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US2751386A - Quinolyl aliphatic alkylene polyamine poly acid - Google Patents

Quinolyl aliphatic alkylene polyamine poly acid Download PDF

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US2751386A
US2751386A US367722A US36772253A US2751386A US 2751386 A US2751386 A US 2751386A US 367722 A US367722 A US 367722A US 36772253 A US36772253 A US 36772253A US 2751386 A US2751386 A US 2751386A
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quinolyl
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Frederick C Bersworth
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Dow Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C07D215/40—Nitrogen atoms attached in position 8

Definitions

  • This invention relates to chelating agents for metal ions in aqueous solutions and has for its object the pr0- vision of water-soluble aliphatic alkylene polyamine poly acids and alkali metal salts and ammonium base salts thereof which react to form metal chelate compounds with metal ions in aqueous solutions.
  • Another object is to provide quinolyl aliphatic alkylene polyamine polyacetic acid compounds which are watersoluble and which form water-soluble salts and chelate compounds.
  • the quinolyl polyamino polyacetic acid when one of the amino hydrogens of an aliphatic alkylene polyamine is displaced by a quinolyl group and the remaining amino hydrogens are displaced by acetic acid groups or by higher fatty acids, the quinolyl polyamino polyacetic acid, its alkali metal salts, ammonium salts, and amine salts, has improved chelate-forming properties, and forms stable water-soluble chelates with a large number of mono and polyvalent metals than normally formed by the alkylene polyamino polyacetic acid compounds in which all amino hydrogens have been displaced by acetic acid groups.
  • R may be an acetic acid residue, a propionic acid residue or higher fatty acid, the alkali metal salts thereof, ammonium salt thereof or amine salt thereof;
  • Alkylene represents bivalent alkyl radicals containingiZ to 4 carbon atoms arranged structurally in such a manner as to interpose at least 2 and not more than 3 carbon atoms between the nitrogen atoms; 11 is a positive integer and is selected from the group consisting of 1, 2, 3 and 4 and higher.
  • polyamine compounds such as diethylenetriamine or dipropylenetriamine, having skeletal configurations characterized by the following:
  • the ratios of the S-quinoline amino acid to metal are 1:1 and 2:1.
  • the 1:1 chelates are rather more stable than those of ammonia triacetic acid, which has been described in considerable detail in the literature.
  • the corresponding chelates of the alkaline earth and rare earth metals are much less stable than those of ammonia triacetic acid.
  • the 2:1 chelates for the transition metals are extremely stable and in neutral solutions even at very low concentrations (10 to 10- molar) the degree of dissociation of the cheiate is so low that it cannot be measured.
  • the chelates are much more stable than those formed with the very powerful chelating agent ethylenediamine tetraacetic acid. With alkaline earth and rare earth metals, however, the chelates are less stable than those of ethylenediamine tetraacetic acid.
  • Increasing the chain length i. e. for higher values of It
  • the stability of these chelates is somewhat less (i. e. the degree of dissociation is slightly higher), but is still sufficiently great to completely deactivate metal ions.
  • the compound is synthesized as its alkali metal salt in a strongly alkaline medium. Subsequently it is isolated in acid form by taking advantage of the fact that symmetry of the compound renders it relatively in: soluble in water and, the synthesis having been completed, the acid form is precipitated by acidifying the reaction medium in which it hasbeen formed.
  • the corresponding alkali metal salts, ammonium salts and amine salts are then formed pure by reacting the acid with the hydroxide or carbonate of the alkali metal or ammonium base and drying the resultant solution.
  • Example I 0 moles of NaCN and three moles of formaldehyde (by the process described in my U. S, Patent No. 2,407,645).
  • the product may be obtained as a crystalline substance 1, ⁇ ? from the aqueous solution strongly acidified with HCl, and is believed to have the following formula:
  • This acid form of the compound is readily converted to the alkali metal salt by reacting it with enough of the corresponding alkali metal hydroxide or carbonate, ammonium hydroxide or amine in aqueous medium to neutralize it, and then recrystallizing the compound. Partial neutralization just removes the HCl from the molecule to form the free acid. Further partial neutralization will give acid salts.
  • a diamine having a substitute alkylene nucleus will give a comparable compound.
  • isopropylene diamine, NI-l2CH(CH3)CH2NHz could be used for ethylene diamine.
  • Example II One mole of 8-aminoquinoline was agitated with one liter of water and heated to the reflux point and vigorously stirred while an aqueous solution of one mole of B-chloroethylamine-N,N-diacetic acid was slowly added over a period of two hours. The reaction mixture was then heated and stirred for two hours more and then brought to a pH of with caustic soda solution. The intermediate ethylenediamine-N-quinolyl-N,N-diacetic acid, was then reacted (according to the process described in my U. S. Patent No. 2,407,645) with one mole of NaCN and one mole of CI-IzO. The reaction product, on acidification with excess hydrochloric acid yielded a crystalline material believed to have the formula:
  • Example III OHrCOOH
  • S-bromoquinoline is treated by the method of Example I with the exception that diethylenetriamine is used in place of ethylenediamine and the intermediate amine is treated with 4 moles of sodium cyanide and 4 moles of formaldehyde.
  • the final product is believed to have the formula:
  • the alkali metal salt can be formed by reacting equimolar amounts of corresponding alkali metal hydroxidc or carbonate, ammonium hydroxide or amine in aqueous medium and then recrystallizing the compound. Partial neutralization just removes the HCl from the molecule to form theireeacid. Further partial neutralization will give acid salts.
  • Example IV One mole of 8-bromoquinoline is reacted according to the process outlined in Example I, with the exception A that trimethylene diamine is used in place of ethylenediamine.
  • the final product has the formula:
  • the alkali metal salt can be formed by reacting equimolar amounts of corresponding alkali metal hydroxide or carbonate, ammonium hydroxide or amine in aqueous medium and then recrystallizing the compound. Partial neutralization just removes the HCl from the molecule to form the free acid. Further partial neutralization will give acid salts.
  • Example V In the fashion demonstrated for Examples I-IV, dimethylenetriamine, triethylenetetramine, tetraethylenepentamine and higher alkylenepolyamines are used to prepare other quinolyl derivatives.
  • the acid form of the compound, its partial salt or completely neutral salt may be prepared.
  • sufficient alkali whether alkali metal base or ammonium base
  • the hydrochloric acid would first be neutralized and three additional moles of base would be needed, for a total of four moles of base.
  • Example III five moles of base would be needed for the neutral salt; four moles in Example IV.
  • Example V each alkyl amino group in the polyamine chain would add an acid function to the compound.
  • the preparation of the salts is carried out as a common acid-base titration and inflections in the acid-base titration curve identify the formation of the mono-, di-, trietc. salts of the compounds. Isolation of the salts calls merely for recrystallization.
  • the calcium ion and the acid ion of the quinolyl ethylenediamine triacetic acid are visualized as forming the chelate set forth.
  • the calcium ion would be present in the solution as chloride or acetate, for example, and the quinolyl chelating agent would be used in the form of its sodium salt, which is the most common form for application.
  • the cobalt can be present in solution as either the chloride or nitrate and the sodium salt of the chelating agent would be used:
  • the higher polyalkylene polyamine derivatives are capable of binding more than one mole of metal per mole of amino acid.
  • the binary compound formed between Cu and N-quinolyl triethylene tetraamine-N,N, N, N', N' pentaacetic acid is visualized as:
  • Alkylene is a lower molecular weight group which places 2-3 carbon atoms in the chain directly between the indicated nitrogen atoms, R is selected from the group consisting of -CH2.COOH and CH2CH2COOH;
  • n is a positive integer having a value in the range from at least 1 to about 4; and the alkali metal, ammonium base and acid addition salts of the said compounds.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)

Description

United States Patent QUINOLYL ALIPHATIC ALKYLENE POLYAMINE POLY ACID Frederick C. Bersworth, Verona, N. L, assignor to The Dow Chemical Company, Midland, Mich, a corporzn tion of Delaware No Drawing. Application July 13, 1953,
Serial No. 367,722 1 8 Claims. (Cl. 260-287) This invention relates to chelating agents for metal ions in aqueous solutions and has for its object the pr0- vision of water-soluble aliphatic alkylene polyamine poly acids and alkali metal salts and ammonium base salts thereof which react to form metal chelate compounds with metal ions in aqueous solutions.
Another object is to provide quinolyl aliphatic alkylene polyamine polyacetic acid compounds which are watersoluble and which form water-soluble salts and chelate compounds.
Other objects will be apparent as the invention is more fully hereinafter disclosed.
In accordance with these objects I have discovered that when one of the amino hydrogens of an aliphatic alkylene polyamine is displaced by a quinolyl group and the remaining amino hydrogens are displaced by acetic acid groups or by higher fatty acids, the quinolyl polyamino polyacetic acid, its alkali metal salts, ammonium salts, and amine salts, has improved chelate-forming properties, and forms stable water-soluble chelates with a large number of mono and polyvalent metals than normally formed by the alkylene polyamino polyacetic acid compounds in which all amino hydrogens have been displaced by acetic acid groups.
The compounds of the present invention fall generally under the following structural formula: j
wherein R may be an acetic acid residue, a propionic acid residue or higher fatty acid, the alkali metal salts thereof, ammonium salt thereof or amine salt thereof;.Alkylenerepresents bivalent alkyl radicals containingiZ to 4 carbon atoms arranged structurally in such a manner as to interpose at least 2 and not more than 3 carbon atoms between the nitrogen atoms; 11 is a positive integer and is selected from the group consisting of 1, 2, 3 and 4 and higher. Thus polyamine compounds such as diethylenetriamine or dipropylenetriamine, having skeletal configurations characterized by the following:
--N--Alkylene -NAlkylene--NAlkylene+ are formed.
In this group of compounds I have found that the ethylene diamine polyacetic acid series of compounds are the most stable" and economically practical series of compounds and the invention will be described as it has been adapted to the manufacture of this series of compounds primarily. In this series of compounds very stable chelate compounds are formed with a large. number of metals, such as Mg, Be, and Fe which are not formed readily with the ethylenediamine tetraacetic acid.
2,751,386 Patented June 19, 1956 Somewhat less stable chelates are formed with Ca, La Fe Zn Cd In the case of Cu it was found that the chelate, while quite stable, is not nearly as stable as the copper chelates formed with other chelating agents, such as ethylenediamine-N,N'-diacetic acid and B, B, B" triamino triethylamine.
in the case of the bivalent transition metals the situation is somewhat complicated by the formation of two types of chelates, in which the ratios of the S-quinoline amino acid to metal are 1:1 and 2:1. The 1:1 chelates are rather more stable than those of ammonia triacetic acid, which has been described in considerable detail in the literature. The corresponding chelates of the alkaline earth and rare earth metals (with the exception possibly of Mg and Be) are much less stable than those of ammonia triacetic acid. The 2:1 chelates for the transition metals are extremely stable and in neutral solutions even at very low concentrations (10 to 10- molar) the degree of dissociation of the cheiate is so low that it cannot be measured.
When n=1, the 1:1 chelates with all metals are much more water soluble and much more stable than the 1:1 chelates formed when 11:0.
Furthermore, with transition metals such as Co, Ni and Cu the chelates are much more stable than those formed with the very powerful chelating agent ethylenediamine tetraacetic acid. With alkaline earth and rare earth metals, however, the chelates are less stable than those of ethylenediamine tetraacetic acid. Increasing the chain length (i. e. for higher values of It) increases the number of metal ionssequestered per mole of chelating agents. Thus when n=3, the one mole of compound sequesters two moles of heavy metals. The stability of these chelates is somewhat less (i. e. the degree of dissociation is slightly higher), but is still sufficiently great to completely deactivate metal ions.
In the following examples illustrating the syntheses of compounds belonging to this family of chelating agents, it is noted that the compound is synthesized as its alkali metal salt in a strongly alkaline medium. Subsequently it is isolated in acid form by taking advantage of the fact that symmetry of the compound renders it relatively in: soluble in water and, the synthesis having been completed, the acid form is precipitated by acidifying the reaction medium in which it hasbeen formed. The corresponding alkali metal salts, ammonium salts and amine salts are then formed pure by reacting the acid with the hydroxide or carbonate of the alkali metal or ammonium base and drying the resultant solution. In this fashion, sodium, potassium, lithium, rubidium, cesium, ammonium and amine salts of the compounds may be formed. crude alkali metal salt can be recovered from the reaction medium itself directly by evaporating to dryness without acidification. However, the grade of compound recoverable then is dependent upon controlling the reaction so that substantially equimolar amounts are reacted thereby to leave behind insignificant residues of reactant.
Example I 0 moles of NaCN and three moles of formaldehyde (by the process described in my U. S, Patent No. 2,407,645). The product may be obtained as a crystalline substance 1,}? from the aqueous solution strongly acidified with HCl, and is believed to have the following formula:
This acid form of the compound is readily converted to the alkali metal salt by reacting it with enough of the corresponding alkali metal hydroxide or carbonate, ammonium hydroxide or amine in aqueous medium to neutralize it, and then recrystallizing the compound. Partial neutralization just removes the HCl from the molecule to form the free acid. Further partial neutralization will give acid salts.
In this and succeeding examples, use of a diamine having a substitute alkylene nucleus will give a comparable compound. For example, isopropylene diamine, NI-l2CH(CH3)CH2NHz could be used for ethylene diamine.
Example II One mole of 8-aminoquinoline was agitated with one liter of water and heated to the reflux point and vigorously stirred while an aqueous solution of one mole of B-chloroethylamine-N,N-diacetic acid was slowly added over a period of two hours. The reaction mixture was then heated and stirred for two hours more and then brought to a pH of with caustic soda solution. The intermediate ethylenediamine-N-quinolyl-N,N-diacetic acid, was then reacted (according to the process described in my U. S. Patent No. 2,407,645) with one mole of NaCN and one mole of CI-IzO. The reaction product, on acidification with excess hydrochloric acid yielded a crystalline material believed to have the formula:
Example III OHrCOOH One mole of S-bromoquinoline is treated by the method of Example I with the exception that diethylenetriamine is used in place of ethylenediamine and the intermediate amine is treated with 4 moles of sodium cyanide and 4 moles of formaldehyde. The final product is believed to have the formula:
The alkali metal salt can be formed by reacting equimolar amounts of corresponding alkali metal hydroxidc or carbonate, ammonium hydroxide or amine in aqueous medium and then recrystallizing the compound. Partial neutralization just removes the HCl from the molecule to form theireeacid. Further partial neutralization will give acid salts.
Example IV One mole of 8-bromoquinoline is reacted according to the process outlined in Example I, with the exception A that trimethylene diamine is used in place of ethylenediamine. The final product has the formula:
The alkali metal salt can be formed by reacting equimolar amounts of corresponding alkali metal hydroxide or carbonate, ammonium hydroxide or amine in aqueous medium and then recrystallizing the compound. Partial neutralization just removes the HCl from the molecule to form the free acid. Further partial neutralization will give acid salts.
Example V In the fashion demonstrated for Examples I-IV, dimethylenetriamine, triethylenetetramine, tetraethylenepentamine and higher alkylenepolyamines are used to prepare other quinolyl derivatives.
It is to be noted from the several examples that the acid form of the compound, its partial salt or completely neutral salt may be prepared. To form the fully neutral salt sufficient alkali (whether alkali metal base or ammonium base) must be used to neutralize all of the acid functions of the compound. In Examples I and II three acetic functions appear. Hence, to form the neutral salt, the hydrochloric acid would first be neutralized and three additional moles of base would be needed, for a total of four moles of base. In Example III five moles of base would be needed for the neutral salt; four moles in Example IV. In Example V, each alkyl amino group in the polyamine chain would add an acid function to the compound. The preparation of the salts is carried out as a common acid-base titration and inflections in the acid-base titration curve identify the formation of the mono-, di-, trietc. salts of the compounds. Isolation of the salts calls merely for recrystallization.
As an example of the reactions of these chelating agents which cause deactivation of metal ions, the interaction of the compound of Example I with Ca and Co are given:
Ca i-quinolyl ethylenediamine triacetic acid In carrying out the above reaction, the calcium ion and the acid ion of the quinolyl ethylenediamine triacetic acid are visualized as forming the chelate set forth. In practice, the calcium ion would be present in the solution as chloride or acetate, for example, and the quinolyl chelating agent would be used in the form of its sodium salt, which is the most common form for application. Similarly, with respect to the following reaction showing the formation of cobalt chelate, the cobalt can be present in solution as either the chloride or nitrate and the sodium salt of the chelating agent would be used:
Co +quinolyl ethylenediamine triacetic acid- Thus it is seen that six active groups are available for chelation with metals using the simpler members of the family of chelating agents herein disclosed, but all of these groups are not necessarily used in every case. In similar fashion as the value of n increases, additional acid groups become available for chelation of heavy metal ions. Thus, formulating it generally the compound may be stated as follows:
The higher polyalkylene polyamine derivatives are capable of binding more than one mole of metal per mole of amino acid. For example, the binary compound formed between Cu and N-quinolyl triethylene tetraamine-N,N, N, N', N' pentaacetic acid is visualized as:
wherein Alkylene is a lower molecular weight group which places 2-3 carbon atoms in the chain directly between the indicated nitrogen atoms, R is selected from the group consisting of -CH2.COOH and CH2CH2COOH;
n is a positive integer having a value in the range from at least 1 to about 4; and the alkali metal, ammonium base and acid addition salts of the said compounds.
2. Compounds in accordance with claim 1, in which alkylene is -CH2.CH2-.
3. Compounds in accordance with claim 1, in which alkylene is CH2.CH2.CH2.
4. Compound corresponding to the following formula:
CHQ'OOOH 5. Compounds corresponding to the following OHz-COOH OHz-COOH CHz-COOH 6. Compound corresponding to the following (iJHz-OOOH CHZ'COOH NCH2'CHz-CH2N 0 H2 C 0 0 H N 7. Compound corresponding to the following oHzoooNa CH COONa N 0 H2 0 Hz-N 0 H20 0 0 Na 8. Compound corresponding to the following

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1. A COMPOUND WHICH IS A MEMBER OF THE GROUP CONSISTING OF COMPOUNDS CONFORMING TO THE FOLLOWING STRUCTURAL FORMULA
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2915535A (en) * 1954-03-26 1959-12-01 Chimiotherapie Lab Franc Process and intermediates to produce substituted 4-bromo-21-acetoxy-pregnane-3, 20-dione compounds

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2511210A (en) * 1946-04-01 1950-06-13 Ilford Ltd Methine dyestuffs
US2520902A (en) * 1947-08-05 1950-09-05 Frederick C Bersworth Quaternary ammonium salts of pyridine compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2511210A (en) * 1946-04-01 1950-06-13 Ilford Ltd Methine dyestuffs
US2520902A (en) * 1947-08-05 1950-09-05 Frederick C Bersworth Quaternary ammonium salts of pyridine compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2915535A (en) * 1954-03-26 1959-12-01 Chimiotherapie Lab Franc Process and intermediates to produce substituted 4-bromo-21-acetoxy-pregnane-3, 20-dione compounds

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