Cupric, nickelous and argentous ion-selective chelating resins

17 Pages·2013·1.32 MB·English

United States Patent [191
1111 3,873,668
Melby
1451 Mar. 25, 1975
1541 CUPRIC, NICKELOUS AND ARGENTOUS Primary [:Ituminw-Melvin Goldstein
ION-SELECTIVE CHELATING RESINS
[75] Inventor: Lester Russell Melby, Wilmington.
[57] ABSTRACT
Del.
A polymer-ligand comprising a high molecular weight
[73] Assignee: E. I. du Pont de Nemours and water insoluble polymer containing certain covalently
Company, Wilmington, Del.
bonded ligand moieties is capable of selectively che
[22] Filed: Mar. 27, 1973 lating cupric and/or argentous ions from aqueous solu
tions containing them and other metal ions. Exem
[21] Appl. No.: 345,314 plary is polystyrene containing the moiety
[52] US. Cl ........... .. 423/24, 75/101 BE, 260/22 R,
423/139
[51] Int. Cl. ..................... .. B0ld 15/04, C08f 27/08
[58] Field of Search .................. .. 260/22 R; 423/24;
75/101 BE PIN-CH2
1 56] References Cited
UNITED STATES PATENTS
3,037,945 6/1962 Morris ............................... .. 260/21
3,337,480 8/1967 Small . . . . . . 1 . . . . . . . . . . . .. 260/22
3.473.921 10/1969 Schmuckler ........................ .. 75/118
OTHER PUBLICATIONS
which is bound to the polymer chain through the oxy
Goodwin et al.. J. Am. Chem. Soc, 82, 5013~5023 gen atom.
1 1960).
16 Claims. N0 Drawings
3,873,668
1
2
CUPRIC, NICKELOUS AND ARGENTOUS
X and X’ independently are NH, O, or S;
ION-SELECTIVE CHELATING RESINS
BACKGROUND OF THE INVENTION
1. Field of the Invention
5 Y is / \ or Qt;
This invention provides insoluble chelating polymers
-Z _Z _z
which selectively bind certain metal ions in the pres
R R
ence of other metal ions and thus are suitable for ob
taining purified concentrates from which the free metal
may be recovered.
.10 and Y' is / \ N_
More specifically this invention provides insoluble
I
chelating polymer systems which (1) selectively bind R _
cupric and argentous ions in the presence of ferric, fer
rous, cobaltous and nickelous ions, or (2) selectively in which
bind cupric, argentous, and nickelous ions in the pres~
2 IS —O__, —S_, __S(CH2)"1 _O(CHZ)H_v
ence of ferric, ferrous and cobaltous ions. These sys
—NH—, or —NH(CH2),,— where n = l to 10;
tems are effective in obtaining puri?ed concentrates ‘Q is N; and
for recovery of copper and/or silver, or copper, nickel Q’ is NH, O, or S;
and/or silver from low grade mine liquors.
with the proviso that at least three of X, X’, Q and Q’
2. Prior Art are nitrogen;
Mine liquors from spent copper mines of the sulfide the said ligand being attached to the methylene car
ore type contain low concentrations of cupric (Cu**) bon by the indicated valence bond and being at
and ferric (Few) ions, the liquors of which are acidic tached to the polymer through the Z group.
(pH 1-3 ). Conventionally, purified cupric ion solutions
Preferred ligands are those where the indicated va
of commercial value are obtained from such mine li lence bond is in the ortho position relative to the ring
quors by liquid-liquid extraction with organo-soluble
nitrogen or the Q or O’ atom. Also preferred are those
chelating agents (ligands) which are more or less selec ligands in which each of X and X’ is a nitrogen atom.
tive for Cu++ in the presence of FeJ+ at low pH. The or The polymer component of the invention has a high
ganic extract containing organo-soluble copper chelate
molecular weight, is insoluble in water and is stable to
is then back extracted (stripped) with strong mineral 30 sulfuric acid of 1-25% concentration. It is preferred
acid, e.g., 15% sulfuric acid, the acidic extract is then that the polymer also be insoluble in the organic sol
electrolyzed to obtain copper metal and the regener vents which may be used in the process of binding the
ated organic solvent-ligand solution is recycled to the polymer to the ligands. The polymer can be in any of
liquor extraction step. High selectivity for Cu++ over
various forms since it acts merely as a base or support
Fe"Pr is necessary because the presence of excessive 35 for the chelating ligands. Thus the polymer may be
amounts of Fe3+ interferes with the electrolytic recov used as beads or other small particles having a large
ery (electro-winning) process.
surface area or may be in the form of a continuous belt
It is well known that a solid-liquid extraction system as described below.
affords several inherent mechanical advantages over Useful polymers include polyvinyl chloride, polyvi
liquid-liquid extraction systems such as elimination or 40 nylidene chloride, and chloro-, bromo-, or iodome
simpli?cation of such steps as mixing, settling, separa thylated polystyrene, etc. The preferred polymer used
tion and recycling of solvents. in making the polymer~ligand is chloromethylated poly
H. A. Goodwin and F. Lions, J. Amer. Chem. Soc. styrene. Typically, such a polymer is made insoluble by
82, 5013 (l960) discuss the preparation of various cross-linking styrene with divinylbenzene. The degree
metal chelating compounds. They show that 2,2'-bis 45 of cross-linking may vary from 0.5—8% by weight of di
(2”-pyridylmethylamino)biphenyl is able to chelate vinylbenzene and the polymers may exist as beads or
copper ions. No mention is made ofa polymer contain pulverized solid. Such polymers are prepared and chlo
ing chelating moieties nor the chelating selectivity as to romethylated by any of a variety of means known and
copper and silver. » described in the prior art, as for example, U.S. Pat.
Nos. 2,614,099 and 2,629,710.
SUMMARY OF THE INVENTION
The polymer may be prepared also by radiation graft
The invention comprises a high molecular weight
ing styrene to an inert polymer such as polyethylene or
water insoluble polymer containing about 0.3 to about polypropylene in the form of a particulate solid or con
2 millimoles ofa covalently bonded ligand per gram of
tinuous material, such as woven fabric, bundled fibers,
polymer, the ligand having the formula 55
or as spunbonded felted material such as Tyvek, a spun
bonded polyolefln. The continuous materials may be in
the form of an endless belt. Such styrene-grafted mate
R R rials are then chloromethylated prior to ligand attach
ment.
The ligand component of the invention is a biphenyl
compound of the general formula above having a hy
H29’ ' ' (line droxy, thiol, thioloalkyl (HS—(CH2),,—), hydroxyalkyl
(HO—(CH2),,), amino (NHz), or aminoalkyl
Y y'
(NH2-(CH2),,—), and the like if the ligand is to be at
65
tached to a preformed polymer by nucleophilic substi
wherein
tution. Such groups can be on any one of the four aro
R is H or alkyl of 1-3 carbon atoms; _matic nuclei comprising the essential ligand structure.
3,873,668
3 4
The ligands are reacted with a polymer having reactive layers were clear. The ether was separated. washed
groups such as chlorine, bromine, or iodine, etc., with 100 ml of water, dried brie?y with sodium sulfate
through a condensation reaction to split out halogen and evaporated to 50 ml on a steam bath. It was cooled
acid, etc. Where the ligand contains a polymerizable to room temperature and magnetically stirred over
vinyl group, it may be connected to the polymer by a 5 night. N-(2-pyridylmethyl)-2,2'-diaminophenyl (A)
copolymerization reaction. As an illustration, a ligand separated as a finely divided crystalline white product.
containing 21 OH group can be attached by condensa- The mixture was stored at —lO°C. overnight and the
tion with the chloromethylated polymer in the presence product was collected and washed with a small amount
of a strong base such as an alkali metal alkoxide, alkali of cold ether; the yield was 912 g (67%), mp 85°-95°(‘.
metal hydroxide or carbonate, quaternary ammonium 10 Another 2.0 g was obtained from the concentrated
hydroxide, or a tertiary amine in an inert solvent, such mother liquor (total yield, 82%). This material was
as dimethylformamide, dimethylacetamide, dimethyl- then recrystallized from benzenehexane giving a mate
sulfoxide, hexamethylphosphoramide or dioxane at rial having a melting point of 93°~94°C.
temperatures ranging from ambient to about 100°C. in
the presence or absence of one molar equivalent of wa- '5
ter- ' Anal. Calcd, for CmHnN, (mol. Wt. 275.3 )
C, 78.5; H, 6.2; N, l5.3
SPECIFIC EMBODIMENTS OF THE INVENTION Found: c, 78.2; H. 6.3; N, 15.0
The following are illustrative examples of the inven- 20
tion in which all parts are by weight unless stated other- The reaction produces an interim monoimine which
wise. is reduced to form the desired starting material. The re
EXAMPLE 1 action is carried out near or in the presence ofa solvent
such as an alkanol of 1-4 carbon atoms (methanol, eth
Ligand . anol propanol etc ) benzene or alkyl benzene (tolu
N-(p-Hydroxyphenylmethyl)-N’-(2-pyr1dylmethyl)- 25 ene ’Xylene et’c) ' ’
2’2 'dlammoblphenylu) The reaction temperature is usually maintained at
‘A. The precursor for this ligand is prepared as fol- 80°—90°C. or at the boiling point of the solvent chosen.
lows: If no solvent is employed, a temperature of 80°—l00°C.
To a stirred, re?uxing solution of 9.2 g (50 moles) of 40 is preferred. In any case, the amine aldehyde mixture
2,2’-diaminobiphenyl in 200 ml of ethanol was added must be in a liquid state. The reaction may occur spon
dropwise during 2 hours a solution of 5.3 g (50 moles) taneously when the reactants are mixed
Of pyridine-2-aldehyde (redislilled. bP 70°C, 15 mm) Reduction of the monoimine to the corresponding
in 100 ml of ethanol. When addition was complete, the amine is accomplished by using any of a number of re
mixture was re?uxed for an additional 30 minutes and 45 ducing agents such as sodium borohydride in lower al
was then cooled to room temperature. Three grams of kanols, sodium metal in lower alkanols, lithium alumi
sodium borohydride was added and the solution was num hydride in ether or tetrahydrofuran, or catalyti~
stirred overnight (16-20 hours). Another 3 g of sodium cally with hydrogen gas at atmospheric or superatmos
borohydride was added and stirring continued for 24 pheric pressure and temperatures from 20°C. to 100°C.
hours more. The solution was transferred to a large Er- 50 in inert Solvents Over typical hydrogenation Catalysts
lenmeyer ?ask and boiled to virtual dryness on a steam ‘Such as nickel, platinum of palladium
bath. Approximately 500 ml of water and 300 ml of B. Precursor A is used in the following reaction to
ether were added and the mixture was stirred until both Produce ligand (1)1
.- H
' / -H2O mono- H2
Q——@ + 1 [imine
\ ,
H H-CH CH -NH
2 2 cao , 2
/ \ l
- \
0H
3,873,668
5 6
Solutions of 8.0 g (29 mmoles) of N-(2~pyridylme crystals. The imine compound was recrystallized from
thyl)-2,2’-diaminobiphenyl (A) and 3.54 g (20 ethanol, mp, 148°—150°C. Recrystallized imine (2.4 g)
mmoles) of p-hydroxybenzaldehyde, each in 40 ml of and 1 g of sodium borohydride in 280 ml of ethanol was
ethanol were mixed and boiled gently for 0.5 hour, stirred at room temperature for 16 hours and then
cooled to room temperature and made up to 100 ml evaporated to dryness. The residue was taken up in a
volume with fresh ethanol. Two grams of sodium boro mixture of 300 ml of water and 150 ml of ether and the
hydride was added and the mixture stirred at room tem mixture was stirred until clear. The ether layer was sep
perature for 5 hours. Another 2 g of sodium borohy arated, dried over anhydrous sodium sulfate and con
dride was added and stirred for an additional 16 hours. centrated to 20 ml volume, then chilled to obtain 0.9
The solution was boiled to dryness on a steam bath and g of N-(3-hydroxy-2-pyridylmethyl)-N’-(2
the residue treated with 400 ml of water. A thick syrup pyridylmethyl)-2,2’ -diaminobiphenyl (2) as white
separated and the water was decanted. The syrup was crystals. The water layer was buffered to pH 8 with so
washed by decantation with water and was taken up in dium bicarbonate to obtain a second crop, weighing 0.5
200 ml of ether. The ether solution was dried with so g. The combined crops were recrystallized from 66%
dium sulfate, ?ltered, and concentrated to 50 ml vol aqueous ethanol to obtain white crystals, mp,
ume. On standing at room temperature overnight, the 181°—183°C.
solution deposited about 5 g of N-(p
hydroxyphenylmethyl )-N ’-( 2-pyridylmethyl )-2,2 ’
diaminobiphenyl ( l) as a white crystalline solid. It was
recrystallized from 98% alcohol, the solution was 20
Anal. Caled. for (‘24H22N|(): C , 75.4; H. 5.3; 7.
chilled at —1 5° to —20°C. overnight and the crystals of Found: C, 75.9; H, 6.0; 5.
ligand monohydrate were collected and dried in a
stream of moist air, mp, l 16°—l 18°C.
This monohydrate was heated at 80°C. in a vacuum Ligands l and 2 are presently preferred. Their donor
to obtain the anhydrous form, mp, 132°—135°C. 25 atoms, which are responsible for coordinating the
metal ion in metal scavenging processes, are all nitro
gen atoms. In tetradentate ligand 2, one of the donor
Anal. Calcd. for CQSHHNKO; C, 78.7; H, 6.0; N, 11.0. atoms may be replaced by an oxygen or sulfur atom. ln
Found: (178-7; H‘ 6-3iN- 11-2 all cases, two of the donor atoms must be attached di
30 rectly to the 2- and 2’- positions of the’ biphenyl nu
EXAMPLE 2 cleus. Ligand 1 is selective for cuprous and argentous
_ ions in the presence of ferric, ferrous, cobaltous and
_ Ligand I ‘ nickelous ions and the ligand 2 moiety is selective for
N'(3'HYdmXYQ'RYQdylmedly])'N '(z'pyndylmethyn‘ cuprous, argentous and nickelous ions in the presence
2,2 'dlammoblphenyl (2) 35 of ferric, ferrous and cobaltous ions.
/ 0H
_ —H2O mono- H
1., H CH2 . mine a;
N CHO
H/ \
5 HO ca —NH Nit-0H2
~
Commercially available 3-hydroxy-2-hydroxyme EXAMPLE 3
thylpyridine hydrochloride was converted to the free
l\l-( Z-Hydroxybenzylidene )-N ’-( 2-pyridylmethyl )-2 ,2 '
base with sodium bicarbonate. The base was oxidized
to the aldehyde with manganese dioxide in re?uxing 60 diaminobiphenyl (3) ‘
benzene in a manner known to the art. The aldehyde
hydrochloride was isolated by passing dry l-lCl into the
?ltered benzene solution.
A mixture of4.3 g ( 15.5 mmoles) of N-(Z-pyridylme
thy1)-2,2'-diaminobiphenyl (A) and 2.5 g (15.5 no .c NH-LHQ
mmoles) of the above hydroxypyridine aldehyde hy
drochloride in 100 ml of ethanol was boiled gently on
steam for 15 minutes and the solution was then chilled
at —-15° to —20°C for 2 days to obtain 1.7 g of yellow - 3
N
3,873,668
7
8 ,
A solution of 2.75 g of N-(2-pyridylmethyl)-2,2’ for ligand 4, the 2-hydroxy isomer, to obtain the imine
diaminobiphenyl (A) and 1.22 g of salicylaldehyde in 5 as slightly yellow matted needles; yield 2.7 g. mp
25 ml. of ethanolwas vigorously boiled on a steam bath 69°—72°C. The air-dried product was the hemlalcohu
until the volume was .10 ml. It was chilled at —20°C. late.
overnight to obtain the crude orange-yellow crystalline
imine 3; yield 3.4g (90%), mp 106°-l10°C.
For analysis a small portion was recrystallized from
ethanol, mp 108°—112°C. Anal. Calcd for C2,,H2,N;|().1/2C2H5OH (MW 402.5): ,
', 77.5; H, 6.9; N, 10.4.
Found: C, 77.2; H, 6.3; N, 10.4.
Anal. Caled for C,,,H,|N_1O(MW 379.4): C.
Found: C, EXAMPLE 6
N-( 3-Hydr0xybenzyl )-N '-( 2-pyridylmethyl )-2,2 ’
NMR(CDC1;,)8 8.42 (S, 1,=CH—), 8.2-8.39 (m, l, diaminobiphenyl (6)
pyridine a), 6.4-7.4 (m, 15 aromatic and pyridine B,
7). 4.35 (S, 3, -CH2— and NH).
EXAMPLE 4
N-( 2-1-lydroxybenzyl )-N '-( 2-pyridylmethyl)-2,2 ’ 20
diaminobiphenyl (4)
25
The 3-hydroxy imine 5 was reduced as described for
the 2-hydroxy compound. The crude mixture was evap
orated to dryness, the residue triturated with water and
solid 6 collected. It was recrystallized from ethanol (~
10 ml/g) to obtain puri?ed product in 66% yield, mp
To a suspension of 15 g of crude imine 3 in 375 ml
l48°-150°C.
ethanol was added 2.25 g of sodium borohydride and
35
the mixture was stirred at room temperature for two
days. The ?rst crop of crystalline solid 4 was collected
and washed with cold ethanol and then with water; Anal. Calcd for C15H23N3O (MW 381
yield 6.5 g, mp 156—158°C. The ?ltrate was evaporated C , 78 .8, H, 6.1
Found; C, 78.6; H, 6.3;
to remove the ethanol and the second crop of solid was
collected and recrystallized from 200 ml of ethanol to
obtain an additional 5.5 g of product, mp 154°-156°C.
The total yield was 80%. EXAMPLE 7
A.
N-( 6-Methyl-2-pyridylmethyl )-2,2 '-diaminobiphenyl
45
(7)
Anal. Calcd for
(‘EH-“N30 (MW 381.4): C. 78.8; H, 6.1;N, 110
Found: C, 78.9; H, 6.2; N. 11 0
50
EXAMPLE 5
N-( 3-Hydroxybenzylidene )-N '-( 2-pyridylmethyl )-2,2 '
diaminobiphenyl) (5)
55
The reaction of 2,2’-diaminobiphenyl with one molar
equivalent of 6-methylpyridine-2-aldehyde and reduc
tion of the intermediate imine with sodium borohydride
HO was carried out as described for the unmethylated ana
log (Example 1). Since the product did not crystallize.
it was used as a crude sirup obtained by evaporating the
6.5 ether extract to dryness.
The reaction of 3-hydroxybenzaldeh'yde and pyridyl N-( 3-Hydroxy-2-pyridylmethylene )-N ’-( 6-methyl-2
methyldiaminobiphenyl was carried out as described pyridylmethyl)~2,2’-diaminobiphenyl (8)
3,873,668
9 10
/ \ EXAMPLE 9
A. 3-Hydroxy-6-methylpyridine-2-aldehyde
Hydrochloride (10)
Z __ j \ __ :
9.’ 6H3 10
To a solution of 22 g of compound 7 in 100 ml of eth
lnto a 2-1, one-neck ?ask was placed 1 liter of ben
anol was added a separate solution of 6.0 g of 3
zene and 20 g of commercially available 2
hydroxypyridine 2-aldehyde hydrochloride in 100 ml of 15
hydroxymethyl-3-hydroxy-6-methyl pyridine. With
ethanol and 5.25 ml of triethylamine was added imme
continuous magnetic stirring 100 g of ?nely-divided,
diately. The mixture was gently boiled on a steam bath
activated manganese dioxide (Shepherd Chemical Co.)
for 5 min. then stored overnight at —20°C. The yellow
was added in portions to ensure uniform suspension.
crystalline product 8 was collected on a filter, washed
The ?ask was equipped with a Soxhlet extractor head
with a small amount of ethanol, then with water, and air
with a cup capacity of about 75 ml, the cup containing
dried. The crude yield was 1 1.8 g (80% based on alde
20 g of 4 A molecular sieves. The mixture was heated
hyde) and the mp l40°~l42°C. It was recrystallized
under re?ux for 5 hrs., cooled to room temperature,
from ethanol (30 ml/g, Darco) to obtain 8.5 g mp
the benzene suspension filtered and the filter cake
148°-151°C.
25 washed with 200 ml of benzene. The ?ltrate was satu
rated with dry hydrogen chloride, the precipitated hy
drochloride 1O collected, washed with benzene and
Anal. Calcd for C25l-l?N4O (MW 394.5): dried. It was vacuum sublimed at 130°—l40°C., 1-2 mm
C , 76 .1-, H, 5.6; N] pressure; yields 12-16 g (50-65%); mp 2l5°-217°C.
Found: C, 76.4; H, 5.7; N, l 30
(dec).
NMR (CDCl;,) 8 12.5 (broad, —OH), 8.74 (S,
l==Cl-l~—), 80-815 (m, 1, pyridine a), 6.5-7.5 (m, 13,
Anal. Calcd for C1HBCINO2 (MW) 173.6): C, 48.4; H. 4.
aromatic and pyridine B, y), 4.7 (broad. NH), 4.2-4.5 N, 8. a
(m, 2, -CH2-) 2.35 (s, 3, -CH_»,). 35 Found: C, 48.]; H, 4.
N, 8.
EXAMPLE 8
N-( 3—Hydroxy-Z-pyridylmethyl )-N ’~( 6-methyl-2
pyridylmethyl)-2,2‘—diaminobiphenyl (9)
4O B.
N-( 3-Hydroxy-6-methyl-2-pyridylmethylene )-N ’-( 2
pyridylmethyl)‘2,2’-diaminobiphenyl ( l 1)
45
H0 /CH2-NH NH-CH
2
G . -- 5O HO CH=N NH- CH2
,9.
CH3
/ \ H3 3
To a suspension of6.0 g of compound 8 in 180 ml of 55
ethanol was added 0.9 g of sodium borohydride and the
mixture was vigorously stirred at room temperature
until the yellow solid had dissolved and decolorized (~ In 50 ml of ethanol was dissolved 15.0 g of N-(2
pyridylmethyl)-2,2’-diaminobiphenyl (from Example
30 min). The solution was evaporated to dryness, taken
I) by warming gently on a steam bath. To it was added
up in 200 ml of water and acidified with acetic acid.
60
a solution of 9.5 g of aldehyde hydrochloride l0 imme
The white solid 9 was collected and recrystallized from
diately followed by 3.3 g of sodium methoxide. The
ethanol (4 ml/g); yield 4.6 g (76%), mp 160°-162°C.
mixture was heated on a steam bath for 30 mins then
stored at —20°C. overnight. The solid was collected,
washed with a small amount of cold ethanol then with
65
water to dissolve by-product NaCl, and dried. The yield
of analytically pure product 11 was 18.2 g (85%), mp
l48°—151°C.
3,873,668
11 12
weight of sand at l75°—l80° for 1 hour. Benzene ex
traction and recrystallization of the crude product from
Anal. Calcd for CQJHHMO (MW 394.5):
C, 76.1; H, 5.6; N, 14.2. ethanol gave puri?ed 2,2'-dinitro-6,6’
Found: C, 76.5; H, 5.7; N, 14.0. dimethylbiphenyl in 70% yields, mp 106°-107°C.
5 Hydrogenation of the dinitro compound in ethyl ace~
tate ( l0 ml/g) with Raney nickel catalyst and hydrogen
NMR (CDC13) 6 12.2 (-OH), 8.80 (S, l =CH-)
8.3-8.5 (m, l, pyridine a), 6.5-7.5 (m, 13, aromatic at 8 atm and room temperature for 4-5 hrs gave the di
and pyridine ,8, 7), 4.40 (broad S, 3, NH and CH2—), amine in 85% yields after recrystallization from ethanol
2.42 (S, 3, CH3). (3m1/g), mp l34°-l36°C.
Reaction of 2,2’-diaminc-6,6’-dimethylbipheny1 with
EXAMPLE l0
1 mole of pyridine-2—a1dehyde followed by reduction
N-(3-Hydroxy-6-methy1-2-pyridylmethyl)-N'-(2
with sodium borohydride as described previously (Ex
pyridy1methyl)-2,2’-diaminobiphenyl ( 12)
amples 1 and 7) gave compound 13 as a crude sirup.
15
B.
N-( 3-1-lydroxy-6-methyl-2-pyridylmethylene )-N ’-( 2
pyridylmethyl )-2,2 ’-diamino-6,6’-dimethy1bipheny1
(14)
HO CH -
2 2O
CH3 CH3
CH3 25
Ho CH=N -CH2
To a suspension of 15 g ofimine l 1 in 200 ml of etha
nol was added 1.5 g of sodium borohydride and the
/ \ /
mixture was stirred at room temperature overnight. It
30 __ N \
was evaporated to dryness, the residue slurried with
200 ml of water and acidified to pH 6 with acetic acid.
CH3 2251'
The white solid was collected, washed with water, dried
and recrystallized from ethanol (20 ml/g) to obtain
To a solution of 9 g of sirupy 13 in 50 ml of ethanol
10.3 g (67% yield) of crystalline product 12, mp
35 was added a solution of 5.2 g of the aldehyde hydro
170°-172°C.
chloride 10 in 50 ml of ethanol. Sodium methoxide
(1.62 g) was added and the mixture was boiled gently
for 30 mins then chilled at —20° overnight. The crude
product 14 was collected, washed with ethanol and
Anal. Calcd for C2_-,H24N4O (MW 396.5):
C, 75.7; H, 6.1; N, 14.1. 40 water and dried. The crude yield was 4.8 g (38%). It
Found: C, 75.7; H, 6.1; N, 14.0. was recrystallized from ethanol (5 ml/g) to recover 3.0
g (24% yield), mp 153°—l56°C.
EXAMPLE 1 l
45 Anal. Calcd for C2,H€,N7,O
, A. , 6.8;
N-( 2-Pyridy1methy1)-2,2’-diamino~6,6' Found: C, 76.7; ,
dimethylbiphenyl (13)
NMR (CDC13) 6 12.9 (S, 1, OH), 8.79 (S, 1,
H3 CH3
=CH—), 8.27-8.47 (m, pyridine a), 7.5-6.4 (m, 11,
aromatic and pyridine {3, 'y), 4.27-4.47(m, 2,
—CH2—), 3.97-4.45 (In, --NH—), 2.44 (s, 3, pheny
1-CH3), 1.86 s, 3, phenyl-CH;,).
2 55 EXAMPLE 12
N-( 3-Hydroxy-6-methyl-2-pyridylm ethyl )-N '-( 2
pyridy1methy1)-2,2’~diamino-6,6'-dimethy1biphenyl
( 15)
2:3 60 c113 CH3
2-1odo-3-nitroto1uene was prepared by a known
method. The crude product was recrystallized from
hexane (10 mI/g, Darco) to obtain 80-85% yields of 65 HO CH2- -CH2
purified material, mp 62°-64°C. Coupling of the iodo
compound was carried out by heating a mixture of the
iodo compound with 50% of its weight of copper
bronze (United States Bronze Powders, lnc., Copper
CH3
Bronze Natural, Copper Fine, type 44) and an equal
3,873,668
13
14
A ?ltered solution of 2 g of sodium borohydride in
H3 H3
100 ml of ethanol was added to a stirred suspension of
8.2 g of imine 14 in 100 m1 of ethanol. Stirring was con
tinued for 4 hrs and the ?rst crop of white product 15
was collected, yield 4.75 g, mp l92°—195°C. The ?l
trate was evaporated to dryness and the residue was
H0 GHQ-Na N'H-CI-Ik
slurried with water to obtain a second crop of crude
solid (3.04 g) which was recrystallized from ethanol to
recover 2.4 g of puri?ed product, mp 192°-195°C. / \N
A portion of the ?rst crop was recrystallized from
ethanol for analysis, mp 194°—l95°C.
17
To a stirred suspension of 5.0 g ofimine 16 in 150 ml
Anal. Calcd for C2,-H2,.N,O (MW 424.5): C. 76.5; H. 6.65; of ethanol was added 1.0 g of sodium borohydride and
N. 13.2.
Found: C. 76.5; H. 7.0; the mixture was stirred overnight at room temperature.
N, 13.3. It was evaporated to dryness and stirred with 200 ml of
water on a steam bath, cooled and the crude solid col
lected and recrystallized from ethanol to obtain 1.8 g
EXAMPLE 13 20 of puri?ed product 17, mp 170K173". The original
aqueous filtrate was acidi?ed with acetic acid, neutra1~
A.
ized with sodium bicarbonate and the solid collected
N-( 3-Hydroxy-2-pyridylmethy1ene )-N '-( 2
pyridylmethyl )-2,2 '-diam ino-6,6 '-dimethy1biphenyl and recrystallized to obtain a second crop, 0.4 g, m.p.
172°-174°C.
( 16)
CH3 CH3
Anal. Calcd for CMHMMO (MW 4105): C. 76.1; H. 6.4;
N, 13.7.
/ \ Found: C. 75.9; H. 6.9;
N, 13.4.
Ho - CH=N Nit-0H2 EXAMPLE 14
A
/ \ ’ \ 35 N-( 3-Hydroxy-6-methyl-2-pyridylmethylene )-N ’-( 6
methyl-Z-pyridylmethyl)-2,2’-diaminobipheny1 ( 18)
16
~
To 13 g of amine 13 (Example 1 1) in 200 ml of etha Ho CHEN H-CH2
\no1 was added a solution of 6.9 g of 3-hydroxypyridine
2-aldehyde hydrochloride in 100 ml of ethanol fol / \ N/ \
lowed immediately by 2.3 g of sodium methoxide. The 45
mixture was boiled on a steam bath for 30 mins., cooled
to room temperature, ?ltered, and the filtrate concen
H3 19 Q 3
trated to 50 ml volume. The solution was chilled at
—10° to —20°C. for 2 days and the yellow crystalline
To a solution of l l g ofa sirupy compound 7 (Exam
product 16 was collected and recrystallized from etha 50 ple 7) in 75 ml of ethanol was added a solution of 3
nol to obtain 5.2 g of purified material, m.p. hydroxy-6-methylpyridine-Z-aldehyde hydrochloride
l40°-l42°C. For analysis a small portion was again re
crystallized. 10 and 1.85 g of sodium methoxide. The mixture was
heated on a steam bath for 30 min., concentrated to 50
ml volume, ?ltered and the ?ltrate chilled overnight at
55
—l0° to —20°C. The yellow solid 18 was collected,
Anal. Calcd for CMHHMO (MW 408.5): N. 13.7. washed with water and recrystallized from ethanol to
Found: N. 13.7. obtain 5.0 g (36%) of yellow needles, mp. 59°-62°. Re
crystallized again from EtOH the m.p. was 64°C.
NMR(CDC]3)812.4(S,1,0H),8.99(S,1.=CH—),
60
8.6-8.4 (m. 1. pyridine a). 8.28 (I. l. J = 3. pyridine
a). 7.5-6.5 (m. 11. aromatic). 4.51 (.r. 1. -NH-—). Anal. (‘ulctl l'or (‘-_.,.H._..N.() (MW 408.5): (I 72);; H. 5.9;
4.44 (.\'. 2. --r (‘H2~ ). 2.16 (.r, 3. “CH0. 1.94 (.r. 3. N. l.. .
-(‘H;,). Found: C. 76.7; H. 6.1‘.
N. 13.6.
65
B. NMR (CDCl;,) 5 12.2 (s, OH), 8.83 (s, =CH—),
N-( 3-Hydroxypyridylmethyl )-N'-(2-pyridylmethy1)
7.5—6.5 (m, aromatic), 4.41 (broad s, —CH2—NH—).
2,2'-diamino-6.6'-dimethylbiphenyl (17)
2.46 (s, CH3), 2.40 (s, CH3).
3,873,668
15 16
B. The reaction of 2,2'-diamino-6.6’-dimethylhiphenyl
N-( 3-Hydroxy-6-methyl-Z-pyridylmethyl )-N '~( 6
with 6-methyl-pyridine-2-aldehyde and reduction with
methyl-2-pyridylmethyl)-2,2'-diaminobiphenyl (19)
sodium borohydride was carried out in the way previ
ously described (Examples 1. 7 and l l) to obtain the
amine 20 as a sirup.
B.
N-( 3-Hydroxy-6-methyLZ-pyridylmethyl )-N ’-( 6
methyl-2-pyridylmethyl )-2,2 ’-diam ino-6,6 ’~
dimethylbiphenyl Trihydrochloride (21)
IO
/ N
CH3 },9,
To a solution of 10 g of the imine l8 in 200 ml of eth
anol was added l.5 g of sodium borohydride and the
20
solution was stirred at room temperature overnight. It
was evaporated to dryness, treated with 200 ml of satu
rated aqueous sodium bicarbonate and the resulting
semi-solid mass was isolated and dissolved in 35 ml of.
ethanol and ?ltered. The filtrate was chilled at —lO° to
25
—20°C. overnight and the resulting white crystalline
solid 19 was collected and dried; yield, 7.7 g, m.p.
93°-99°C., unchanged on further recrystallization.
To a solution of 15 g sirupy compound (20) in 50 ml
of ethanol was added a solution of 5.2 g of the methyl
Anal. Calcd for C2,,H2,,N4O (MW 410.5 ): N, l 3.7. hydroxypyridine aldehyde 10 in 50 ml of ethanol, and
Found: N, 13.7.
1.62 g of sodium methoxide was added. The mixture
was heated on a steam bath for 30 mins., filtered free
of NaCl, cooled to room temperature, and stirred over
EXAMPLE IS 35
night with 2 g of sodium borohydride. The mixture was
A. evaporated to dryness, dissolved in 50 ml of hot 3 N
N-( 6-Methyl-2-pyridylmethyl )-2,2 ’—diamino-6,6 ’ HCl, treated with Darco, filtered and chilled overnight
dimethylbiphenyl (20)
to obtain the product 21 as fine, yellowish needles, mp.
164°—l70°C. (dec.).
40
45
N, 10.2.
Found: C, 6L0; H, 6.3;
N, 10.3.
50
Examples of operable ligands in which one of the
donor nitrogen atoms has been replaced by O or S in
a tetradentate ligand analogous to ligand 2 are:
N- ( S-hydroxymethyl-Q- ?n‘yl
—CH2 methyl)-N'-(2-pyridylmethyl)
2,2- '-diaminobiphenyl
3,873,668
18
N- (B-hydroxy- 2-pyr1dylmethyl) -
N‘ - (2- thienylmethyl) -
2, 2' -diaminobiphenyl
These compounds may be prepared by stepwise con
EXAMPLE 17
densation of 1 mole of the appropriate aldehyde with
one mole of 2,2’-diaminodiphenyl followed by reduc 1% crosslinked Polystyrene with Hydrated Ligand 2
tion of the intermediate imine to the corresponding 15 A. The reaction between 2.0 g of 1% crosslinked
amine. Condensation with a mole of a second aldehyde chloromethylated polystyrene, 5.15 g ofligand (2), 243
and subsequent reduction results in the desired prod l of water and 0.75 g of sodium methoxide in 50 m1
uct. of DMF was carried out as described in Example 16,
EXAMPLE l6 part D above.
Crosslinked Polystyrene With Ligand l Product yield was 5.35 g and the nitrogen content
was 10.4% corresponding to 1.86 mmoles ofligand per
A. Polystyrene beads, 200-400 mesh, crosslinked
gram of polymer.
‘with 2% divinylbenzene, were chloromethylated ac-'
B. The reaction of part A immediately above was re‘
cording to known methods. In the procedure 50 g of
peated but without added water. The polymer yield was
crosslinked polystyrene beads was allowed to swell in
25 5.63 g and the nitrogen content was 10.8% correspond
200 g of chloromethyl methyl ether for 1 hour at room
ing to 1.93 mmoles of ligand per gram of polymer.
temperature. A mixture of 7 ml of anhydrous stannic
chloride in 100 ml of chloromethyl methyl ether was EXAMPLE 18
added and the mixture stirred and boiled under re?ux Chloromethylated Polystyrene, 1% Crosslinked,
for 1 hour. The beads were collected on a ?lter and 30 200-400 Mesh Beads
washed successively with dioxane-water, dioxane-cone.
hydrochloric acid, dioxane and ?nally, methanol or A commercial sample* of 1% crosslinked polysty
ethanol. After vacuum drying the product contained rene, 200-400 mesh beads, was chloromethylated to
21% chlorine. obtain an 89% yield of product.
A mixture of 2.26 g of ligand (1) in monohydrate * Bio-Rad Laboratories, Richmond, Calif.
35 Anal. Found: C], 20.5, 20.7% equivalent to 5.8 mga
form and 0.32 g of sodium methoxide in 20 ml of anhy
torn per gram
drous freshly distilled dimethylformamide (DMF) was
stirred under nitrogen at room temperature for 10 min EXAMPLE 19
utes and then 1.0 g of the chloromethylated polysty
Polymer-Ligand 4 Prepared in Anhydrous Medium
rene was added. The mixture was stirred and heated at
40
85°—90°C. for 16 hours. A 2.0 g portion of chloromethylpolystyrene (Exam
The product was collected on a course frit ?lter and ple 18) was treated with molar equivalents of ligand 4
washed successively with 20 ml-portions of DMF con and sodium methoxide in DMF as previously described.
taining 10, 20, 50 and 75% water (v/v) by volume, then The yield of product was 5.3 g (83%).
with 20 ml of DMF and then successively with 20 ml Anal. Found: N, 7.5%, equivalent to 1.79 mmoles of
45
portions of DMF containing 10, 20, 50 and 75% etha ligand per gram of polymer.
nol (v/v); then, ?nally, with ethanol alone. The product
EXAMPLE 20
was vacuum-dried at 90°C. for 18 hours, yielding 2.25
g. Analysis: Found: N, 6.7%. 6.5%, corresponding to Polymer-Ligand 4 Prepared in Hydrous Medium
1.57 millimolcs of ligand per gram of polymer.
The reaction above was repeated, but one molar
B. A two-fold scale reaction analogous to part A
equivalent of water was added to the reaction mixture.
above was carried out to obtain 5.14 g of the product. The product weighed 5.2 g (80%).
Analysis: Found: 7.6% N, corresponding to 1.81
Anal. Found: N, 7.4% equivalent to 1.76 mmoles of
mmoles of ligand per gram of polymer.
ligand per gram.
C. A preparation analogous to the one described in 55
part B above was carried out using one molar equiva EXAMPLE 21
lent of anhydrous ligand (1) instead of the monohy
Polymer-Ligand 6 Prepared in Anhydrous Medium
drate. The yield was 5.23 g and the product contained
7.5% nitrogen corresponding to 1.79 mmoles ofligand A 2.00 g portion of chloromethylpolystyrene (Exam
per gram of polymer. This polymer, using the anhy ple 18) was treated with ligand 6 and sodium methox
drous ligand, produces a product with different han ide in anhydrous DMF as described previously to ob
dling and selectivity characteristics. tain 5.65 g (91%) of polymer. Anal. Found: N, 7.5,
D. A polymer preparation analogous to that of part 7.8% equivalent to 1.82 mmoles of ligand per gram.
A above was carried out using a 1% crosslinked chloro
EXAMPLE 22
methylated polystyrene containing 23.4% chlorine
65
(6.75 mmoles per gram) and appropriate molar equiva Polymer-Ligand 6 Prepared in Hydrous Medium
lents of ligand monohydratc (1) and other reagents. The above experiment was repeated but with one
The yield was 5.47 g and the polymer contained 7.8% molar equivalent of water in the reaction mixture.
nitrogen. corresponding to 1.85 mmoles of ligand per
Product yield was 5.16 g (79%). Anal. Found: 7.7,
gram of polymer.
7.9% equivalent to 1.86 mmoles of ligand per gram.