GB1571863A - Sulphonamidoquinoline derivatives and their use in the extraction of metals from aqueous solutions thereof - Google Patents

Description

(54) 8-SULPHONAMIDOQUINOLINE DERIVATIVES AND THEIR USE IN THE EXTRACTION OF METALS FROM AQUEOUS SOLUTIONS THEREOF (71) We, HENKEL CORPORATION, formerly General Mills Chemicals Inc., a corporation organised and existing under the laws of the State of Delaware, United States of America, of 4620 West 77th Street, Minneapolis, Minnesota 55435, United States of America, do hereby declare the invention, for which we pray that apatentmay be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to the liquid ion exchange extraction recovery of certain metal values from their aqueous solutions. More particularly, it relates to such a process wherein the extractant is an 8-sulfon-amidoquinoline compound dissolved in an essentially waterimmiscible organic solvent. The invention further relates to certain new sulfonamidoquinoline and to solutions thereof in water-immiscible organic solvents.

Liquid ion exchange recovery of metal values from aqueous solutions thereof has in the past ten years or so become an established commercial operation. Such processing has been described as being deceptively simple since all that is really happening is the transfer of a metal value from Phase A (aqueous) to Phase B (organic) and thence from Phase B to Phase C aqueous). However, complexities of liquid ion exchange arise in a number of areas including (1) synthesis and manufacture of a suitable organic system, (2) evaluation of the system's capabilities and (3) engineering application leading to large scale metal recovery.

The main key to a successful application of liquid ion exchange is the reagent acting as the extractant in the organic phase. In this respect, the reagent must complex with or react with a metal or group of metals and such complexing or reaction should be relatively fast in order to avoid having to use large holding tanks or reaction vessels. It is also desirable that the reagent shows a preference for a single metal where it is desired to extract a single metal from aqueous starting solutions containing a number of metal values. Such selectivity can often be optimized by the use of appropriate pH ranges. The reagent should also desirably complex or react quantitatively with the metal under the extraction conditions employed. Additionally, the reagent, as well as the resultant metal complex, must exhibit satisfactory solubility in the essentially water-immiscible organic solvent being used. Further, the reagent metal reaction or complexing must be reversible so that the metal can subsequently be stripped from the organic phase. For economic reasons, the reagent must have an acceptable stability such that it can be recycled repeatedly. Also, it should be essentially water insoluble to prevent significant loss into the aqueous phase or phases. Furthermore, the reagent should not cause or stabilize emulsions between the organic and the aqueous phases. Again and principally for economic reasons, it is preferred that the reagent should not react with or load significant quantities of acid, for example, from aqueous acidic stripping solutions. Of course, it is also desirable that the cost of the reagent should be low in order to reduce the operating costs of the liquid ion exchange process.

Of significant, but lesser, importance in such extraction processes is the selection of a suitable essentially water-immiscible solvent for use in the organic phase. Such selection is important principally from a cost standpoint, especially in the recovery of the more common metals. Existing commercial operations for copper recovery, for example, generally employ aliphatic kerosenes because of their relative low cost. Thus the cost of the reagent and the organic solvent is intertwined in providing the desired overall economics of the process being commercialized.

One of the most extensively used systems in commercial operation for copper recovery during the last decade has employed benzophenoximes or combination reagents including a benzophenoxime component as the extractant. Whilst being economic, such systems suffer from the disadvantage that the said benzophenoximes do not have total selectivity for copper over, for example, iron. Other types of reagents which have previously been proposed for use in copper recovery such as the alkenyl substituted 8-hydroxyquinolines also have certain drawbacks. Thus the latter compounds in addition to having a poor selectivity for copper over iron also tend to load considerable quantities of sulfuric acid.

In Billman and Chernin, Analytical Chemistry, Vol. 34, No. 3, March 1962, pp 408-410 there are described certain low molecular weight sulfonamidoquinolines and their use in the precipitation of certain metal ions by chelation. The article discloses the following four specific compounds:

These compounds were shown to chelate with Ag+, CU++, Zn++, Pb++, Co++ and Hg++ when dissolved in 95% ethanol or acetone and contacted with certain buffered solutions of the metal ions. The authors stated that 'The chelates differ greatly from those of 8-mercaptoquinoline in their solubility. They do not dissolve in the common nonpolar organic solvents or in the polar ones such as dimethylformamide, pyridine and nitromethane' (p. 408). Subsequently, United States Patents Specifications Nos. 3,268,538 and 3,337,555 were issued to Billman and Chernin. No additional specific compounds are disclosed in these patents which are directed to essentially the same data and concept as set forth in the earlier publication -- i.e. the precipitation of chelates of specified metals with low molecular weight sulfonamidoquinolines. A generic formula

is set forth in the said patents with R being defined as a member of the group consisting of L1 -L;5 alkyl, (g2-tf5 aikenyl and

where m is a number from 0-2, R' is Cl-Cs alkyloxy, nitro, halo and

where Z is oxygen, sulfur, sulfonyl or sulfoxide.

We have now found that 8-sulfonamidoquinolines whic hare soluble in essentially waterimmiscible organic solvents can be used in a liquid ion exchange process to extract certain metal values from their aqueous solutions. Such 8-sulfonamidoquinolines generally meet most or all of the reagent characteristics set forth hereinabove, including low sulfuric acid loading and high selectivity for copper over iron. Further, the said 8-sulfonamidoquinolines appear to have long term stability when in use equal to or greater than the aforementioned benzophenoximes. This discovery is particularly surprising in view of the findings of Billman and C ernin as to the lack of solubility in organic solvents of the chelates of the low molecular weight 8-sulfonamidoquinolines specifically synthesized and tested by them since the formation of precipitates in the organic phase would not lead to a commercially practical metal recovery process due to handling and cost problems.

Additionally, Billman and Chernin give no indication that metal complexes may be formed with 8-sulfonamidoquinolines dissolved in essentially water-immiscible organic solvents such that the metal complex remains in solution or that the metal values in such complexes may be stripped therefrom leaving the 8-sulfonamidoquinoline still in solution in the essentially water-immiscible solvent.

According to the present invention there are provided compounds having the formula:

where R represents an alkyl or alkenyl radical containing 8-20 carbon atoms or a group of the

formula: AR4)q -- (R3)p -- (AY - (R3)p - R5)r where R3 represents an alkylene radical containing from 1 to 20 carbon atoms; p isO or 1; A is a mono- or bi-cyclic radical wherein the ring or rings are 5- or 6-membered; q is 1,2 or 3; r is 0 or 1; and q + r is 1,2 or 3; each R4 independently represents an alkyl or alkenyl radical containing up to 20 carbon atoms; the total number of carbon atoms in (R4)q being at least 8, with the provisos that when q is 2 at least one R4 radical contains 5 or more carbon atoms and quen q is 3 at least one R4 radical contains 3 or more carbon atoms; and each R5 independently represents -Cl, -Br, -NO2 or O R6 wherein R6 is a hydrocarbyl radical containing from 1 to 20 carbon atoms; n is0, 1 or 2; and m isO or 1; and R1 and R2, which may be the same or different, each represents a hydrocarbon radical containing from 1 to 5 carbons, -Cl, -Br, -NO2 or O R6 (wherein R6 is as defined above), or (when n is 2) the two R' groups may together form a divalent hydrocarbon group.

The above compounds may be further characterised as having solubilities of at least 2% by weight in essentially water-immiscible solvents and the CU++ complexes thereof also having solubilities of at least 2% by weight in the said solvents; as well as solutions thereof in essentially water-immiscible organic solvents containing at least 2% by weight of the said 8-sulfonamidoquinoline.

According to a further feature of the present invention there is provided a process for recovering metal values selected from Cu++, Ni++, Co++, Zn++, Cd++, Hg++, Ag+ and Pb++ from aqueous solutions thereof which comprises contacting the said aqueous solutions with a solution of an 9-sulfonamidoquinoline of formula I (as defined above) in an essentially water-immiscible organic solvent to extract at least a portion of the metal values into the organic phase, separating the loaded organic phase from the aqueous phase and stripping at least a portion of the metal values from the organic phase into an aqueous stripping medium, such process being further characterized in that the said 8-sulfonamidoquinoline compound and the metal complex thereof formed during the extraction step have solubilities of at least 2% by weight in the essentially water-immiscible organic solvent.

The 8-sulfonamidoquinolines useful in the process of the present invention are those which are soluble in essentially water-immiscible organic solvents at least to an extent of 2% by weight and whose metal complexes are also soluble to the indicated amount. The 8sulfonamidoquinoline base moiety can be illustrated as follows:

wherein solubility in the essentially water-immiscible organic solvents is achieved by substituents on the quinoline nucleus and/or the radicals completing the NHSO2-group, preferably the latter. As indicated, it is necessary that these 8-sulfonamidoquinolines have the requisite solubility characteristics. It is also requisite that the nitrogen of the quinoline nucleus and the NHSO2-group remain active since the metal complexing takes place through the interaction of such groups. A substantial number of useful 8-sulfonamidoquinolines is illustrated hereinafter in the examples.

In formula (I) above, R may, for example, represent a C8-20 alkyl or alkenyl radical which is preferably branched chain. R however, preferably reDresents a moun of formula

as hereinbefore defined. When p is 1, R3 is an alkylene radical of 1 to 20 carbon atoms, preferably 1 or 2 carbon atoms.'A' is a mono- or bi-cyclic radical wherein the ring or rings are 5- or 6-membered. While the said mono- or bi-cyclic radical may be saturated or unsaturated, it is preferred that the same is unsaturated and 6-membered and A is most preferably selected from the phenyl and naphthyl radicals. The R4 groups are preferably alkyl. R6 may be, for example, alkyl, alkenyl, aryl, aralkyl, alkaryl or alkenylaryl.

R' and R2 in the preferred compounds for use in the present invention can be hydrocarbon groups such as alkyl, alkenyl, aryl, aralkyl, alkaryl or alkenylaryl containing from 1 to 5 carbon atoms, ether groups, -O-R6, as defined hereinabove, or C1, Br or nitro groups. Preferably, when present, R1 and R2 are alkyl groups of 1 to 5 carbon atoms or Cl, Br or nitro groups.

Preferred compounds are those wherein n is 0 or 1.

Preferred 8-sulfonamidoquinoline compounds are those characterized by their solubility (and the metal complexes thereof -- i.e. Cu++) in aliphatic or aromatic hydrocarbons or mixtures thereof having flash points of 1500F. and higher to the indicated level of at least 2% by weight.

As will be further evident from the examples to follow, alkyl and alkenyl chain length and/or branching and type of branching in the R radical of the preferred compounds (including in the aralkyl, alkaryl and the alkenylaryl compounds) can contribute to the solubilities as set forth above. Thus the preferred compounds have in the R radical sufficient chain length and/or branching and type of branching in the alkyl and alkenyl groups contained therein to provide at least the minimum solubility characteristics as set forth in the respective solvents to be used. In this latter respect, we have discovered that in order for the compounds (and their metal complexes -- i.e. Cu++) to meet the solubility requirements in the above designated aliphatic and/or aromatic solvents having flash points of 1500F. and higher, the same have 8 or more carbon atoms in the R radical when R is alkyl or alkenyl and, when R is

(R4)q contains 8 or more carbon atoms with the proviso that when q is 2 and one R4 radical contains five carbon atoms, the second R4 radical will also contain at least five carbon atoms.

The 8-sulfonamidoquinoline compounds may be prepared by reaction of an appropriate 8-aminoquinoline with an appropriate sulfonyl chloride. In a preferred method the 8aminoquinoline or substituted 8-aminoquinoline is first dissolved in an organic base or a solution of an organic base in an organic solvent. The resultant solution is then preferred cooled to 0-100C. and the desired sulfonyl chloride is added slowly thereto preferably with stirring while the reaction temperature is maintained at 0 to 20"C. After addition of the sulfonyl chloride is complete, the reaction mixture is desirably allowed to warm to room temperature, preferably with stirring for one to three hours for example. The reaction mixture may then be heated to 80-100 C. for approximately 30 minues after which time water may be added and the reaction mixture thus obtained (at 75-95"C. for example) may then be stirred for an additional period - i.e. 30 minutes. Subsequently the reaction mixture is convenientlypoured into water (e.g. ratio of 25(i ml. - to one litre) and the sulfonamidoquinoline may then be recovered, for example (1) by extraction with an organic solvent, such as Skellysolve C (available from the Skelly Oil Co. and consisting mainly of n-heptane, b.p. range 88-100"C., hereinafter referred to as 'Skelly C'), benzene or chloroform or (2) by filtration in the case of those sulfonamidoquinolines which crystallize out. If the sulfonamidoquinoline is recovered by organic extraction then the organic extract is desirably washed (e.g. 3 times) with 2-5% by weight sodium bicarbonate in 20-30% aqueous methanol, then with 25 g./l. aqueous sulfuric acid (e.g. 3 times) and again with the sodium bicarbonate solution. Finally, the organic phase is preferably washed with brine then dried over sodium sulfate and filtered. The filtrate may then be evaporated in vacuo. Further details as to the preferred methods of synthesising the 8-sulfonamidoquinolines useful in the present invention will be found hereinafter in the examples.

In the extraction process of the present invention, the sulfonamidoquinoline compounds are dissolved in an essentially water-immiscible organic solvent and then the resultant solution is contacted with the metal-containing aqueous phase whereby at least a portion of the metal values are extracted into the organic phase. The phases are then separated and metal values may be subsequently stripped from the loaded organic phase by the use of an aqueous stripping medium.

A wide variety of essentially water-immiscible organic solvents can be used in the metal recovery process of the present invention. These include, for example, aliphatic and aromatic hydrocarbons such as, e.g. kerosenes, benzene, toluene and xylene. The choice of essentially water-immiscible organic solvent for a particular commercial operation will depend on a number of factors including the design of the solvent extraction plant (i.e. mixer-settlers, Podbielniak extractors, etc.), the value of the metal being recovered and disposal of plant effluent. The process of the present invention is particularly useful in the extraction recovery of the major, non-ferrous, transition metals, i.e. copper, nickel, zinc, cobalt (II), cadmium, mercury and silver (I), and lead as will be described more fully hereinbelow. Essentially all of the major plants currently in operation for the recovery of these metals (particularly Cu) use mixer-settlers with relatively large organic inventories and some loss of solvent invariably occurs by evaporation and entrainment in the aqueous phase. Under these circumstances, preferred organic solvents for use in the metal recovery processes of the present invention are the aliphatic and aromatic hydrocarbons having flash points of 1500F. and higher (measured, for example, according to ASTM D-56) and solubilities in water of les than 0.1% by weight.

These solvents have the advantage that they are essentially non-toxic, chemically inert and the costs are currently within practical ranges. Representative commercially available solvents are Kermac 470B (an aliphatic kerosene available from Kerr-McGee - Flash Point 175"F.), Chevron Ion Exchange Solvent (available from Standard Oil of California -- Flash Point 195"F.), Escaid 100 and 110 (available from Exxon-Europe -- Flash Point - 1800F.), Norpar 12 (available from Exxon-U.S.A. -- Flash Point 1600F.), Conoco C-1214 (available from Conoco -- Flash Point 1600F.), Aromatic 150 (an aromatic kerosene available from Exxon U.S.A. - Flash Point 1500F.) and various other kerosenes and petroleum fractions available from other oil companies; the words 'Chevron','Escaid', 'Exxon' and 'Conoco' are Registered Trade Marks.

For use in the extraction process of the present invention the 8-sulfonamidoquinolines are dissolved in water-immiscible organic solvents such as, for example, those described hereinabove. For direct use in the extraction process such compositions comprising the 8-sulfonamidoquinoline in the essentially water-immiscible organic solvent will contain at least 2% by weight of the 8-sulfonamidoquinoline compound and preferably from 2 to 50%, more preferably 5 to 20% O/o by weight of the 8-sulfonamidoquinoline. In some cases it may be desirable to formulate concentrates comprising the 8-sulfonamidoquinoline in the essentially water-immiscible organic solvent, preferably in amount of from 25 to 75% by weight for ease of transport and handling, the concentration of which may be adjusted as required before use.

In the extraction process, the organic:aqueous phase ratios can vary widely since the contacting of any quantity of the sulfonamidoquinoline solution with the metal-containing aqueous phase will result in some extraction of metal values into the organic phase. However, for commercial practicality, the organic:aqueous phase ratios are preferably in the range of 5:1 to 1:5. For practical purposes, the extractions (and stripping) are normally carried out at ambient temperatures and pressures although higher or lower temperatures and/or pressures can be used if desired. The entire extraction process can be carried out continuously with the stripped organic solvent solution being recycled for contacting further quantities of metal containing solutions.

The metal recovery process of the present invention is useful for the recovery of the following metal values from their aqueous solutions: Cu++, Ni++, Co++, Zn++, Pb++, Cd++, Hg++ and Ag+. Except for Pub++, these metal values are all transition metals of Groups I B, II B and VIII. The extraction of these various metals from their aqueous solutions depends upn a number of factors including, for example, the concentration of the metal ion, the particular anions present and the pH and/or ammonia concentration in or of the aqueous solutions and the concentration of and the particular sulfonamidoquinoline used in the organic phase. Thus for each aqueous metal solution and reagent solution of sulfonamidoquinoline there will be a preferred or optimum set of extraction conditions and those skilled in the art, based on the mformation given herein especially in respect of the examples to follow, will be able with a limited number of trial runs to determine such preferred or optimum conditions for the respective systems under consideration. This is equally true of the stripping operations. By stnpping is meant that at least a portion of the metal values in the loaded organic phase are transferred to the aqueous stripping medium. The metal values may then be recovered from the aqueous stripping medium by conventional techniques, preferably electrolysis. The loaded organic:aqueous stripping phase ratios can also vary widely. However, the overall object of the process is to provide a metal-containing stripping solution of known composition and concentration suitable for conventional recovery techniques such as electrolysis. Thus normally the metal will preferably be present in higher concentrations in the aqueous stripping medium than in the starting metal-containing solution. Accordingly, the loaded organic:aqueous stripping medium phase ratio will preferably be in the range of 1:1 to 10:1.

Based upon extensive data obtained to date especially in respect of the sulfonamidoquinolines of Example I and II to follow, certain preferred conditions for the extraction and stripping operations are outlined as follows in regard to specific metal ions to be extracted. Thus we have found that Cu++ is readily extracted at acid pH's with the preferred range falling at a pH of from 0.5 to 7.0. Likewise copper is readily extracted from ammoniacal solutions wherein the preferred concentration of ammonia in the latter is from 10 to 150 g./l.

The loaded organic phase is readily stripped of Cu++ with, for example, aqueous acid stripping solutions such as 25 to 250 g./l. H2SO4.

Zinc (Zn"), nickel (Nit+), cobalt (Co++ and cadmium (Cd++) are readily extracted from ammoniacal solutions in the same manner as Cu++. Preferred acid pH ranges for these metals are from 4.0 to 6.0 for Zn++ from 4.5 to 7.0 for Nix', from 5.0 to 7.0 for Co" and from 4.0 to 7.0 for Cd++. All of these metals are readily stripped from the loaded organic phases thereof with aqueous acidic stripping mediums, preferably 25 to 250 g./l. H2SO4. Lead (Pb++) is preferably extracted at pH's above from 5.0 with the metal being stripped from the loaded organic phase by aqueous acidic stripping solutions, which are preferably from 100 to 150 g./l. nitric acid solutions (lead has little solubility in aqueous H2SO4). Pb++ does not form a soluble ammonia complex. Mercury (Hg++) is (from somewhat limited data) preferably extracted from its aqueous solutions over a pH range of from 0.5 to 6.0. One preferred aqueous acidic stripping medium therefore is hydrochloric acid at a concentration of from 20 to 50 g./l Silver (Ag+) may be extracted from an ammoniacal solution, for example, at an ammonia concentration of 10 g./l. Specific aqueous stripping solutions for the silver loaded organic phase include 63 g./l. nitric acid, 37 g./l. HCI and 150 g./l. H2SO4. The above discussion is based on actual extraction and stripping operations in accordance with the procedures used in the following examples. As indicated previously, each starting metal-containing aqueous solution will have its own optimum conditions as will be readily apparent to those skilled in the art.

The extract structural nature of the metal complexes formed during the extraction process of the present invention has not been determined. However, from the analytical data obtained wherein the sulfonamidoquinolines have been maximum loaded with the metals, particularly Cu++ and ZnC', it would appear that the metal complexes (i.e. maximum loaded) comprise the metal and the sulfonamidoquinoline in a molar ratio of 1:2. However, the sulfonamidoquinolines do not need to be maximum loaded to perform acceptably in the extraction process according to the invention, it being only necessary that a portion of the metal values in the starting aqueous phase be complexed in the organic phase and ultimately stripped from such organic phase.

The startingmaterials for the preparation of the sulfonamidoquinolines useful in the present invention may be prepared (if not readily available commercially) by various methods as will now be described in detail. Such description aids in defining preferred embodiments of the invention since branching of the alkyl or alkenyl groups in R and type of branching in

is dependent somewhat on the derivation of the starting materials. As mentioned above, the 8-sulfonamidoquinolines may be prepared by reaction of an 8-aminoquinoline with a sulfonyl chloride.

8-Aminoquinoline is commercially available and can also, for example, be prepared from 8-hydroxyquinoline or 8-nitroquinoline by methods well known in the art. Substituted 8 aminoquinolines may be prepared by analagous methods as illustrated hereinafter in the examples.

The sulfonyl chlorides may, for example, be prepared from a corresponding alkylbenzene, alkylbenzenesulfonic acid, sodium sulfonate salt or alkyl halide. According to one method an appropriate alkylbenzene may be treated with chlorosulfonic acid. The chlorosulfonic acid may either be used in excess or the resultant mixture may be subsequently treated with a chlorinating agent such as thionyl chloride in order to give the desired sulfonyl chloride.

Thus, for example, in one particular embodiment, the alkylbenzene, in 1,1,2trichloroethane (TCE), may be cooled to 100C. and chlorosulfonic acid may be added slowly thereto with stirring. The pot temperature is maintained at 10-150C. during the addition. After the addition is complete, the reaction mixture is stirred at 10-150C. for 15 minutes and then allowed to warm to ambient temperature while stirring for 2-3 hours. Thionyl chloride is then added to the stirred rreaction mixture and the resultant mixture is then heated slowly (1-3 hours) to 90-120"C. and held at this temperature for 30 minutes. A sample is preferably then withdrawn from the reaction mixture for analysis. If the presence of the sulfonic acid anhydride is detected by IR, an additional mole of thionyl chloride is added and the reaction mixture is stirred at 90-1200C. for one additional hour. The excess thionyl chloride and TCE are stripped from the reaction mixture in vacuo and the crude sulfonyl chloride may be purified by molecular distillation. Ratios of reactants, reaction temperatures and yields employed in a number of preparations using the above method are given in Table 1: Table I Product Run Alkyl- ClSO3H SOCl2 TCE Rxn Distilled benzene (m) (m) (ml) Temp. Yield (m) C (%) Dodecylbenzenesulfonyl 4.34 4.34 8.68 367 115-120 64 chloride Decylmethylbenzene- A 5.53 5.53 11.07 442 110 73 sulfonyl chloride B 0.25 0.275 0.55 10 116 56 Decylethylbenzene- A 0.7 0.7 1.4 40 110 46 sulfonyl chloride B 0.56 0.56 1.13 33 110 41 C11-C14 Alkylmethyl- 0.6 0.6 1.2 40 120 38(1) benzene sulfonyl chloride Nonylmethylbenzene- 0.25 0.275 0.55 30 110 84 sulfonyl chloride Decylcumenesulfonyl chloride 0.46 0.46 0.93 20 90 34(1) Heptylbenzenesulfonyl 0.67 0.67 1.0 (2) 120(3) 50 chloride (1)Repeated addition of thionyl chloride did not convert the sulfonic acid anhydride to the sulfonyl chloride quantitatively.

(2)TCE was replaced with 30 ml. of Skelly C (3)Dimethylformamide (0.4ml.) was added while holding the temperature at 120 C. to catalyze the conversion.

Octylmethylbenzenesulfonyl chloride may be prepared from octyltoluene in 70% yield by the method of Cross and Chaddix (U.S. Patent Specification No. 2,694,727). Other starting sulfonyl chlorides may be prepared by mixing the corresponding alkylbenzene with chlorosulfonic acid in the manner set forth by Bistline and co-workers (J. Am. Oil Chem.

Soc., 51, 126 (1974)). Preferably the reaction will be carried out with the following modifications. The acid layer is drained off after the reaction mixture has been allowed to stand overnight and Skelly C is added to the organic phase with gentle swirling. An additional volume of sulfuric acid settles out of the organic phase after one hour and is drained off. The organic phase is carefully washed with ice-water (with extreme caution), then with brine, dned over sodium sulfate and filtered. The filtrate is evaporated in vacuo to give an oil. Ratios of reactants and solvents employed in a number of preparations according to this method are given in Table 2.

Table 2 Product Alkyl- CIS03H 1,2-Dichloro- Skelly C Yield benzene (m) ethane (ml) (m) (ml) Dodecylben- 0.615 1.45 100 500 80 zenesulfonyl chloride Diamylbenzene- 0.224 0.67 25 100 (1) sulfonyl chloride n-Hexadecylbenzene 0.33 1 50 100 (2) sulfonl chloride Hexadecylbenzene- 0.2 0.6 50 (3) (2) sulfonyl chloride (l)Aproximately 40% of the material was lost during the ice water wash due to vigorous nothing and spattering. The crude product was purified by distillation (37% yield).

(2)The conversions were incomplete. The isolated material was a mixture of the sulfonic acid and sulfonyl chloride. Conversion to the sulfonyl chloride was completed by refluxing with excess thionyl chloride as described in the following procedure.

(3)Addition of the Skelly C was omitted.

The alk lbenzenes employed in the above preparation may themselves be obtained by a number of routes, for example by acylation of an appropriate aromatic substrate with an acid chloride followed by reduction of the compound thus obtained to the desired alkylbenzene.

This procedure is described in more detail hereinafter in relation to the preparation of sulfonamidoquinoline compounds where R is diamylphenyl and n-hexadecylphenyl.

The alkylbenzenes may also be obtained by a Friedel-Crafts alkylation of benzene or a suitable alkyl-benzene such as, e.g. toluene or cumene. The alkylations are preferably carried out using the procedure of Oleson (Ind. Eng. Chem., 52, 833 (1960) ). Thus in a preferred method approximately one-half to two-thirds of the starting aromatic hydrocarbon and the aluminum chloride are placed in a round bottom three-neck flask fitted with a mechanical stirrer, additional funnel, thermocouple well or thermometer and a condenser. A small portion of water (2 to 10 drops) is added and then a solution of the olefin in the remainder of the aromatic hydrocarbon is added slowly with stirring to the reaction vessel. The reaction temperature is maintained in the range from 0 C to 500C. After addition is complete, the reaction mixture is stirred for an additional 15 to 20 minutes while the reaction temperature is maintained as indicated. A 10% by weight aqueous hydrochloric acid solution (500 ml.) is then added and the resultant mixture is stirred for five minutes. The phases are then separated and the organic phase is washed twice with 2-5% by weight aqueous sodium hydroxide, once with brine and the excess aromatic is stripped of in vacuo. The product may be fractionally distilled through a Vigreaux column under vacuum. The ratios of reactants, boiling points and yields in a number of preparations employing the above method may be found in Table 3.

Table 3 Product Run Aromatic Olefin AlCl3 Reaction Boiling Point Yield Hydrocarbon (moles) Temp. C mm of % Hg C Hexadecylbenzene Benzene 3.5m(1) 1-Hexadecene 0.025 50 0.45 140-155 56 0.5m(1) Decylmethylbenzene A Toluene 10m 1-Decene 1m 0.025 0-5 (2) 150-155 79.9 B Toluene 71.4m 1-Decene 7.6m 0.357 40 0.55-0.8 106-124 76 Decylethylbenzene A Ethylbenzene 5m 1-Decene 1m 0.025 40 0.3-0.5 121-125 55 B Ethylbenzene 5m 1-Decene 1m 0.025 0-5 (3) 85-105 58 Octylmethylbenzene Toluene 5m 1-Octene 1.5m 0.45 25 0.20 60-90 69 C11-C14 Alkylmethyl- Toluene 5m C11-C14 Chevron (4) 0.025 40-44 0.04 83-120 66 benzene α-olefin~1m Decylcumene Cumene 5m 1-Decene 1m 0.025 40 0.05 119-135 75 Heptylbenzene Benzene 7m 1-Heptene 1m 0.05 50 Atmos. 227-233 69 (1)Amounts in moles (2)Water aspirator vacuum (3)Pressure was not recorded (4)Available from Standard Oil of California and is further described as follows: A mixture of predominantly straigth chain mono-olefins designated by the formula CH3-(CH2)n CH=CH2, where n=7 to 12, with an average molecular weight of 170-176.

It is to be noted that this method yields alkyl-benzenes of the so-called 'soft alkylate' type which are preferred starting materials for the preparation of the alkaryl substituted sulfonamidoquinolines useful in the invention. The terms 'soft' and 'hard' alkylate are descriptive and are based on the biodegradability of the alkyl-benzene sulfonic acids containing the respective groups. The soft alkylate types are biodegradable whereas the hard alkylate types are not. The 'soft alkylate' type can also be referred to as linear alkylates meaning that the alkyl group is attached to the benzene nucleus in a definite manner, i.e.

where a and b would be 0 or whole integers such as to complete the chain length of the alkyl group. For illustration purposes, the alkylation of benzene with 1-dodecene can theoretically yield a mixture of alkylbenzene isomers including the following:

In preparing the starting alkylbenzenesulfonyl chlorides from alkylbenzenesulfonic acids, the sulfonic acid is treated with a chlorinating agent such as thionyl chloride. Thus, for example, in one embodiment, the sulfonic acid may be added slowly over a four hour period to a stirred solution of thionyl chloride (1 litre) in Skelly C (500 ml.). The temperature controller is set for 95"C. and the reaction mixture is heated to reflux. Such a reaction mixture requires approximately two hours to reach 95"C. After stirring at 950C. overnight, the excess thionyl chloride and the Skelly C are stripped off under aspirator vacuum. An additional 50 ml. of Skelly C is added and then distilled off under aspirator vacuum to remove the last traces of thionyl chloride. The crude product may then be purified by molecular distillation. Amounts of starting acid and yields in two preparations according to this method are given in Table 4.

Table 4 Product Alkylbenzene Yield Sulfonic Acid (m) Dodecylbenzenesulfonyl 5.82(1) 94 chloride Pentadecylbenzenesulfonyl 4.79(2) 77(3) chloride (')The starting dodecylbenzenesulfonic acid was Bio Soft S-100R, a biodegradable linear alkyl aryl sulfonic acid available from Stephen Chemical Co.

(2)The starting pentadecylbenzenesulfonic acid was Petrostep A-70 with an equivalent weight of 369 available from Stephan Chemical Co. The pentadecyl group was a branched chain hard alkylate group.

(3)Based on distillation of a 75 g. sample.

The starting alkylbenzenesulfonyl chlorides may also be obtained by chorination of an appropriate sodium sulfonate salt, for example, with phosphorus pentachloride. Thus, in one embodiment, dinonylnaphthalenesulfonyl chloride was prepared in the following manner. A mixture of 1 mole of sodium dinonylnaphthalene sulfonate (NaSul 55 available from R.T.

Vanderbilt Co., wherein the nonyl groups are branched chain) and phosphorus pentachloride (1.25 mole) was warmed very slowly on a steam bath with mechanical stirring. At approximately 40"C. a very vigorous exothermic reaction took place and some material was lost due to foaming. The reaction mixture was cooled and Skelly C (100 ml.) was added to lower the viscosity of the reaction mixture. The stirred reaction mixture was heated on a steam bath for five hours. The reaction mixture was then cooled, allowed to stand overnight and heated on a steam bath with the volatiles being stripped off under water aspirator vacuum.

The residue was dissolved in Skelly C (1.5 litre). The Skelly C solution was washed with ice water, then with brine, dried over sodium sulfate and filtered. The filtrate was evaporated to give an oil (76% yield) in vacuo. The crude product analysed as 6.6% Cl (theoretical = 7.2%) by x-ray and was used without purification in Example X to follow.

The preparation of sulfonyl chlorides from corresponding alkyl halides is illustrated hereinafter in the Examples.

The following non-limiting Examples serve to illustrate the present invention. The first series of examples show the preparation of preferred sulfonamidoquinolines useful in the present invention and the second series show metal extractions in accordance with the present invention.

Example l-A To a solution of 43.2 g. (0.3 mole) 8-amino-quinoline in 100 ml. pyridine and 200 ml. toluene was slowly added 103 g. (0.3 mole) dodecylbenzenesulfonyl chloride. The sulfonyl chloride was prepared as described above (see Table 1) from dodecylbenzene (Ucane (Registered Trade Mark) Alkylate 12 obtained from Union Carbide which is a linear alkylate with average molecular weight of 244) and was an isomeric mixture wherein the dodecyl group is mostly in the para position. The reaction mixture was allowed to stir overnight. It was then heated to reflux for one hour and 500 ml. distilled water was added. Stirring was continued for an additional hour with heat after which the reaction mixture was poured into a separatory funnel. The phases were separated and one liter of Skelly C was added. Then the organic phase was washed two times with 2.5 g./l. aqueous H2SO4 (100 ml. portions), four times with freshly prepared 5% by weight NaHCO3 in 40% aqueous methanol (200 ml. portions), two more times with the sulfuric acid solution (200 ml. portions), one more time with the sodium bicarbonate solution and then with brine. The reaction mixture was then dried over sodium sulfate, filtered and evaporated to drynes in vacuo. There was obtained 115.9 g. of product (85% yield, product was an oil) which was 8-(dodecylbenzenesulfonamido)quinoline having the structure

- Podecyl NHSOZ where the dodecyl group is as described in respect of the starting sulfonyl chloride. Structures were confirmed in this and succeeding Examples by Infra Red (IR) and Nuclear Magnetic Resonance (NMR) analyses.

Example I-B To a solution of 12.9 g. (0.09 mole) 8-aminoquinoline in 150 ml pyridine was added 31.0 g.

(0.09 mole) dodecylbenzenesulfonyl chloride in 100 ml. Skelly C at OOC. The sulfonyl chloride was prepared from dodecylbenzenesulfonic acid (a technicalgrade of linear alkylate available from Pfaltz & Bauer) and the dodecyl group was mostly in the para position. The reaction mixture was stirred for one hour at 0C.andthen allowed to stir at room temperature overnight. It was then heated to 70"C. and poured into 600 ml. of ice water. The aqueous mixture was extracted with Skelly C and the resulting extract was washed four times with 5% by weight NaHCO3 in 40% methanol-water. It was then dried over sodium sulfate, filtered, heated to boiling and 10 g. of decolorizing charcoal was added. The product solution was filtered through celite and evaporated to a pale yellow oil (32.3 g.) in vacuo The product, 8-(dodecylbenzenesulfonamido quinoline had the structure as defined in Example I-A above and where the dodecyl group was as in the starting dodecylbenzene.

Example I-C Example I-B was essentially repeated except that the starting dodecylbenzene was Chevron Alkylate 21 (available from Standard Oil of California which is a synthetic alkylbenzene in which the side chain is branched (hard alkylate) and contains an average of 12 carbon atoms) and the resulting sulfonyl chloride and 8-(dodecylbenzenesulfonamido)quinoline were isomeric mixtures wherein the dodecyl group was as in the startig dodecylbenzene (in this and succeeding examples the alkyl groups on the ring are in the positions as in the starting alkylbenzenes or alkylbenzenesulfonyl chlorides and the sulfonamidoquinolines will thus normally be a mixture of isomers).

Example II To a five liter round bottom flask fitted with an air stirrer, thermometer, addition funnel and ice water bath were charged 365.7 g. (2.54 mole) 8-aminoquinoline and 2 liters pyridine.

Then 838 g. (2.54 mole) decylmethylbenzenesulfonyl chloride was added slowly enough to maintain the temperature at 9-130C. (time of addition was 45 minutes). The sulfonyl chloride was that prepared in Run A of Table 1 from the decylmethylbenzene of Run B in Table 3.

After addition of the sulfonyl chloride was completed, the reaction mixture was heated to room temperature and allowed to stir for three hours. It was then heated to 850C. and held at 80"C. for 45 minutes after which one liter of water was added. The temperature was brought back to 80"C. and the water-reaction mixture held at that temperature for thirty minutes. The mixture was transferred to a six liter separatory funnel and two liters Skelly C and one liter water were added. After standing overnight, the phases were separated and two liters water were added to the aqueous phase which was then extracted with Skelly C and the Skelly C extract separated. The organic phases were combined and washed as follows: 3 times with 4% NaHCO3 in 25% MeOH-water, 3 times with 25 g./l. aqueous H2S04, 2 additional times with the NaHCO3 solution, 2 additional times with the H2S04 solution and then 1 time with brine.

The product solution was dried over sodium sulfate and the Skelly C solvent was evaporated off givin 1066.9 g. of a light brown oil which was 8 (decylmethylbenzenesulfonamido)quinoline (90+ % purity) having the structure

WISOZ~ decyl RS5 24s decyl Example 111 Example II was essentially repeated except using 196 ml. pyridine, 36.0 g. (.25 mole) 8-aminoquinoline and 86.5 g. (.25 mole) decylethylbenzenesulfonyl chloride. The said sulfonyl chloride was that prepared in Run A of Table 1 which in turn was prepared from the decylethylbenzene as prepared in Run A of Table 3. There was obtained 94 g. of a dark oil.

The product was 8-(decylethylbenzenesulfonamido) quinoline having the structure

1w ethyl decyt Example IV Example II was essentially repeated except using 120 ml. pyridine, 23.0 g. (.16 mole) 8-aminoquinoline and 56 g. (.16 mole) dialkylbenzenesulfonyl chloride. The said sullonyl chloride was that designated as C22-C24 alkylmethylbenzenesulfonyl chloride in Table 1 which in turn was prepared from the C22-C24 alkylmethylbenzene of Table 3. The product was a dark oil in a yield of 83%. It had the following structure

methyl t C 11 C1 , otk91 Example V Octyltoluene (50 g. - .245 mole) as prepared in Table 3 was added slowly at 5-10"C. with stirring over one half hour (some exotherm) to 81 g. (.69 mole) chlorosulfonic acid in a 250 ml. round bottom flask fitted with air stirrer, thermometer, addition funnel, reflux condenser, scrubber and ice bath. The reaction mixture was allowed to stir for three hours at 25-30"C. and then stand overnight. It was poured onto 900 g. ice, 500 ml. diethyl ether was added and the mixture was stirred until the ice melted. The resulting organic phase was washed with water, 30% aqueous Na2CO3, again with water, dried over Na2SO4 and the solvent was evaporated. Thirty nine g. of octylmethylbenzenesulfonyl chloride was obtained.

To 14.4 g. (.10 mole) 8-aminoquinoline mixed with 14.4 g. (.15 mole) triethylamine and 25 ml. benzene was added 20.4 g. (0.067 mole) of the octylmethylbenzenesulfonyl chloride as above prepared at 14-180C. The reaction mixture was stirred for two hours at room temperature and then heated to 800C. for one hour. Two hundred fifty ml. water and 250 ml.

Skelly C were combined with the reaction mixture and the phases were allowed to separate overnight. The organic phase was washed as in Example II above, dried over Na2SO4 and stripped of solvent giving 26.7 g. of a dark oil which was 8 (octylmethylbenzenesulfonamido)quinoline having the structure:

Imethy HSO2 cctyt HHS02 < > octyl Example VI Example II was essentially repeated using 23.04 g. (0.16 mole) 8-aminoquinoline, 100 ml. pyridine and 49.5 g. (0.16 mole) of nonylmethylbenzenesulfonyl chloride as prepared in Table 1. The said nonylmethylbenzenesulfonyl chloride was in turn derived from a nonyltoluene having a branched nonyl group derived from tripropylene (available from Sunoco -- Registered Trade Mark). There was obtained 55.1 g. of a dark oil which was 8-(nonylmethylbenzenesulfonamido)quinoline having the structure:

me thy 02- nonet Example VII Example II was essentially repeated using 20 g. (0.139 mole) 8-aminoquinoline, 120 ml. pyridine and 50 g. (0.139 mole) decylisopropylbenzenesulfonyl chloride (also termed decylcumenesulfonyl chloride) as prepared in Table 1. The sulfonyl chloride was in turn denved from decylcumene as prepared in Table 3. There was obtained 50 g. of a dark viscous oil which was 8-(decylisopropylbenzenesulfonamido)quinoline having the structure:

( > j NH oz dodecyl decyl Example VIII Diamylbenzenesulfonyl chloride was prepared as in Table 2 above from diamylbenzene.

The latter starting material was prepared in the following manner. To a suspension of 175.2 g.

(1.29 mole) AITCH in 660 ml. carbon tetrachloride was added 155.8 g. (1.29 mole) valeric acid chloride slowly so as not to bring the temperature of the ice-salt-water bath cooled reaction mixture above 5"C. (addition time was 20 min.). After this addition was complete, the mixture was cooled to OOC. and addition of 159.2 g. (1.07 mole) of sec-amylbenzene (available from Phillips Petroleum) was begin (the addition was carried out at 0-20C. over a period of 3.5 hours). The reaction mixture was allowed to warm to 10 C. over a one hour period and was then dumped into an HCI-ice mixture and stirred overnight. The phases were allowed to separate, the aqueous was extracted with carbon tetrachloride and then the aqueous was discarded. The resulting organic phases were combined and washed as follows: 2 times with 7% wt./vol. aqueous HCI, 2 times with 10% by weight aqueous Na2CO3, 1 time with water and 2 times with brine. The product was dried over Na2-SO4, stripped of solvent and distilled to yield fractions which were mostly p-sec-amyl-valerophenone (some ortho isomer was present). This product (104.8 g.) was mixed with 86.3 g. KOH, 61 ml. of 98-100% -NH2NH2.H20 and 500 ml. diethylene glycol and heated to reflux. It was refluxed overnight and then heated from 140"C. (pot temp.) to 1550C. by collecting H20 off the reaction mixture with a take-off condenser. The reaction mixture was heated at 1950C. for one hour with some refluxing, a total of 50 ml. of distillate was collected and it was then cooled and poured into 500 ml. water and 250 ml. of Skellysolve B (available from the Skelly Oil Co. and consists mostly of n-hexane, b.p. range 60-71"C.). The phases were separated, the organic was washed 2 times with 10% aqueous HCl, dried over Na2SO4, filtered and evaporated to an oil. There was obtained 83.1 g. of product which was vacuum distilled to yield a 49.8 g. fraction (pot temp.- 125-145"C; head temp. - 105-1100C.) which was diamylbenzene having the structure:

where a + b equals 2.

The diamylbenzenesulfonyl chloride (25.5 g. - 0.081 mole), as above prepared, 8aminoquinoline (12.24 g. - 0.085 mole), and 75 ml. pyridine was reacted in essentially the same manner as set forth in Example II to obtain 33.5 g. of 8 (diamylbenzenesulfonamido)quinoline having the structure:

n-amy sec.amfl NHSOZ sec-amyl Example IX Example II was essentially repeated using 28.8 g. (0.2 mole) 8-aminoquinoline, 150 ml. pyridine and 49.35 g. (0.2 mole 4-sec-amylbenzenesulfonyl chloride. There was obtained 5 g. of a thick oil which was 8-(sec-amylbenzenesulfonamido)quinoline having the structure

where A + b equals 2.

Example X Dinonylnaphthalenesulfonyl chloride (125 g. - 0.26 mole) prepared as described hereinabove was dissolved in 150 ml. toluene and added with stirring to a solution of 37 g.

(0.26 mole) 8-aminoquinoline in 100 ml. pyridine while the temperature was maintained between 10-20"C. (there was some exotherm). The reaction mixture was allowed to stir overnight at room temperature. It was then heated to 800C. for 30 minutes after which 25 ml. conc. NH3 was added and stirring was continued at 800C. for 20 minutes. The reaction mixture was poured into 500 ml. Skelly C and 300 ml. water, the phases were separated and the organic was washed with 5% by weight NaHCO3 (40% MeOH in water) until a good phase break was obtained. It was washed also with 25 g./l. H2/SO4 until a good phase break was obtained. After these washings, the reaction mixture was heated to boiling, treated with five g. of decolorizing charcoal, dried over Na2SO4, filtered and evaporated to dryness in vacuo to give 152.2 g. of a black oil. The product was 8-(dinonylnaphthalenesulfonamido)quinoline of the structure.

) (nonyl 50l nlnonyl )2 wherein the nonyl groups are as in the starting dinonylnaphthalene.

Example XI Example II was essentially repeated using 46.4 g. (0.32 mole) 8-aminoquinoline, 180 ml. pyridine and 82.35 g. (0.3 mole) heptylbenzenesulfonyl chloride. The latter reactant was as prepared in Table 1 from the heptylbenzene of Table 3. There was obtained 112.6 g. (97,35% yield) of 8-(heptylbenzenesulfonamido)quinoline of the structure

where a + b equals 4.

Example XII Example II was essentially repeated using 28.8 g. (0.2 mole) 8-aminoquinoline, 50 ml. pyridine and 74.9 g. (0.2 mole) pentadecylbenzenesulfonyl chloride (see Table 4 for the preparation of the sulfonyl chloride). There was obtained 79.1 g. of 8 (pentadecylbenzenesulfonamido)quinoline having the structure

4 penlodeoy HH502 Example XIII Example II was essentially repeated using 36 g. (0.25 mole) 8-aminoquinoline, 100 ml. pyridine and 100 g. (0.25 mole) p-n-hexadecylbenzenesulfonyl chloride (see Table 2 above).

There was obtained 24.6 g. (approximately 2/3 of reaction mixture was lost when a stop cock came out of a separatory funnel) of a yellow oil which crystallized. The product was 8-(p-nhexadecylbenzenesulfonamido)quinoline having the structure:

nhexndetyl riHS02- 118502 4 Example XIV Example XIII was essentially repeated using 22.68 g. (0.157 mole) 8-aminoquinoline, 75 ml. pyridine and 63 g. (0.157 mole) hexadecylbenzenesulfonyl chloride prepared as in Table 3 from the hexadecylbenzene of Table 3. There was obtained 49.25 g. (62% yield) of a golden oil which was 8-(hexadecylbenzenesulfonamido)quinoline of the structure

> n-he x n dec yl kH502 e Example XV Example II was essentially repeated using 28.8 g (0.2 mole) 8-aminoquinoline, 75 ml. pyridine and 60.4 g. (0.2 mole) 2,4,6-triisopropylbenzenesulfonyl chloride. There was obtained 71.4 g. of a purplish white solid which was 8-(2,4,6triisopropylbenzenesulfonamido)quinoline of the structure

Example XVI Part A -- Preparation of -methyl-8-aminoquinoline To a cooled solution of 560 g. sodium metabisulfite in 1 liter of water was added 290 ml. ammonium hydroxide. This mixture was placed in a two liter stainless steel pressure reactor and 200 g. 8-hydroxyquinaldine was then added and the mixture was allowed to stand overnight. The reactor was sealed and heated to 1500C. The reaction mixture was then stirred at 150 C. for seven hours during which period the pressure rose to 50 p.s.i.g. The reaction mixture was allowed to cool overnight with stirring and then the reactor was heated to 800C.

After reaching this temperature, the reactor was drained and washed with one liter of benzene at 70-80"C. The benzene solution was added to the reaction mixture. The mixture was filtered and the phases separated. The organic was washed with dilute aqueous NaOH, then brine, dried over Na2SO4 and stripped of solvent to yield 84 g. of crude product. This was vacuum distilled to yield 50 g. of a yellow solid which was 2-methyl-8-aminoquinoline (also termed 8-aminoquinaldine) Part B of Preparation 8-(dodecylbenzenesulfonamido)-2-methylquinoline Example II was essentially repeated using 79.8 g. (0.505 mole) of 2-methyl-8aminoquinoline as prepared in Part A of this Example, 100 ml. pyridine in combination with 200 ml. toluene and 173.7 g. (0.505 mole) dodecylbenzenesulfonyl chloride as prepared in Table 4 above. The product was 8-(dodecylbenzenesulfonamido)-2-methylquinoline having the structure

CHX1 dodec91 4H S02 t/ Example XVII Example XVI, Part B was essentially repeated using 25 g. (.158 mole) 2-methyl-8 aminoquinoline, 125 ml. pyridine and 52.3 g. (.158 mole) decylmethylbenzenesulfonyl chloride as prepared in Run B of Table 1. There was obtained 63.7 g. of 8 (decylmethylbenzenesulfonamido-2-methylquinoline having the structure

NH502 4 decyl Example XVIII Part A - Preparation of 8-Amino-6-methylquinoline Thirty g. 8-nitro-6-methylquinoline (prepared by the procedure of F. Richter and G.F.

Smith, JACS, 66, 396 (1944)) was dissolved in 30 ml. ethylacetate, 50 ml. absolute ethanol and 50 ml. ethyl ether. This was divided into two parts and 0.4 g. PtO2 added to each portion.

Both were hydrogenated in a Parr shaker. Lots 1 and 2 were combined and distilled at pot temperatures of 110-1900C. (0.45 mm Hg.). There was obtained 20.7 g. of high purity 8-amino-6-methylquinoline .

Part B of Preparation 8-(decylmethylbenzenesulfonamido)-6-methylquinoline Example II was essentially repeated using 19.4 g. (0.123 mole) of 8-amino-6-methylquinoline as prepared in Part A of this Example, 100 ml. pyridine and 41.3 g. (0.125 mole) decylmethylbenzenesulfonyl chloride as prepared in Run A of Table 1 above. There was obtained 51.4 g. of a light coloured oil which was 8-(decylmethylbezenesulfonamido)-6methylquinoline of the structure

CH3 G, Imelhyl IHSO1 decyl Example XIX Example XVIII, Part B was essentially repeated using 25 g. (0.14 mole) 8-amino-6methoxyquinoline (available from Aldrich Chemical), 100 ml. pyridine and 47.3 g. (0.14 mole) of the decylmethylbenzenesulfonyl chloride. There was obtained 58.6 g. of a dark oil Example XXI Part A - Preparation of8-Amino-5, 7-dichloroquinoline Chlorine gas was bubbled through a solution of 10 g. 8-aminoquinoline in 50 ml. of glacial acetic acid while the temperature was maintained at 40-500C. by cooling. The Ck flow was stopped when the exotherming ceased (a total of 16.5 g. Cl2 was added). The red precipitate was filtered from the reaction mixture and slurried with 100 ml. of 2% by weight aqueous NaOH and 300 ml. of ethyl ether. This mixture was filtered and the phases separated. The ether phase was washed with brine, dried over Na2SO4, filtered and evaporated to dryness to yield 5.6 g. crude product which was then recrystallized out of an ether-Skelly C mixture.

There was obtained 5.1 g. of tan to brownish needles (melting point 121-123 C.) which was 8-amino-S ,7-dichloroquinoline.

Part B -- Preparation of8-(decylmethylbenzenesulfonamido)-5, 7-dichloroquinoline Example XX, Part B was essentially repeated using 7.2 g. (0.034 mole) 8-amino-5,7dichloroquinoline as prepared in Part A of this Example, 25 ml. pyridine and 11.9 g. (0.036 mole) decylmethylbenzenesulfonyl chloride as prepared in Run B of Table 1 above. There was obtained 12.2 g. of a reddish oil which was 8-(decylmethylbenzenesulfonamido)-5,7dichloroquinoline having the structure

Cl methyl NHSU2 - decyl Example XXII Part A - Preparation ofp-Dodecylphenylmethanesulfonyl chloride A mixture of 147 g. (0.5 mole) dodecylbenzyl chloride (available as Conoco DBCl from Continental Oil Co. with the dodecyl group being a branched chain hard alkylate group),79 g.

(0.5 mole) anhydrous sodium thiosulfate, 250 ml. methanol, and 250 ml. distilled water was heated to reflux for three hours while stirring. Volatiles (about 75 ml.) were distilled off under aspirator vacuum until excessive foaming was encountered. The reaction mixture was transferred to a two liter flask fitted with a dry ice condenser, thermometer, mechanical stirrer and gas dispersion tube. The flask was cooled to 0 C. with an ice bath and then 250 ml. glacial acetic acid and 500 g. ice were added. Chlorine gas was bubbled in at a minimum rate to maintain a minimum amount of Ck refluxing in the flask. The temperature was maintained at 10 C. or less (Cl2 bubbled in for one hour). Five hundred ml. Skelly C were then added, the reaction mixture was stirred and the phases were separated. The organic phase was washed with 500 ml. of 5.0% by weight aqueous NaHSO3, then with brine, dried over Na2SO4 and evaporated to give a golden oil. This product was partially purified by molecular distillationto yield p-dodecylphenylmethanesulfonyl chloride (approximate purity of 50%).

Part B of Preparation 8-(dodecylphenylmethanesulfonamido)quinoline The crude sulfonyl chloride as prepared in Part A of this example was added directly to a stirring solution of 8-aminoquinoline (0.064 m) and triethylamine (0.07 m) in 25 ml. of 1,1 ,2-trichloroethane at 5-10 C. The temperature was maintained at 5-10"C. during the addition and then allowed to warm to room temperature. After stirring for 2 hours at room temperature, the reaction mixture was heated to 600C. The reaction mixture was poured into 200 ml. of water and 300 ml. of Skelly C. After shaking, the phases were separated. The organic phase was washed three times with 100 ml. of 5% by weight of NaHCO3 in 30% MeOH-H2O, three times with 100 ml. of 25 g./l. sulfuric acid, repeat of bicarbonate washes, and finally with brine. The organic phase was dried over sodium sulfate and evaporated to dryness in vacuo. The reddish oil (50.4 gm; -=30-50% sulfonamide by IR) was further purified by molecular distillation followed by column chromatography on silica gel to yield a viscous oil (8.2 gm, =75% sulfonamide). The compound had the structure

) HHSOI - cS2-t3-dodecyl Example XXIII Example II was essentially repeated using 22.1 g. (0.154 mole) 8-aminoquinoline, 75 ml. pyridine and 50 g. (0.154 mole) n-hexadecanesulfonyl chloride. There was obtained 60.7 g. of 8-(n-hexadecanesulfonamido)quinoline having the formula

Example XXIV Part A -- Preparation of -Ethylhexane-1 -sulfonyl chloride A mixture of 57.9 g. (0.3 mole) 2-ethylhexyl-1-bromide, 22.8 g. (0.3 mole) thiourea and 75 ml. absolute ethanol was allowed to stir at reflux for approximately 20 hours. After cooling overnight, the ethanol was evaporated in vacuo to yield a waxy white solid. This was dissolved in 250 ml. 80"C. water and 40% aqueous NaOH was added until no further white cloudiness formed in the aqueous. The oilyproduct was separated and dissolved in 75 ml. acetic acid and 25 ml. water. This was cooled to OOC. and Cl2 was bubbled in until the oxidation reaction was complete (total C12 use was 80.2 g.). The resulting colourless oil was 2-ethylhexane-1-sulfonyl chloride.

Part B -- Preparation of 8-(2-ethylhexanesulfonamido)quinoline Example II was essentially repeated using 43.2 g. (0.3 mole) 8-aminoquinoline, 200 ml. pyridine and the total amount of sulfonyl chloride as prepared in Part A of this Example.

There was obtained 40.2 g. of product which was 8-2-ethylhexanesulfonamido)quinoline having the structure

Example XXV Part A - Preparation oflsodecyl Bromide One hundred ninety six g. (0.72 mole) PBr3 was added slowly with stirring to 316 g. (2.0 mole) isodecanol (available from Union Carbide and is a mixture of isomeric alcohols containing ten carbon atoms) while maintaining the temperature below 0 C. After addition of the PBr3 was complete, the reaction mixture was allowed to warm to room temperature while stirring was continued. The reaction mixture was allowed to stand overnight after attaching a drying tube to the reaction equipment. The crude product was distilled off at 60-65"C. (0.45 mm Hg.), washed two times with cold H2SO4 (density = 1.84), two times with 50% MeOH NH3 and one time with brine, and dried over Cask. The product was then further distilled to yield a 244.1 g. fraction (pot temp. -- 70"C. pressure -- 0.45 mm Hg. and head temp. - 48"C.) of isodecylbromide.

Part B -- Preparation oflsodecanesulfonyl chloride A mixture of 110 g. (0.5 mole) of isodecylbromide as prepared in Part A of this Example, 38 g. (0.5 mole) thiourea and 250 ml. 95% ethanol was heated to reflux. Refluxing was continued for eight hours and then the reaction mixture was cooled and allowed to stir over the weekend. Approximately one hundred twenty five ml. ethanol was stripped off and a solution of 30 g. NaOH in 200 ml. water was added. The reaction mixture was again heated to reflux with stirring (three hours) after which it was poured into 300 ml. water and extracted with 200 ml. diethyl ether. The ether extract was dried over Na2SO4, filtered and evaporated to a slightly ink oil. This oil was dissolved in 250 ml. glacial acetic acid, 50 ml. of water was added, the mixture was cooled to OOC. and sparging with Ck gas was begun. Chlorine addition was very slow to avoid excessive heat evolution (temperature was controlled at approximately 0 C.). Chlorine was added until a refluxing atmosphere of Ck was maintained for one hour (total Ck addition was 137 g.). Excess Ck was removed by a N2 sparge into NaHSO3 solution.

The reaction mixture was poured into 500 ml. water and then extracted with hexane. The hexane extract was washed two times with 5% by weight aqueous NaHSO3 and one time with brine, dried over Na2SO4, filtered and evaporated in vacuo to a white oil. There was obtained 107 g. of isodecanesulfonyl chloride.

Part C -- Preparation of8-(isodecanesulfonamido)quinohne Example II was essentially repeated using 43.2 g. (0.3 mole) 8-aminoquinoline, 200 ml. pyridine and 72 g. (0.3 mole) of isodecanesulfonyl chloride as prepared in part B of this Example. There was obtained 92.0 g. of 8-(isodecanesulfonamido)quinoline having the structure

\I!S02-isydecyl where the isodecyl group was characterized by NMR as follows: CH2CH2(CsH27) where the C8H27 group is a mixture of branched chain alkyl groups.

Example XXVI Part A -- Preparation of Cl 4-Cl 6 alkenylsulfonyl chloride A mixture of 84.3 g. (0.405 mole) PCls and 96.7 g. (0.324 mole) of a sodium C14-C16 alkenyl sulfonate (Bio TergeR AS-90F available from Stephan Chemical Co.) was placed in a 500 ml. three-neck round bottom flask fitted with a condenser and mechanical stirrer. The mixture was heated on a steam cone for two hours with stirring. The initial reaction was very vigorous and exothermic. Addition of 50 ml. Skelly C was followed by distillation under water aspirator vacuum on the steam cone. The residue was dissolved in 300 ml. Skelly C and the resulting solution was filtered. The solution was evaporated in vacuo to an oil (62.5 g.) which was used in Part B of this Example.

Part B - Preparation of8-(Cl 4-Clo - alkenyleulfonamido)quinoline The sulfonyl chloride prepared in Part A was added slowly to a stirring solution of 30.6 g (0.212 mole) 8-amino-quinoline in 100 ml. pyridine at a temperature of 10-20"C. The reaction mixture was allowed to stir overnight at room temperature. It was then heated to 800C., 200 ml. of water was added, and after 30 minutes 25 ml. of 28% aqueous ammonia was added.

The mixture was poured into 300 ml. of water and 500 ml. of Skelly C. The phases were separted and the organic phase was washed with methanolic sodium bicarbonate and then with 25 g./l. sulfuric acid. The acid wash generated an emulsion, which was allowed to break over the weekend. The organic was washed with methanolic sodium bicarbonate until a good phase break was obtained. The organic was then dried over anhydrous sodium sulfate, filtered, treated with 5 g. of norite, filtered and evaporated to an oil. The oil was passed through a 100 g. silica gel column with 11. of Skelly C. The Skelly C was evaporated in vacuo to 41.8 g. of an oil. The oil was further purifiedby molecular distillation. Some decomposition was evident during the distillation. The distillation yielded to 10.1 g. of an oil that was estimated to be 60-65% sulfonamide by IR and NMR. The sulfonamido-quinoline active portion of the product had the formula

where R is the Cl4-C16 alkenyl group.

Example XXVII Example II was essentially repeated using 21.6 g. (0.15 mole) 8-aminoquinoline, 100 ml. pyridine and 31.8 g. (0.15 mole) n-octanesulfonyl chloride. There was obtained 39.2 g. of a yellow oil which was 8-(octanesulfonamido)quinoline having the structure

Example XXVIII Example II was essentially repeated using 45 g. (0.26 mole) crude n-pentanesulfonyl chloride, 37.4 g. (0.26 mole) 8-aminoquinoline and 150 ml. pyridine. There was obtained 35.6 g. of product which was 8-(n-pentanesulfonamido)quinoline having the structure

The Examples to follow show the use of sulfonamidoquinolines in the extraction of metals from their aqueous solutions in accordance with the present invention. Unless otherwise indicated, the extractions were carried out in accordance with the following process procedures.

Procedure I A 0.1 molar solution of the sulfonamidoquinoline in an identified essentially waterimmiscible solvent is first prepared. Five aqueous solutions of the following compositions are used: Metal Composition Cu++ 0.05 M CuSO4 (3.2 g./1. Cu++), 0.4 MNH3, and 0.1 M (NH4)2SO4 Ni++ 0.05MNiSO4 (2.9 g./1. Ni++), 0.4MNH3, and 0.1 M (NH4)2SO4 Zn++ 0.05MZnSO4 (3.2 g./1. Zn++), 0.4 MNH3, and 0.1 M (NH4)2SO4 Co++ 0.025MCoSO4 (1.5 g./1. Co++), 1.7MNH3, and 0.1 M (NH4)2SO4 prepared as needed under an atmosphere of nitrogen Cho+++ 0.025 M CoSO4 (1.5 g./l. Co++), 1.7 M NH3, and 0.1 M (NH4)2CO3 (air oxidized to Co+++) Portions of the organic solution are shaken with the various aqueous solutions at an organic:aqueous phase ratio of 1:1 for one hour at ambient temperature. The organic phases are then analyzed for metal content. If a third phase is present, both the organic and aqueous phases are clarified and analyzed.

Procedure 2 In this procedure, the purpose is to determine the extent of extraction of various metal ions as a function of pH over the pH range 1-6. A 0.1 molar solution of the sulfonamidoquinoline in an identified essentially water-immiscible organic solvent is prepared as in Procedure 1.

Portions thereof are then contacted at an organic:aqueous phase ratio of 1:1 with shaking for one hour at ambient temperature. The aqueous phases are made up from equivolumes of two components: Component A -0.2 M metal sulfate solution in water Component B water on sulfuric acid or sodium hydroxide solutions ranging from 0.005 M toOSM Several extractions are performed at varying pH values. The first is done using water as component B. After determining raffinate pH, Component B is then selected such that raffinate pH values range from 1 to 6 in units of approximately 1. By analyzing the organic phases for metal extraction and the aqueous for pH, data is generated which gives the degree of metal extraction as a function of pH for the particular system under study.

Procedure 3 The objective of this process procedure is to determine the extent of extraction of the various ions as a function of total ammonia concentration in the aqueous phase. Organic solutions of the sulfonamidoquinoline are prepared as in the previous procedures and contacted with shaking at 1:1 organic:aqueous phase ratios for one hour at ambient temperatures with aqueous solutions made up as follows: A ueous Metal NH3 (NH4)2SO4 Total NH3 Solution Sulfate conc. conc. conic. conc.

1 0.005M 0.60M 0.15M 0.90M(15.3g./1.) 2 0.005M 1.20M 0.30M 1.80M(30.6g./1.

3 0.005M 2.40M 0.60M 3.60M(61.2g./1.

4 0.005M 3.60M 0.90M 5.40M (91.8 g./1 5 0.005M 4.80M 1.20M 7.20M (12.4 g./1.) 6 0.005M 6.00M 1.50M 9.00M(153.0g./1.) The separated organic and aqueous phases are analyzed for metal concentration. The effect of increasing ammonia concentration on degree of extraction can thus be determined.

Procedure 4 The objective of this procedure is three-fold: (1) To determine the extent of metal stripping as a function of acid concentration; (2) To determine the extent of ammonia loading during extraction; and (3) To determine the extent of acid loading during stripping. Organic solvent solutions are prepared as in the other procedures and the following aqueous solutions are prepared: A. 0. 1M metalsulfate, 0.6M NH3 and 0.15M (NH4)2SO4 B. Five solutions containing 25, 50, 75, 100 and 150 g./l. H2SO4, respectively.

In the first step, the sulfonamidoquinoline solution is contacted with aqueous solution A at an organic:aqueous phase ratio of 1;2 with shaking for one hour at ambient temperatures. The phases are separated and the loaded organic contacted a second time as indicated with fresh aqueous Solution A. The resulting separated organic phase is analysed for metal concentration. It is divided into five portions, each of which is shaken with one of the five aqueous B solutions (organic: aqueous phase ratio of 1:1, contact time - one hour). The phases are separated and the organics are analyzed for metal content, the aqueous for NH3.

The stripped organics are then washed with water at an organic:aqueous phase ratio of 1:1 (contact time -1 hour). The aqueous wash solutions are then analyzed for H2SO4.

Example A A 0.1M solution of the 8-(dodecylbenzenesulfonamido)quinoline of Example I B in an aromatic kerosene (Aromatic 150) was first prepared. This was then used in accordance with Procedure 1 and the following results were obtained: Metal Organic g./1. metal Co+3 0.0170 Cu++ 3.06 Ni++ 2.75 Zn++ 3.87 This same process when run with a solution of the sulfonamidoquinoline in an aliphatic kerosene (Kermac 470 B) gave good extraction of Co++ (1.35 g./l.) but precipitates formed with Cu++ and Ni++ and the organic phase gelled with Zn++. Thus for this sulfonamidoquinoline a more aromatic solvent yields best results.

The Aromatic 150 solution of the 8-(dodecylbenzenesulfonamido)quinoline was used in accordance with process Procedure 2 to study the pH isotherms for Cu++, Zn++, Co++, Fe++, anl Ni++. Results are set forth in the following Tables A-1 through A-5. In all cases, 10 ml of the sulfonamidoquinoline solution and 5 ml. of the 0.2M metal sulfate solutions were used with varying amounts (in milliliters) of water and NaOH and/or H2SO4 solutions as indicated.

Table A-I - Cu++ NaOH H2SO4 Extracted Cu++ H20 0.1M 0.5M 0.1M 0.5M Aqueous Organicg./1.

5.0 0 0 0 0 1.56 2.45 4.5 0.5 0 0 0 1.69 2.53 4.0 1.0 0 0 0 1.63 2.55 3.5 1.5 0 0 0 1.66 2.54 3.0 2.0 0 0 0 1.67 2.58 4.5 0 0 0.5 0 1.54 2.43 0 5.0 0 0 0 1.98 2.88 3.0 0 2.0 0 0 4.40* 3.04 3.0 0 0 2.0 0 1.44 2.25 3.5 0 0 0 1.5 2.24 2.94 3.0 0 0 0 2.0 0.83 1.62 1.0 0 0 0 4.0 0.60 1.02 *Slight precipitate observed Table -Zn++ NaOH H2SO4 Extracted Zn++ H20 0.1M 0.5M 0.1M 0.5M AqueouspH Organicg./1.

5 0 0 0 0 3.03 0.116 0 5 0 0 0 4.10 2.04 0 0 0 5 0 1.21 0.00054 4 0 0 1 0 2.23 0.00203 2 0 0 3 0 1.73 0.0004 3 0 0 0 2 1.12 0.00074 4 1 0 0 0 3.59 0.461 2 3 0 0 0 3.96 1.20 3 0 2 0 0 6.18* 3.40 *Some precipitate observed TableA-3-Co++ NaOH H2S04 Extracted Co++ H20 0.1M 0.5M 0.1M 0.5M AqueouspH g./1.

5 0 0 0 0 3.48 0.0028 0 5 0 0 0 5.21 1.46 0 0 0 5 0 1.29 0.002 3 0 2 0 0 7.25* 2.72 2 3 0 0 0 5.41 0.860 4 1 0 0 0 4.94 0.275 3 0 0 0 2 1.17 0.002 2 0 0 3 0 1.70 0.0008 4 0 0 1 0 2.18 < 0.0002 *Some precipitate observed Table A-4 - Fe+++ NaOH H2SO4 Extracted H20 0.1M 0.5M 0.1M 0.5M Aqueous pH Organicg./1.

5 0 0 0 0 1.77 0.00017 0 5 0 0 0 2.26* 0.00033 0 0 0 5 0 1.19 0.00011 3 0 2 0 0 2.44* 0.00045 1 0 4 0 0 2.59* 0.00063 3 0 0 0 2 0.90 0.00012 *Precipitate observed Table A-5 - Ni++ NaOH H2SO4 Extracted Ni++ H20 0.1M 0.1M Aqueous pH Organic, g./1.

5.0 0 0 3.51 0.0425 2.0 3.0 0 7.11 0.840 3.0 2.0 0 4.83 0.610 3.5 1.5 0 4.33 0.477 4.5 0.5 0 3.93 0.183 4.75 0.25 0 3.74 0.101 0 0 5.0 1.33 0.0002 3.0 0 2.0 1.67 0.0003 4.0 0 1.0 -- 0.0004 The data of Tables A-1 through A-5 show extractions for Cu++, Co++, Zn++ and Ni++ and substantially no extraction of Fe+++ indicating excellent selectivity of Cu++, for example, over Fe+++ at relatively low pH's.

The process of Procedure 3 was also used with the 8 (dodecylbenzenesulfonamido)quinoline solution (Aromatic 150). Results are set forth in the following Tables A-6 through A-8: Table A-6 - Cu++ Metal Concentration (g./1.) Loaded Organic Aqueous Raffinate 0.317 0.0002 0.314 0.0002 0.310 0.0002 0.316 0.0002 0.322 0.0006 0.302 0.0014 Table A-7 - Ni++ Metal Concentration (g./1.) Loaded Organic Aqueous Raffinate 0.299 0.0003 0.299 0.0012 0.305 0.0032 0.278 0.0342 0.202 0.118 0.140 0.184 Table A-8 - Zn++ Metal Concentration (g./1.) Loaded Organic Aqueous Raffinate 0.456 < 0.0005 0.445 < 0.0005 0.448 0.0029 0.424 0.0150 0.414 0.0346 0.379 0.0710 The process of Procedure 4 was also followed with the Aromatic 150 solution of the 8-(dodecylbenzenesulfonamido)quinoline in respect of Cu++, Ni++ and Zn++. Results are set forth in the following Tables A-9 through A-11: Table A-9 - Cu++ Loaded Organic From Step 2 - 2.99 g./1. Cu++ Strip Stripped Aqueous Washed Wash Solution Org. Raffinate Org. Solution g./1. H2SO4 g./1. Cu++ NH3-M g./l. Cu++ H2SO4-N* 25 1.15 0.002 1.15 < 0.001 50 0.563 0.003 0.560 75 0.267 0.003 0.253 100 0.144 0.010 0.143 150 r0.05 0.003 0.0580 *Normality Table A-iO -i"i+ Loaded Organic From Step 2-2.80 g./1. Ni++ Strip Stripped Aqueous Washed Wash Solution Org. g./1. Raffinate Org. g./1. Solution g./1. H2S04 Ni + NH3-M Ni++ H2SO4-N 25 0.294 0.068 -- < 0.001 50 0.050 0.069 0.0875 75 0.0007 0.067 0.0012 100 0.0012 0.067 0.0016 < 0.001 150 0.0005 0.067 0.0006 Table A-il IZn++ Loaded Organic From Step 2-3.92 g./1. Zn++ Strip Stripped Aqueous Washed Wash Solution Org.+g./1. Raffinate Org. g./l. Solution g./1. H2SO4 Zn NH3-M Zn++ H2SO4-N 25 0.0019 0.020 0.0007 < 0.001 50 0.0014 0.021 0.0008 75 0.0010 0.020 0.0006 100 0.0009 0.020 0.0005 150 0.0009 0.018 0.0008 The above data show that the metal values are readily stripped from the loaded organic and that the 8-(dodecylbenzenesulfonamido)quinoline loads very little sulfuric acid.

In processes as described above in this Example, the solubility of certain metal complexes, especially zinc, is best by using the 8-(dodecylbenzenesulfonamido)quinoline of Example I-A or I-B instead of I-c. In this respect, the branching in the dodecyl group is different as generally described hereinabove.

Example B A 0.1M solution of the 8-(decylmethylbenzenesulfonamido)quinoline of Example II in Kermac 470B aliphatic kerosene was first prepared. This was then used in accordance with process Procedure 1 and the following results were obtained: Table B-l Metal Organic, g/l. metal Cu++ 3.04 Ni++ Co++ 1.46 Co+++ < 0.0005 Zn++ 2.99 *The starting aqueous contained 2.69 g./1. Ni++. There was some precipitate so the aqueous raffinate was analyzed rather than the organic. The raffinate contained only 0.0080 g./1. Ni++.

Subsequent tests with Ni++ showed little or no precipitation.

The aliphatic kerosene (Kermac 470B) solution of the sulfonamidoquinoline of Example II was also used in accordance with process Procedure 2 to study the pH isotherms for Cu++, Ni++, Co++, Zn++ and Fe+++. Results are set forth in the following Table B-2 (same quantities of phases and the like as in Example A above except herein the equivolume of aqueous phase mixed with the metal containing solution is indicated as being H20 or specified molarities of NaOH or H2SO4): Table B-2 - Cu++ pH Extracted Metal Adjusting Aqueous Organic Metal Metal Solution pH g./1.

Cu++ 0.5M H2SO4 0.66 0.565 0.1MH2SO4 1.17 1.98 0.05M 1.22 1.98 " H20 1.38 2.30 0.005MNaOH 1.41 2.34 " 0.05M NaOH 1.68 2.46 " 0.1M NaOH 1.77 2.65 Ni++ 0.5MH2SO4 0.60 < 0.0005 " 0.1M H2SO4 1.59 < 0.0005 "" 0.05M H2SO4 1.68 < 0.0005 " H2O 3.92 0.0057 0.005MNaOH 4.77 0.0785 0.05MNaOH 6.76* 0.397 Cot+ 0.5M H2SO4 0.59 < 0.0005 " 0.1M H2SO4 1.59 < 0.0005 " 0.05M H2SO4 1.67 < 0.0005 " H2O 3.38 < 0.0005 " 0.005M NaOH 4.73 0.0510 " 0.05M NaOH 5.54 0.635 0.1M NaOH 7.00* 1.00 Zn++ 0.5M H2SO4 0.6 < 0.0005 " 0.1M H2SO4 1.57 < 0.0005 " 0.05M H2SO4 1.67 < 0.0005 " H2O 3.36 0.0501 " 0.005M NaOH 3.54 0.113 " 0.05M NaOH 4.03 0.780 " 0.1M NaOH 4.34 1.52 Fe+++ (at pH's 0.59 - 2.00+ - less than 0.0005 g./1. Fe+++ extracted) *Precipitate in aqueous observed at this pH indicating that the metal oxide was precipitating.

Similarly when the 8-(decylmethylbenzenesulfonamido)quinoline is dissolved in Aromatic 150 and used according to the Procedure 2 process, cadmium is extracted as follows: Table B-3 - Cd++ pH Adjusting Extracted Cd++ Solution Aqueous pH Organic g./1.

0.5MH2SO4 0.82 0.00015 0.1MH2SO4 1.76 0.00028 H20 4.10 0.00240 0.05M NaOH 5.52 1.21 0.1MNaOH 5.89* 1.53 *See footnote to Table B-2 The process of Procedure 3 was used with the aliphatic kerosene (Kermac 470B) solution of 8-(decylmethylbenzenesulfonamido)quinoline. Results are set forth in the following Table B-4: Table B4 Metal Metal Concentration in Organic g./l.

Cu++ 0.315 0.315 0.306 0.316 0.318 0.319 Ni++ 0.296 0.300 0.309 0.283 0.230 Zn++ 0.343 0.346 0.334 0.308 0.259 0.211 Procedure 4 processing was followed with the aliphatic kerosene-sulfonamido solution with results being set forth in the following Tables (stripped organic, NHs in raffinate and pH of water wash data only were collected): Table B-5 Loaded Organic From Step 2 - 3.04 g./1. Cu++ Strip Solution Stripped Organic Aqueous Wash Solution g./1. H2SO4 g./1. Cu" RaffinateNH3-M pH 25 0.895 0.0043 7.7 50 0.311 0.0052 7.4 75 0.124 0.0026 7.2 100 0.075 0.0030 7.1 150 0.008 0.0060 6.6 Table B-6 -Ni++ Loaded Organic* From Step 2 - about 2.5 g./1. Ni++ Strip Solution Stripped Organic Aqueous Wash Solution g./1. H2SO4 g./1. Ni++ Raffinate NH3-M pH 25 < 0.0005 0.036 7.4 50 " 0.0037 7.5 75 ,, 0.033 7.3 100 " 0.0037 7.1 150 " 0.030 8.1 *The starting loaded organic was not analyzed, thus the Ni++ was estimated.

Table B-7-Zn++ Loaded Organic From Step 2-2.99 g./1. Zn++ Strip Solution Stripped Organic Aqueous Wash Solution g./1. H2SO4 g./1. Zn RaffinateNH3-M pH 25 < 0.005 0.011 7.6 50 " 0.014 6.8 75 " 0.012 7.3 100 " 0.014 7.3 150 " 0.012 7.3 To further check the low sulfuric acid loading property of the sulfonamidoquinolines, the 0.1M solution of 8-(decylmethylbenzenesulfonamido)quinoline in Kermac 470B kerosene was contacted (one hour, organic:aqueous phase ratio of 2:1) with H2SO4 stripping solutions.

This was followed by water washing and pH analysis of the wash solution. Results were as follows: Table B-8 Aqueous g./l. H2SO4 Water Wash pH 100 5.38 150 5.83 200 4.90 250 4.42 In a further process to determine the kinetics of loading and stripping of Cu++, a 4% wt./vol. solution of the 8-(decylmethylbenzenesulfonamido)quinoline of Example II in Kermac 470B was contacted at a 1:1 organic:aqueous phase ratio with an aqu Table C Reagent Loaded Organic Metal Concentration g./1. Metal Cu++ 5 2.83 10 5.41 15 8.25 Zn++ 5 2.82 10 5.90 15 8.30 The 15% zinc loaded organic was washed once at an organic:aqueous phase ratio of 1:1 for 15 minutes with 1M (NH4)2SO4. The pH of the aqueous wash went from 5.7 to 8.1 and it had a Zn++ content of 0.193 g./l. The organic phase was then contacted with 100 g./l. H2S04 to strip the zinc. The stripped organic had a Zn++ content of < 0.0005 g./l. and the aqueous strip solution had an NH3 content of 0.026 M.

A corresponding 8-(decylethylbenzenesulfonamido)quinoline prepared ultimately from a decylethylbenzene wherein the alkylation had been carried out at 0-5 C. (see Table I) yielded a Cu+ + complex which caused gelling when aliphatic kerosene (Kermac 470B) was used but which was readily soluble in Aromatic 150 kerosene.

Example D Example C was essentially repeated except using the sulfonamidoquinoline of Example IV.

The resulting Cu++ complexes caused the kerosene solution to gel. The Zn++ complexes produced a hazy organic but the same analyzed 3.40 and 7.05 g./l. Zn++ at 5 and 10% wt./vol. concentrations, respectively. The reagent and its Cu++ complex were soluble in Aromatic 150 kerosene and the Procedure 1 process yielded a separated organic which analyzed 3.06 g./l.

Cu++ with no precipitation.

Example E Example C was partially repeated except using the 8 (octylmethylbenzenesulfonamido)quinoline of Example V. At 15% wt./vol. in Aromatic 150, the reagent maximum loaded 9.80 g./l. Cu++ and 10.3 g./l. Zn++. In Kermac 470B kerosene, pills were formed during the extractions indicating partial insolubility of the metal complexes.

Example F The process Procedure 1 was used with the 8-(nonylmethylbenzenesulfonamido)quinoline of Example VI in Aromatic 150. Results were as follows: Table F-l Metal Organic g./1. Metal* Cu++ 2.08 Ni" 1.86 Co++ 1.76 Co+++ 0.00325 Zn++ 2.09 *Some emulsion problems were encountered thus the samples were centrifuged prior to the analysis of the organic phases.

Example G A 10% wt./vol. solution of the 8-(decylisopropylbenzenesulfonamido)quinoline of Example VII in aliphatic kerosene (Kermac 470B) was maximum loaded as in Example C with Cu". . The organic phase analyzed 6.25 g./l. Cu++. The process Procedure 2 was also followed using a 0.1M solution of the sulfonamidoquinoline in the aliphatic kerosene. The 0.2M CuSO4 aqueous solution was mixed with pH adjusting solutions as indicated in the following Table.

Table G-l pH Adjusting Aqueous Organic Solution Raffinate pH g./1. Cu++ 0.5M H2SO4 0.47 0.411 0.1M H2SO4 1.02 1.48 0.05M NaOH 1.61 2.27 Example H The process of Procedure 1 was carried out with the 8 (diamylbenzenesulfonamido)quinoline of Example VIII dissolved in Aromatic 150. Results are set forth in the following Table H-1: Table H-l Metal Organic g./1. Metal Cu++ 2.90(1) Ni++ 2.47 Co+++ 0.0090 Co++ 1.74 Zn++ 3.31 (')When a 5.0% wt./vol. solution of the sulfonamidoquinoline in Aromatic 150 was contacted twice with the Cu++ aqueous solution, the organic analyzed 3.62 g./1. Cu++ but some precipitation was evident. Precipitation was also evident when Kermac 470B was substituted for Aromatic 150. When benzene was used as the solvent in the Procedure 1 process with one contact with the Cu++ solution, the separated organic analyzed 2.99 g./1. Cu++ with no precipitation.

The Procedure 2 process was also followed using the Aromatic 150 solution with the 0.2M CUSP4 aqueous solution being mixed with pH adjusting solutions as indicated in the following Table H-2: Table H-2 pH Aqueous Adjusting Raffinate Organic Solution pH g./l. Cu++ 0.5MH2SO4 0.49 0.148 0.1MH2SO4 1.08 0.930 0.05M NaOH 1.71 1.99 Example Process Procedure 1 was used with a 0.1M solution of the 8-(secamylbenzenesulfonamido)quinoline of Example IX in benzene and the Cu++ containing aqueous solution. The resulting organic phase analyzed 3.58 g./l. Cu++. In repeating Procedure 1 with a corresponding solution of the sulfonamidoquinoline of Example IX in Aromatic 150, precipitates formed with Cu++ and also with Ni++ (the filtered organics analyzed 1.01 g./l. Cut and 0.396 g./l. Ni++, respectively) and an emulsion formed with Zn++ (the organic analy7ed 0.367 g./l. On++). Co++ did not form a precipitate and the organic analyzed 1.70 g./l. Cote.

In comparison to the data of Examples H and J, an attempt was made to extract Cu++ in accordance with Procedure 1 with a 0.1M solution of 8-(2,5dimethylbenzenesulfonamido)quinoline in benzene. After contact for one hour, a granular precipitate adhered to the sides of the sample bottle and phase separation was slow. The aqueous was pipetted off and the organic phase was again contacted with fresh Cu++ aqueous solution. After setting overnight, most of the resulting Cu++ complex had settled out. When Aromatic 150 was substituted for the benzene, the 8-(2,5- dimethylbenzenesulfonamido)quinoline dissolved with heating and initially remained in solution after cooling but crystals formed overnight. Prior to crystal formation, an attempt was made to maximum load the solution with Cu++ (2 contacts with the Cu++ aqueous solution of Procedure 1). Precipitate formed and was filtered off and the organic analyzed only 0.0610 g./l. Cu. Similarly, an attempt was made to dissolve 8-(4methylbenzenesulfonamido)quinoline at a level of 0.1M in Aromatic 150. Even with heating and shaking, not all of the compound went into solution. The excess was filtered off and the resulting solution of unknown concentration (less than 0.1M) was used in the Procedure 1 process. Emulsions and precipitates formed in all cases with Cu++, Ni++, Co++ and Zn++. The respective organics after centrifuging analyzed 0.0985 g./l. Cu++, 0.0215 g./l. Ni++, 0.130 g./l.

Co++ and 0.025 g./l Zn++. When an attempt was made to dissolve the 8-(4 methylbenzenesulfonamido)quinoline in benzene at a concentration of 0.1 molar, heating was required and some of the compound crystallized out after cooling overnight. The resulting organic was contacted with a Cu++ containing solution in accordance with Procedure 1. The separated organic analyzed only 0.22 g./l. Cu++.

Example K The Procedure 1 process was carried out with the 8 (dinonylnaphthalenesulfonamido)quinoline of Example X dissolved in Kermac 470B kerosene at the 0.1M level. Results are as follows: Table K-l Metal organic g./1. Metal Cu++ 2.19 Ni++ 1.91 Co++ 1.35 0.0710 Zn++ 2.20 The process of Procedure 2 was also followed using a 0.15 molar aliphatic kerosene (Kermac 47.0B) solution of the reagent of ExampleX with the 0.2M CuSo4 aqueous solution being mixed with pH adjusting solutions as indicated in the following Table K-2: Table K-2 pH Adjusting Aqueous Organic Solution Raffinate pH g./1. Cu++ 0.5MH2SO4 0.6 1.19 0.25MH2SO4 0.7 1.32 0.1MH2SO4 1.1 1.70 H20 1.3 2.40 0.005M NaOH 1.4 2.62 Example L Process Procedure 1 was used with a 0.1M solution of the 8 (heptylbenzenesulfonamido)quinoline of Example XI in benzene and the Cu++ containing aqueous solution. The resulting organic phase analyzed 3.28 g./l. Cu++ with some slight precipitation evident which might be attributed to trace impurities. When this was repeated with an 0.1M solution of the sulfonamidoquinoline of Example XI in Aromatic 150 (two contacts with the Cu++ containing aqueous solution) some granular precipitate settled out of the organic upon standing overnight, and the organic analyzed 1.66 g./l. Cu++.

Example M Procedure 1 was followed with the 8-(pentadecylbenzenesulfonamido) quinoline of Example XII dissolved in Aromatic 150. Results were as follows: Table M-l Metal Organic g./1. Metal Cu++ 3.26 Ni++ 2.83 Cozy 1.84 Co+++ 0.0053 Zn++ 3.25 In other tests according to Procedure 1 with the Cu++ aqueous solution, a precipitate formed when the reagent of Example XII was dissolved in Kermac 470B kerosene at 5% wt./vol.

However, when 10% wt./vol. solutions ineither 50:50 or 75:25 volume mixtures of Kermac 470B and Aromatic 150 were used, no precipitates formed and the organic and aqueous phases showed a clean break after the extraction-contacting period.

As in previous examples, the process of Procedure 2 was followed with a 0.1M solution of the 8-(pentadecylbenzenesulfonamido)quinoline in Aromatic 150 and results are set forth in the following table: Table M-2 pH Adjusting Aqueous Organic Solution Raffinate pH Raffinate pH g./1. Cu++ 0.5M H2SO4 0.50 0.745 0.1M H2S04 0.99 2.03 0.05M NaOH 1.49 2.75 Example N The 8-(n-hexadecylbenzenesulfonamido)quinoline of Example XIII was dissolved in benzene at a level of 0.1M and contacted with the Cu++ containing solutionin accordance with process Procedure 1. The separated organic analyzed 2.10 g./l. Cu++ and there was some precipitation (slight to moderate) during the extraction.

Example O The 8-(hexadecylbenzenesulfonamido)quinoline of Example XIV was dissolved in Aromatic 150 at a level of 15% wt./vol. and contacted with the Cu++ and Zn++ aqueous solutions in accordance with Procedure 1. The resulting organic phases analyzed 10.3 g./l.

Cu++ and 8.8 g./l. Zn++.

Example P The process of Procedure 1 was repeated using the 8 (triisopropylbenzenesulfonamido)quinoline of Example XV in Aromatic 150. Results were as follows: Table P-1 Metal Organic g./l. Metal Cu++ 2.91 Ni++ 2.50 Co++ 1.66 Co++ 0.005 Zn++ 1.28* *Some precipitation was evident Example Q *Some precipitation was evident A 5% wt./vol. solution of the 8-(dodecylbenzenesulfonamido)-2-methylquinoline of Example XVI in Aromatic 150 was prepared and used in the Procedure 1 process with the Cu++ and Zn++ aqueous solutions. The resulting solution of the Cu++ complex analyzed 3.03 g./l.

Cu++ and was an iridiscent blue-green colour (a slight precipitate was removed by filtration). A ball of precipitate formed during the zinc extraction and dissolved upon the addition of an equal part of benzene. The reagent per se was not soluble in Kermac 470B.

Example R The process of Procedure 1 was used with the 8-(decylmethylbenzenesulfonamido)-2methylquinoline of Example XVII in both Kermac 470B and Aromatic 150. Results were as follows: Table R-1 Solvent and Metal Organic g. /1. Metal Kermac 470B Cu++ 2.88 Ni++ 0.273 Co++ 0.477 Co+++ < 0.0005 Zn++ 0.518 Aromatic 150 Cu++ 2.21 Ni++ 1.69 Co+++ 0.0006 Zn++ 2.32 The Procedure 2 process was followed with the Aromatic 150 solution of the 8 (decylmethylbenzenesulfonamido)-2-methyl-quinoline as in previous Examples: Table R-2 pH Adjusting Aqueous Organic Solution Raffinate g./1. Cu++ 0.5MH2SO4 0.63 < 0.0005 0.2MH2SO4 1.33 0.0019 0.1M H2S04 1.65 0.0068 H20 2.54 0.226 0.05MNaOH 2.89 0.930 0.1MNaOH 3.37 1.52 Procedure 4 processing was also followed with the Aromatic 150 solution as follows (raffinate NHs content was not determined): Table R-3 Loaded Organic From Step 2 - 3.14 g./1. Cu++ Strip Solution Stripped Organic Wash g./1. H2SO4 g./1. Cu++ Solution 100 1.08 3.84 150 1.45 5.45 200 1.20 3.99 250 0.378 3.84 The Procedure 3 process using the Aromatic 150 solution of 8 (decylmethylbenzenesulfonamido)-2-methylquinoline was followed in respect of Cu++ and Zn++ and results are set forth in the following Table: Table R4 Metal Metal Concentration In organic g./1.

Cu++ 0.315 " 0.300 0.149 0.0416 Cu++ 0.0114 0.0045 Zn+ 0.351 0.342 0.322 0.218 0.115 0.0535 Example S The 8-(decylmethylbenzenesulfonamido)-6-methylquinoline of Example XVIII was dissolved at a concentration of 0.1M in Aromatic 150 and used in accordance with the processes of Procedures 1-4 with results as reported in the following Tables.

Table S-l Metal Organic g./1. Metal Cu++ 3.08 Ni++ 2.63 Co++ 1.80 Co+++ 0.0007 Zn++ 2.98 Table S-2 - Procedure 2 pH Adjusting Aqueous Organic Solution Raffinate pH g./l. Cu++ 0.5M H2SO4 0.61 0.232 0.2MH2SO4 1.20 1.05 0.1MH2SO4 1.40 1.28 H20 1.59 1.89 0.05M NaOH 1.74 2.29 0.1M NaOH 1.93 2.54 Table S-3 - Procedure 3 Metal Organic g./1. Metal Cu++ 0.320 0.316 0.329 0.319 0.336 0.325 Zn++ 0.355 0.349 0.339 0.348 0.248 0.240 Table S-4 - Procedure 4 Loaded Organic From Step 2-3.16 g./1. Zn++ Strip Solution Stripped Organic Aqueous g./1. H2SO4 g./1. Zn++ Raffinate NH3-M 25 0.0051 0.018 50 0.0035 0.020 75 0.0030 0.020 100 < 0.0005 0.022 150 0.0020 0.021 Example T As in Example S, a 0.1M solution of the 8-(decylmethylbenzenesulfonamido)-6methoxyquinoline of Example XIX in Aromatic 150 was prepared and used in accordance with the processes of Procedures 1, 2 and 4 with the results being reported in the following Tables: Table T-I - Procedure I Metal Organic g./1. Metal Cu++ 3.30 Ni++ 2.32 Co++ 1.42 Co+++ 0.0019 Zn++ 3.14 Table T-2 - Procedure 2 pH Adjusting Aqueous Organic Solution Raffinate pH g./1. Cu++ 0.5MH2SO4 0.54 0.220 0.2MH2SO4 1.01 0.765 0.1M H2SO4 1.25 1.05 H20 1.59 1.36 0.005M NaOH 1.60 1.57 Table T-3 - Procedure 4 Loaded Organic From Step 2-3.24 g./1. Cu++ Strip Solution Stripped Organic g./1. H2SO4 g./1. Cu++ 100 1.05 150 0.358 250 0.0395* *The stripped organic was washed with water. The pH of the water before the wash step was 5.7 and after was 4.6.

Example U The process of Procedure 1 was followed using the 8-(decylmethylbenzenesulfonamido)-5nitroquinoline of Example XX dissolved at a concentration of 0.1M in Aromatic 150 and also in benzene. Results are set forth in Table U-1 which follows: Table U-l Solvent and Metal Organic g./1. Metal Aromatic 150 Cu++ 2.58 Zn++ 2.56 Benzene Cu++ 2.73 Zn++ 2.72 Likewise in the Procedure 2 process with the Aromatic 150 solution, the results were as follows: Table U-2 pH Adjusting Aqueous Organic Solution Raffinate pH g./1. Cu++ 0.5MH2SO4 0.60 0.147 0.2MH2SO4 1.13 0.391 0.1MH2SO4 1.39 0.530 H20 1.83 0.945 0.05M NaOH 1.82 1.05 When the Aromatic 150 solution was maximum loaded with Cu++ (2.80 g./l.) and stripped, 250 g./l. aqueous H2S04 yielded a stripped organic with a Cu++ content of 0.0550 g./l. and 150 g./l. aqueous H2S04 yielded a stripped organic with a Cu++ content of 0.523 g./l.

Example W Process Procedures 1 and 2 were employed with a 0.1m Aromatic 150 solution of the 8-(decylmethylbenzenesulfonamido)-5 ,7-dichloroquinoline of Example XXI. Results were as follows: Table W- 1 - Procedure 1 Metal Organic g./1. Metal Cu++ 2.62 Ni++ 2.19 Zn++ 2.15 Table W-2 - Procedure 2 pH Adjusting Aqueous Organic Solution Raffinate pH g./1. Cu++ 0.5MH2SO4 0.54 < 0.0005 0.2MH2SO4 1.10 0.0067 0.1MH2SO4 1.49 0.0204 H20 2.37 0.253 0.05M NaOH 2.50 0.316 The reagent of Example XXI maximum loaded 2.74 g./l. Cu++ using the aqueous Cu++ solution of Procedure 1. The data of Table W-2 shows that this reagent extracts Cu++ at a higher pH than the new compound of Example II which does not have chloro substituents.

Example Y Example W was essentially repeated except using the 8-(dodecylphenylmethanesulfonamido)quinoline of Example XXII. Results were as follows: Table Y- I - Procedure I Metal Organic g./1. Metal Cu++ 2.61 Ni++ 2.10 Zn++ 2.60 Table Y-2 - Procedure 2 pH Adjusting Aqueous Organic Solution Raffinate pH g./1. Cu++ 0.5M H2SO4 0.57 0.130 0.1M H2SO4 1.31 1.15 0.05M H2SO4 1.36 1.24 H20 1.55 1.59 0.05M NaOH 1.83 1.95 0.1M NaOH 2.13 2.21 When dissolved at a 0.1M concentration in Kermac 470B and contacted with the aqueous Cu++ solution of Procedure 1, the compound of Example XXII yielded an amber coloured emulsion which gelled upon setting.

Examples The Procedure 1 process was used with a 0.1M Aromatic 150 solution of the 8-(nhexadecanesulfonamido)quinoline of Example XXIII. Table Z-1 gives the results: Table Zl Metal Organic g./1. metal Cu++ 3.07 Ni++ 2.65 Co++ 1.76* Zn++ *Some precipitate **Precipitate thus organic not analyzed When process Procedure 1 was repeated with the Cu++ containing aqueous solution and a 0.1M solution of the 8-(n-hexadecanesulfonamido)quinoline in benzene, the separated organic analyzed 1.59 g./l. and some precipitation was evident.

Example AA Procedures 1, 2 and 4 were used with a 0.1M solution of the 8-(2ethylhexanesulfonamido)quinoline of Example XXIV in Aromatic 150. Results are set forth in t e following Tables: Table AA-I - Procedure I Metal Organic g./1. Metal Cu++ 2.85 Ni++ 2.42 Zn++ 2.80 Table AA-2 -- Procedure 2 pH Adjusting Aqueous Organic Solution Raffinate pH g./1. Cu++ 0.5MH2SO4 0.74 0.164 0.2MH2SO4 1.16 0.930 0.1MH2SO4 1.32 1.27 H20 1.55 1.72 0.05M NaOH 1.75 2.00 Table AA-3 - Procedure 4 Loaded Organic* From Step 2 - about 2.80 g./1. Cu++ Strip Solution Stripped Organic Wash Solution g./1. H2SO4 g./1. Cu++ pH 100 0.100 5.36 150 0.0025 5.36 200 0.0025 3.93 250 -- 4.8 *The starting loaded organic was not analyzed, thus Cu++ content was estimated.

Example BB A 0.1M solution of the 8-(n-octanesulfonamido)quinoline jof Example XXVII in Aromatic 150 was contacted two times at an organic:aqueous phase ratio of 1:1 for one hour each time with the Cu++ aqueous solution of Procedure 1. The maximum loaded organic analyzed 2.20 g./l. Cu++. There was no evidence of precipitation.

Example CC Process Procedure 1 was used with a 0.1M solution of the 8-(n pentanesulfonamido)quinoline of Example XXVIII in benzene and the Cu++ containing aqueous solution. The separated organic analyzed 3.44 g./l. Cu++. However, when an attempt was made to maximum load a 0.1M solution of the 8-(n-pentylsulfonamido)quinoline in Aromatic 150 as in Example BB, a moderate amount of precipitate fell out of solution and was filtered off. The filtered organic analyzed 0.860 g./l. Cu++.

Example DD Procedures 1-4 were also used with the 8-(isodecanesulfonamido)quinoline of Example XXV. These results are as follows (0.1M solution in Aromatic 150): Table DD-1 - Procedure I Metal Organic g./1. Metal Cu++ 2.80 Ni++ 2.50 Co++ 1.80 Co+++ 0.0006 Zn++ 2.70 Table DD-2 - Procedure 2 pH Adjusting Aqueous Organic Solution Raffinate pH g./1. Cu++ 0.5M H2SO4 0.49 0.206 0.2MH2SO4 1.06 1.14 0.1M H2SO4 1.23 1.50 H20 1.61 2.25 0.05M NaOH 1.62 2.13 0.1M NaOH 1.87 2.39 Table DD-3 - Procedure 3 Metal Organic g./1. Metal Cu++ 0.306 0.312 0.318 " 0.316 0.317 0.314 Zn++ 0.356 0.356 0.340 " 0.275 0.230 0.171 Table DD-4 - Procedure 4 Loaded Organic From Step 2-2.87 g./1. Cu++ Strip Solution Stripped Organic Wash Solution g./1. H2SO4 g./1. Cu++ pH 75 0.0148 3.33 100 0.0083 3.39 150 0.0029 5.85 200 0.0271 4.52 Loaded Organic From Step 2-2.95 g./1. Zn++ Strip Solution Stripped Organic Aqueous g./1. H2SO4 g./1. Zn++ Raffinate NH3-M 25 0.0012 0.018 50 < 0.0005 0.020 75 < 0.0005 0.019 100 < 0.0005 0.020 150 < 0.0005 0.020 Example EE An 8% wt./vol. solution of the 8-(C24-C26-alkenylsulfonamido)quinoline of Example XXVI in Kermac 470B kerosene was contacted in accordance with the Procedure 1 process.

The resulting organic analyzed 3.66 g./l Cu++.

Example FF A 0.05M Ag+ solution was prepared by dissolving 0.84g. AgNO3 and 13.2g. (NH4)2SO4in 20 ml. of 2.OM NH40H and diluting to 100 ml. with water. A 0.1M solution of the 8 (decylmethylbenzenesulfonamido)quinoline of Example II in Aromatic 150 was then contacted at a 1:1 organic:aqueous phase ratio with the Ag+ solution for one hour with shaking. After separation of the phases, the organic analyzed 2.96 g./l. Ag+. Portions of the loaded organic phase were then contacted with shaking for one hour with equal volumes of various aqueous solutions to strip the Ag+ therefrom. Results were as follows: Table FF-I Aqueous Stripped Organic Strip Solution g./1. Ag+ 150g./1. H2SO4 < 0.01 1 .0M NHO3 < 0.01 1.OMHC1 0.04 Example GG Example FF was repeated except that the starting aqueous solution was prepared by attempting to dissolve 1.71 g. Hg (NO3)2 in 100 ml. water. Almost all of the Hg(NO3)2 dissolved with residual precipitate being filtered off to yield a solution which was close to 0.05M in Hg+ (pH 2.02). The separated loaded organic analyzed 10.5 g./l. Hg++. When stripped with an equal volume of 1.0M HCI, the organic analyzed 0.93 g./l.

Example HH A 5.5% wt./vol. solution of the 8-(decylmethylbenzenesulfonamido)quinoline of Example II in Kermac 470B kerosene was contacted with stirring at an organic:aqueous phase ratio of 1:4 with an aqueous solution containing 2.5 g./l. Pb++ from Pb(NO3)2 in water (pH adjusted to 7.1 during extraction). The contact time was 2.0 minutes. The separated organic analyzed 9. 56 g./l. Puff. The loaded organic was stripped with aqueous HNO3 (150 g./l. at an organic:aqueous phase ratio of 6:1 to yield a barren stripped organic. Some precipitation of Pb(NO3)2 was noted in the aqueous strip solution.

The above Examples show metal recovery from various starting aqueous solutions. It is clear that the metal content of such starting solutions is not critical and can vary widely, it being only necessary that the process extracts at least a portion of the metal values therefrom.

Claims (99)

1. In preferred aspects, the metal content will range from 0.1 to 80 g./l. of the respective metals being extract AT WE CLAIM IS: 1. A compound having the formula:

   wherein R represents an alkyl or alkenyl radical containing 8-20 carbon atoms or a group of formula:

   (in which R3 represents an alkylene radical containing from 1 to 20 carbon atoms; p isO or 1; A represents a mono- or bi-cyclic radical wherein the ring or rings are 5- or 6-membered; q is 1, 2 or 3; r is 0 or 1; and q + is 1,2 or 3; each R4 independently represents an alkyl or alkenyl radical containing up to 20 carbon atoms; the total number of carbon atoms in (R4)q being at least 8, with the provisos that when q is 2 at least one R4 radical contains 5 or more carbon atoms and when q is 3 at least one R4 radical contains 3 or more carbon atoms; and each R5 independently represents -Cl, -Br, -NO2 or -OR6 represents a hydrocarbyl radical containing from 1 to 20 carbon atoms); n is 0, 1 or 2; and m is 0 or 1; and R1 and R2, which may be the same or different, each represents a hydrocarbon radical containing from 1 to 5 carbon atoms, -Cl, Br, NO2 or -OR6 (wherein R6 is as defined above) or (when n is 2) the two R' groups may together form a ivalent hydrocarbon group.
2. 2. A compound as claimed in claim 1 wherein R represents a straight chained alkyl radical.
3. 3. A compound as claimed in claim 2 wherein R represents an n-octyl or n-hexadecyl radical.
4. 4. A compound as claimed in claim 1 wherein R represents a branched alkyl or alkenyl radical.
5. 5. A compound as claimed in claim 4 wherein R represents a 2-ethyl-hexyl or isodecyl radical.
6. 6. A compound as claimed in claim 1 wherein R represents a group of formula:

   (wherein R , R4, R5, A, p, q and rare as defined in claim 1).
7. 7. A compound as claimed in claim 6, wherein p isO.
8. 8. A compound as claimed in claim 6 wherein p is 1.
9. 9. A compound as claimed in claim 8 wherein R3 represents an alkylene radical containing 1 or 2 carbon atoms.
10. 10. A compound as claimed in any of claims 6 to 9 wherein A represents an unsaturated mcno- or bi-cyclic radical.
11. 11. A compound as claimed in any of claims 6 to 10 wherein the ring or rings represented by A are 6-membered.
12. 12. A compound as claimed in claim 11 wherein A represents aphenylornaphthylradical.
13. 13. A compound as claimed in any of claims 6 to 12 wherein one R4 radical contains at least 8 carbon atoms.
14. 14. A compound as claimed in any of claims 6 to 13, wherein at least one R4 radical is an alkyl radical.
15. 15. A compound as claimed in claim 14 wherein the alkyl radical is straight chained.
16. 16. A compound as claimed in claim 15 wherein at least one R4 radical represents an n-hexadecyl radical.
17. 17. A compound as claimed in claim 14 wherein the alkyl radical is branched.
18. 18. A compound as claimed in claim 17 wherein the branched alkyl radical is a linear alkyl group. A
19. 19. A compound as claimed in claim 18 wherein the linear alkyl group is a dodecyl, pentadecyl, heptyl, nonyl or hexadecyl radical.
20. 20. A compound as claimed in any of claims 6 to 19, wherein r is 0.
21. 21. A compound as claimed in any of claims 6 to 20 wherein q is greater than 1 and two or more R4 radicals contain at least 5 carbon atoms.
22. 22. A compound as claimed in any of claims 6 to 21 wherein q is 2 and A represents a phenyl radical.
23. 23. A compound as claimed in claim 22 wherein one R4 represents a methyl, ethyl or isopropyl radical.
24. 24. A compound as claimed in claim 22 wherein one R4 represents an octyl radical and the other R4 a methyl radical.
25. 25. A compound as claimed in claim 22 wherein one R4 represents a decyl radical and the other R4 a methyl radical.
26. 26. A compound as claimed in claim 22 wherein one R4 represents a decyl radical and the other R4 an ethyl radical.
27. 27. A compound as claimed in claim 22 wherein one R4 represents a decyl radical and the other R4 an isopropyl radical.
28. 28. A compound as claimed in claim 22 wherein one R4 represents a dodecyl radical and the other R4 a methyl radical.
29. 29. A compound as claimed in any of the preceding claims wherein m and n are both 0.
30. 30. A compound as claimed in any of claims 1 to 28 wherein m is 1 and n is 0.
31. 31. A compound as claimed in any of claims 1 to 28 wherein n is 1 and m is 0.
32. 32. A compound as claimed in any of claims 1 to 28 wherein n is 2 and m isO.
33. 33. A compound as claimed in any of claims 1 to 28 and 30 wherein m is 1 and R2 represents an alkyl radical.
34. 34. A compound as claimed in claim 33 wherein R2 represents a methyl radical.
35. 35. A compound as claimed in any of claims 1 to 28 and 31 to 34 wherein n is 1 or 2 and R' represents a chloro, nitro, methyl or hydrocarbon radical.
36. 36. A compound as claimed in any of claims 1 to 28 and 31 wherein R represents a methoxy radical.
37. 37. 8-(2-Ethylhexanesulfonamido)quinoline.
38. 38. 8-(n-Octanesulfonamido)quinoline.
39. 39. 8-(n-Hexadecanesulfonamido)quinoline.
40. 40. 8-(Isodecanesulfonamido)quinoline.
41. 41 8-(Dodecylbenzenesulfonamido)quinoline.
42. 42. 8-(Decylmethylbenzenesulfonamido)quinoline.
43. 43. 8-(Decylethylbenzenesulfonamido)quinoline.
44. 44. 8-(Octylmethylbenzenesulfonamido)quinoline.
45. 45. 8-(Nonylmethylbenzenesulfonamido)quinoline
46. 46. 8-(Decylisopropylbenzenesulfonamido)quinoline.
47. 47. 8-(Diamylbenzenesulfonamido)quinoline.
48. 48. 8-(Dionylnaphthalenesulfonamido)quinoline.
49. 49. 8-(Heptylbenzenesulfonamido)quinoline.
50. 50. 8-(Hexadecylbenzenesulfonamido)quinoline.
51. 51 8-(2,4,6-Triisopropylbenzenesulfonamido)quinoline.
52. 52. 8-(Dodecylbenzenesulfonamido)-2-methylquinoline.
53. 53. 8- Decylmethylbenzenesulfonamido)-2-methylquinoline.
54. 54. 8-(Decylmethylbenzensulfonamido)-6-methylquinoline.
55. 55. 8-(Decylmethylbenzenesulfonamido)-6-methoxyquinoline.
56. 56. 8-(Decylmethylbenzenesulfonamido)-5-nitroquinoline.
57. 57. 8-(Decylmethylbenzenesulfonamido)-5,7-dichloroquinoline.
58. 58. 8- Dodecylphenylmethanesulfonamido)quinoline.
59. 59. A compound as claimed in claiml and herein described in any one of Examples I to XXVII, with the exception of those compounds specifically claimed in claims 37 to 58.
60. 60. A composition comprising a solution of a sulfonamidoquinoline as defined in claim 1 in an essentially water-immiscible organic solvent, said solution containing at least 2% by weight of the sulfonamidoquinoline.
61. 61. A composition as claimed in claim 60 wherein the water-immiscible solvent comprises an aliphatic or aromatic hydrocarbon or a mixture thereof.
62. 62. A composition as claimed in claim 61 wherein the water-immiscible solvent is a kerosene, benzene, toluene, xylene or a mixture of such solvents.
63. 63. A composition as claimed in claim 61 wherein the water-immiscible solvent has a flash point of at least 1500F, as measured according to the A.S.T.M. method D-56 (closed cup method).
64. 64. A composition as claimed in any of claims 60 to 63 containing from 2 to 75% by weight of the sulfonamidoquinoline.
65. 65. A composition as claimed in claim 64 containing from 2 to 50% by weight of the sulfonamidoquinoline.
66. 66. A composition as claimed in claim 65 containing from 5 to 20% by weight of the sulfonamidoquinoline.
67. 67. A composition as claimed in claim 64 containing from 25 to 75% by weight of the sulfonamidoquinoline.
68. 68. A composition as claimed in claim 60 substantially as herein described.
69. 69. A composition as claimed in claim 60 substantially as herein described in the examples.
70. 70. A metal complex of a sulfonamidoquinoline as defined in claim 1 with Cu++, Ni++, Co++, Zn++, Cd++, Hg++, Ag++ or Pb++.
71. 71. A metal complex as claimed in claim 70 in solution in an essentially water-immiscible solvent.
72. 72. A metal complex as claimed in claim 71 wherein the water-immiscible solvent is as defined in any of claims 61 to 63.
73. 73. A metal complex as claimed in claim 70 substantially as herein described.
74. 74. A metal complex as claimed in claim 70 substantially as herein described in the Examples.
75. 75. A process for the preparation of a sulfonamidoquinoline as claimed in claim 1 which comprises reacting an 8-aminoquinoline of formula:

    (wherein Ra, R2, m and n are as defined in claim 1) with a sulfonyl chloride of formula: Cl-SO2-R wherein R is as defined in claim 1.
76. 76. A process for the preparation of a sulfonamidoquinoline as claimed in claim 75 substantially as herein described.
77. 77. A process for the preparation of a sulfonamidoquinoline as claimed in claim 75 substantially as herein described in the examples.
78. 78. Sulfonamidoquinolines as defined in claim 1 whenever prepared by a process as claimed in any of claims 75 to 77.
79. 79. A process for extracting Cu++, Ni++, Co++, Zn++ Cd++, Hg++, Ag+ and/or Pb++ metal values from aqueous solutions thereof which comprise (a) contacting said aqueous solutions with an organic phase comprising a solution of an 8-sulfonamidoquinoline as claimed in claim 1 in an essentially water-immiscible organic solvent whereby at least a portion of the metal values are extracted into the organic phase, (b) separating the loaded organic phase containing the extracted metal values in the form of a complex with the 8 sulfonamidoquinoline from the aqueous solution and (c) subsequently stripping at least a portion of the metal values from the organic phase by contact with an aqueous stripping medium; the 8-sulfonamidoquinoline and the metal complex thereof formed during the extraction process each having a solubility of at least 2% by weight in the water-immiscible solvent.
80. 80. A process as claimed in claim 79 wherein the essentially water-immiscible organic solvent is benzene.
81. 81. A process as claimed in claim 79 wherein the essentially water-immiscible organic solvent is an aliphatic or an aromatic hydrocarbon or a mixture thereof having a flash point of at least 1500F as measured by the ASTM method D-56 (closed cup method).
82. 82. A process as claimed in any of claims 79 to 81 wherein the sulfonamidoquinoline is present in the essentially water-immiscible organic solvent in an amount of from 2 to 50% by weight.
83. 83. A process as claimed in claim 82 wherein the sulfonamidoquinoline is present in the essentially water-immiscible organic solvent in an amount of from 5 to 20% by weight.
84. 84. A process as claimed in any of claims 79 to 83 wherein the metal value being extracted is Cu".
85. 85. A process as claimed in claim 84 wherein the aqueous Cu+±containing solution also contains Fe+++ ions.
86. 86. A process as claimed in claim 84 or claim 85 wherein the aqueous Cu+±containing solution is acidic.
87. 87. A process as claimed in claim 84 or claim 85 wherein the aqueous Cu+±containing solution is an ammoniacal solution.
88. 88. A process as claimed in any of claims 79 to 83 wherein the metal value being extracted isNi++.
89. 89. A process as claimed in any of claims 79 to 83 wherein the metal value being extracted is Co+.
90. 90. A process as claimed in any of claims 79 to 83 wherein the metal value being extracted is Zn+.
91. 91. A process as claimed in any of claims 79 to 83 wherein the metal value being extracted is Cd++.
92. 92. A process as claimed in any of claims 79 to 83 wherein the metal value being extracted is Hug++.
93. 93. A process as claimed in any of claims 79 to 83 wherein the metal value being extracted is Ag+.
94. 94. A process as claimed in any of claims 79 to 83 wherein the metal value being extracted is Pb++.
95. 95. A process as claimed in any of claims 79 to 94 wherein the aqueous stripping medium is acidic.
96. 96. A process as claimed in claim 95 for extracting Zn++, Ni++, Co++, Cd++, Cu++ and Ag+ wherein the aqueous stripping medium is an aqueous sulfuric acid solution.
97. 97. A process as claimed in claim 79 substantially as herein described.
98. 98. A process as claimed in claim 79 substantially as herein described in any one of Examples A to HH.
99. 99. Cut', Ni++, Co++, Zit+, Cd++, Hug++, Ag+ and Pb++ whenever extracted by a process as claimed in any of claims 79 to 98.