US3158635A

US3158635A - Bis-adduction products and methods of preparing same

Info

Publication number: US3158635A
Application number: US800116A
Authority: US
Inventors: Kezerian Charles; William M Ramsey
Original assignee: Stauffer Chemical Co
Current assignee: Stauffer Chemical Co
Priority date: 1959-03-18
Filing date: 1959-03-18
Publication date: 1964-11-24
Anticipated expiration: 1981-11-24

Description

United States Patent 3,153,635 BIS-ADDUCTION PRODUCTS AND METHGDS 0F PREPAG SAME Charles Kezerian, Los Angelles, and William M. Ramsey, .Dovv'ney, Califi, assignors to Sta'utier Chemical Company, a corporation of Delaware No Drawing. Filed Mar. 18, 1959, Ser. No. 800,116 28 Claims. (Cl. 260- 329) This invention relates to products, and methods of producing same, from the group consisting of:

. (a) A compound essentially of the formula:

r a r r Z Z wherein Z and Z are the same or different bis-adduction reaction residues of a member of the class consisting of unsaturated polycarboxylic acids and salts (includes acid addition salts and salts having a cation bonded to a carboxyl group) thereof and R is the substituent defined below;

(b) Chelates comprising the product of (a) and a polyvalent metal ion; and

(c) Esters comprising the product of (a) and a lower alkyl substituent bonded to at least one carboxyl group.

Stated in a different manner, this invention relates to bis-adduction products, and methods of producing same, from the group consisting of:

(a) A compound essentially of the formula:

BOOC-Rr-Bs Ra-RsCOOB wherein R is a member of the class consisting of alkylene,

, phenylene -lower alkylene phenylene, lower alkylenephenylene-lower alkylene, and lower alkylene-'NH-lower alkylene groups; and R and R are members of the class consistingof hydrogen, lower alkyl groups, -COOB groups, and lower alkylene-COOB groups; R and R are members of the class consisting of lower alkylene groups and lower alkylene groups having an additional free bond; n is a positive .integer of not less than 1 and not more than 2; R and R are lower alkylene groups when n is 1; R and R are members of the class consisting of hydrogen, lower alkyl radicals, and lower alkylene- COOB groups; and B in the above formula is the same or different radical from the class consisting of hydrogen,

organic base radicals, inorganic base radicals, and lower alkyl radicals;

(b) Chelates comprising the compound of (a) and a polyvalent metal ion; and

ene groups, respectively. The term carboxyl is herein intended to include the fil; o..

ice

lower alkylene-ITI-lower alkylene H radical (a) that is repeated a desired (the term desired may be zero) number of times, (b) wherein each lower alkylene radical may be the same or diiferent, and (0) wherein each repeating radical need not be the same as the preceding one. The

lower alkylene-I Hower alkylene radical may be illustrated by the following groups:

R and R in the above formula may be hydrogen, a lower alkyl group, a lower alkylene-COOB group, or a 'COOB group. R and R are lower alkylene groups such as methylene or a lower alkylene group having an additional free bond; R and R are lower alkylene groups such as methylene. R and R may be hydrogen, a lower alkyl radical, or a lower alkylene-COOB radical. B may be the same or diiferent radical from the group consisting of hydrogen, an organic base radical'such as triethanolamine, an inorganic base radical such as sodium, or a lower alkyl ester radical such as CH CH Products of the above formulae may be produced by reacting an organic poly primary amine with one mole of an alkali metal or tertiary amine salt of an unsaturated polyoarboxylic acid for each primary amine group present in the organic poly primary amine. The adduction reaction involves a reaction between the nitrogen atoms of the amine and the double bond of the acid, ester, or salt thereof. This reaction may be illustrated by the following equation:

where R and R are hydrogen or lower alkyl groups and R and B are 'asdefined above. The salts formed in this manner may be converted to the free amino acids by treatment with stronger acids. In most cases the free amino acid is precipitated and may be separated by filtram l-o OTca orn- Q-N112),

Obviously, mixed or unsymmetrical amino acid products may be produced by employing mixtures of different unsaturated polycarboxylic starting materials.

The unsaturated polycarboxylic acids which are suitable for use in producing the compounds of this invention include aconitic, citraconic, itaconic, maleic, fumaric, methylitaconic, glutaconic, methylglutaconic, muconic acids, and the like, their salts, anhydrides, nitriles, etc. These acids are characterized by the presence of the 1,4 conjugated moiety:

Suitable organic poly primary amines include ethylenediamine, diethylenetriamine, tetraethylenepentamine, propylenediamine, hexamethylenediamine, beta hydroxypropylenediamine, 2,2-diaminodiethyl ether, 2,2'-diaminodiethyl sulfide, phenylenediarnines, 2,2',2"-triaminotriethylamine, benzidine, diaminocyclohexane, diaminophenyl, polygylcoldiamine, lysine, ornithin, methylenedianiline, O-aminoethyl aniline, ammeline, melamine, tris-3-aminopropylamine, etc.

Our novel process for the preparation of the adduction products of the present invention is accomplished by heating a basic aqueous solution or melt of the poly primary amine with the unsaturated polycarboxylic acid for a period of time sufiicient to complete the reaction (from a few hours to a few days). The molecular proportions of the reactants are approximately one mole of the unsaturated polycarboxylic acid per primary amine group present in the poly primary amine. The alkalinity of the reaction mixture is established and maintained by means of a strong inorganic base or nonreactive strong organic base. Suitable bases include NaOH, KOH, triethylamine, triethanolamine, and the like. The basicity of the reaction mixture is preferably held at a pH above 9.5. The speed of the reaction may be varied to some extent by varying the temperature and pressure conditions under which the reaction is carried out. In general, the most satisfactory procedure is to heat the mixture to a refluxing temperature at atmospheric pressure for a period of at least several hours. It is essential to maintain alkaline reaction conditions during such polyadduction reactions in order to prevent unnecessary complex side reactions involving carboxylic hydrogens with excess amine groups.

a} The following typical examples illustrate the general nature of the new process and show a variety of hisadducts of diprimary amines with unsaturated polycarboxylic acids.

EXAMPLE I Elhylenediamine Bis-N,N-Succinic Acid CHGOONa CHzNHz A e H-COONa HzNHz HOH -CH2NOH COOH HgCOOH 2 400 grams of maleic anhydride (4.1 moles) were added to 400 ml. water, and the mixture was set aside for one hour. This mixture was neutralized slowly under a reflux condenser, while cooling (7585 C.) and stirring during the dropwise addition of 700 g. of 50% by Weight NaOH (8.75 moles). Extreme caution should be exercised at this stage, since if NaOH accumulates in quantity unreacted in the reaction media, it may suddenly react with nearexplosive violence. However, during this neutralizationhydrolysis, the temperature should not be allowed to drop below 70 C. in order to prevent the separation of sodium maleate.

The hot reaction solution of disodium maleate was treated with 170 g. of 70% by weight ethylenediamine (2.0 moles). The solution was then digested above C., and finally treated under reflux for 48 hours in a stainless steel reactor. The final reaction solution 36 B.) was cooled to room temperature, then acidified to a pH of 2.0 with 680 ml. of concentrated HCl (8.2 moles). When no further product separates (6-16 hours), the white slurry of micro-crystals was filtered, washed with three, 250 ml. portions of water, and then dried to a constant weight at 90100 C. The products melted at 220222 C. and constituted 540 g. yield (92.2% of the theoretical 548 g. yield).

The product, ethylenediamine bis-N,N'-succinic acid (EDDS-4H), was found to be only slightly soluble in water and insoluble in ethanol, acetone, benzene, and most organic solvents. 0.77 gram of the product dis solved in ml. of H 0 at 28 C.

A 292 g. (1.0 mole) portion of EDDS-4H was dissolved in 400 ml. of water containing g. (4.0 moles) of NaOH. The solution was cooled, and acidified to a pH of 2.0 with 330 ml. of concentrated HCl (4.0 moles). The solution was seeded, and was set aside (undisturbed) for 24 hours, filtered, and then washed with 500 ml. of water. The product was air dried to the dihydrate. Recrystallization yielded 280 g., that is, 85.4% of the theoretical yield of 328 g. The product was divided into two portions: (A), which was analyzed as such and (B), which was dried to a constant weight at 90 C. A pentahydrate of EDDS-4H was prepared by passing boiling water through a pad of EDDS-4H; rapid cooling of the clear filtrate yielded long, transparent needles (C). Analytical data have confirmed the samples as:

(A) EDDS-4H-2H O (B) EDDS4H, anhydrous (C) EDDS-4H-5H O Molecular weight determined by pH titration:

(B) C10H1 NgO found 290, theory 292; inflections at pH of 5.5, 8.7 and 11.25.

(C) C H N O -5H O: found 383, theory 382; inflec tions at pH of 5.5, 8.7 and 11.25.

Total N values determined by Kjeldahl:

(B) C H N O percent N: found was 9.51; theory 9.59 (C) C H N O -5H O, percent N: found was 7.34;, theory 733. V

A 269.5 g. sample of EDDS-4H-2H O (0.8216 mole) was dried at 95 C. to a constant Weight. The 28.5 g. (1.583 moles) loss of water corresponds to the theoretical loss from the dihydrate.

The reactions were usually carried out in metal reactors, preferably stainless steel, in order to avoid contamination by glassware. The conditions described were designed from the viewpoint of simplicity, economy, and convenience, but departure from these conditions may be tolerated Without detrimental elfects.

The quantity of solvent water, time of reaction, pH of precipitation, and total time of precipitation may all be varied, somewhat, without any serious drop in product yield.

The rate of formation of EDDS-4H by the procedure described in Example I was determined by periodic isolation of product during the over-all reaction time. Table I below shows the quantity of product which approaches a maximum value:

When the yield of EDDS-4H is plotted against the log of the reaction time, a straight line is obtained. Extrapolation to 100% yield shows the obtaining of the theoretical yield after 155 hours of refluxing.

The true amphoteric nature of these polyamino polycarboxylic acids is shown by their ability to form salts with mineral acids.

EXAMPLE II Ethylenrzdiamine Bfs-N,N-Succinic Acid Dihydrogen Sulfate GH1NCHCOOH:I H2804 HgOOOH a H ---CH21GCH3COOH] SO4- H HZOOOH 40 grams of ethylenediamine bis-N,N'-succinic acid (0.144 mole) were added to .100 g. of 98% sulfuric acid, The mixture was kept below 30 C. in an ice bath and stirred so as to form a solution. The solution, when diluted at room temperature with 100 ml. of H 0, formed a white microcrystalline precipitate. The product was collected on a sintered glass funnel, and then dried several days in a vacuum desiccator. A yield of 30 g. was obtained.

Analytical data.C H N O S, percent N: found 6.86; theory 7.18. Molecular weight determined by pH titration: found 391; theory 392; inflections at pH of 3.0, 5.5, 8.5 and 11.25.

EXAMPLE III Ethylenediamine Bis-N,N'-Su'ccinic Acid Dihydrochloride H CHgCH-OOOH] 21101 HzCOOH g hydrochloric acid at room temperature to form a solution. After several minutes, a fine white crystalline precipitate tion: found 373; theory 365; inflections at pH of 5.5,

8.5 and 11.25..

Ethylenediamine bis-N,N'-succinic acid. may easily be converted to an ester as shown. a

H CH GOOH 11+ I: I?! omoooomcur A 146 g. 0.5mm sample of EDDS-4H in 400 m1. of ethanol was treated dropwise with g. of concentrated H 50 The admixture was refluxed for 7 hours (a solution was formed after 4 hours). The clear liquor was diluted with ethanol, at 20 C., to 750 ml. and 168 g. (2 moles) of NaHCO were added thereto. The slurry was filtered and washed with 100 ml. of ethanol. The combined liquor was again filtered with norite carbon and concentrated in vacuo at 80 C. The viscous, strawcolored syrup was soluble in water, alcohol, and acetone. The yield was 200 g. of crude product, which is 99% of theoretical yield of 202 g.

In addition to forming salts with acids, these amphoteric amino acids also form crystalline salts with suitable bases. The disodium dih-ydrogen salt forms a crystalline product; however, the tetrasodium salt is extremely soluble and hygroscopic.

EXAMPLE IV Disodium Ethylerrediamine Bis-N,N'-Succinute L 11,0 OOH i L omoooH 2 86.9 grams of ethylenediamine bis-N,N-succinic acid (0.3 mole) were added to 50 ml. of Water, then dissolved by the addition of 59.2 ml. of 10.07 N NaOH (0.6 mole). The slurry was heated to form a solution, which was allowed to cool slowly. The product was filtered as dry as possible in vacuum. The white crystalline product was recrystallized from 200 ml. of water. The yield was 32.6 g., 32% of the theoretical 100.9 g. (anhydrous) yield. I

One-half of the above product was dried at C.

- and was analyzed.

Analytical data.C H N O Na -4H O, percent N: found 6.71; theory 6.81. C H N O Na percent N: found 8.13; theory 8.33. Molecular weight by pH titration: EDDS-2Na-4H O, M.W.: found 411; M.W.: theory 408. EDDS-2Na, M.W.: found 342; M.W.: theory 336.

EXAMPLE V H [oHn IoHoooH:| 2NH3OH 89.6 grams of ethylenediamine bis-N,N'-succinic acid (0.307 mole) were added to 50 ml. of water, then dissolved with 40 ml. of concentrated NI-I OH (29% by weight NH while stirring and heating. When the solution was cooled to 0 C., a large crop of White crystals formed. These crystals were filtered, washed with 4 ml. of water and filtered dry on a Buchne'r funnel. The

7' product was air dried to a constant weight. The product Weighed 65.6 g., 65.6% of the theoretical 100 g. yield.

Analytical data.C H N O -2H O, total percent N: found 15.27; theory 15.47. Percent N as free NH found 756; theory 7.73.

While ethylenediamine bis-N,N'-succ-inic acid has been found to be stable in boiling alkaline or neutral solutions, prolonged boiling at its isoelectric point does result in a change.

The preparation of ethylenediamine bis-N,N-succinic acid is not limited to the use of maleic acid as the starting material. With little modification, the trans isomer, fumaric acid is easily substituted.

EXAMPLE VI Ethylelzediamine Bis-N,N'-Succinic Acid (EDDS-4H) CH-COONa CH2NHz A 2Nn0 o-lin H NH EOE 232 grams of fumaric acid (2.0 moles) were added to 200 ml. of water, and the mixture was stirred. 320 grams of 50% by weight of NaOH (4.0 moles) were added to the reaction mixture. Again, the exothermic reaction required moderate cooling (80 C.), a reflux condenser, and good agitation. The reaction suspension was treated with 70 g. (86% by weight) of ethylenediamine (1.0 mole) diluted with 300 m1. of water, and was refluxed 56 hours. The partially soluble disodium fumarate gradually dissolved as it was consumed in the reaction.

The final clear reaction solution was cooled, then acidified to a pH of 2.0 with 360 m1. of concentrated HCl. When no further product separated from the solution (8-16 hours), it was filtered, washed with several portions of water, and dried to a constant weight at 100 89.6 grams of ethylenediamine bis-N,N-succinic acid C. Yield: 220 g., 75% of theory (292 g.); M.P.: 220 222 C. (MP. of EDDS=4H; 220-222 C.).

The melting point of this product was not changed when admixed with the crystalline product of Example I, which identifies the product made with fumaric acid as being the same as that made with maleic acid.

While KOH may be freely substituted for NaOH in the preparative procedure of EDDS-4H, a volatile tertiary amine such as triethylamine can be used with some reservation. The lower boiling point of this amine lowers the reflux temperature, and cuts the yield to a less favorable 32%. A higher boiling amine such as triethanolamine will be shown to be a favorable substitute for NaOH.

Attempts to react the secondary nitrogen of EDDS-4H with additional maleic groups were not successful under the mild conditions of Example I.

EXAMPLE VII Diethylenetriamine Bis-N,N-Succinic Acid I :I L CI-I COOH -1 DETA DS Repeating the conditions of Example I, diethylenetriamine was substituted for ethylenediamine, as is described in the following example.

The reaction was carried out as described in Example I, combining 200 g. of maleic anhydride (2.02 moles) in ml. of water with 320 g. of 50% by weight NaOI-I. This solution was then treated with 103 g. of diethylenetriamine (1.0 mole) and was refluxed for 48 hours. The reaction mixture had to be diluted to 800 ml. during the reflux period so as to keep the reactants and product in solution.

The reaction solution was cooled and then acidified with 320 ml. of concentrated I-ICl to a pH of 3.3. Upon setting overnight, the product, a fine white microcrystalline product, was filtered and washed with two, 100 ml. portions of water. This material was dried at 100-105 C. to a white free-flowing powder. Yield: g., 57% of theory (335 g.); M.P.: 208210 C.

The sample of diethylenetriamine bis-N,N"-succinic acid was recrystallized in the normal manner, that is, by dissolving it first in NaOH solution, followed by reprecipitation in the cold at a pH of 3.3 with concentrated I-ICl. The resulting product was filtered and washed thoroughly with water. The product was divided into fraction (A) which was air dried to a constant weight and fraction (B) which was dried at 100 C. to a constant weight.

The series of polyethylene polyamines was continued with the next member, triethylenetetramine. Since the product is water soluble, a modification in procedure for isolating the product was required.

EXAMPLE VIII Triethylenetetramine Bis-N,N-Succinic Acid CH-COONa 2 I A 011 NCH 0 1 NH H OON I 2 2 l 2 2)2 (EHzCO ONDiIz i I I -CHgNCHgCHgN-CHC O 011 TEDADS The reaction was carried out in the same manner described in Example I, that is, by combining 200 g. of maleic anhydride (2.04 moles) in 100 ml. of H 0 with 320 g. of 50% by weight NaOH. The solution was treatedwith 146 g. of triethylenetetramine (1.0 mole) and was refluxed for 48 hours.

The reaction solution was filtered, cooled, and diluted to 1 liter. This corresponds to a 1 molar solution of tetrasodium triethyienetetramine bis-N,N-succinate. A 100 ml. (0.1 mole) aliquot was acidified with 25 ml. of concentrated HCl, but did not yield any precipitate.

Another 100 ml. (0.1 mole) aliquot of the tetrasodium salt was passed through Amberlite lR-lOO cation exchange resin (acid form). The 800 ml. of acidic efiluent were concentrated under vacuo to a syrup. The syrup was further dried by washing with ethanol, and desiccation for several weeks. The brown product hardened to a friable brown solid. This brown solid was insoluble CHOOONa 9 in ethanol or acetone, but soluble in water. The product was very hygroscopic.

A 2.8227 g. sample of desiccated product was dried to constant weight in an oven kept at 100 C. The sample fused, foamed, and finally hardened to a brittle spongelike mass. The 0.2098 g. loss of water left 2.6129 g. of anhydrous material. This loss corresponds closely to a dihydrate.

Analytical data.-C H O N percent N: found 13.73; theory 14.80.

The next in the series of polyethylene polyarnines, tetraethylenepentamine, reacted similarly. The brown, hygroscopic amino acid was prepared by the following procedure.

' EXAMPLE IX Tetraelhylenepentamine Bis-N,N Succinic Acid 1r HN(CH2CH2I1ICHZOH2NH2)2 A' HC 0N9,

H HN CH2CHzI ICHgCHgNCH-COOH] HZCOOH z The reaction was again carried out in the same manner described in Example I, that is, by combining 200 g. (2.04 moles) of maleic anhydride in 100 ml. of water with 320 g. of 50% by weight NaOH. The hot solution was treated with 189 g. (1.0 mole) of tetraethylenepentamine, and was then refluxed for 28 hours.

The final reaction solution was cooled, filtered, diluted to 1 liter and stored as a 1 molar solution of tetrasodium tetraethylenepentamine bis-N,N -succinate. Since acidification does not liberate the water soluble free acid, a 0.1 mole aliquot (100 ml.) of the tetrasodium salt was passed through a column of Amberlite IR-100 cation resin (acid form). The 800 ml. of acidic effluent were concentrated under vacuo to a syrup, which was washed with ethanol and desiccated for several days until it solidified. The brown solid was insoluble in ethanol and acetone, but soluble in Water. The product was very hygroscopic.

A 4.9871 g.'sample of dessicated acid was dried to constant weight at 100 C. The product fused, foamed, and then hardened to a brittle mass. The 0.5713 g. loss of water left a 4.415 8, g. residue. This would be the theoretical loss from a trihydrate.

Analytical dam.-C H O N percent N: found 14.72; theory 16.61.

The next example incorporates a polyamine of a differentnature, specifically one which contains a 6-carbon chain between the amino groups.

EXAMPLE X Y 1,o-Hexamethylenediamine Bis-N,N'-Succinic Acid 011-0 0 O Na 1 F i CHQGHZOH2N H COOH L rncoon' 2 The reaction was carried out in the same manner as described in Example I, that is, by combining 100 g. of

1.0 maleic anhydride (1.02 moles) in 200 m1. of water with 160 g. of 50% by weight NaOH. The hot solution was then treated with 58 g. (0.5 mole) of 1,6-hexamethylenediamine, and was refluxed for 48 hours.

The final liquor was cooled, and acidified with 160 ml. of concentrated HCl to a pH of 2.6. The white crystalline product was allowed to settle for several hours, and was then filtered and washed with 800 ml. of water. The crystals were dried to constant weight at 105 C. The yield was g., 64.6% of the theoretical yield of 116 g.

A 60 g. sample of the above product was dissolved in 10% NaOH, and reprecipitated by acidification to a pH of 2.6 with concentrated HCl. The product precipitated in two distinctly separate fractions.

The first crop (No. 1) of crystals separated immediately from the acidified solution. This crop was collected, washed, and dried at 105 C. The yield was 10 g., 16.6% of theory.

A second crop (No. 2) of crystals separated from the clear filtrate upon standing for 15 minutes. The yield of dried product was 35 g., 58% of theory. This second crop was divided into two portions: (A), which was dried in air at room temperature, and (B), which was dried at 105 C. to a constant weight.

Analytical data of crop N0. 2:

C14H23N2032H20, percent Ni fOund theory 7.11. (213) C I-1 N 0 percent N: found 7.63; theory 7.82. M.W. determined by pH titration: found 328; theory 348. Inflection pH was 7.0. 0

Crop No. 1 appeared to be the product formed by an impurity present in the 1,6-hexamethylenediamine, namely, 1-hydroxy-6-aminohexane. This probably results from the following side reaction:

H CH-OOONa A u H0 0119mm no oHmNorr-o OONa CH-COONa H20 0 ONa HQCOOH:

This by-product may be separated from the desired bisadduct by fractional crystallization as shown above.

In the following example, a diprimary amine is utilized which contains a substituted alkyl chain linking the primary amine groups.

EXAMPLE XI Z-Hydroxypropylene-J,3-Diamine Bis-N,N-Succinzc Acid OH NHz A I'- 111 1 H-0H HOCH--CHiNCE-OOON& HgNHg L H 00 ONa orr-oooNa HCOONa L orrzooorr The reaction was carried out as described in Example I, that is, by combining 200 g. of maleic anhydride (2.04

moles) in 400 ml. of water with 330 g. of 50% by weight NaOH. The solution was then treated with g.,of2-

hydroxypropylene-1,3-diamine (1.0 mole), and was then refluxed for 60 hours.

The reaction solution was diluted to 1.5 liters with water, filtered, cooled to room temperature andthen to an amber oil (volume: approximately 450 Inl.). This product was washed with 500 ml. of acetone and then EXAMPLE YII Barium Dihya'rogen Ethylenediamine Bis-N,N'-Succinate CH NCHCOONa 132.01;

| L CHzCOOH The barium dihydrogen salt is readily obtained from an aqueous solution.

29.2 g. of ethylenediamine bis-N,N-succinic acid (0.1 mole) were dissolved in 200 ml. of H containing 8 g. of NaOH (0.2 mole). The solution was stirred and rapidly treated with 100 ml. of 1.0 molar BaCl (0.1 mole). The insoluble salt separated after a short period. After settling for 1 hour, the mass was filtered, washed with 100 ml. of water and dried at 110 C. to a constant weight. The 40 g. yield was 93.5% of the theoretical 42.7 g. yield.

Analytical data.C I-I N O Ba, percent N: found 6.44; theory 6.56.

A lead dihydrogen salt was similarly prepared from lead acetate solution and ethylenediamine-N,N-bis-succinic acid.

Aconitic acid was utilized in order to show the adaptability of unsaturated tricarboxylic acids to this process.

The substitution of triethanolamine for NaOH as neutralizing base is also described in the following example.

EXAMPLE XIII Diethylenetriamine Bis-N,N"-Tricarballylic Acid fiH-C O OTea -COOTea I-IN(CH GH NH H 0 0 OTea L H C OOH DETDT 174 grams of aconitic acid (1.0 mole) were treated with ml. of water, followed by 450 g. of triethanolamine (3.0 moles) and, finally, 51.5 g. of diethylenetriamine (0.5 mole). The thick mixture was then set aside to digest under gentle reflux at 125130 C. for 36 hours.

The reaction solution, a dark red-brown syrup, was diluted to 1 liter and was used as a 0.5 molar solution of the product.

A 200 ml. (0.1 mole) aliquot of the reaction solution were treated with 24 g. (0.6 mole) of NaOH and 1 liter of ethanol. Prolonged stirring gave a-thick oily sediment of hexasodium salt, which was washed free of triethanolamine with two, ml. portions of ethanol and was dissolved in 200 ml. of water. This solution was H CIlzCOOTGQ] 2 passed through a column of Amberlite IR-lOO cation exchange resin (acid form). The acidic effluent was concentrated under vacuo to 65 ml., then treated with 800 ml. of ethanol. A brown solid separated, which was dried in a vacuum desiccator. The yield was 8 g., 21% of theoretical 33.8 g. yield. Its decomposition point was approximately 230 C.

Analytical data.C H N O percent N: found 10.91; theory 9.31. M.W. determined by pH titration: found 447; theory 451. Infiections at pH of 6.8 and 10.5.

The position of adduction of the primary amine to the unsaturation of aconitic acid may be either a or (3. Possibly the beta isomer may predominate.

H20 0 OH and/ or CH COOTea] z 174 grams of aconitic acid (1.0 mole) were treated with 40 ml. of water, followed by 450 g. (3.0 moles) of triethanolamine (TEA) and, finally, 58 g. (0.5 mole) of hexamethylenediamine. This mixture was then set to digest under gentle reflux at 125-130 C. for 36 hours.

The reaction mixture, a dark red-brown syrup, was diluted with water to 1 liter and was used as a 0.5 molar solution. Acidification of a sample of this solution precipitates the free acid as an oil; however, it is quite unstable in air and soon auto-oxidizes to a black resinous mass. Thus, it was considered more feasible to prepare one of its metal salts, in this case, the trizinc salt.

EXAMPLE XV A ml. (0.05 mole) aliquot of the above reaction solution of Example XIV was diluted with 100 ml. of water. The solution was then treated, while stirring, with 150 ml. of 1 molar ZnCl solution. The reaction mixture had a pH of 7.3. The product was filtered, was sequentially washed with 200 ml. of water and 100 ml. of ethanol, and was then dried to a constant weight at -130 C. The yield was 20 g., 63% of the theoretical 32.5 g. yield.

Analytical data on Zn salt.C H N O Zn percent N: found 4.06; theory 4.28.

The reactivity of aliphatic primary amines has been conclusively shown in the previous examples. The next step incorporated aromatic polyamines into our process. The expected difiiculty was encountered with these adducts, that being the tendency of the free amino acids to oxidize in open air. Because of this, the adduct was identified after conversion to a suitable metal salt.

EXAMPLE XVI p-p-Methylenedianiline Bis-N,N-Succinic Acid .H.{@ t t.. m...l

E 01120 O OH MDDS The aryl amine incorporated into this reaction is water insoluble, as well as being insoluble in any alkaline aque ous media. Thus, triethanolamine was again used as both solvent and neutralizing base.

100 grams of maleic anhydride (1.02 moles) were added to 25 ml. of water and allowed to hydrolyze slowly to maleic acid. The mass of crystals were gradually dissolved in 330 g. (2.2 moles) of triethanolamin. Finally, 99 g. (0.5 mole) of p,p'-methylenedianiline were added and the reaction mixture digested under reflux at 130- 140 C. 'for 26 hours. The reaction solution remained as one clear phase.

The solution was cooled and diluted with 250 ml. of water. Since the reaction solution remains as one phase,

. this is evidence that the amine has reacted, otherwise it would have separated on dilution.

The diluted solution Was acidified with 183 ml. of concentrated HCl (2.2 moles). A gray'oil separated immdiately and was decanted free of the mother liquor. This residue was washed with 200 ml. of water, dissolved in 280 ml. of water containing 80 g. (2.0 moles) of NaOH, and repre'cipitated with 166 ml. of concentrated HCl (2.0

moles). The residue was again decanted free of mother liquor, washed with three, 200 ml. portions of water and two, 150 ml. portions of ethanol. The free acid solidified when desiccated; however, the surfaces turned red when exposed to air, evidencing oxidation. The yield was 150 g., 70% of the theoretical 215 g. yield.

Dizinc p,p-Methyl enedianiline Bis-N,N-Succinate' CH C O ONa 43 grams of p,p'-methylen'edianiline bis-N,N-succinic acid (0.1 mole) were dissolved in 120g. of water containing 16 g. (0.4 mole) of NaOH. The solution was filtered with Norite carbon and was then treated while stirring with 200 ml. of 1 molar ZnCl solution for 1 hour."

polyamine with another type of unsaturated acid, displays a phenomenon which occurs when the resultant secondary amine is 'y to a carboxyl group. An intramolecular cyclization takes place upon acidification, resulting in a pyrrolidone derivative.

l 4 EXAMPLE XVII Diphenylmethane p,p-Di-N-Pyrr0lid0ne-2,4-

. Carboxylic Acid H 00 OTea i /OHzCH-O O OH L H.

120 grams of itaconic acid (0.92 mole) were added to 10 m1. of water, and the resulting salt was treated with 300 g. of triethanolamine (2.0 moles). The slurry was heated and stirred until completelydissolved. The resultant viscous solution was treated with 91 g. of p,p'- methylenedianiline (0.46 mole) and digested under gentle reflux at 120-130 C. for 48 hours. The reaction mixture, which contained some insolubles, was diluted to 600 m1., and filtered through a pad of diatomaceous earth. The clear filtrate was then acidified with 165 ml. of concentrated HCl. The oil, which separated, was decanted free of mother liquor, washed with two, 100 ml. portions of water, and was then redissolved in 250 ml. of Water containing g. (2.0 moles) of NaOH. The product was reprecipita-ted with 165 ml. of concentrated HCl (2.0 moles) washed with two, ml. portions of water, and was then dried in a vacuum desiccator for several days. The final product was a dark-brown crystalline mass. The yield was 40 g., 21% of the theoretical 194 g. yield. The melting point was 200-210 C.

Analytical data.C H N 0 percent N: found 6.92; theory 6.64. M.W. determined by pH titration: found 458; theory 422. Inflections at pH of 9.0. 7

EXAMPLE XVIII a,a'-Diamino, m-Xylene-N,N'-Disuccinic Acid r lrnNn,

CHOOONa II CHCOONa l oH,NoH-o OONa H orno o ONa H2NCHCO ONa HY crnoo ONa CH COO ANaCl H Ca I CH N-OH-OOO H Ca CHQCOO/ H CH COOH 210 grams of the dicalcium salt (0.95 mole) were slurried with 1 liter of water. The 120 g. of oxalic acid dihydrate (0.96 mole) were added and stirred therewith for hours. The white slurry was filtered, and washed with 300 of water. The combined mother liquor and washings were then evaporated to 400 ml. (at room temperature). The residual syrup was treated with 500 ml. of acetone. The oily residue was then washed with two, 500 ml. portions of acetone and a 500 m1. portion of ethanol. The final semi-solid was dried in a vacuum oven at 90 C.; it foamed. The friable mass was crushed and further dried to constant weight. The over-all product, a pale yellow mass, was water soluble and non-hygroscopic. The melting point was 155 C.

Analytical data.C H N O percent N: found 7.79; theory 7.61. M.W. determined by pH titration: found 362; theory 368. Infiections at pH of 6.5 and 11.25.

The series of amino acids which may be obtained from the union of poly primary amines with unsaturated polycarboxylic acids can be seen as nearly limitless The examples shown are intended to illustrate our invention and should not be interpreted as limiting it.

The utilization of the products of our process are varied and numerous. Many of its outstanding uses are based upon its unique properties as a chelating compound. Some of the ions successfully tested are shown below. In the test, a ml. sample of 0.1 molar chelate was added to 50 ml. of water treated with 10 m1. of 0.1 molar of the metal ion and 1 ml. of precipitant such as saturated Na l llo or oxalic acid. The solution was adjusted to the recorded pH. The solution was studied in the cold for 1 hour and was then boiled. All solutions below remained clear throughout.

*Identilied by initials assigned to formulas in the various examples.

The orelates of the amino acids were in some cases quite easily prepared in a pure form. The procedure be low may be used for many of the amino acids, and many metal ions.

EXAMPLE XIX Cupric Dihydrogen Ethylenediamilze Bis-N,N-

29.2 grams of ethylenediamine bis-N,N'-succinic acid, EDDS-4H (0.1 mole) were mixed with 25 1111. of water that was treated with 20 g. of cupric acetate monohydrate (0.1 mole). The admixture was warmed and stirred to form a solution. When the blue liquor was diluted with 200 ml. of ethanol, the water soluble cupric chelate of ethylenediamine bis-N,N' -succinic acid separated out. This was filtered and dried to provide a nearly quantitative yield of the product. Recrystallization of the product from water and ethanol yielded a purified product.

The crystalline manganous dihydrogen chelate of EDDS was prepared analogously except that 24.5 g. of

manganous acetate tetrahydrate was used instead of 20 g. of cupric acetate monohydrate.

Analytical data.-Cu H chel ate (from Cu (C H O C H N O Cu; percent N: found 7.82; theory 7.90. Mn l-l chelate (from Mn(C H O C H N O Mn; percent N: found 7.58; theory 8.12.

These and other metal chelates of the new bis-adducts of this invention are relatively soluble in water and have utility as a source of normally insoluble metal compounds in soluble form. As such they may be used as sources of trace elements in fertilizer mixtures, insecticide formulas, etc.

EXAMPLE XX The new bis-adduct compound described in the above examples have been found to be quite effective in removing rust and oxide coatings from metal surfaces at pH values below about 9.0 in aqueous solutions containing a reducing agent such as a sulfite, hyposulfite, sugar hydroquinone, etc. For example, uniformly rusted iron (aged) strips were immersed for three hours (without agitation) at C. in a cleaning solution having the formula:

Bis adduct compound grams 15.0 Sodium bisulfite (58.5% S0 do 7.5 Water, suflicient amount to form a 300.0 ml. soln.

The pH of the solution was adjusted to 8.0 with NaOH.

The weight of the rust lost from the 81.6 sq. cm. surface of the metal strips and the condition of the resulting metal surfaces were noted as follows.

TABLE III Examples Compounds Wt. of Rust Results Lost (g.)

I H I OH1 I--OHCOOH b. 589 Clean surface, 15v L H20 0 OH I 11151; spots.

I- H vII HN-CH1CHzI IOHCOOH b.697 Do.

I. 0320 0 OH 2 l- H H vIII --cHzI- I-oH,oH,I- I-(mo 0 OH 6. 072 Do.

I. omo 0 OH H H IX I- HN-oH2oH,-1 IoH,oH,1 IoIIoo0H o. 754 Clean.

L CH2C 0 OH 2 l' H x; -1 oinomoni i fincoon oi 112s M11111 r1121 i'fiaifis'; L V 6 OH I XI keenwake "1i 1. on 01152116211111 action).

XIII mr emcmwcebofi o. 050 Spotted rust.

L 011200 0H1 Ir- H CHECOOH omiwbfioo OH XVIII 0. 531 Do.

H Ha r-b15100 OH 121m: 0. 0 343 Rizsty.

When the test strips were freshly fusted (36 hours) with a 5% NH C1 solution, the removal of rust was much rapid {and complete. Under the same conditions the re- 'sults a're tabulated below.

TABLE IV Examples Combounds Wt. of Rust Results Lost (g.)

I'- H I -CHI1ICHOOOH 1.249 Clean.

L omcoofi 11 VII finT-omoml korrooog 0.911 sg oged rust (rinsed 0111000121 2 II 11 VIII --ofi;1 i oHgoHz1 -I-o11c0o11 1.151 Clean.

H H IX HN- -oI'IIoH,-1 rcH,cHz1 1- 0HcooH 0.992 Do.

I- V 7 H X -CHZCHQCH I I-CE@6OH 0.579 Largerust spots.

L moooH 2 I- H X'I fi66fiofiI I-ofioo0fi 1.281 Clean (rapid action).

1 mcoon 2 TABLE IVContinued Examples Compounds Wt. of Rust Lost (g.)

Results H onto on HNOHnOHzN-CC 0 on L CHzC O OH 2 mm-01100 OH XIII XVIII I OHaN-CHCOOH CHQCOOH 0.105 Rusty.

0. 763 Clean.

The above compounds show excellent rust removal The pH of the solution was adjusted to 11.5 with NaOH capability.

The addition of the above adduct amino acids to alkaline solutions, such as sodium carbonate or phohphate, speeds the cleaning or etching of aluminum. Test solutions were prepared containing the following ingredients:

at C.

A Reynolds 3S-H-14 aluminum test strip of 30.1 sq. cm. surface area was immersed in each solution for hour. The results are tabulated below.

The addition of the new adduct acid compounds to solutions of strong mineral acids was found to greatly A i id 4 decrease the acid attack on plain iron. 0.5%, 1.0% Trisodium phosphate crystal 2 and 3% y w samples in z 4 at Water, sufficient amount to form a 200 m1. soln. were tested on a 7 x 4.5 x 0.5 cm. strip of lIOIl for five 30 hours. The following results were produced.

TABLE V Examples Compounds Wt. of Al. I.P.Y.

Lost (g.) 5 hr.

H I CHgl I-OHCOOH 0.101 8.14

i. CHQCOOH 1 H v11 ran-omonnh-onooon 0.0965 7.73

L 011100011 2 H VIII -oH21 I-oH2oHz1 I-o11oooH 0.118 9.47

i. CHzCOOH a I'- H H IX HNCH2OH2-1 IOH;CHgI ICHCOOH 0.055 4.42

i. omoooH 2 I" H X CHzOHzCH2I T-CHCOOH 0.038 3.01

L CHnCOOH 2 F H XI H0oHcH2I IoHo00H 0.005 7.50

L CHaCOOH 2 I- H omoooH XIII HN-OHzOHgN-iJ-OOOH 0.077 6.17

i. ongooou 7 H OHzCOOH (fHzN-CHCOOH XVIII o. 044 a. 53

CHzN-CHCOOH Blank o. 026 2.08

When the solutions were later lowered to a pH 8.5, they all deposited a white floc exee t the 2-h dro ro-- pylene-1,3-d1amme b1s-N,N-suee1nic acid, which displays its superior sequestration of luminum xyp TABLE VI Examples Compounds Steel I)? (g') H I -oHn r-o11o OH 0.112 0. 071 0. 055

L (H2 o 0 OH 1 I- H VII HN-CHzOH ILFCHCOOH] 0.02s 0. 01s 0. 012

L (31120 0 OH 1 l' H VIII -CHgII-CHzOH;ILT-OHO 0 on ll 0. 074 0. 03s 0. 024

L ame 0 0H 1 p I- H H IX nN- ofiion. i roniofin r-ofio 0 OH :I 0.063 0. 026 o. 015

L (E1110 0 OH 2 I H X -omomormh-onooon o. 072 o. 048 0. 020

L CHzC 0 0H I- H XI HOOH-CHzI IOHCOOH] 0.09s 0. 01s

L omo 0 on a I- H 011,00 0H xm HN-CH1OH2NC-C 0 OH :I 0. 025 o. 022 '0. 011

L une 0 0H 2 E 01120 0 on omN-on c 0 on XVIII H 0.087 0. e69 g Hal i-"CHO 0 OH 01120 0 OH Blank... 0.19s

The results which are underlined represent data from by weight, foams were obtained which were stable for solutions where the added adduct acid was incompletely dissolved.

EXAMPLE XXI The soap-acid amines form. amides with EDDS -adducts to yield compounds of interest. Armeen OD, a-mixture of high molecular weight amines (Armour and Co.) with oleyl amine predominatory, was fused with ethylenediamine bis-N,N'-succinic acid.

53 grams of Armeen CD (0.2 mole) were treated with 29.2 g. of ethylenediamine bis-N,N'- succinic acid (0.1 mole). The mixture was warmed slowly with stirring to 160 C. and kept at this temperature (under a short air condenser) for one hour. The liquor was cooled, dissolved in 250 ml. of ethanol, and was filtered free of insolubles. The liquor was then heated free of ethanol in a vacuum oven at 80 C. The product, a clear brown viscous liquid, weighed 75 g. a The product of this reaction is an eifective wetting and foaming agent suitable for use in cleaning and ore flotation operations. In concentrations of less than 0.25%

30 minutes or more. These foams were formed in alkaline (pH of 10), neutral, and acid (pH of 1.5 or less) solutions. Armeen OD itself forms stable foams in acid and neutral solutions, but in alkaline solutions it deposits much insoluble amine.

Similar results were obtained With Armeen CD, and coco oil base amine, the latter also being a product of Armour and Co.

These soap-acid amides are soluble in ethanol, chloroform, benzene and kerosene, but are almost insoluble in water and acetone. One g. of compound was tested with 25 g. of solvent.

EXAMPLE XXII A water-soluble polymer may be prepared by the fusion of ethylenediamine bis-N,N'-succinic acid with urea.

F ---OH N-CHC OOH 4Urea Polymer HQCOOH 2 grams of urea were melted at -l40 C. and were then treated in small portions with 146 g. of ethylenediamine bis-N,N'-succinic acid (0.5 mole) while stirring the liquid mass to keep down the foam. When foaming had diminished (after some 2 hours of heating) the heating was discontinued. The clear amber syrup was cooled and thereby hardened to a brittle amber glass. The glass was hygroscopic and water soluble. The residue totaled 244 g., a loss of 22 g.

This product may be incorporated into urea and other resin formulations as a modifier.

A titration curve showed two inflections, at a pH of 6.0 and 11.0 The molecular weight was calculated as 415 g. This corresponds closely to a ratio of one mole of ethylenediamine bis-N,N'-succinic acid to two moles urea molecules. The pH of an aqueous solution of the polymer was found to be 6.92.

Because of their general chelating and metal solubilizing characteristics and the reaction characteristics with other organic compounds the new compounds of this invention may readily suggest themselves for uses not enumerated above.

The foregoing detailed description has been given to clearness of understanding only, and no unnecessary limitations should be understood therefrom, as modifications will be obvious to those skilled in the art.

We claim:

1. A compound selected from the group consisting of:

(a) a compound of the formula:

wherein Z and Z are saturated acyclic bis-adduction groups derived from the class consisting of lower alkenyl, 1,4 conjugated polycarboxylic acids having at least 2 and not more than 3 carboxyl groups, and salts thereof and R is a member of the class consisting of lower alkylene, phenylene-lower alkylene-phenylene, lower alkylene-phenylene-lower alkylene, and

lower alkylene-ll -lowcr alkylene H groups; (b) chelates of the compound of (a) and a polyvalent metal ion; and (c) esters of the compound of (a) and a lower alkanol. 2. A compound of the formula:

wherein Z and Z are saturated acyclic bis-adduction groups derived from the class consisting of lower alkenyl, 1,4 conjugated polycarboxylic acids having at least 2 and not more than 3 carboxyl groups, and salts thereof and R is a member of the class consisting of lower alkylene, phenylene-lower alkylene-phenylene, lower alkylenephenylene-lower alkylene, and

lower ulkylenelTI-lower alkylenc 4. The product:

i i N (lower alkylene-N-lowor alky1ene)-N HOgG- H H- C 0 H HOzO- I H H I CO;H H H 5. The product I (lower alkylenc-N-Iower alkylene) bis-N,N'-tricarballylic acid.

6. The product:

wherein n is a positive integer of not less than 1 and not more than 2 and R and R are lower alkylene groups when n is 1.

7. The product:

1 L (lower alkylene-phenylene-lower alkylene) H03C- H H C 0 11 HOgO- -H H- --O 0 11 8. Chelate of a compound of claim 2 and polyvalent metal ion.

9. Ester of a compound of claim 2 and lower alkanol.

10. Metal salt of the product of claim 3.

11. Chelate of the product of claim 3 and polyvalent metal ion.

12. Ester of the product of claim 3 and lower alkanol.

13. Metal salt of the product of claim 4.

14. Chelate of the product of claim 4 and polyvalent metal ion.

15. Ester of the product of claim 4 and lower alkanol.

16. Metal salt of the product of claim 5.

17. Chelate of the product of claim 5 and polyvalent metal ion.

18. Ester of the product of claim 5 and lower alkanol.

19. Metal salt of the product of claim 6.

20. Chelate of the product of claim 6 and polyvalent metal ion.

21. Ester of the product of claim 6 and lower alkanol.

22. Metal salt of the product of claim 7.

23. Chelate of the product of claim 7 and polyvalent metal ion.

24. Ester of the product of claim 7 and lower alkanol.

25. The method of producing bis-adduction products comprising reacting an organopolyprimary amine with one mole of a member from the group consisting of lower alkenyll, 1,4 conjugated polycarboxylic acids having at least 2 and not more than 3 carboxyl groups, salts thereof and lower alkyl esters thereof for each primary amine group present in the organopolyprimary amine.

26. The method of producing bis-adduction products comprising reacting in an alkaline medium anorganopolyprimary amine with one mole of a member from the group consisting of lower alkenyl, 1,4 conjugated polycarboxylic acids having at least 2 and not more than 3 carboxyl groups, salts thereof and lower alkyl esters 25 thereof for each primary amine group present in the organopolyprimary amine.

27. The method of producing bis-adduction products comprising reacting in an alkaline medium an organopolyprimary amine with one mole of a member from the. group consisting of lower alkenyl, 1,4 conjugated polycarboxylic acids having at least 2 and not more than 3 carboxyl groups, salts thereof and lower alkyl esters thereof for each primary amine group present in the organopolyprimary amine, and adding acid to the resulting product to form an acidic bis-adduction product.

28. The method of producing a chelate of a bis-adduction product comprising reacting an organopolyprimary amine with one mole of a member from the group consisting of lower alkenyl, 1,4 conjugated polycarboxylic acids having at least 2 and not more than 3 carboxyl groups, salts thereof and lower alkyl esters thereof for each primary amine group present in the organopolyprimary amine to form a 'bis-adduction product, and adding a polyvalent metal to said product to form a chelate.

References Cited in the file of this patent UNITED STATES PATENTS 2,195,974 Reppe Apr. 2, 1940 2,532,391 Bersworth Dec. 5, 1950 2,761,874 Bersworth et a1 Sept. 4, 1956

Claims

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF: (A) A COMPOUND OF THE FORMULA: