Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~`^ :1~15728
The present invention relates to N-sulphohydroxyalkane-
aminoalkallepllosphonic acids, their alkali salts, and a process
for their preparation.
Canadian Patent ~o. 1,100,995 des-
cribes N-sulphoalkane-aminoalkanephosphonic acids and a process
for their preparation, in which chloro- and hydroxy-alkane-
sulphonates, respectively are reacted at elevated temperatures
with aminoalkanephosphonic acids, which aminoalkanephosphonic
acids have at the amino group at least one hydrogen atom capable
of being substituted.
According to the present invention there are provided
N-sulphohydroxyalkane-aminoalkanephosphonic acids having the ~-~
general formula
P3~2
R1 C - N ~ 3
¦ R~
R 2
wherein R is H, CH3, C2H5~ C6H5~ CnH2nNH2' n 2n n 2n
(where n is 1 to 6) or C2H4PO3H2, R2 3 2 3
CnlH2n1_1(OH)SO3H or CH2PO3H2 where nl is 3 to 12, and R4 is
H, when R3 is other than CH2PO3H2 or CnH2n-1( ) 3
is 3 to 12 or alkali metal salts thereof such as a sodium and
potassium salt thereof.
The N-sulphohydroxyalkane-aminoalkanephosphonic acids
of the present invention differ from known aminoalkanephosphonic
acids insofar as either one or both of the two hydrogen atoms of
the amino group, which can be substituted, are replaced by sulpho-
hydroxyalkane groups.
The sulphohydroxyalkane-aminoalkanephosphonic acids
of formula I may be prepared by reacting alkali metal salts of
aminoalkanephosphonic acids represented by the general formula
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,
:. . ., .~; : ,
1~157~8
P3H2
1 C N~' 3 II
¦ H
R2 ~:.
1 1 is H, CnH2nOH, CnH2ncooH (where n is l to 6)~ CH
C i C2H5~ C6H5~ C2H4PO3H2, or-CH ~ nR~is H, or PO3H2, and R3
H, or CH2PO3H2, in an alkaline medium at a pH in excess of 9 at -
the boiling temperature of the solution o~ under pressure and
at temperatures of between 110C and 150C, with alkali metal
salts of alkanesulphonic acids, the alkane group of said alkane~
sulphonic acids containing between 3 and 12 carbon atoms and
furthermore, containing an exchangeable substituent such as a
halogen or an epoxy group, said aminoalkanephosphonic acids and
said alkanesulphonic acids being reacted in molar ratios between
l:l and 1:2, preferentially between l:l and 1:1.5.
In general, all the aminoalkanephosphonic acids of
. ~ ~ormula II, i.e. aminoalkanephosphonic acids which contain at
least one substituent on the amino group which has replaced one :-
20~ ~exchangeable hydrogen thereon are useful as the phosphonic acid
componént in~the process such as the sodium or potassium salts
~ of the aminome:thanephosphonic acid of~the l-aminoethane-2-
..~ ;: : phosphonic acid of the imino-bis-methanephosphonic acid, as well
as of the l-aminoalkane~ diphosphonic acids, for instance the
:ami~nomethane-diphosphonic~aoid, the l-aminoethane~ diphosphonic
acid~, the l-aminopropane~ diphosphonic àcid, the bezylamino-
diphosphonic acid, the 1,2-diaminoethane-l,l-diphosphonic acid,
~ the 3-hydroxy-1-aminopropane-l,l-diphosphonic acid, the 2-carboxy-
: I-hydroxy-3-aminopropane-l,l-diphosphonic acid-l-aminoethane-
l,l-diphosphonic acid, and the l-aminopropane-1,1,3-triphosphonic
acid. In the process for the preparation of said N-sulphohydroxy-
alkane-aminoalkanephosphonic acids, use of the alkali metal salts
- ' ' ,
. ~ - 2 -
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. . . . . ~ , .
i~57Z~
of 2,3-epoxypropane-1-sulphonic acid is preferred, said epoxy-
propanesulphonic acid being easily prepared from epichlorohydrin
and an alkali metal sulphite. ~ther epoxy sulphonates for use
in said preparation may be obtained by epoxidizing alkenesulphon-
ates, such other epoxysulphonates including for instance 2,3-
epoxyhexane-l-sulphonate, 2,3-epoxyhexane-4-sulphonate, 1,2-
epoxyoctane-3-sulphonate, 2,3-epoxyundecane-1-sulphonate, 2,3-
epoxydodecane-l-sulphonate, and 9,10-epoxyoctadecane-l-sulphonate. -
The N-sulphohydroxyalkane-aminoalkanephosphonic acids
may also be prepared by reacting chloro-hydroxy-alkane-sulphonates
in an alkaline medium, at temperatures between 90 and~150C with
aminoalkanephosphonic acids, the reaction being preferably
effected in an autoclave at temperatures of between lO0 and 130C.
Chloro-hydroxy-alkanesulphonates, which for instance can be used
in the preparation of N-sulphohydroxyalkane-aminoalkanephosphonic
acids include 2-hydroxy-3-chloropropane-1-sulphonate, 3-hydroxy-
4-chlorobutane-1-sulphonate, 2-hydroxy-3-chlorobutane-l-sulphon-
ate, and 2-methyl-2-hydroxy-3-chloropropane-1-sulphonate.
The phosphonic acid compounds of the present invention
are good complexing agents for bivalent and polyvalent metal
cations. They can be used with advantage where good complex
forming qualities towards polyvalent metal cations are required.
~ The acids particularly exhibit fastness against hydrolysis even
;~ at elevated temperatures. They can thus be used under all those
conditions where temperatures in excess of 100C are required.
:
~ ~ Thus, they can be used in all media in which the hard-
:
ness builders which water contains will interfere with a process,
or in ~hich the influence of polyvalent metal cations has to be
eliminated. Such uses include the treatment of hard water, baths
used in textile processing, the paper industry, and the tanning
of hides These phosphonates, when used in substoichiometric
quantities, will stabilize the hardness builders in water when
: - 3
~.
: ,: . , . , . .
1~1572~3
they are used in the so called threshold proc~ss.
The phosphonic acid compounds of the present in~ention
combine the characteristics of phosphonic acid compounds which
carry a hydroxy group as well as subphonic acid compounds which
carry an amino ~roup. An outstanding feature of these phosphonic
acid compounds is, specifically, their excellent solubility in
aqueous media, when said compounds are in the form of the free
acids, a ~eature which is lacking in the known alkaneamino phos-
phonic acid compounds. 100 ml of water will for instance, dis-
sol~e at least 100 grams of each of the acidic phosphonic acidcompounds described more in detail in the following Examples.
Example 1
48 grams of aminomethane-diphosphonic acid and 57 grams
of potassium hydroxide are dissolved in 200 ml of water. Into
this solution are mixed 42 grams of the sodium salt of 2,3-epoxy-
propane-l-sulphonic acid and the mixture boiled under reflux for
between 6 and 8 hours. The charge is neutralized with acetic
acid, The neutralized solution is then treated with a cation
exchange resin to remove the alkali metal ions. Thereafter, the
solution is evaporated to dryness. The residue which consists,
essentially of N-sulphohydroxypropane-aminomethane-diphosphonic
~;~ acid, is washed with methanol, and dried. Yield: 72 grams.
Analysis: found: C: 15.0%, N: 4.3%, P: 18.6%, S: 9.9%
caluculated: C: 14.6%, N: 4.26%, P: 18.82%, S: 9.74%
A byproduct: bis(N-sulphohydroxypropane)-aminomethane-
diphosphonic acid, which forms in minor quantities, could be iso-
- lated and identified analytically by applying thin layer- as well
as column-chromatography techniques.
N-sulphohydroxypropane-l-aminoethane-l,l-diphosphonic
acid is obtained-from 50 grams of l-aminoethane-l,l-diphosphonic
acid when process-in this manner. Yield: 68%.
~ 4 -
... . :
157Z~
Analysis: found: N: 4.3%, P: 18.1%, S: 9.1%
calculated: N: 4.08%, P: 18.05%, S: 9.34%
In addition, bis(N-sulphohydroxypropane)-l-aminoethane-
l,1-diphosphonic acid is formed, particularly when the proportion
of 2,3-epoxypropane-1-sulphonic acid is increased.
N-sulphohydroxypropane-2-carboxy-1-aminoethane-1,1-
diphosphonic acid is obtained when 60 grams of 2-carboxy-1-amino-
ethane-l,l-diphosphonic acid is used as starting material.
Yield: 66%.
N-bis(phosphonomethyl)-3-amino-2-iihydroxy-propane-1-
sulphonic acid is obtained, with a yield of 74~, when 51 grams
of imino-bis-methylenephosphonic acid are appliéd.
Analysis: found: N: 4.1%, P: 17.8%, S: 9.4% ;
calculated: N: 4.08%, P: 18.05%, S: 9.34% --
Example 2
50 grams of aminoethane~ diphosphonic acid, in the
form of its tetrapotassium salt, are heated in an autoclave
together with 56 grams o the potassium salt of 2,3-epoxyhexane-
l-sulphonic acid for three;hours to temperatures of between 130
and 135C. The autoclave is cooled thereafter and its contents
processed as in Example 1. 68 grams of N-sulpho-hydroxy-hexane-
- ~
aminoethane-l,l-diphosphonic acid were obtained.
Analysis: found: N: 3.8~, P: 15.9%, S: 8.5%
calculated: N: 3.63%, P: 16.04%, S: 8.30%
; Example 3
48 grams of aminomethane-diphosphonic acid, 72 grams ,~
of potassium hydroxide, and 58 grams of the potassium salt of -
methyl-hydroxy-chloropropanesulphonic acid are dissolved in 500
ml of water in an autoclave equipped with a stirrer. The mixture
3Q is stirred continuously, heated, and kept at between 130 and 135C
for four hours. The contents of the autoclave are cooled, then
acidified slightly, with hydrochloric acid.
~ ~ 5 ~
:'
~157Z~
The solution, if needed is filtered to remove precipi-
tated aminomethane-diphosphonic acid, the free N-sulpho-methyl-
hydroxy-propane-am;nomethane-diphosphonic acid was recovered as
in Example 1. Yield: 74%.
Analysis: found: N: 4.2~, P: 1~.0%, S: 9.6~
calculated: N: 4.08~, P: 18.05~, S: 9.34%
Correspondingly when the potassium salt of 2-hydroxy-
3-chloro-butane-1-sulphonic acid is used the N-sulpho-hydroxy-
butane-aminomethane-diphosphonic acid is obtained.
Example 4:
51 grams of l-aminoethane-l,l-diphosphonic acid and
87 grams of potassium hydroxide are dissolved in 400 ml of
water. 40 grams of 3,4-epoxybutane-1-sulphonic acid are dis-
solved separately in 80 ml of water. The solution of the phos-
phonate compound is stirred vigourously when the sulphonic acid
solution is dropped into it. The mixture is heated and boiled
under reflux for seven hours. The reaction product is worked
up thereafter, as in Example 1 to yield N-sulpho-hydroxybutane-
l-aminoethane-l,l-diphosphonic acid.
;20 Analysis: found: N: 4.0%, P: 17.3%, S: 9.2%
calculated: N: 3.92~, P: 17.34~, S: 8.98%
~hen 52 grams of 1,2-epoxy-octane-3-sulphonic aaid is
substituted for 40 grams of 3,4-epoxy-butane-1-sulphonic acid
N-(sulpho-hydroxy-pentyl-propane)-l-aminoethane-l,l-diphosphonic
acid is obtained.
` Analysis; found: N: 3.5%, P: 15.2~, S: 7.5%
; calculated: N: 3.39%, P: 14.99%, S: 7.76%
~hen 65 grams of 2,3-epoxy-undecane-1-sulphonic acid
is used 92 grams of N-(sulpho-hydroxy-undecane)-l-aminoethane-
l,l-diphosphonic acid is obtained.
Analysis: found: N: 3.2%, P: 13.4%, S: 7.4%
calculated: N: 3.08~, P: 13.60%, S: 7.04%
:
~ 6 -
-
11157ZB
Example 5
53.5 grams of phenyl-aminomethane-diphosphonic acid
and 36 grams of 2-hydroxy-3-chloro-propane-1-sulphonic acid are
dispersed in 200 ml of water. To this vigourously stirred dis-
persion are added, dropwise and under cooling, 175 grams of a
50% solution of potassium hydroxide in water. Thereafter, the
mixture is heated and stirred in an autoclave for between 3 and
4 hours, whereby the temperature is kept at 130C. Afterwards
the solution is cooled, then acidlfied slightly, with hydro-
chloric acid, and filtered, if needed, to remove the smallamount of insoluble phenyl-aminomethane-diphosphonic acid. The
filtrate is then treated with a cation exchange resin. The
resulting aqueous solution of N-(sulpho-hydroxy-propane)-phenyl-
aminomethane-diphosphonic acid is evaporated to dryness. The
residue is washed twice with methanol and dried. Yield: 73.9
grams.
Analysis: found: N: 3.6%, P: 15.1%, S: 7.7%
calculated: N: 3.46%, P: 15.29%, S: 7.91%
In a similar manner with 40 grams of 3-hydroxy-4-chloro-
butane-l-sulphonic acid, 71 grams of N-(sulpho-hydroxy-butane)-
phenyl~aminomethane-diphosphonic acid were obtained.
Analysis: found: N: 3.5~, P: 14.5%, S: 7~8
~ ca]culated: N: 3.34%, P: 14.78~, S: 7.65%
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