulfonic acid, sulfuric acid half 11 esters, phosphonic acid and phosphoricacid partial ester groups, an'd also basic groups, such as primary, secondary, tertiary and quaternary ammonium groups. Amphoteric compounds with quaternary ammonium groups belong to the type of the betaines. Carboxy, sulfate and sulfonate betaines having a particularly practical interest because of their good compatibility with other tensides.

The foaming power of the tenside can be increased or reduced by combination of suitable tenside types, as well as changed by additions of non-tenside organic substances.

Suitable foam stabilizers, particularly in tensides of the sulfonate or sulfate type, are surface-active carboxy or sulfobetaines, as well as the above-named nonionics of the alkylolamide type. Moreover, fatty alcohols or higher terminal diols have been suggested for this purpose.

A reduced foaming power, that is desirable for the use in washing machines, is often attained by combination of different tenside types, such as of sulfates and/or sulfonates and/or of nonionics, on the one hand, with soaps, on the other hand. In soaps, the foam inhibition increases with the degree of saturation and the number of carbons in the fatty acid residue. Soaps derived from saturated C2044 fatty acids have been proven good as foam inhibitors.

The non-tenside foam inhibitors included N-alkylated aminotriazines, optionally containing chlorine, which are obtained by the reaction of 1 mol of cyanuric acid chloride with 2 to 3 mols of a monoand/or dialkylamine with 6 to 20, preferably 8 to 18 carbon atoms in the alkyl radicals. Similarly effective are propoxylated and/or butoxylated aminotriazines, such as, products that are obtained by the addition of from to 10 mols of propylene oxide to 1 mol of melamine and further addition of from 10 to 50 mols of butylene oxide to this propyleneoxide derivative.

Other non-tenside foam inhibitors are water-insoluble organic compounds, such as paraffins or halogenated paraffins with melting points below 100 C., aliphatic C to C ketones as well as aliphatic carboxylic acid esters which contain in the acid or alcohol residue, optionally also in both of these residues, at least 18 carbon atoms (such as triglyceride or fatty acid/fatty alcohol esters). These compounds can be used for the inhibition of foam, above all in combinations of tensides of the sulfate and/ or sulfonate type with soaps. As particularly low-foaming nonionics which can be used both alone, particularly in the agents for automatic dishwashing, and also in combination with anionic, amphoteric and nonionic tensides and to reduce the foaming power of better foaming tensides, addition products of propylene oxide to the above-described surface active polyethyleneglycol ethers are suitable as well as the also above-described Pluronic, Tetronic and Ucon-Fluid types.

All weakly acidic, neutral and alkaline reacting organic or organic salts, particularly inorganic or organic sequestering agents, are suitable as builders.

Weakly acidic, neutral or alkaline reacting salts usable according to the invention are, for example, the bicarbonates, carbonates, borates or silicates of the alkali metals, also mono-, dior trialkali metal orthophosphates, dior tetraalkali metal pyrophosphates, alkali metal metaphosphates known as sequestering agents, alkali metal sulfates as well as the alkali metal salts of organic nonsurface-activc sulfonic acids, carboxylic acids and sulfocarboxylic acids, containing from 1 to 8 carbon atoms. To them belong, for instance, the water-soluble salts of benzene-, tolueneor xylene-sulfonic acid, water-soluble salts of sulfoacetic acid, sulfobenzoic acid or salts of sulfodicarboxylic acids as well as the salts of the acetic acid, lactic acid, citric acid and tartaric acid.

Further usable as builders are the water-soluble salts, such as the alkali metal salts, of higher-molecular weight polycarboxylic acids, particularly polymerizates of maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, methylenemalonic acid and citraconic acid. Also mixed polymerizates of these acids with each other, or with other polymerizable substances, such as, ethylene, propylene, acrylic acid, methacrylic acid, crotonic acid, 3-butenecarboxylic acid, 3-methyl-3butenecarboxylic acid as well as with vinylmethyl ether, vinyl acetate, isobutylene, acrylamide and styrene, are usable.

Also suitable as sequestering builders are the weakly acidic reacting metaphosphates and the alkaline reacting polyphosphates, particularly tripolyphosphate. These compounds may be replaced completely or partially by organic sequestering agents.

The organic sequestering agents include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, polyalkylenepolyamine-N-polycarboxylic acids and other known organic sequestering agents. Also combinations of different sequestering agents may be used. The other known sequestering agents include also diand polyphosphonic acids of the following constitutions:

OH x on OH X 0H X OH A L J I I O=P-- --P=O O: -I-1|=O R-N --I-II=O )H H on z OH Y 011 2 x OH HO X X OH l s ate. Ga t- WI-4 M Y (5H J 0 Y 2 Y off I wherein R represents alkyl and R represents alkylene residues with l to 8, preferably 1 to 4 carbon atoms; X and Y represent hydrogen atoms or alkyl radicals with 1 to 4 carbon atoms and Z represents the groups OH, -NH or NXR. For a practical use, the following compounds are considered above all: methylenediphosphonic acid, l-hydroxyethane-1,1-diphosphonic acid, l-aminoethane-1,1-diphosphonic acid, aminotri(methylenephosphonic acid), methylaminoor ethylaminodi-(methylenephosphonic acid), and ethylenediaminetetra-(methylenephosphonic acid). All these sequestering agents may be present as free acids, or preferably as their alkali metal salts.

Soil-suspending agents which keep the dirt loosened from the fiber suspended in the liquor, and thus prevent the graying, can also be utilized in the washing agents and washing auxiliaries. For this, water-soluble colloids, mostly organic in nature, are suitable, such as the watersoluble salts of polymeric carboxylic acids, glue, gelatins, salts of ethercarboxylic acids or ethersulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also water-soluble polyamides, containing acidic groups, are suitable for this purpose. Furthermore, soluble starch preparations and starch products other than the above-named, such as degraded starch, aldehyde starches, etc. may be used. Also polyvinylpyrrolidone is usable.

The ingredients of the washing agents and washing auxiliaries, particularly the builders are mostly so selected, that the preparations react neutral to distinctly alkaline in aqueous solution. Preferably, the pH-value of a 1% solution of the preparation mostly lies in the range from 7 to 12. Fine-washing agents have mostly a neutral to weakly alkaline reaction (pH-value=7 to 9.5); while soaking, pre-washing and boiling-washing agents are more strongly alkaline (pH value from 9.5 to 11.5, preferably from 10 to 11.5). The action of the activators is associated with alkali consumption. Thus, the builders present should prevent the pH value from dropping below the stated minimum values during the entire treatment period.

The enzyme preparations to be used are mostly a mixture of enzymes with different effects, such as proteases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, desmolases, or nucleases. Of particular interest are the enzymes, obtained from bacteria strains of from fungi, such as Bacillus subtilis or Streptomyces griseus, particularly proteases and amylases, which are relatively stable towards alkalis, percompounds, and anionic tensides and are still effective at temperature up to 70 C.

Enzyme preparations are marketed by the manufacturers mostly as aqueous solutions of the active substances or as powders, granulates or as cold-sprayed products. They frequently contain sodium sulfate, sodium chloride, alkali metal ortho-, pyroand polyphosphate, particularly tripolyphosphate, as fillers. Dust-free preparations are particularly valued. These are obtained in a known manner by incorporating of oily or pasty Nonionics or by granulation with the aid of melts of water-of-crystallization-containing salts in their own water-of-crystallization.

Enzymes may be incorporated which are specific for certain types of soil, for example, proteases or amylases or lipases. Preferably, combinations of enzymes with different effects are uxd, particularly combinations of proteases and amylases.

The optical brighteners which can be utilized in the compositions are mostly, it not exclusively, derivatives of aminostilbenesulfonic acid, or of diaminostilbenedisulfonic acid, of diarylpyrazolines, of carbostyril, of 1,2-di- (2-benzoxazolyl)-ethylene or 1,2 di-(Z-benzimidazolyl) ethylene, of benzoxazolyl-thiophene and of the commarms.

Examples of brightcners from the class of the diaminostilbenedisulfonic acid derivatives are compounds, according to formula 1:

In the formula, R and R represent alkoxy, amino, or residues of aliphatic, aromatic or heterocyclic, primary or secondary amines as well as residues of aminosulfonic acids, where the aliphatic residues present in the above groups, contain preferably 1 to 4 and particularly 2 to 4 carbon atoms, while the heterocyclic ring systems are mostly 5 to 6 membered rings. As aromatic amines the residues of the aniline, of the anthranilic acid or the anilinesulfonic acid are preferred. Brighteners, derived from the diaminostilbenedisulfonic acid, are mostly used at cotton brighteners. The following products, derived from formua I, are commercially available, where R represents the residue -NHC H and R may represent the following residues: NH --NHCH -NHCH CH OH,

NHCH CH OCH --NHCH CH CH OCH --N CH CH CH OH, N(CH CH OH) morpholino-, --NHC H -NHC H SO H, OCH Some of these brighteners are, in regard to their fiber afiinity, regarded as transitional types to the polyamide brighteners, such as the brightener with R =-NHC H The compound 4,4-bis-(4-phenyl- 1,2,3-triazole-2-yl)-2,2'-stilbenedisulfonic acid belongs also to the cotton brighteners of the diaminostilbenedisulfonic acid type.

The polyamide brighteners, some of which have a certain afiinity for W001 fibers, include diarylpyrazolines of the formulae II and III:

II: R: R:

R;I -I\ ta. A N An III: C 2- z In the formula II R and R represent hydrogen, alkyl and aryl, optionally substituted by carboxyl, carbonamide or carboxylic acid ester groups, R and R represent hydrogen or lower alkyl, Ar and Ar represent aryl radicals, such as phenyl, diphenyl or naphthyl, which may carry further substituents, such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, carboxylic acid esters, sulfonic acid, sulfonamide and sulfone groups or halogen atoms. Commercially available brighteners of this type are derived from the formula III, where the radical R may represent the groups Cl, SO NH -SO CH=CH and C0OCH CH OCH while R mostly represents a chlorine atom. Also the 9 cyanoanthracene belongs to the polyamide brighteners.

The polyamide brighteners further include aliphatically or aromatically substituted aminocourmarins, such as 4- methyl 7 dimethylamino-coumarin or 4 methyl 7- diethylaminocoumarin. Further usable as polyamide brighteners are the compounds 1 (2-benzimidazolyl)-2 (l hydroxyethyl 2 benzimidazolyl) ethylene and 1 ethyl 3 phenyl 7 diethylamino-carbostyril. Suitable as brighteners for polyester and polyamide fibers are the compounds 2,5-di-(2-benzoxazolyl) thiophcne and 1,2-di-(S-methyl-Z-benzoxazolyl)-ethylene.

If the brighteners together with other ingredients of the invention products are present as aqueous solution or paste, and are to be transformed to solids by heat drying, it is recommended to incorporate organic sequestering agents in amounts of at least 0.1%, preferably 0.2% to 1% by weight of the solid products in order to stabilize the brighteners.

The present invention will be further described with reference to the following specific examples which are, however, not to be deemed limitative in any respect.

EXAMPLES The Examples designated H describe the manufacture of the products produced in accordance with the invention; the Examples designated V describe the use of said products, and the Examples designated A and B describe compositions containing the activators of the invention.

The propylenedicarbamide used as the raw material was produced by treating urea with 1,1,3,3-tetramethoxypropane in accordance with Kageyama et al., Chemical Abstracts, 57 (1962), column 13627(i) or in accordance with Kobayashi, Chemical Abstracts, 58 (1963), column 4552(c). The propylenedicarbamide so produced had a melting point of 310 to 311 C. According to the data in the literature, the melting point is 310 C. A molecular weight of 156.15 is calculated from the empirical formula C H N O A molecular mass m/e=1-56 was determined by mass spectography. The analysis data found are compared with the calculated values below:

Calculated: C, 38.46%; H, 5.16%; N, 35.88% Found: C, 38.51%; H, 5.15%;N, 36.18%

The 9,9-dimethyl-2,4,6,8 tetraaza bicyclo (3,3,1)- nonan-3,7-dione also used as the raw material was produced in accordance with the data in German Published Application DAS 1,212,978 by condensation of urea with a-chloroisobutyl-methylether in the presence of dimethyl formamide and SOCl or COClg- The melting point of the product was in excess of 360 C. A molecular weight of 184.20 was calculated from the empirical formula C7H12N407- A molecular mass m/e=184 was determined by mass spectography. The analysis data, calculated and found, were as follows:

Calculated: C, 44.65%; H, 6.62% N, 30.44% Found: C, 45.04%; H, 6.26%; N, 30.64%

The IR, NMR and mass spectra of the products of the process of Examples 1, 5 and 8 to 11, the IR spectra of the products of the process of Examples 2, 3 and 4, and the IR and mass spectra of the products of the process of Example 7 were obtained. In all cases, the spectra ob- 15 tained corresponded to the anticipated spectra. The molecular masses found by mass spectography, and the elementary analysis of the process products, are given in the individual examples. For further identification of the tetraacetyl compounds obtained in accordance with Examples 2, 3 and 4, the melting points of mixtures of these substances were checked with the tetraacetyl compound obtained in accordance with Example 1. The melting point was not lowered in any instance.

Example H1 The production of 2,4,6.8-tetraacetyl-2,4,6,8-tetraazabicyclo-(3,3,1)-nonan-3,7-dione by reaction of propylenedicarbamide with acetic acid anhydride.

1 ml. of 70% perchloric acid was added to a suspension of 8.1 gm. (0.052 mol) of propylenedicarbamide in 55 gm. (0.54 mol) of acetic acid anhydride at room temperature. The temperature increased to 35 C. While heating to 50 C., stirring was carried out for 7.5 hours and the solution obtained was then filtered off from the nonconverted starting material (0.8 gm. of propylenedicarbamide). The tetraacylated propylenedicarbamide, which separated from the clear filtrate after adding isopropanol, had a melting point of 181 to 183 C. after recrystallization from isopropanol. The yield amounted to 5.4 gm., corresponding to 35.7% of theory relative to propylenedicarbamide converted.

A molecular weight of 324.3 was calculated from the empirical formula C H N,O (m/e=324). The calculated analysis data corresponded to the analysis data found:

Calculated: C, 48.15%; H, 4.97%; N, 17.28% Found: C, 47.89%; H, 4.94%; N, 17.59%

Example H2 The production of 2,4,6,8-tetraacetyl-2,4,6,8-tetraazabicyclo-(3,3,l )-nonan-3,7-dione by reaction of propylenedicarbamide with acetic acid anhydride.

15.6 gm. (0.1 mol) of propylenedicarbamide was slowly added to a solution of 4 ml. of 100% sulfuric acid in 110 ml. of acetic acide anhydride over a period of 2.5 hours at 55 to 60 C. The mixture was stirred for 10 hours at 55 to 60 C. and the undissolved portions were filtered ofi'. isopropanol was added, under cooling, to the residue obtained after reduction in volume of the filtrate 18.5 gm. (56.5% of theory) of the tetraaeetyl derivative having a melting point of 174. 5 to 177.5 C. was precipitated after scratching on the vessel wall.

Example H3 The production of 2,4,6,8-tetraacetyl-2,4,6,8-tetraazabicyclo-(3,3,1)-nonan-3,7-dione by reaction of propylenedicarbamide with acetylchloride.

After adding 2 ml. of 100% sulfuric acid to a mixture of 15.6 gm. (0.1 mol) of propylenedicarbamide and 78.5 gm. (1 mol) of acetylchloride, the mixture was stirred for 34 hours while refluxing. The residue, obtained after filtering off the undissolved portions and distilling off the excess acetylchloride in vacuo, was dissolved in chloroform and washed three times with water until a neutral reaction was obtained.

After drying the chloroform solution over anhydrous Na SO and evaporating the chloroform in vacuo, 17.2 gm. (65.7% of theory) crude product was obtained. The yield amounted to 10.5 gm. (40.2% of theory) after recrystallization from ethanol. The recrystallized product had amelting point of 178 to 182 C.

Example H4 The production of 2,4,6,8-tetraacetyl-2,4,6,8-tetraazabicycle-(3,3,1)-nonan-3,7-dione by reaction of propylenedicarbamide with ketene.

Ketene was introduced for 8 hours into a suspension of 15.6 gm. (0.1 mol) of propylenedicarbamide in 60 gm. of glacial acetic acid and 1 ml. of 100% sulfuric acid.

16 The mixture was allowed to cool and the non-converted propylenedicarbamide (about half the amount used) was filtered off. By adsorptive filtration on a column of silica gel (0.05-0.12 mm.; eluting mixture, benzene/chloroform=:5), 2.3 gm. of raw product having a melting point of 170 to 182 C. was obtained from the viscous oil obtained after vaporizing the filtrate. The melting point rose to 181.5 to 183.5 C. upon recrystallizing once from isopropanol.

Example H5 The production of 2,4,6,S-tetrapropionyl-2,4,6,8-tetraaza-bicyclo-(3,3,1)-nonan-3,7-dione by reaction of propylenedicarbamide with propionic acid anhydride.

A suspension of 15.6 gm. (0.1 mol) of propylenedicarbamide in 150 ml. of propionic acid anhydride and 4 ml. of sulfuric acid was stirred for 9 hoursat 60 C. The slightly cloudy solution was filtered after standing overnight and subsequently concentrated in vacuo. The raw product was isolated from this solution in the same manner as described in Examples H1 and H2 for the tetraacetyl derivative. 18.4 gm. (48% of theory) of raw product, having a melting point of 142 to 144.5 C. was obtained. The melting point of the pure product obtained upon recrystallization was 144.5 to 146 C.

A molecular weight of 380.4 is calculated from the empirical formula C H N O (m/e=380); the calculated analysis data corresponded to the analysis data found:

Calculated: C, 53.68%; H, 6.36%; N, 14.73% Found: C, 53.56%; H, 6.63%; N, 14.74%

Example H6 The production of mixed tetraacylated 2,4,6,8-tetraaz abicyclo-(3,3,1)-nonan-3,7-diones by reaction of diacetyl- 2,4,6,8-tetraaza-bicyclo-(3,3,1)-nonan-3,7-dione with propionic acid anhydride.

A suspension of 48.0 gm. (0.2 mol) of diacetyl- 2,4,6,S-tetraaza-bicyclo-(3,3,1)-nonan 3,7 dione (manufactured in accordance with Example H8) in 78.0 gm. (0.6 mol) of propionic acid anhydride and 6 ml. of 100% sulfuric acid was stirred at 98 to 100 C., until a clear solution had formed after 6 hours. The residue obtained after evaporation was dissolved in chloroform and extracted three times with water. After drying the chloroform solution with anhydrous Na SO and evaporating, a light yellow oil was produced which crystallized after adding isopropanol, cooling and scratching the glass wall. After vacuum filtering the isopropanol and washing the residue with isopropanol and methanol, there remained l't) gm. of a substance mixture which had a melting point of to 141 C. and which, according to the mass spectrum, constituted a mixture of tetrapropionyl-, monoacetyltripropionyland diacetyl-dipropionyl 2,4,6,8 tetraaz abicycle-(3,3,1)-nonan-3,7'diones (m/e=380 or 366 or According to a thin layer chromatogram, the reaction mixture contained the said three compounds in substantially the same proportions. The empirical formula C H N O and an average molecular weight of 366.38, is calculated therefrom. The calculated analysis data corresponded to the analysis data found:

Calculated: C, 52.45%; H, 6.05%; N, 15.29% Found: C, 52.49%; H, 6.01%; N, 15.59%

Example H7 product was isolated as described in Example H6. 5.2 gm. (22.8% of theory) of the raw product was obtained having a melting point of 103 to 107 C. The melting point was 113 to 116 C. after recrystallization twice from methanol or ethanol.

A molecular weight of 380.4 (m/e=380) is calculated from the empirical formula C H N O The calculated analysis data corresponded to the analysis data found:

Calculated: C, 53.68%; H, 6.36%; N, 14.73% Found: C, 52.34%; H, 6.07%; N, 15.08%

Examples H8 to H10 The production of N,N'-diacylated 2,4,6,8 tetraazabicycle-(3,3, 1 -nonan-3,7-dione.

Suspensions of 0.1 to 0.2 mol of propylenedicarbamide in 0.3 to 0.6 mol of the corresponding carboxylic acid anhydride were heated in the presence of 100% sulfuric acid, cooled to to C. after the reaction was completed, and methanol or acetonitrile was added. The precipitated diacyl derivatives were vacuum filtered and recrystallized. The working conditions used in each case and the characteristic values of the process products are given below.

Example H8 The production of N,N'-diacetyl 2,4,6,8 tetraazabicyclo- (3 ,3,1)-nonan3,7-dione.

Starting mixture:

15.6 gm. (0.1 mol) propylenedicarbamide 30.6 gm. (0.3 mol) acetic acid anhydride, 3 ml.

H 80 Reaction conditions: 2.5 hours, 60 C. Raw yield: 11.3 gm. (47.2% of theory) Melting point after recrystallization from water: 249 C.

to 251 C. Values: Empirical formula C H N O Molecular weight: 240.2 (m/e=240) Analysis:

Calculated: C, 45.00%; H, 5.05%; N, 23.32% Found: C, 45.04%; H, 5.00%; N, 23.83%

Example H9 The production of N,N-dipropionyl-2,4,6,S-tetraazabicyclo- 3,3, 1 -nonan-3,7-dione.

Example H10 The production of N,N'-dibutyryl-2,4,6,8-tetraaza-bicylo- 3,3,1 )-3,7-dione.

Starting mixture:

15.6 gm. (0.1 mol) propylenedicarbamide 47.4 gm. (0.3 mol) butyric acid anhydride, 2.5 ml.

H SO Reaction conditions: 4 hours, 60 to 70 C. Raw yield: 9.0 gm. (30.4% of theory) Melting point after recrystallization from acetonitrile:

216 to 219 C. Values: Empirical formula C H N,O Molecular weight: 296.3 (m/e=296) Analysis:

Calculated: C, 52.69%; H, 6.80%; N, 18.91% Found: C, 52.61%; H, 6.75%; N, 19.63%.

18 Example H11 The production of 2,4,6,8 tetraacetyl-9,9-dimethyl- 2,4,6,8-tetraaza-bicyclo-(3,3,1)-nonan-3,7-dione by reaction of dimethylpropylenedicarbamide with acetic acid anhydride.

A suspension of 21 gm. (0.114 mol) of dimethylpropylenedicarbamide in 116 gm. (1.14 mol) of acetic acid anhydride and 3.5 ml. of 100% sulfuric acid was stirred for 5 hours at to C. After evaporating the clear dark reaction solution in vacuo, a residue was obtained which was purified by dissolution in isopropanol, cooling and vacuum filtering, and recrystallizing from approximately 400 ml. isopropanol. The yield then amounted to 18.0 gm. (25% of theory). The melting point of the product was 164 to 174 C. This product was purified by column chromatography through silica gel (eluent: benzene:chloroform=60:40) and recrystallizing from isopropanol. The melting point was then 180 to 183 C.

A molecular weight of 352.35 is calculated from the empirical formula C H N O (m/e=352). The calcu-- lated analysis data corresponded to the analysis data found:

Examples H12 to H17 The production of the tetrabenzoyl derivatives, chloroor nitro-substituted, if required, of 2,4,6,8-tetraaza-bicycle-(3,3,1)-nonan-3,7-dione or of 9,9-dimethyl-2,4,6,8- tetraaza-bicyclo-(3,3,1)-nonan-3,7-di0ne.

The substances produced are given in the following tables. They were produced in accordance with the following general specification.

0.15 to 0.3 mol of benzoylchloride, substituted if required, were added drop by drop at room temperature to an agitated suspension of 0.05 mol of the substance to be benzoylated in 100 ml. of dry pyridine. The starting substances went into solution during 3 hours heating of this reaction mixture to to C. The liquid was filtered oft, insofar as the reaction product separated as in the case of p-nitrobenzoylchloride, for example. However, if the reaction product remained in solution, the pyridine was distilled in vacuo and the product of the process was isolated from the dried residue by mixing with water. Heavily colored impurities could be removed by washing with chloroform.

The following tables contain details concerning the process conditions, the yields, the solvents used for recrystallization and the melting points. The raw yields relate to the tetrabenzoyl derivatives.

EXAMPLES H12 'IO H14.-Tetrahenzoy1 derivatives of 2,4,6,8-tetraaza-bicyclo-(3,3,1)-nonan-3,7-dione EXAMPLES H15 '10 H17.Tetrabenzoyl derivates of 9,9-dimethyl- 2,4,6,8-tetraaza-bicyclo-(3,3,1)-nonan-3,7-dione Melting point Example Benzoylating after recrystal- No. agent Raw yield hzation from- 15 0.3 mol benzoyl- 29.5 gm., 98% 255 to 257 C./

chloride. theory. acetone. 16. 0.3 mol p-ehloro- 32.0 gm., 87% 254 to 258.5 C./

benzoylchloride. of theory. chloroform. 17 0.3 mol p-nitro- 17.0 gm., 44% 267 to 270 C./

benzoylchlorlde. of theory. dimgthylionnam! e.

(4 mMol) and 2.5 gm. of Na P O -H O per liter, after addition of either 1, 2 or 4 mMol of activator (corresponding to 0.25, 0.5 and 1 mol of activator per mol of active oxygen) were heated to 24, 45 and 60 C., respectively. The solutions were agitated and maintained at the stated temperatures during the entire experiment.

100 ml. of the solution were drawn oif by means of a pipette at specific intervals of time, immediately added to a mixture of 250 gm. of ice and 15 ml. of glacial acid and then, after addition of about 0.35 gm. of potasium iodide, were titrated with 0.1 N sodium thiosulfate solution using starch as an indicator.

Under the stated experimental conditions, about 8 ml. of thiosulfate solution were consumed with a 100% activation of the peroxy compound used. The thiosulfate consumed and the percentage amount of the activated peroxy compound are given in the tables. The blank value characterizes the consumption of thiosulfate of the test solutions before adding the activator and thus the maximum quantity of the activated oxygen.

2,4,6,8-tetraaza-bicyclw(3,3,1)-nonan-3,7-dione Activation obtained- At 24 C. At 45 C. At 60 C Percent Percent Percent Sampling after 1 M1. 0.1 N 0 300- M1. 0.1 N 0 acti- M1. 0.1 N O actiminutes N81310: vated N 82310! vated Nazslox vated 60 6. 37 79. l 6.25 64. 8 1. 46 18.0 Blank value 8.05 100. 0 8. 10 100. 0 8.11 100. 0

2 ,4,6,8-tetraaza-bicyc1o-(3,3,l)-nonan-3,7-dione Activation obtained- At 24 C. At C. At 0.

Percent Percent Percent Sampling after 1: M1. 0.1 N acti- M1. 0.1 N O acti- M1. 0.1 N 0 actiminutes NmSzO; vated N81320: vated N82510: vated EXAMPLE V-1e.Activation of 1 mol of perborate with 1 mol of 2,4,6,8-tetraacctyl' 2,4,6,8-tetraaza-bicyc1o-(3,3,1)-nonnn-3,7-dione EXAMPLE V-2a.-Activation of 1 ol of perborate with 0.5 mol of 2,4,6,8-tetrapropionyi 2,3,G,8-tetraaza-bicyclo-(3,3,1)-nonan-3,7dione Activation obtained- At 24 C. At 45 C At 60 C Percent Percent erccnt Sampling alter 1 M1. 0.1 N 0 actl- M1. 0.1 N 0 acti- M1. 0.1 N 0 aetimmutes NaiSzOa vated N82310: vated NaiSzOa vated tetraazabicyelo-(3.3,l)-nonan-3,7-dione Activation obtained- At 24 C At 45 C. At 60 0.

Percent Percent Percent Sampling alter I M]. 0.1 N O acti- Ml 0.1 N acti- M]. 0.1 N O actirnlnutcs N 82510: vated N 32370: voted NazSzOs vated EXAMPLE V-6a.-Aetivatlon of 1 mol of perborate with 0.5 mol of 2.4.6.8-tetraacetyl- 9,9 dimethyl-2,4,6,8-tetraaza-bicyclo-(3,3,l)-nonan-3,7-dione Activation obtained- At 24 C. At 45 C. At 60 0.

Percent Percent Percent Sampling alter 2 M1. 0.1 N O acti- M1. 0.1 N O acti- 0.1 N 0 actiminutes N 211810: vated Na; S10: vated N82570: voted 1 1. 08 13. 5 4. 48 b5. 9 7.14 89. 0 5 6.20 64.8 7.15 80.2 7.13 88.9 10.-.. 7. 29 90. 9 7. 28 90. 8 6. 75 84. 2 15.. 7. 65 95. 4 7. 29 90. 9 6. 44 80. 3 80.. 7. 72 96. 3 7. 03 87. 7 5. 67. 3 60.. 7. 90 98. 6 6. 34 79. l 3. 51 44. 1 Blank valu 8.02 100. 0 8. 02 100. 0 8. 02 100. 0

EXAMPLE V-5b.-Activation 0t 1 mol ol perborate with 1 mol of 2,4.6,8-tetraaeetyl'9,9-

At 24 C. At c. .At 60 0.

Percent Percent Percent. Sampling after 1 M1. 0.1 N 0 ac l. 0.1 N O acti- M]. 0.1 N 0 aetiminntes NaiSlO: vated NmSzOi vated N82510: vated 1 7.10 as. 7.10 87.9 e. 95 se. 0 5.-. 5. e2 70. a 7. 42 91.8 7. 05 87.3 10 6.60 70.0 7.65 94.3 6.58 81.4 15...-

5.98 74.8 7.50 92.8 0.20 70.7 30. 6.98 87.3 7. 3a 90. 7 7. 14 e3. 5 so 7. 48 93.5 6.88 85.1 a. 70 46.8 Blank value... 8.00 100.0 8.08 100.0 8.08 100.0

It is preferred that solutions of H 0 or of compounds ABS" signifies the salt of any alkylbenzenesulfonic yielding H 0 having a concentration of from 10 to 200 acid, having from 10 to 15, preferably from 11 to 13, gm. R 0, per liter are used for oxidative treament of hair carbon atoms in the alkyl chain, obtained by condensing and, advantageously, the solutions have a pH value of straight chain olefins with benzene and sulfonating the from 7 to 11, preferably from 8 to 10.5. The pH value alkylbenzene thus obtained. I may be adjusted by adding buffer substances. Mixtures of Alkanesulfonate signifies a sulfonate obtained from ammonium salts of strong acids and aqueous ammonia 45 parafiins having from 12 to 16. carbon atoms by way of have proved to be successful. The amount of activator sulfoxidation. to be used corresponds to the above date. HPK-sulfonate or HT-sulfonate signifies the a-sul- Example V6 fonates obtained from the methyl esters of a hardened palm kernel or a hardened stearic fatty acid by sulfonat- For the purpose of bleaching hair, dyeing hair by 50 ing with $0 means of oxidation dyes, and oxidative after-treatment Olefinsulfonate signifies a sulfonate which is obtained of hair after setting under the efiect of reducing thio comfrom olefin mixtures having from 12 to 18 carbon atoms pounds, an aqueous solution produced in the following by sulfonating with S0; and hydrolyzing the sulfonation manner is used, for example: product with aqueous sodium hydroxide. The olefinsulfo- 6gm. of (NH4)QSO, 15ml. ofa25% aqueousNH and nate consists substantially of alkenesulfonate and hy- 37 ml. of a 30% B 0, solution are dissolved in 30 ml. of droxyalkanesulfonate, but also contains small amounts of water, and made up to 100 ml. with water. disulfonates. Products may also be used which are manu- If such a solution is used to make dark-blonde hair factured from a-position or non-terminal olefins. lighter, the hair is made perceptibly lighter within 30 to CA-sulfate and TA-sulfate signify the salts of sul- 90 minutes at 20" to 30 C. However, if 40 gm. of 2,4, fated, substantially saturated fatty alcohols produced by 6,8-tetraacetyl 2,4,6,8 tetraaza-bicyclo-(3,3,1)-nonanreduction of coconut fatty acid or tallow fatty acid. 3,7-dione or its 9,9-dimethyl derivative is added, the hair CA-EO-sulfate" signifies the sulfated products of adis made considerably lighter within the same time. Alterdition of 2 mols of ethyleneoxide to 1 mol of coconut natively, however, the treatment time can be shortened. fatty alcohol.

If the equivalent amount of 2,4,6,8-tetrapropionyl-2,4, OA+10EO," CA+20EO and .Fs-amide-l-8EO 6,8-tetraaza-bicyclo-(3,3,l)-nonan-3,7-dione or its 9,9-disignifiy the products of addition of ethyleneoxide (E0) methyl derivative is used, the bleaching activation is less to industrial oleyl alcohol (0A) or coconut alcohol (CA) at the beginning. Thus it is an easier matter to make the or coconut fatty acid amide, the number characterizing oolor only partially lighter up to a specific desired tint. the molar amount of ethyleneoxide added to 1 mol of the The following examples describe compounds of some initial compound. of the preparations in accordance with the invention. The CA-l-9EO+12PO signifies a non-ionic obtained by salt-like constituents, salt-like tensides, other organic salts converting 1 mol of CA-l-9EO" with .12 mols of proand inorganic salts are present as sodium salts unless pyleneoxide. otherwise expressly stated. The designations and abbre- Carboxybetaine and sulfobetaine signify the betaine viations used are as follows: obtained by reacting 1 mol of coconut alkyldimethylamine with 1 mol of chloroacetic acid or 1 mol of propane sultone.

CMC signifies the salt of carboxymethyl cellulose.

NTA, EDTA, DETPA, HEDP and ATMP signify the salts of the nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethanediphosphonic acid and aminotrimethylenephosphonic acid.

Perborate (mono) and perborate (tetra) signify a perboratemonoand perboratetetrahydrate of the approximate compositions NaBO -H O and NaBO -H O 3H O.

Activator signifies 2,4,6,8-tetraacetyl-2,4,6,8 tetraazabicyclo- (3,3,1 -nonan-3,7-dione.

The composition of the fatty acid mixtures from which the soaps B, C and D were produced is given in the following table. The table also includes the composition of the fatty acid mixtures of a soap G. If the soaps B, C and Any of the substances mentioned in the specification can be used as tensides, preferably one of the anionic or non-ionic substances mentioned under the examples. If these preparations are also to have the ability to absorb heavy metal ions, 0.2 to 5% by weight of EDTA, DETPA or ATM-P are added to them with a corresponding reduction in the content of the Na P O and/or Na CO Constituent of the preparation Percent by weight of the constituent in the preparation according to example- B1 B2 B8 B9 B10 COMPOSITION OF THE FATTY ACID MIXTURES CORRESPONDING TO THE SOAPS Percent by weight of the fatty acid constituent in the No. of carbon atoms soap present in the fatty acid D G 2 C10 2 2 4 1 012.-" 19 21 16 6 C14. 8 6 10 C10. 4 25 28 01 22 33 60 0 8 4 C22 37 18 Iodine number of the fatty acid mixture- 4 8 6 4 A mixture of about 45% of a di-(alkylamino)-monochlorotriazine and about 55% of a N,N',N-trialkylmelamine was used as a foam inhibitor. In all these triazine derivatives, the alkyl residues were present as a mixture of homologs with from 8 to 18 carbon atoms. Monochlorotriazine derivatives or trialkylmelamine could be used with a similar result. In the described products which contained synthetic sulfates or sulfonates together with soap, the other non-tenside-like foam inhibitors mentioned in the specification could be used, such as parafiin oil or parafiin. During the manufacture of the agents or preparations, the foam inhibitor used was dissolved in a suitable organic solvent or was sprayed in the melted state onto the moving pulverulent preparation by means of a nozzle.

The following Examples A1 to A7 and B1 to B10 described the composition of some of the preparations in accordance with the invention which may be used as special products in the textile industry, in commercial laundries, and, even if to a smaller extent, in the home. The products in accordance with Examples A1 to A7 do not contain percompounds. They can be used together with percompounds or bleaching, washing or auxiliary washing agents containing percompounds. On the other hand, the preparations according to Examples B1 to B10 themselves contain percompounds.

Percent by weight of the constituent in the preparation according to example- Constituent oi the preparation W1 W2 W3 W4 W5 CA+9 EO+12PO Fs-arnide+8 E0...

1.1 0.6 1.0 0.3 0.5 1.5 MgSiO; 1.4 2.4 2.2 1.0 1.0 Perborate (mono) 17.4 16.3 16.0 Perborate (tetra) 21.4 25.0 Activator 11.8 13.7 9.0 17.0 7.0 N21200:" 8.2 9.4 5.7 11.0 5.0 Bnghtener- 0.50 0.25 0.25 0.35 0.36 Residual water.

Percent by weight of the constituent in the preparation according to example- Constituent 01 the preparation W6 W7 W8 W9 W10 ABS Alkenesulionate- HT-sulionate.- CA-sulfate..-. TA-sulfate CA-EOsuliate-.

SoapC 7.5 OA+10EO 5. 0 2.7 CA+9E0+12P0. 1.8 Carboxyhetaine. 0. 5 Sulfobetaine 0.7 s... 0.6 Foaminhibltor 0.5 0.5 0.6 0.0 .0 36.4 41.1 38.0

0.0 7.0 9.0 ATMP. 1.5 MgSiOs 2.3 2.5 2.0. Perborate (mono) "14.0 10.0 14.0 15.6 Perborate (tetra)- 19.0 Activator 10.2 11.0 6.0 3.0 12.0 1003..- 0.5 7.0 4.0 2.0 8.0 Bnghtener 0.25 0.40 0.35 0.25 0.29 Residual water.

..41 m... L Ma...

The bleaching liquors, particularly 'waishing. liqi brs manufactured by'usirig the agents in accordance with the invention exhibit a better bleaching effect than obtained with known activators, both at treatment temperatures of, for example, 30 to 45 C. and at higher temperatures up to boiling. The higher degree of whiteness of the wash is' perceptible particularly when optical brighteners are simultaneously present.

In principle, these statements also apply to working at lower temperatures of, for example, to C., although a correspondingly longe'r" treatment 'period is necessary-'inthis lower range of temperature.

Similar results are obtained if the tetraacetyl derivative serving as activator in the preparations in accordance with the invention is replaced by the tetrapropionyl or tetrabenzoyl compounds, or the mixed acylated derivatives for example, acetyl and propionyl'residues or acetyl and benzoyl residues. This also applies to the 9,9-dimethyl derivatives. Similar results are also obtained if the perborates contained in the examples are replaced by other compounds, such as percarbonates, yielding H 0, in aqueous solution.

The preceding specific embodiments are illustrative of the practice of the'invention. It is to be understood, however, that other expedients disclosed herein or known to those skilled in the art, may be employed without departing from the spirit of the invention or the scope of the appended claims.

We claim:

1. An N-acylated 2,4,6,8 tetraaza-bicyclo (3,3,1)- nonan-3,7-dione of the formula wherein each of the R- CO, R CO, R CO and R CO are the same acyl of organic carboxylic acids selected from the group consisting of alkanoic acids having 2 to 4 carbon atoms, haloalkanoic acids having 2 to 4 carbon atoms, benzoic acid, alkylbenzoic acids having 8 to 10 carbon atoms, halobenzoic acids, nitrobenzoic acids, nitrotoluic acids, and halotoluic acids, and R and R, are members selected from the group consisting of two hydrogens and two methyls.

2. The compound of claim 1 wherein R CO, R CO, R,CO and R CO are acetyl and R and R are hydrogen.

3. The compound of claim 1 wherein R CO, R CO, RpCO and R CO are acetyl and R and R are methyl.

4. The compound of claim 1 wherein R7CO, R CO, R CO and R CO are propionyl and R 'and R are hydrogen.

5. The compound of claim 1 wherein R CO, R CO, R,CO and R CO are benzoyl and R and R, are hydrogen.

6. The compound of claim 1 wherein R CO, R CO,

v R CO and R CO are benzoyl and R and R are methyl.

8. The compound'of claim 1 wherein R CO, R,CO,

R CO and R CO are-p-chlorobenzoyland R and R, are methyl.

' 9. The compound of claim 1 wherein R CO, R CO, R CO and R' CO are p-nitrobenzoyl and R and R, are hydrog'en'. 10. The compound of claim 1 wherein R' CO, R CO, R CO and R CO are p-nitrobenzoyl and R and R, are methyl.

11. An N-diacylated 2,4,6,8 tetraaza-bicyclo-(3,3,l)- nonan-3,7-dione produced by the steps of partially acylating 1 mol of a 2,4,6,8-tetraaza-bicyclo-(3,3,1)-nonan-3,7- dione of the formula wherein R and R, are members selected from the group consisting of two hydrogens and two methyls, by the action of about 3 mols of an acylating derivative of an organic carboxylic acid selected from the group consisting of alkanoic acids having 2 to 4 carbon atoms, haloalkanoic acids having 2 to 4 carbon atoms, benzoic acid, alkylbenzoic acids having 8 to 10 carbon atoms, halobenzoic acids, nitrobenzoic acids, nitrotoluic acids, and halotoluic acids, said acylating derivative being selected from the group consisting of acids, acid anhydrides, acid chlo rides and ketenes, at a temperature of from 40 C. to C. under acylating conditions, whereby two of the nitrogen atoms of said 2,4,6,8-tetraaza-bicyclo-(3,3,1)-nonan- 3,7-dione are acylated.

12. The compound of claim 11 wherein two of said nitrogen atoms are acetylated and the remaining are bonded to hydrogen, and R and R, are hydrogen.

13. The compound of claim 11 wherein two of said nitrogen atoms are propionylated and the remaining are bonded to hydrogen, and R and R are hydrogen.

14. The compound of claim 11 wherein two of said nitrogen atoms are butyrylated and the remaining are bonded to hydrogen, and R and R are hydrogen.

15. An N-tetraacylated 2,4,6,8-tetraaza-bicyclo-(3,3,1)- nonan-3,7-dione produced by the step of acylating the product of claim 11 by the action of a sutficient amount of an acylating derivative of said organic carboxylic acid as defined in claim 11, but other than that employed in claim 11, at a temperature of from 40 C. to 100 C. under acylating conditions, whereby all of the nitrogen atoms of said 2,4,6,8-tetraaza-bicyclo-(3,3,1)-nonan-3,7- dione are acylated.

References Cited UNITED STATES PATENTS 3,445,383 5/1969 Horvath et al. 210-62 R. V. RUSH, Primary Examiner US. Cl. X.R.