US RE23904 E
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I Jnited States Patent SUBSTITUTED ALKYLENE DI-AMINO DI-ACETIC ACIDS AND SALTS Frederick C. Bersworth, Verona, N. I.
No Drawing. Original No. 2,624,757, dated January 6,
1953, Serial No. 193,543, November 1, 1950'. Application for reimue August17, 1953, Serial No. 374,838
6 Claims. (Cl. 260-518) Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
heavy metal In accordance with these objects I have discovered that alkylene polyamino acids conforming to the general structural formula- CHrC 0 on ous-coon N-alkylena-N CHe-COOH OKs-COOK X X X X xQn-lt-nk nne-N-n-Q where X=hydrogen, alkyl, halogen, hydroxyl or alkoxyl; I
where R represents an alkylene radical or an alkylene radical containing ether linkages, the resulting polyamino polycarboxylic [acid acquires] acids acquire solubility in organic solvents as well as bactericidal and fungicidal properties in aqueous solutions and [retains] retain strong chelating properties towards heavy metal ions in aqueous as well as in organic solvent solutions.
The compounds described are all soluble in water in the form of their alkali metal, ammonia or amine salts. They are not soluble as the acids in water media but are soluble in organic solvents. The amine salts are also highly soluble in organic solvents. The chelates are soluble in organic solvents being non-ionic.
This solubility may be modified particularly as to water systems by means of sulfonation in the aromatic ring and/ or alkyl sulfonation in accordance with known means to form soap-like products.
There are a large number of compounds conforming to this general structure given above and the compounds may include mono or poly halogenated, alkylated, and hydroxylated phenyl groups without departure from the invention. As specific examples of the compounds within the scope of the invention the following are given by way of illustration and not by way of limitation.
Re. 23,904 Reisaued Dec. 14,1954
tion N,N'(2,6 dichloro-4-nitro-] the precipitation of N,N'-
(2,6-dichloro-4-nitro-benzyl) ethylene diamine diacetic acid as the solid monohydrate. The product is believed to have the formula:
GHs-C 0 OH CHz-COOH 01 I o1 CINQCHrNCHI-CHI-NGHQNOI 1 1 011.0001; cmcoorr at l l at For example, the N02 group in the aromatic nucleus may be reduced to an amino group, which may then be diazotized and converted to a halogen by means of the Sandmeyer reaction. Also, the diazonium salt may hydrolyzed to a phenolic group by well-known methods.
The amino hydrogens of the phenyl amino group may be substituted by various functional groups, such as acetic acid groups to further modify the properties of the compoun The aromatic [group] groups may also be further modified by substitution on the aromatic [ring] rings by known reactions to give derivatives thereof which are valuable chelating agents.
EXAMPLE II The diazonium salt of Example I is treated with cuprous chloride and excess alkali chloride (Sandmeyer reaction), in the usual manner, except that a molar amount of cupric ion is used to take care of the tendency of the amino acid to combine with copper. The resulting compound is a chelate of copper, which may be separated from the metal in ethanol solution by treatment with excess HaS. The resulting acid may be crystallized on evaporation of the solvent, and is believed to have the formula:
EXAMPLE III The product of Example II may also be obtained [by condensing 2,4,6 trichlorobenzyl chloride with ethylene diamine, N,N' diacetic acid disodium salt as described in the first step of example] by condensing 2,4,6-trichlorobenzyl chloride with ethylene diamine-N,N'-diacetic acid disodium salt as described in the first step of Example I. Acidification of the reaction mixture yields the desired product as a crystalline substance.
EXAMPLE IV Two moles of p-chlorophenylethyl chloride,
ClCsHsCHzCHzCl is treated with an aqueous solution of one mole of discdium ethylene diamine diacetate as described in Example I. On acidification of the reaction mixture the follow ng substance is obtained in crystallizable form:
CHz-OOOH CHs-COOH l (no-curcnrit-onrcnr-N-onronrQOi 7 EXAMPLE V Two moles of 2-hydroxy-3,6-dichlorobenzyl chloride dissolved in ethanol are gradually added to a gently re- Gem-linemen? C'Hr precipitates from the aqueous solution as the monohydrate (when considerable alcohol is present precipitation may be incomplete. Under such conditions it is advisable to distil off the alcohol solvent).
The precipitated monohydratc product need not be purified for further synthesis. However, if desired the hydrate may be recrystallized from aqueous ethanol. The crude reaction product is then carboxymethylated according to the process of my prior Patents Nos. 2,387,735 and 2,407,645 with NaCN and CHzO using about 80% tertiary butyl alcohol as the solvent and keeping the temperature just below the boiling point of the mixture. The product, which is primarily the di-substituted ethylene diamine diacctie acid may be obtained by crystallization from dilute aqueous HCl solution after removal of the tertiary butyl alcohol by distillation. It has the following structure:
01 on no or [@CHz-N-CEz-CflrN-CIb-O 1 (Lin-coon rLnreoon at on H or I prefer to use it, however, in the form of its alkali metal salt (somewhat water soluble) directly as obtained from the reaction mixture. It is a strong chelating agent for heavy metal ions.
These compounds are particularly useful, as germicides,
fungicides and/or sterilizing and stabilizing agents (antioxidants) in oily and hydrocarbon systems and emulsions or where it is desired to introduce the water soluble salt but precipitate the complex from aqueous solution. The aromatic group also may act as plasticizer in rubber, synthetic rubber. Then the entire molecule follows a stabilizer and plasticizer.
EXAMPLE VI This material may be converted to the desired chelating agent by substitution of two acetic acid (or salt) groups on the amino hydrogens. This may be done by a number of methods; carboxymethylation using [NaCHz] NaCN and CHzO, treatment with sodium chloroacetate, or [use] by the familiar nitrile method (Strecker synthesis using formaldehydeyfllfhe carboxymethylation reaction seems to give best resultsfburrequires a mixed organic aqueous solvent as in Example V. The resulting disubstituted [ethylene] trimethylene diamine diacetic acid is insoluble in water and may be obtained by acidification of an aqueous solution of its salts. It has the formula:
(|J'HrCOOH cnrcoon 01G exams-onion.-crn-u-rennroei In addition to having strong chelating properties, it is surface active (as its salts) in aqueous solutions, is a germicide, and the acid and its metal chelates are soluble in polar and non-polar organic solvents.
It is believed apparent from the above disclosure of genus and species compounds falling within the scope of the invention that the di-(substituted phenyl)-di-alkylene substituted alkylene diam'inediacetic acid compounds of the present invention form a definite group of compounds whose chemical properties are closely similar and analogous though varying somewhat in degree. An analogous series of compounds are obtained [where] when the acetic acid groups are replaced by an acetic acid analogue but the chelate-forming properties of the compounds decrease as the carboxylic groups is moved further away from the amino nitrogen by intervening groups. Therefore, I
. prefer to employ theacetic acid group compounds for the chelating agents of the present invention.
The bactericidal and germicidal properties of these compounds are due to the halogenated phenyl groups which are substituted in the alkylene groups displacing the amino hydrogens of the base alkylene polyamine diacetic acid,-
the intervening alkylene group spacing the halogenated phenyl groups remote from the amino nitrogen sufiiciently to permit same to function as solubilizing groups in aqueous and organic solvent solutions. In these phenyl groups at least one of the hydrogens in the aromatic nucleus must be displaced by a halogen, preferably chlorine, for bactericidal action.
Having hereinabove described the invention generically and specifically and given several specific examples of the same to illustrate the generic scope thereof it is believed apparent that the compounds may be widely varied structurally without essential departure from the invention and all such are contemplated as may fall within the scope of the following claims.
What is claimed is:
1. A compound conforming to the following formula:
CH|.OO 0H 011213003 X X x X XQR-IL-olkylene-N-RQ wherein R is an alkylene group containing from 1 to 5 carbon atoms, alkylene is one of the group consisting of three of the X groups being halogen, and the alkali metal, ammonium and amine salts thereof.
6 2. The compound conforming to the structure: 6. The compound conforming to the structure:
Cl 01 c1 01 I 01 OKs-N-OHrGHn-N-C o1 GHa-N-CHz-CHz-N-CH 5 l l 1 CHrCOOH CHrCOOH- c rCOOH l I References Cited in the file of this patent HYCOOH or the original patent 3. The compound conformmg to the structure: 10 UNITED STATES PATENTS am-coon am-coon Number Name -Q- -C 868,294 Schmidlin Oct. 15, 1907 4. The compound conforming to the structure: 15
01 0H 0H 01 2,539,212 Strobel et al. Jan. 23, 1951 CHa-N-CHr-ClIz-N FOREIGN PATENTS J Number Country Date 1 HrCOOH moon]! 0! 20 18,095 Great Britain of 1913 Cl 0H 0H 01 642,244 Germany Mar. 6, 1937 g i, OTHER- REFERENCES Alphen: Chem. Abs., vol. 38, co]. 4943 (1944). C Bischolf et al.: Beilstein (Handbuch, 4m 1. vol. 12,
5. The compound conforming to the following struc HrOOOH HrCOOH HIC 0 OH 500 OH