US 3321497 A
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United States Patent 3,321,497 COMPOSITIONS OF MATTER Edwin A. Matzner, St. Louis, Mo., assignor to Monsanto Company, a corporation of Delaware N0 Drawing. Filed Oct. 7, 1963, Ser. No. 314,552 11 Claims. (Cl. 260397.7)
The present invention relates to novel chemical compounds and more particularly to novel sulfonamide compounds and to processes for preparing these compounds. The present invention further relates to novel compounds which accelerate or promote the release of oxygen from oxygen releasing compounds in aqueous media and which are useful in bleaching and washing operations. The term oxygen releasing compoun as used herein is intended to include hydrogen peroxide and all compounds which when placed in water form hydrogen peroxide.
The present invention has particular reference to novel products and processes disclosed in my copending application for Letter Patent filed in the US. Patent Office Apr. 23, 1962, Ser. No. 189,281, now abandoned. The disclosure contained in the present application should be taken in conjunction with said application Ser. No. 189,- 281 and considered as a continuation-in-part of said application.
Sulfonamide compounds are compounds whose molecules contain an S0 group linked to a nitrogen atom. A number of these compounds, specifically the so called sulfa drugs, including sulfadiazine, ulfaguanidine, sulfamerazine, sulfanilamide, sulfapyridine, sulfathiazole and the like are well known and have been widely used as drugs in combating bacterial infections. These and other sulfonamide compounds of the prior art have occasionally been employed in the manufacture of dyes and/or dye intermediates.
The novel sulfonamide compounds of the present invention have a novel, unrelated and unexpected utility, namely, the acceleration of the bleaching activity of oxygen releasing compounds not possessed by the abovementioned sulfonamides.
Detergent compositions containing an oxygen releasing compound, for example, an inorganic per salt such as an alkali metal perborate or percarbonate, or a peroxide such as urea peroxide have been disclosed heretofore as useful for washing and bleaching purposes. Although such compositions provide a satisfactory bleaching action when they are used in water at or near the boiling point (e.g. 95 C.l00 C.), the bleaching activity is unsatisfactory when the water is at lower temperatures, that is temperatures below 75 C. Detergent and/or bleaching compositions containing oxygen releasing compounds thus have the disadvantage of being unsatisfactory for many uses such as the washing and/ or bleaching of textiles and fabrics which cannot withstand higher temperatures, that is temperatures above about 70 C. Compositions containing these oxygen releasing compounds are also unsatisfactory in that they cannot be efficiently employed in modern automatic washing machines and laundering devices utilizing water at relatively low temperatures such as 50 C. to 70 C.
Such disadvantages have been recognized and the prior art indicates that attempts have been made to find compounds which would promote or accelerate the release of oxygen from oxygen-releasing compounds in water at low temperatures (e.g. 50 C.70 C.) with the goal of providing more effective bleaching and washing activity of such oxygen releasing compounds.
Examples of the prior art compounds are those disclosed in the following: US Patent 2,898,181, issued Aug. 4, 1959, discloses the use of certain carboxylic acid amides such as acetamide or acrylamigj: to, accelerate or cases REFERENCE EXAM I NEH promote the release of oxygen from aqueous solutions containing inorganic per salts, US. Patent 2,955,905, issued Oct. 11, 1960, discloses the addition of esters such as the benzoyl esters of alkali metal phenol sulfonates and glucose penta acetate as oxygen releasing promoters to washing compositions containing inorganic per salts; German Patent 1,081,181, published July 8, 1955, discloses the addition of certain compounds such as maloni-trile or ethylene dicyanide in compositions containing inorganic per salts; and German Patent 1,038,693, published Nov. 22, 1956, discloses certain carboxylic anhydrides such as benzoic anhydride and phthalic anhydride in compositions containing sodium per-borate to promote or accelerate the release of oxygen therefrom.
However, the promoter compounds of the above-mentioned patents have certain disadvantages in that, when incorporated in compositions containing oxygen releasing compounds, the compositions either do not bleach efficiently in water at temperatures of between 50 C. or C. or the oxygen releasing compound in the composition tends to decompose, resulting in a loss of available oxygen therefrom, when the compositions are stored under normal storage conditions for periods of from one week to several months.
It has presently been found, however, that the novel sulfonamides of the present invention are, surprisingly, highly effective in accelerating or promoting the bleaching properties and the release of oxygen from oxygen releasing compounds in water at temperatures as low as 40 C. Additionally these novel sulfonamides overcome the disadvantages of instability above referred to of the prior art compounds.
It is one object of the invention to provide novel sulfonamide compounds. It is also an object of this invention to provide processes for preparing these novel sulfonamide compounds.
It is another object of this invention to provide a class of novel sulfonamide compounds which are useful in promoting and/ or accelerating the release of oxygen from oxygen releasing compounds in water.
It is a further object of this invention to provide a class of novel N-acyl-nitrobenzenesulfonamides which will increase the bleaching and washing efiiciency of oxygen releasing agents in water at temperatures as low as 50 C.
Still further objects and advantages of this invention are disclosed in or will become apparent from the following description and appended claims.
The present invention provides a class of N-substituted N-acyl-nitrobenzenesulfonamides having the general forwhere one of A and B is :1 nitro group and the other is hydrogen and where C is selected from the group consisting of N0 and H and where R and R" are, as hereinafter defined, organic radicals. Compounds of this class are generally stable crystalline solids having a limited, but effective, solubility in water and are useful in increasing the bleaching efficiency of oxygen releasing compounds, when incorporated therewith in water. The term N-acyl as used herein is intended to include N- alkanoyl and N-aroyl groups or radicals.
Preferred compounds falling within the scope of the above formula are compounds where one of A and B is a nitro group and the other is hydrogen; where C is N0 or H; where R is selected from the group consisting of aryl and alkyl groups or radicals and where R" is an aryl group or radical. Compounds in which R is an alkyl group and compounds wherein R is an aryl group are especially useful in increasing the bleaching efficiency of oxygen releasing compounds.
Particularly advantageous N-acyl-nitrobenzenesulfonamides of the present invention and falling within the scope of the above formula are N-acyl-orthoand para-nitrobenzenesulfonamides characterized in having the general formula:
where either one of A and B is a nitro group and the other is hydrogen and where R and R" are organic radicals, as hereinbefore defined. Compounds of this class include certain N-substituted-N-acyl mono-nitro and di-nitrobenzenesulfonamides and are stable, crystalline solids, and generally have sufficient water solubility to be used in increasing the bleaching efiiciency of oxygen releasing compounds in water at relatively low temperatures, e.g. 40 C. N-acyl-nitrobenzenesulfonamide compounds of this class may also be employed in dry compositions containing oxygen releasing compounds and such compositions are generally stable with respect to loss of available oxygen when stored under ordinary storage conditions for prolonged periods of time, that is, for periods of six months and longer.
Preferred compounds falling within the scope of Formula II are compounds where one of A and B is a nitro group and the other is hydrogen; where R is an alkyl group and where R" is an aryl group. Other preferred compounds falling within the scope of Formula II include compounds wherein A and B are as above-described and R and R are aryl groups. Preferred specific compounds falling within the scope of'Formula II include compounds wherein A and B are as above described and where R. is either a methyl or a phenyl group and R" is a phenyl group.
In the formulae referred to above the organic radical R may be any of a wide variety of substituted and unsubstituted aliphatic or aromatic groups or radicals. Thus, in the above general formula R may be aliphatic or aromatic groups or radicals and may be any of a combination of a wide variety of substituted or unsubstituted aliphatic or aromatic groups or radicals. The aliphatic radicals preferably contain from 1 to carbon atoms in the aliphatic group. Although such aliphatic radicals may contain more than 10 carbon atoms, compounds contain ing them often have limited Water solubility. Thus, the unsubstituted aliphatic hydrocarbon groups or radicals in the above structure may include, for example, alkyl groups or radicals having a straight or branched chain, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secbutyl, t-butyl, n-amyl, isoamyl, n-hexyl, isohexyl, nheptyl, isoheptyl, n-octyl, isooctyl, 2 ethyl hexyl, etc. groups or radicals.
The su'bstituents of substituted aliphatic groups or radicals may be halogen atoms, sulfo, nitro, carboxy, methoxy, carbethoxy, amino, ethyl, or carboxyl groups or radicals to provide the aforementioned substituted groups or radicals. The unsubstituted aromatic groups or radicals may be phenyl, pyridyl, benzyl, alpha and beta naphthyl, quinolyl, anthryl, benzquinolyl and the like. The substituents of substituted aromatic groups or radicals include halo-, nitro-, sulfo-, and alkyl-substituted groups or radicals. The alkyl substituted aromatic groups or radicals preferably contain from 1 to 20 carbon atoms in the alkyl group. In the above formulae R may be any of the above described aryl or aromatic groups or radicals.
Illustrative examples of some specific N-substituted N-acyl-nitrobenzeuesulfonamides of this invention and falling within the scope of Formula I and which are contemplated by this invention are:
N phenyl, N benzoyl orthoor para-nitrobenzenesulfonamide,
N phenyl, N benzoyl-orthoor para-dinitrobenzenesulfonamide,
N phenyl, N acetyl-orthoor para-nitrobenzenesulfonamide,
N phenyl, N aeetyl-orthoor para-nitrobenzenesulfonamide,
N phenyl, N chloroacetyl-orthoor para-nitrobenzenesulfonamide,
N phenyl, N beta-phenylacetyl-orthoor para-nitrobenzenesulfonamide,
N phenyl, N hydrocinnamoyl-orthoor para-nitrobenzenesulfonamide,
N (4 pyridyl), N propionyl-orthoor para-nitrobenzenesulfonamide,
N phenyl, N (p-bromobenzoyl)-orthoor para-nitrobenzenesulfonamide,
N phenyl, N butyroyl-orthoor para-nitrobenzenesulfonamide,
N nitrophenyl, N acetyl-orthoor para-nitrobenzenesulfonamide.
A particularly useful group of N substituted, N-acylnitrobenzenesulfonamides of Formula II are those wherein R is an unsubstituted aliphatic or aromatic group or radical, and R is an unsubstituted aryl or aromatic radical. The unsubstituted aliphatic groups or radicals usually have from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, and more preferably 1 or 2 carbon atoms.
Compounds of this invention which have been found to be particularly useful in promoting or accelerating the release of oxygen from oxygen releasing compounds, as hereinbefore described, are N-substituted N-acyl-paraor ortho-nitrobenzenesulfonamides having the general formula:
I ll SOz-N-C-R where one of A and B is a nitro group and the other is a hydrogen and where R is a methyl and/ or phenyl group and R" is a phenyl group.
Particularly useful N-substituted, N-acyl-para-nitrobenzenesulfonamides of this invention are those having the general formula:
H (IV) where R is selected from the group consisting of methyl and phenyl groups, and R" is a phenyl group.
Preferred compounds falling within the scope of.
Formula IV are compounds where R is an alkyl group and where R" is an aryl group. Other preferred compounds falling within the scope of Formula IV include compounds wherein R and R are aryl groups. Preferred compounds falling within the scope of Formula IV include compounds wherein R' is either a methyl or a phenyl group and R is a phenyl group.
Specific N substituted N acyl para nitrobenzenesulfonamide compounds of this invention which have been found to be particularly suitable in promoting or accelerating the bleaching properties and the release of oxygen from oxygen releasing compounds in water are:
N phenyl, N acetyl para nitrobenzenesulfonamide, N phenyl, N benzoyl para nitrobenzenesulfonamide.
Particularly useful N substituted, N acyl orthonitrobenzenesulfonamides are those having the general formula:
R O H- SO2I I( )R NO: (V) wherein R is selected from the group consisting of methyl and phenyl groups, and R" is a phenyl group.
Preferred compounds falling within the scope of Formula V are compounds wherein R is an alkyl group and R" is an aryl group. Other prefererd compounds falling within the scope of Formula V include compounds wherein R and R" are aryl groups. Preferred specific compounds falling within the scope of Formula V include compounds where R is either a methyl or a phenyl group and R is a phenyl group.
Specific N substituted, N acyl-ortho-nitrobenzenesulfonamides of this invention which have been found to be particularly suitable in promoting or accelerating the bleaching properties and the release of oxygen from oxygen releasing compounds are:
N-phenyl, N-acetyl-ortho-nitrobenzenesulfonamide, N-phenyl, N-benzoyl-ortho-nitrobenzenesulfonamide.
The N-substituted, N-acyl, nitrobenzenesulfonamides of this invention may be suitably prepared by a process which comprises mixing together and reacting an N-substituted orthoor para-nitrobenzene sulfonamide with an acyl compound until an N-substituted, N-acyl-orthoor para-nitrobenzenesulfonamide is formed.
The N-substituted nitrobenzenesulfonamides which may be employed in the above process are characterized in having the formula:
where either one of A and B is a nitro group and the other is hydrogen and C is selected from the group consisting of N and H and wherein R" is an organic radical as hereinbefore described, namely an aryl or aromatic radical.
Such N-substituted orthoor para-nitrobenzenesulfonamides may be readily obtained by reacting a suitable nitrobenzene sulfonyl chloride with an organic amine in a liquid alkaline medium, the reaction being exemplified by the following equation.
where A, B, C and R" have the same meaning or significance as hereinbefore described.
The organic amines which may be employed in the above process include aryl amines such as analine, naphthylamine, aminopyridine, aminoanthracene, etc.
The acyl compounds which may be reacted with the above-described N-substituted orthoor para-nitrobenzenesulfonamides in accordance with the processes of this invention include organic acid anhydrides having the formula (RCO) O, organic esters having the formula RCOOX and acyl halides having the formula R-COY. In the above formulae R is an organic radical as hereinbefore described and X is an alkyl or aryl group or radical and Y is a halogen, preferably chlorine or bromine.
Examples of acyl compounds which are preferably employed in the processes of this invention include alkanoyl compounds for example alkyl acid anhydrides such as acetic anhydride or butyric anhydride and the like; alkanoyl halides such as acetyl chloride, acetyl bromide and the corresponding butyroyl halides and the like; aroyl compounds, such as for example, benzoic anhydride, benzoyl chloride and the like; mixed anhydrides, for example acetyl benzoate, butyroyl benzoate, etc. and aroyl esters such as benzoyl acetate, benzoyl butyrate, etc., carboxylic acid esters such as ethyl benzoate, benzyl propionate, ethyl acetate, ethyl propionate and the like.
The particular N-substituted nitrobenzenesulfonamide and the particular acyl compound employed in the processes of this invention will depend on the particular N- substituted N-acylnitrobenzenesulfanomide desired.
The compounds of this invention are most suitably prepared by a process which comprises mixing and reacting about one molecular proportion of the hereinbefore described organic amine, e.g. aryl amine, with about one molecular proportion of a nitrobenzenesulfonyl chloride in a liquid alkaline medium until N-aryl-nitrobenzenesulfonamide is formed and thereafter mixing and reacting the nitrobenzenesulfonamide so formed with the hereinbefore described acyl compound, e.g. an alkanoyl or an aroyl compound, at a temperature in the range of from about 50 C. to about 200 C., until an N-substituted, N-acyl-nitrobenzenesulfonamide is formed.
A wide variety of liquid alkaline media may be employed in the above process including non-aqueous, water soluble, alkaline organic liquids such as pyridine or lutidine or aqueous alkaline liquids such as aqueous solutions or alkaline inorganic compounds for example, aqueous solutions of alkali metal hydroxides or alkali metal carbonates.
It is preferred that the liquid alkaline medium be one in which the organic amine is soluble for the reaction usually proceeds slowly if the organic amine is insoluble or partially soluble in the medium. In order to insure a relatively rapid reaction between the organic amine and the nitrobenzenesulfonyl chloride, it is preferred that the organic amine be soluble in the liquid alkaline medium in an amount of at least 5%, preferably at least 10%, by weight in the medium. Since the reaction between the organic amine and the nitrobenzenesulfonyl chloride is exothermic, it is preferred that the organic amine be first dissolved in the liquid alkaline medium and that the nitrobenzenesulfonyl chloride be slowly added with agitation, preferably by mechanical means, to the solution. If desirable, the liquid medium may be cooled during the addition of the nitrobenzenesulfonyl chloride and maximum yields of the N-substituted nitrobenzenesulfonamide are generally obtained when the process is carried out at temperatures below 45 0, preferably at temperatures in the range of about 30 C.45 C. Although temperatures below 30 C. may be employed there is no significant advantage and the reaction time is usually significantly prolonged.
The N-substituted nitrobenzenesulfonamide so obtained may be mixed and reacted with any hereinbefore described acyl compound either in situ, that is in the abovedescribed liquid alkaline medium or alternatively, the sulfonamide may be recovered as a solid and thereafter reacted with the acyl compound. When it is desired to carry out the reaction in situ, the acyl compound, for example, either an alkanoyl compound or an aroyl compound, is slowly added with agitation to the mixture comprising the liquid alkaline medium and the N-substituted nitrobenzenesulfonamide During and/or after the addition of the acyl compound the mixture may be heated to or maintained at a temperature in the range of between 30 C. and 200 C. until the N-substituted N- acyl-nitrobenzenesulfonamide is formed. Although temperatures below 30 C. may be employed the reaction tends to proceed more slowly than may be desirable. Higher temperatures which may be employed are, in gen- 7 eral, limited by the boiling point of the liquid alkaline medium.
The time required for the N-substituted nitrobenzenesulfonamide to completely react with the acyl compound will vary considerably depending upon the amount of the reagents to be reacted, the alkaline medium used and the temperature employed. Complete reaction normally occurs over a period of from about 30 minutes to 4 hours, the smaller quantities of reagents and higher temperatures of the reaction medium requiring shorter reaction times.
After the reaction is completed the N-substituted N- a-cyl-nitrobenzenesulfonamide may be recovered by neutralizing the liquid alkaline medium with a suitable acid and thereafter concentrating and cooling the neutralized medium to precipitate out the crystalline compound. Alternatively, the N-substituted N-acyl-nitrobenzenesulfonamides may be recovered from the neutralized medium by extraction in a water-immiscible, low boiling solvent such as for example, ligroin, carbon tetrachloride or chloroform which can be readily cooled and/or evaporated and from which the crystalline compounds may be directly recovered.
Where the N-substituted nitrobenzenesulfonamides are available or have been previously prepared such compounds may be dissolved in a liquid alkaline medium and mixed and reacted with an acyl compound as abovedescribed or alternatively since the acyl compounds are usually liquid organic solvents having boiling points ranging from about 30 C. to 200 C., the N-substituted nitrobenzenesulfonamide may be added directly to an excess of the acyl compound and heated preferably at or near the boiling point or the acyl compound more preferably by refluxing for from 30 minutes to 4 hours until the reaction is completed. The excess acyl compound may then be removed by distillation to obtain the crystalline N substituted, N acyl nitrobenzenesulfonamide.
Where the boiling point of the acyl compound is below 30 C., the acyl compound may be mixed with a higher boiling'liquid such as, for example, glacial acetic acid and the N-substituted nitrobenzenesulfonamide added thereto and heated, preferably by refluxing, until the desired compound is formed, The compound may then be separated or crystallized as above described.
By way of illustration N-phenyl, N-benzoyl-paranitrobenzenesulfonamide may be prepared by mixing and reacting para-nitrobenzenesulfonyl chloride and aniline in a liquid alkaline medium in a molecular ratio of about 1:1 to obtain N-phenyl-para-nitrobenzenesulfonamide which may then be mixed and reacted with aroyl compounds such as benzoic anhydride, benzoyl chloride or benzoyl acetate to form N-phenyl, N-benzoyl-para-nitrobenzenesulfona-mide.
Any of the N-substituted N-acyl-nitrobenzenesulfonamides of this invention may be mixed with a wide variety of organic and/or inorganic oxygen releasing compounds to provide novel bleaching compositions. Examples of organic, oxygen-releasing compounds include organic peroxides such as urea peroxide, benzoyl peroxide, methylethyl ketone peroxide and the like. Examples of inorganic, oxygen-releasing compounds include inorganic peroxides such as, alkaline earth met-a1 peroxides, for example, calcium, magnesium, zinc, and barium peroxides. Other suitable inorganic peroxides include alkali metal carbonate peroxides such as sodium carbonate peroxide; and alkali metal pyrophosphate peroxides such as sodium pyrophosphate peroxide. Particularly suitable inorganic, oxygen-releasing compounds include inorganic persalts such as metal and ammonium persulfates, perchlorates, and perborates. Of these persalts, water-soluble alkali metal persulfates, and perborates are preferred, and alkali metal perborates especially sodium and potassium perborates are particularly preferred.
Useful bleaching compositions comprise, as noted above, a mixture of an oxygen-releasing compound and one or more of the novel compounds of this invention. These ingredients can be used in the compositions in various proportions depending upon whether the composition is to be used as a bleaching composition or a Washing composition or both. However, in most instances, the compositions contain either an organic or an inorganic oxygen releasing compound and from about 0.1 to about 2.0 mols, per mol of the oxygen-releasing compound, of any of the N-acyl-nitrobenzenesulfonamides of this invention.
The novel compounds of this invention promote and accelerate the release of a greater amount of oxygen from oxygen releasing compounds in water at 60 C.- C. than occurs when such oxygen-releasing compounds are dissolved in water at these temperatures,
Suitable compositions comprise a mixture of an inorganic persalt such as an alkali metal perborate and from about 0.1 to about 2.0 mols per mol of perborate of any one or more of the novel compounds of this invention, and one or more of an inorganic detergent builder salt, and/or an inorganic diluent salt, and/or an organic surfactant.
A further understanding of the novel compounds of this invention as well as the utility and the processes of preparing such compounds may be obtained from the following specific examples which are intended to illustrate the invention but not to limit the scope thereof, parts and percentages being by weight unless otherwise indicated.
Example I To a glass reaction vessel equipped with a mechanical stirrer there was charged 8 liters of a 5% solution of aqueous sodium hydroxide, after which 250 grams (2.7 mols) of aniline was added to the reaction vessel and dissolved in the NaOH solution. Thereafter, there was slowly added, over a 10 minute period at room temperature (25 C.) and with agitation, 500 grams (2.25 mols) of para-nitrobenzenesulfonyl chloride. The resulting mixture was mechanically agitated for 2 hours at room temperature (25 C.) after which time it was filtered and acidified with 400 grams of concentrated hydrochloric acid. A white precipitate consisting of N-phenyl-paranitrobenzenesulfonamide formed in the reaction mixture. The precipitate was filtered, dried and transferred to a second reaction vessel equipped with a heater and reflux condenser. One liter of acetyl chloride and 800 ml. of glacial acetic acid were added to the reaction vessel thereby dissolving the solid crystals. The resulting solution was refluxed at a temperature of 52 C. for 2 /2 hours. At the end of this time the excess acetyl chloride was distilled off and 3 liters of cold (5 C.) distilled water was added to the liquid residue. A White crystalline precipitate which formed during the addition of the cold water was separated by filtration, washed with a cold (5 C.) saturated solution of sodium bicarbonate, and recrystallized from chloroform. The crystalline material obtained, which consisted of N-phenyl, N-acetylpara nitrobenzenesulfonamide, weighed 620 grams amounting to a yield of 86% of that theoretically possible, based on the para-nitrobenzenesulfonyl chloride charged. The crystalline material had a melting point of 194 C.
An elemental analysis of the crystalline material was conducted. The actual elemental content, compared with the theoretical elemental content of N-phenyl, N-acetylpara-nitrobenzenesulfonamide was as follows:
The elemental analysis was in substantial agreement with the formula for N-phenyl, N-acetyl para-nitrobenzenesulfonamide.
X-ray diffraction analysis on the crystalline compound was conducted using nickel filtered copper K-alpha radiation at a wave length of 1.541 Angstroms. The X-ray diffraction pattern obtained was as follows:
Interplanar spacings Relative intensity,
(d), Angstroms: percent An infrared absorption analysis of the compound was determined. The infrared absorption peaks indicated below establish the presence of pertinent structural elements that is S0 the CN bond and the acyl structure of the compound.
Absorption peak (wave length in microns): Relative intensity The above procedure was repeated except that orthonitrobenzenesulfonyl chloride was used instead of the para-compound. By so proceeding N-phenyl, N-acetylortho-nitrobenzenesulfonamide was obtained.
Example 11 To a three necked reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser there was charged 700 ml. of pridine and 210 grams (2.25 mols) of aniline which almost immediately dissolved in the pyridine. Thereafter there was slowly added to the solution with agitation and cooling to keep the temperature at 30 C., 500 grams (2.25 mols) of para-nitrobenzenesulfonyl chloride. The stirring was continued for 10 minutes during which time the contents of the reaction vessel were permitted to rise to 40 C. There was then added to the reaction vessel, slowly and with agitation, 316 grams (2.25 mols) of benzoyl chloride.
The reaction mixture was continuously agitated and heated to 110 C., and maintained at that temperature for 3 hours after which it was cooled to room temperature. The reaction mixture consisted of a solution comprising N phenyl, N-benzoyl-para-nitrobenzenesulfonamide dissolved in pyridine. After cooling, the solution was added to a separatory funnel containing 6 liters of chloroform. The chloroform solution containing the compound was washed 4 times with 2 liters each of 10% HCl to remove residual pyridine and reaction impurities. Thereafter the chloroform solution was washed three times with IV: liters each of a saturated solution of aqueous sodium bicarbonate followed by three washings with 2 liter quantities of Water. The chloroform solution was dried over anhydrous magnesium sulfate. About 75% of the chloroform was evaporated after which time yellowish white crystals formed and precipitated from the solution. The crystals were separated by filtration and dried. A yield of 78.2 grams of crystalline N-phenyl, N benzoyl-para-nitrobenzenesulfonamide was obtained and constituted 91% of that theoretically possible, based on the reagents charged. The crystalline material had a melting point of 189 C.
An elemental analysis for C, H, N and S was conducted on the material. The actual elemental content compared with the theoretical elemental content was as follows:
Element, Actual (Found), Theoretical percent percent Carbon 59. 98 56. 69 Nitrogen 3. 72 3. 69 Hydrogen 7. 14 7. 33 Sulfur 8. 43 8. 4
Interplanar spacings (d),
Angstrorns: Relative intensity, percent 8.84 100 3.70 51 5.01 39 4.62 28 4.09 28 2.95 21 4.39 19 3.26 18 4.06 15 3.15 14 3.63 14 13.18 10 3.02 9 5.34 9 6.55 9 8.42 7 7.31 7 5.40 7 5.94 6 3.83 6 5.75 4 3.35 4
Angstroms: percent 4.29 3.46 3.21 2.77
An infrared absorption analysis of the compound was conducted as described in Example I. The infrared absorption peaks indicated below establish the presence of pertinent structural elements that is S the CN bond and the acyl structure in the compound.
Absorption peak (wave length in microns): Relative intensity The procedure of this example was repeated except that 01tho-nitrobenzenesulfonyl chloride was employed instead of the para-compound. By so preceding N-phenyl, N- zenzoyl-ortho-nitrobenzenesulfonamide was obtained.
Example III Dry mixed compositions containing the following ingredients in the percentages given in the following table were prepared.
Composition Number Ingredient Sodium dodecyl benzene sulfonate..- Sodium tripolyphosphate Tetrasodium pyrophosphate- Sodium silicate Sodium sulfate Lauryl isopropanol amide N-phenyl, N-atetyl-ortho-nitrobenzenesulfonamide. N-phenyl, N-benzoyl-para-nitrobenzenesulfonamide. Sodium perborate u- N 9?? OvIOUIOOO The bleaching capacity of each of compositions 1 through 4 was determined by dissolving 0.25% by weight of each composition in 1 liter of water in separate cylindrical receptacles. The receptacles were provided with mechanical agitation and the solutions therein were maintained at a temperature of 60 C. Each solution had an available oxygen concentration of about 11.5 parts per million. The solutions contained a mol ratio of sodium perborate to acy-l sulfonamide of 1:1.
Eight 5" x 5" swatches of unbleached naturally yellowed muslin were analyzed for reflectance (Rd) and (a)+(b) color values on a Gardner automatic color difference meter. Two swatches were placed in each of the 4 receptacles containing the dissolved compositions and washed for 10 minutes. After this period the swatches were dried, pressed and again analyzed on the Gardner automatic colorimeter. The reflectance ARd (brightening) and bleaching efficiency A(a) and A(b) were calculated by subtracting the differences in the readings before and after the washing operation. The loss of available oxygen was also determined for each solution. The results are summarized in the accompanying table.
The Gardner automatic color difference meter is a tristimulus colorimeter, that is, it contains three photocells which measure 1) reflectance (Rd); (2) green to red color (a); (3) blue to yellow color (b).
Loss of Composition Available ARd 2 A(a) A(b) 1 Number Oxygen, percent 1 l Determined by iodometric titration of spent wash solutions. 1 Positive values indicate degree of increase in reflectance or brighteng. a Negative values indicate degree of color dissappearanee or bleaching;
Example IV The bleaching acceleration properties of some of the novel compounds of this invention are further indicated.
To one liter of standard full strength borate-carbonate pH 10 buffer solution there was added the following.
0.460 gram of Orange II [p-(Z-hydroxy-1-naphthyl-azo)- benzenesulfonic acid-sodium salt]. 2 grams of a detergent having the composition:
Percent Sodium dodecylbenzenesulfonate 25.0 Lauryl isopropanol amide 3.0 Sodium silicate 6.0 Sodium tripolyphosphate 28.0 Tetrasodium pyrophosphate 12.0 Anhydrous sodium sulfate 17.3 Sodium carboxymethyl cellulose 0.7 Moisture 8.0
A ml. portion of this solution was added to each of eight individually numbered tubes which were numbered and mechanically shaken in a water bath at 60 C. The initial color concentration was determined in a Bausch and Lomb spectrophotometer by measuring the intensity of its absorption maximum at 483 millimicrons. While recording the time, the materials indicated in the following table were added to the numbered tubes.
Dye Concentration, Percent of Original Tube No. Compound Minutes 1 Solution only 100 100 100 100 2 0.080 g. sodium perborate 100 80 62 51 3 0.080 g. sodium perborate N- 100 51 18 7 phenyl, N-acetyl-para-nitrobenzenesulionamide. 4 0.080 g. sodium perborate N- 100 78 56 34 phenyl-N-benzoyl-para-nitrobenzenesulfonamide. 5 0.080 g. sodium perborate N- 100 25 7 5 phenyl, Nacetyl-ortho-nitrobenzenesulfonamide. 6 0.080 grams sodium perborate N- 100 75 41 19 phenyl, N-acety1-2.4-dinitrcbenzenesulfonamide.
In the above table the nitrobenzenesulfonamides were added in equimolar amounts with respect to the sodium perborate that is 0.00052 gram mol of each compound were added to the tube as indicated. The results indicate that the compositions of this invention effectively promote the bleaching of standard dyes when in solution at 60 C.
The novel compounds disclosed in this application have been disclosed as incorporated components of novel bleaching and washing compositions in my co-pending US. patent application Ser. No. 181,449, filed in the US. Patent Office, Mar. 21, 1962.
What is claimed is:
1. A compound of the formula where one of A and B is a nitro group and the other is hydrogen; where C is selected from the group consisting of N0 and H; where R is selected from the group consisting of unsubstituted alkyl radical having from 1 to 10 carbon atoms and unsubstituted phenyl radical, and where R" is an unsubstituted phenyl radical.
2. A compound as in claim 1 where R is an alkyl group having from 1 to 10 carbon atoms.
3. A compound of the formula:
where one of A and B is a nitro group and the other is hydrogen; where R is an alkyl group having 1 to 10 carbon atoms and R" is an unsubstituted phenyl radical. 4. A compound as in claim 3 where R is a. methvl group.
5. A compound of the formula:
Where one of A and B is a nitro group and the other is hydrogen and where R and R" are unsubstituted phenyl radicals.
6. A compound of the formula:
I l NOr-QSOz-N-C-R Where R is an alkyl group having from 1 to 10 carbon atoms and R" is an unsubstituted phenyl radical.
7. N-phenyl, N-acetyl-para-nitrobenzenesulfonamide. 8. N-phenyl, N benzoyl-para-nitrobenzenesulfonamide. 9. A compound of the formula: i
Reverdin et al.: Ben, vol. 43, pp. 3460-64 (1960). Schreiber et al.: I. Am. Chem. Soc., vol. 57, p. 1309 WALTER A. MODANCE, Primary Examiner.
HARRY I. MOATZ, Assistant Examiner.