US 3882035 A
Iminodiacetonitrile compounds of the formula: A-N(CH2CN)2 wherein A represents an acyl group selected from aroyl, substituted aroyl, lower alkanoyl and the residue of a heterocyclic acid chloride, or a 4,6-substituted-s-triazinyl group in which the 4 and 6 positions can contain an -N(CH2CN)2 group, are bleach activators of high strength and good storage stability in peroxygen bleaching compositions.
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Description (OCR text may contain errors)
United States Patent 1w] Loffelman et al.
I451 May6, 1975 l l IMINUDIACETONITRILE DERIVATIVES AS PEROXYGEN BLEACH ACTIVATORS  Assigncc: American Cyanamid Company,
 Filed: Mar. 2], 1973 121] Appl. No.: 343,314
 U.S. Cl. 252/95; 8/1 I l; 252/186; 260/465 H; 260/4658 R  Int. Cl Clld 7/54  Field of Search 252/186. 95, 99, 102; SN ll; 260/248 CS, 465 F, 465 H, 465.6, 465.8 R
 References Cited UNITED STATES PATENTS 2.927.840 3/l960 Dithmar et al 8/1 ll 3172.869 3/]965 Saxon 260/4658 R Primary ExaminerBenjamin R. Padgett Assistant Examiner-Christine M. Nucker Attorney, Agent, or Firm-John Lw Sullivan  ABSTRACT lminodiacetonitrile compounds of the formula:
AN(CH CN) wherein A represents an acyl group selected from aroyl, substituted aroyl, lower alkanoyl and the residue of a heterocyclic acid chloride, or a 4,6-substituted-striazinyl group in which the 4 and 6 positions can contain an N(CH CN) group, are bleach activators of high strength and good storage stability in peroxygen bleaching compositions.
13 Claims, No Drawings IMINODIACETONITRILE DERIVATIVES AS PEROXYGEN BLEACH ACTIVATORS This invention relates to bleaching compositions, and more particularly to improved bleaching compositions containing hydrogen peroxide releasing compounds and activators for such compounds as defined below, and to compositions of the activators and hydrogen peroxide releasing compounds with detergents.
The invention provides improved bleaching compositions comprising hydrogen peroxide or a hydrogen peroxide releasing compound and an effective amount of an. activator. The activators are derivatives of iminodiacetonitrile represented by Formula l:
AN(CH CN) (I) wherein A is an acyl group selected from aroyl, substituted aroyl, lower (C -C alkanoyl and the residue of a heterocyclic carboxylic acid chloride; or a 4,6-disubstituted-s-triazinyl group in which the substituent groups are selected from amino, diethylamino and N(CH CN) groups,
U.S. Pat. No. 2,927,840 discloses bleaching compositions comprising a peroxygen compound and an organic nitrile, including iminodiacetonitrile. The use of various N-acyl compounds as bleach activators has previously been disclosed. For example, French Pat. No. 1,583,330 discloses the use of N-acyl derivatives of heterocycles such as imidazole, pyrazole and triazole, and British Pat. No. 1,046,251 discloses the use of N-acyl derivatives of pyridazine, triazole and pyrazole as peroxygen salt activators in bleaching compositions for textile materials. French Pat. No. 1,489,926 discloses the use of the acyl-containing non-heterocycles N- acetyl-N-methyl-p-toluenesulfonamide and N- propionyl-N-methyl-p-toluenesulfonamide. Indeed, a perborate bleaching composition containing an activator such as any of these can be shown to remove a greater percentage of tea stain from a textile material than the same bleaching composition in which activator is omitted.
However, many peroxygen bleaching compositions containing such activators have not proved satisfactory for one or more reasons, such as inadequate bleaching or instability at 50 to 70C., the typical working temperature range of modern laundry washing machines; or because of unsatisfactory compatibility with detergents or other materials with which associated; or because of objectionable odor; or because the activators tend to deteriorate during storage of the bleaching composition under a variety of conditions of tempera ture and humidity.
To be useful, a bleach activator must, in particular, maintain its high activity in a formulation over a long period of time as such or in the presence of a peroxide releasing agent or in the presence of a detergent composition. Commercial products are often subject to storage for considerable periods of time in hot, humid warehouses or on the supermarket shelf before consumer use, and to be satisfactory the activity must be maintained without appreciable loss during such periods.
Thus, there is a continued need for a variety of improved bleaching compositions, especially those which maintain their activity over such long periods of time and which are stable and effective in the presence of various detergents as used in home and commercial laundries.
It has now been found that certain derivatives of iminodiacetonitrile, represented by Formula I, provide new and improved activators for peroxygen bleaching compositions. These new bleaching compositions exhibit good bleaching effectiveness at relatively low temperatures, cg, 10C. to C. Moreover, because of the good storage stability of the activators, the bleaching compositions may be stored for surprisingly long periods of time under a wide variety of temperature/hum dity conditions without significant loss of activity.
A preferred species of activator within the definition of Formula I is benzoyliminodiacetonitrile (Formula ll):
As shown in accompanying Example 2, a perborate bleaching composition containing (ll) as the activator removes more than twice as much tea stain from the textile as the same bleaching composition without the activatorv Furthermore, (II) has excellent storage stability as illustrated herein.
An additional advantage of the compositions of the invention is the provision of dry oxygen bleaching compositions which not only exhibit good bleaching activity at relatively low-water temperatures, but also are safer and easier to handle than liquid bleach products. They are relatively safe for all fabrics as well as for dyes thereon, for human and animal hair bleaching compositions, and exhibit germicidal activity. In addition, the compositions are useful for bleaching ground wood pulp.
As is known to those skilled in the art, ordinary monoamides (R-CONR'R") such as N,N- dimethylacetamide are inactive as peroxygen salt bleach activators. A unique aspect of the compounds which are the peroxygen salt bleach activators of this invention is that, unlike the preponderance of disclosed types, these compounds do not rely on the structural unit as would be found in molecular structures of known activators such as, for example:
on H CH3? i :N\
(benzoyldimethylhydantoin) (N-benzoylsuccinimide) (ii-acetylsaccharin} The phenomenon is evidenced by the excellent activity of the compounds of this invention. lt is surprising. l'lUWC\ er. that this effect is absent in the case of the ana ogous propionitrile homologs, which are inactive as peroxygen salt bleach activators (Examples IU. l l and ll below J. We are thus concerned with a very spe cifit' effect obtained with compounds of Structure i.
The novel bleach activators of this invention can be prepared by well known methods. Ben zoyliniinodiacetonitrile for example. can be prepared by reaction of benzoyl chloride with iminodiacetoni trile according to the following equation.
Other aroyl. substituted aroyl. alkanoyl and heterocy clic acyl derivatives can be prepared similarly from the appropriate carbosylic acid halides (or anhydrides in some instances).
Typical carboxylic acid halides lor anhydridesi that can be chosen for reaction with the iminodiacetonitrile to give the products of this invention include those such p-chlorobenzoyl chloride salicyloyl chloride o nitrobenzoyl chloride p-nitrobenzoyl chloride o-hromobenzoyl chloride terephthaloyl chloride p-fluorohenzoyl chloride m-methoxybenzoyl chloride I.4-dimethylhenzoyl bromide pltrifluoroniethyllbcnzoyl chloride o methylbenzoyl bromide p ethylhenroyl bromide l-naphthoyl chloride 3-hydrosyCataphthoyl chloride acetic anhydride propionic anhydride propionyl chloride butyryl chloride hutyric anhydride eaproie anhydride caproy'l chloride furoyl chloride thenoyl chloride nicotinoyl chloride pieolinoyl chloride il l cyanuric chloride, and the like.
The preferred species of the invention are those derived from aromatic carboxvlic acid halides. cyanuric chlorides, and lower aliphatic carboxvlic acid halides.
The bleaching compositions of the invention contain the activating compound and the hydrogen peroxide releasing; compound in a molar ratio ranging from aiiout l:l to about l.lll. respectively, with a preferred range of about ill to 5;]. The actual ratio of activator to bleach can. of course. be varied widely for varying applications.
The oxygen bleaches useful in these bleaching com positions are hydro ien peroxide and organic peroxides and inorganic pero: salts that liberate hydrogen peroxide in Water. nnples of peroxide bleaching compounds are urea peroxide. bcnzoyl peroxide. methyl ethyl kctonc peroxide. and the like. l isamples of inorganic pero' en hie-aching compounds are alkali metal pcri'iorates. percarbonates. perphosphates per sulfates. rnoiiopcrsulfates. and the like. Mixtures oftivo or more bleaching compounds can, of course. be used if desired.
Although the various peroxide releasing compounds as mentioned above may be used in the compositions of the invention preferred peroxide releasing; compounds are sodium perborate l for economic conside ationsi and sodium pcrearbonate [for ecoli'igieal con sidcrationsl.
The activated bleach compositions of the invention are useful for bleach klflpllcliilllllfi for various substrates including fabrics. particularly when incorporated with detergent compositions for household or commercial launderin purposes A most iniprotant property of such detergent compositions is the ability to remove stains inchiding food stains such as those of coffee. tea. wine and the like as well as to maintain purity of white in uncolo ed textile Aside from food stains, soiling in general may be removed such as grass stains. urine and the like.
in addition to the detergent. peroxygen releasing compound and eroxvgen bleach. activator. such detergent compositions may contain other optional additives such as germicides gieides. enzymes. optical bright eners. Colorants. perfun' 2. thickeners. emulsion or suspension stabilizers. and the like, including builders. such as sodium p'nospluitc. salts. carbonates. silicates. and the like as usually encountered in the art.
The detergent component of such activated bleach compositions may be any of the conventional types such kit anionic. cationic. nonionic or arnphoteric.
Examples of typically suitable anionic detergents in eludes the alkali metal or alkaline earth metal salts of and also polyglycol ethers of higher alkanols and higher fatty acids.
Bleaching compositions may generally be used also for their germicidal properties in various applications Two of the stained cotton swatches are placed in a stainless steel Terg-O Tometer manufactured by US. Testing Company. One liter of distilled water at 120F. is introduced and 40 grams of unstained cotton fabric for control of microbial growth. Applications may be 5 are added so as to provide a typical household washing made to any surface or substrate where such control is hi lmh r ti f ab ut 20 to 1. Then 2,0 desired. grams of anionic detergent available commercially as The treatment of Swimming P00 Water and SWim- Tide" is added, followed by 0.33 gram sodium perbomiflg p001 u s with 6 Compositions of the inveflrate and 0.60 gram of benzoyliminodiacetonitrile. The tion is especially efficacious since the usually lower l0 T .()-T i rated at 100 cycles per minute temperatures of these environments prevent effective f r min tes at a temperature of 120F. The swatches use of other antimicrobial agents. A related utility is the are th ved, rinsed with cold water and dried at treatment of water supplies to render the same fit for room temperature. human consumption or for industrial use, such as the Both before and after laundering, reflectance readsanitization of field water for consumption by military 15 ings of the swatches are taken on a Hunter Model 25M personnel or the treatment of industrial process water Reflectometer with a blue filter. The swatches are so it can be reused in industrial processes or by the surbacked with a white porcelain plate and read once on rounding community. The compositions also may be both sides. Fluorescent effect is excluded from all reademployed in admixture with detergents for use as home g or industrial germicidal detergents, or in hair bleaching The reflectance readings are averaged and the P compositions containing peroxygen compounds cent stain removal is obtained in accordance with the The following examples will serve to illustrate the infollowing formula in which R is the Symbol for reflecvention. tance:
EXAMPLE 1 Total stain removal Preparation of Benzoyliminodiacetonitrile R (bleached) minus R (Stained) A mixture of 4.0 grams (0.04 mole) of X 100 iminodiacetonitrile and 5.8 grams (0.04 mole) of ben- R (unstained) minus R (stained) zoyl chloride in 50 ml of dry dimethylformamide is heated with occasional stirring over a steam bath for l Comm] runs are also made the descflbed hour. This solution is then cooled, diluted with about 2:21:23 the detergent and Sodlum perborate wnh no l150 ml of water and the resultant white precipitate col- It was found that the bleaching Composition of this ected and recrystallized from methanol. Yield 6.8
85% of them m 124 255C. example removed an average of 61.8% of the stain grams or from the swatches, whereas the control composition Other aroyl derivatives of immodlacetomtrlle are obremoved only 26% of the stam. Similar results are obtamed Similarly. by.use of an equwalgm amgum of 2mtained if one uses a nonionic detergent such as All other aroyl halide In place of benzoyl chloride. detergenL EXAMPLE 2 EXAMPLES 3-9 Evaluation of Benzoyliminodiacetonitrile as Activator Testing of Derivatives of [minodiacemnitrile as for Sodium Perborate Activators for Sodium Perborate A PQ was Prepared F Bleaching compositions comparable to the bleaching zoylimmodiacetomtrile of Example 1 and sodium percompositions of Example 2 were prepared in Examples bPram m a "'9 z and bleaching effec' 3-9. In each case, the formulation was such as to protiveness of this composition determined by the followvide 20 grams of Tide detergent 033 gram of sodium mg test Procedure: perborate and the indicated amount (grams) of activa- Five'gfflm Swatches of deslzed, X 80 cottongfabnc tor per liter of solution. The molar ratio of activator to are stained with tea in the following manner. Five tea Sodium perborate in each instance was 1.11 The test bags are placed in one liter of water and boiled for five procedure was the Same as described in Example 2. minutes. The swatches are then immersed in the tea Suits f the testing i Examples 3-9 as we as Examp|e and the is continued for another five minutes. 2 are ummarized in Table AS shown in the Table the The swatc s a he removed from the tea, wrung control result is apt to vary somewhat from one set or out, dried at 2002l5F., rinsed in Cold Water and series of tests to another due to variations in the cloth again dried. and the tea used to produce the stains.
TABLE I Bleach Activator Wt. of Activator Example No. Structure (Grams) 3E Stain Removed 2 Owe-Man es) 0.60 g 61.8 (26.0)
3 02N-C0-N(CH2CN)2 0.72 a 59.9 53.7)
TABLE I 1 CONTINUED 2 Bleach Activator -Contr'o1 result EXAMPLES 10-12 Testing of Aroyl Derivatives of Iminodipropionitrile as Activators for Sodium Perborate In the testing of the aroyl derivatives of iminodipropionitrile, bleaching compositions comparable to the bleaching compositions of Example 2 were prepared in Bleach Activator Example No.
wt of Activator (Grarrcl 76 Stain Removed Examples l0-l2. In each case, the formulation was such as to provide 2.0 grams of Tide detergent, 0.33 gram of sodium perborate and the indicated amount (grams) of activator per liter of solution. The mole ratio of activator to sodium perborate in each instance was l:l.1. The test procedure was the same as described in Example 2. Results of the testing in Examples 10-12 are summarized in Table II.
TABLE II Wt. of Activator Structure (Grams) 5 Stain Removed 1o -CO-N(CH-gc|'! -CN)2 0.68 g 32.1 (33.7)
11 N0 -CO-N(CH CH -CN)2 0.82 g 26.3 (33.7)
12 Cl'@-CO-N(CH=CH:-CN) 0.78 g 29.0 (33.7)
Control test result The results in Table II show that the aroyl derivatives of iminodipropionitrile are ineffective as activators for sodium perborate.
EXAMPLE 13 Evaluation of Benzoyliminodiacetonitrile as Activator for Sodium Percarbonate Following the procedure of Example 2, except for the use of 0.35 gram of sodium percarbonate instead of 0.33 gram of sodium perborate, 53.2% of the tea stain was removed. The control test in this case showed 32.6% stain removed.
EXAMPLE 14 Storage Stability of Benzoyliminodiacetonitrile The storage stability of benzoyliminodiacetonitrile in a dry bleaching composition was determined by testing the bleaching effectiveness of such a composition after three months storage (a) at room temperature in a closed container, and (b) at 80F. and 80% relative hurnidity in an open container with the bleaching effectiveness of a freshly prepared composition. The bleach composition and the test procedure were the same as that described in Example 2, except that the dry composition in each case was prepared by mixing the dry ingredients (detergent, perborate and benzoyliminodiacetonitrile) and, after storage, adding the mixture to the bleach bath water. The freshly prepared composition was made as described in Example 2 (by adding the dry ingredients, separately, to the bleach bath water).
TABLE lll Stain Removed 35 Bleach Composition Freshly Prepared Stored 3 Months at RT in Closed Container Stored 3 Months at 80F.
and 80% RH in Open Container Control test result It is seen that the benzoyliminodiacetonitrile maintains its full activity over the storage period in the closed container and about 50% of its activity in the open container.
EXAMPLE 15 Preparation of 2-( Biscyanomethylamino )-4, 6-diamino-s-triazine 2,4-Diamino-6-chloro-s-triazine (14.2 g, 0.1 mole),
EXAMPLE 16 Preparation of 2,4,6-Tris( biscyanomethylamino )-s-triazine EXAMPLE 1? Preparation of 2,6-Diethylamino-4-bis( cyanomethyl)amino-s-triazine 2,6-Dichlor0-4-bis( cyanomethyl )amino-s-triazine (2.0 g, 0.008 mole) was added to 10 ml diethylamine in 20 ml dimethylacetamide at steam bath temperature. After about 5-10 minutes, a solid precipitated and the reaction mixture was drowned in water. The solid was filtered and recrystallized from methanol, mp 94-96C.
EXAMPLE 18 Preparation of 2,4-Bis( cyanomethyl )amino-6-diethylamino-s-triazine (C235 121 a me men cin In a manner similar to Example 17, 4.0 g (0.0013 mole) of 2-chloro4,6-bis(cyanomethyl)amino-striazine was added to 10 ml diethylamine in 25 ml dimethylacetamide. After 20 minutes, the reaction mixture was poured over ice and the resulting solid filtered. Recrystallization from methanol gave needles, mp 163-l64C.
Testing of Triazinyl Derivatives as Activators for Sodium Perborate Using the triazinyl derivatives of Examples l18, bleaching compositions comparable to the bleaching compositions of Example 2 were prepared and tested by the procedure described in Example 2. In each case, the formulation was such as to provide 2.0 grams of Tide detergent, 0.33 gram of sodium perborate and the indicated amount (grams) of activator per liter of solution. The mole ratio of activator to sodium perborate in each instance was l:l.l. Results of the testing are summarized in Table IV.
g (0.2 mole) of iminobisacetonitrile and 75 ml of propionic anhydride were heated to reflux for 4 hours and the hot solution poured over ice. The solution was then neutralized with concentrated ammonium hydroxide. extracted with 150 ml benzene. and the dried benzene solution evaporated to give the product as an amber oil.
EXAMPLE 20 Preparation of N,N-dicyanomethylthiophene C arbonamide 2-Thiophene carboxyl chloride (10 g, 0.067 mole). iminodiacetonitrile (6.7 g, 0.067 mole) and 50 ml dimethylformamide were heated for 2 hours at steam bath temperatures and the hot solution poured over ice. The resulting solid was filtered, suspended in 500 ml methanol, decolorized. and then cooled to give 8.4 g (58%) of white crystals. mp l37138.5C.
EXAMPLE 2] Preparation of N,N-dicyanomethylfuran Carbonamide Z-Furoyl chloride (13.2 g, 0.1 mole). iminodiacetonitrile (10 g. 0.1 mole) and 100 ml dimethylformamide were heated for about 2 hours at steam bath temperatures and the reaction mixture poured into ice. The resulting solid was filtered. suspended in 250 ml methanol, decolorized and filtered. Long white needle-like crystals formed which were washed with methanol and dried; 14.2 g. mp 1l2l 135C.
' Testing of Alkanoyl and Heterocyclic Carboxylic Acid Chloride Derivatives as Activators for Sodium Perborate Using the compounds of Examples l92l. bleaching compositions comparable to the bleaching compositions of Example 2 were prepared and tested by the procedure described in Example 2. In each case. the formulation was such as to provide 2.0 grams of Tide detergent, 0.33 gram of sodium perborate and the indicated amount (grams) of activator per liter of solution. The mole ratio of activator to sodium perborate in each instance was 1:1.1. The test results are given in Table V.
TABLE V Compound of Wt. (gl
Example No. Activator 7r Stain Removed Control result 1 claim:
1. A bleaching composition comprising hydrogen peroxide or a hydrogen peroxide releasing compound of the group of organic peroxides and inorganic peroxygen salts and an activating amount of an iminodiacetonitrile compound represented by the formula:
wherein A is an acyl group selected from aroyl. substituted aroyl, lower alkanoyl and the residue of a heterocyclic carboxylic acid halide; or a 4,6-disubstituted-s triazinyl group in which the substituent groups are se lected from amino. diethylamino and bis(cyanomethyl- )amino groups. 4
2. A composition according to claim 1 wherein A in the iminodiacetonitrile compound represents an unsubstituted benzoyl or naphthoyl radical or a substituted benzoyl or naphthoyl radical having a substituent se lected from halo, nitro, hydroxy, carboxy, C C alkyl. C -C alkoxy and halosubstituted C C alkyl groups.
3. A composition according to claim 2 wherein the iminodiacetonitrile compound has the formula:
4. A composition according to claim 2 wherein the iminodiacetonitrile compound has the formula:
5. A composition according to claim 2 wherein the iminodiacetonitrile compound has the formula:
6. A composition according to claim 2 wherein the iminodiacetonitrile compound has the formula:
-CO-N (CH CN 7. A composition according to claim 1 wherein A in the iminodiacetonitrile compound is a C C alkanoyl group.
8. A composition according to claim 7 wherein the iminodiacetonitrile compound has the formula:
9. A composition according to claim 1 wherein A in the iminodiacetonitrile compound is the residue of a heterocyclic carboxylic acid halide selected from furoyl, thenoyl and picolinoyl groups.
10. A composition according to claim 9 wherein the iminodiacetonitrile compound has the formula:
[ i-co-mca czn (circa )2N 2 )2 men cin 13. A composition according to claim 1 containing a detergent.