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LB 2003 Refrew 08 Ev
LB 2003 Refrew 08 Ev
49
Lenzinger Berichte, 82 (2003) 49-57
H H
HO3SOCH2CH2O2S N CH2=CHO2S N
N N
N Cl N Cl
N N
Cl Cl
1 2
Compound (1) exhibits very poor water mL/min; Temperature 40°C; injection volume
solubility and was sold and applied as an 10 µl; wavelength 254nm. The following
aqueous dispersion. During its application the gradient programme was used:
suspension was added to an aqueous bath at
60°C, containing fabric and Glauber’s salt min. %A %B
followed by the addition of alkali to give an
0 65 35
approximate pH of 11. These changes resulted
in the dispersion of compound (1) forming a 1 65 35
clear solution. However, it is well known [9] 20 45 55
that the application of both heat and alkali to a 25 20 80
compound containing a sulphatoethylsulphone 26 10 90
group will result in β-elimination of the
30 65 35
sulphato group. Such a process would result in
the loss of the water solubilising group of Stop time 35
compound (1) and convert the agent to the
vinylsulphone form (2). A priori, this would be
expected to be even less soluble than the parent HPLC Method B
compound. HPLC was performed with a Hewlett Packard
1100 series fitted with a quaternary pump.
Despite the loss of its only anionic group in The column was a 10 cm Purospher RP-18
alkaline medium, compound (1) dissolves (5µm) packing and a LiChrocart 125-4 HPLC
completely during application. This work was column cartridge; solvent A; acetonitrile;
undertaken to rationalise the technical success solvent B, water with 0.25% dicyclohexyl-
and mode of action of 2,4-dichloro–6-(β- ammonium phosphate; flow rate 2ml/min;
sulphatoethylsulphonyl)anilino-s-triazine (1) as temperature 40oC; injection volume 5µl;
a cross-linking agent. samples were analysed using a diode array
detector at a wavelength of 450 nm (BW
400nm). The following gradient programme
EXPERIMENTAL was used:
50
Lenzinger Berichte, 82 (2003) 49-57
Mass spectra were recorded with a Micromass HPLC (Method B) showed a complex mixture
Instruments LCT orthogonal time-of-flight with no starting material (tR 2.6 ) and a major
mass spectrometer fitted with a Z-Spray peak at tR 4.13.
electrospray ion source operating in negative
mode at 3Kv needle potential. Nitrogen was The solid gave a strong and instantaneous
used as a drying and sheath gas. Data was yellow coloration on treatment with pyridine
stored in the continuum mode on a Micromass and sodium hydroxide, indicative of the
Instruments MassLynx data station utilizing presence of a dichlorotriazinyl group [10].
Version 3.5 software pack. Infusion was at a
rate of 20µl/minute with a Harvard Instruments
syringe pump utilized for sample introduction. β-
Reaction of 2,4-dichloro–6-(β
Mixed phosphate buffer comprised potassium sulphatoethylsulphonyl)anilino-s-triazine (1)
dihydrogen phosphate (2 parts) and disodium with sodium carbonate solution
hydrogen phosphate (1 part).
A small sample of laboratory prepared [8] 2,4-
dichloro–6-(β-sulphatoethylsulphonyl)anilino-
β-
Reaction of 2,4-dichloro–6-(β s-triazine (1) was placed in a HPLC sample vial
sulphatoethylsulphonyl)anilino-s-triazine (1) and dissolved in aqueous acetonitrile. Five
with sodium hydroxide solution drops of sodium carbonate solution (2M) were
added and the sample analysed by HPLC
1. At room temperature (Method B; see Table 1)
A dispersion of commercially available 2,4-
dichloro–6-(β-sulphatoethyl-sulphonyl-anilino- Peak Retention Time % Area Assignment
s-triazine (1) (90 g/l) was stirred in a beaker. 1 0.50 2.27 -
Starting at pH 4.6, sodium hydroxide solution 2 0.68 5.85 -
(1M) was added dropwise. After initial 3 1.92 4.75 -
precipitation of a white solid, the suspension 4 2.53 12.50 Cibatex AE 4425
changed to an opalescent solution at pH 12.6 5 4.03 74.80 Compound (2)
and a clear stable solution at pH 12.8-12.9.
Table 1
(b) At 60°°C
A suspension of laboratory prepared 2,4-
β-
Synthesis of 4,6-bis-(p-β
dichloro–6-(β-sulphatoethylsulphonyl)anilino-
sulphatoethylsulphonyl)anilino-1,3,5-triazin-
s-triazine [8] (1) (2.5 g) in water (200 mL) was
2(1H)-one (9)
stirred at pH 6.8 at room temperature then
heated to 50°C . Sodium hydroxide solution
Cyanuric chloride (10g; 98%; 0.053 mol),
(2M) was added dropwise, with heating to give
dissolved in acetone (100mL), was added to
initially a white precipitate, then an opalescent
water (200 mL) to give a white suspension.
solution and finally a clear solution at pH 12.9
The suspension was stirred at 20°C, pH 7-7.4
and 60°C. The solution was stirred for 2
for 4 hours to give a clear solution which was
minutes at 60°C before the addition of dilute screened and allowed to stand overnight. The
hydrochloric acid solution (2M) to give a pH of
solution was then cooled to 1°C, and a pH 7.1,
6.8, resulting in the formation of a white
before the portion wise addition of solid p-
precipitate. Mixed phosphate buffer (1 g) and
aminophenyl-β-sulphatoethylsulphone
sodium chloride (20 g) were added and the
(PABSES; 15.6g, 95.5%; 0.053 mol.), keeping
white solid that formed was filtered off. To the
wet solid was added mixed phosphate buffer (1 the temperature at 1-2°C and pH at 3.0-4.5.
g) and resulting solid dried in an electric oven The reaction, which was followed by HPLC
(Method B), initially indicated the presence of
at 65°C.
only one new peak, at tR 1.20
(dichlorohydroxytriazine, tR 0.90, and
PABSES, tR 0.80). After 3 hours, and
51
Lenzinger Berichte, 82 (2003) 49-57
consumption of all the PABSES, HPLC maintaining the pH at 6.4-6.5 with 2M sodium
analysis showed the presence of two peaks at tR carbonate solution. The reaction was very
0.90 and 1.20, approximately in equal amounts. slow, as evidenced by HPLC and a falling pH.
A further addition of solid PABSES (15.6 g) Heating was maintained at 79-80ºC for 3 hours.
was made at 3°C, pH 4-4.5. The reaction During this period the reaction solution became
mixture was allowed to stir over the weekend to cloudy and HPLC showed a main peak (approx.
give, by HPLC analysis, 93% product and 7% 50%) at tR 1.03 (method B) but also the build
PABSES and a pH of 3.4. Potassium chloride up of impurities. The reaction was stopped and
(10% w/v) was added portion wise to give a allowed to stand overnight. Filtration of the
grey solid which was isolated by filtration, white solid (4.8 g) gave a gross mixture
washed with potassium chloride solution (15%) containing PABSES, NHDT, a new band at tR
and dried in an electric oven at 65°C for one 1.03, bis-condensation and six minor bands at
week to give the product (42.2 g). HPLC higher tR. A pure sample of the desired
analysis (Method B) gave a peak at tR 1.12 material was not obtained by selective salting
(100%) and mass spectral analysis showed ions of the filtrates.
at m/z 654 (M - H)- (78%), 574 (M-H-SO3)-
(5). There was also a doubly charged ion at 327
(M-2H)2- (100). Results and Discussion
β-
Attempted synthesis of 6-chloro-4-(p-β A prerequisite for effective cross-linking of
sulphatoethylsulphonyl)anilino-1,3,5-triazin- Lyocell with any agent is good substantivity for
2(1H)-one (8). the fibre. In turn, substantivity can only be
achieved through a solution state. Accordingly,
Cyanuric chloride (9.3 g; 99%; 0.05 mol) was the anticipated loss of solubility of compound
dissolved in acetone (100 mL) and the solution (1), by elimination of the water solubilising
poured into water (300 mL) containing mixed sulphato group seemed to run counter to
phosphate buffer (2 g). The suspension was expectations for good solubility and good
stirred at 25°C and a pH of 6-7 maintained by substantivity. One possible explanation for its
the addition of 2M sodium hydroxide solution. mode of action is that, following the
After 1 hour a faintly turbid solution was given elimination reaction to the corresponding
which was filtered through filter aid to give a vinylsulphone (2), the more reactive
clear solution. The solution was allowed to dichlorotriazinyl group hydrolyses to the
stand for a further 2 hours at pH 6-7, then potentially more alkali soluble
mixed phosphate buffer (5 g) was added. chlorohydroxytriazine, (3; Scheme 1).
Chlorohydroxytriazines are tautomeric and
ρ-Aminophenyl-β- sulphatoethylsulphone depending on pH compound (3) can exist also
(PABSES; 14.7; 95.5%; 0.05 mol) was as 4-chloro-6-(p-vinylsulphonyl)anilino-1, 3,
suspended in water (200 mL) and mixed 5-triazin-2(1H)-one.
phosphate buffer (1 g) was added. The
suspension was cooled to 10ºC and 2M sodium This potentially more soluble derivative (3)
hydroxide added with stirring to give pH 3. might then be regarded as the effective cross-
Finally 2M sodium carbonate solution was linking agent.
added to give pH 5.6, and a brown solution, at a
temperature of 13 ºC. Chlorohydroxytriazines are weakly acidic and
readily form sodium salts, e.g. compound (4)
The PABSES solution was added to the exists as the anion in neutral solution and 2-(N-
solution of sodium dichlorohydroxytriazine methylpyrrol-2-yl)-4-chloro-6-hydroxytriazine
(NHDT) and heating commenced until a (5) has a pKa of 5.2 [11].
temperature of 75-80ºC was reached while
52
Lenzinger Berichte, 82 (2003) 49-57
OH−
Cl
heat N
Cibatex AE 4425
CH− O2S NH N
||
N
CH2 Cl
2
OH−
O
OH
N
N
CH − O2S NH NH
CH − O2S NH N ||
|| CH2 N
CH2 N Cl
Cl
3
Scheme 1
OH OH
N N
N
Cl N N
N
N Cl
Cl CH3
4 5
While the hydroxyl group on the triazine ring in dichlorohydroxytriazine (4) is an effective
structure (3) would be expected to improve cross-linking agent for Lyocell in the presence
prospects for alkali solubility, it would also have of alkali [12]. However, in this case the mono
a deactivating effect on the remaining chlorine reacted species (7), containing an alkoxy
atom on the triazine ring. Indeed dyes of substituent attached to the triazine ring, is more
general structure (6; R = a chromophore residue) susceptible to nucleophilic attack by
do not readily react with cotton in the presence cellulosate anions than compounds of type (7;
of alkali. On the other hand R = a chromophore residue).
OH
OH
N
N
RNH N Cellulose O N
N N
Cl Cl
6 7
53
Lenzinger Berichte, 82 (2003) 49-57
In an attempt to resolve the efficiency of remaining chlorine atoms and the product was
compound (3) (or its masked sulphato precursor the bis-arylaminotriazine (9). This is in
(8) as a cross-linking agent for Lyocell, its keeping with the previously observed [11] pH
synthesis via dichlorohydroxytriazine was dependency of the relative rates of
attempted (see Scheme 2). displacement of the first and second chlorine
atoms of 2-substituted dichloro-s-triazines. In
Cyanuric chloride was initially converted to its acidic media k2 > k1 (Scheme 3).
monohydroxy derivative (4), which, in turn,
was reacted with ρ-aminophenyl-β- In an attempt to reduce the role played by
sulphatoethylsulphone (PABSES). When this protonation, this reaction was run at pH 6.4-6.5
reaction was conducted at pH 3-4.5 and at 0- (a greater pH was desirable but could not be
2ºC, it was not possible to isolate, nor indeed used for fear of eliminating the sulphato group).
detect, a stepwise substitution of the two
H
N N Cl N O
Cl Cl Cl OH
N N
N N N N
hydrolysis
Cl
Cl Cl
4a 4b
pH 3-4.5 pH 6.4-6.5
T = 0-2°C T = 80°C
OH
N
8 + 9 + eliminated + self
NaO3SOCH2CH2O2S NH N condensed products.
8 N
Cl
OH
N N
9 Scheme 2
However under these conditions relative high experimental) but a gross mixture resulted and
temperatures were necessary (80ºC) to induce the desired product could not be isolated
the reaction to take place. In this case a cleanly.
stepwise substitution appeared to occur (see
54
Lenzinger Berichte, 82 (2003) 49-57
Cl N Cl H
Cl N OH Cl N+ OH
k1
N N
N N N N
k2
R
R R
HO N OH
N N
Scheme 3
the sodium salt at pH 6-7 and would be expected to show some water solubility.
Accordingly, the solubility of compound (1) attached to the dichlorotriazinyl group (Scheme
under alkaline conditions is explained in terms 4), and not as a result of initial formation of a
of the abstraction of the weakly acidic chlorohydroxytriazine derivative.
hydrogen atom from the arylamino group
Cl
Cl
N
H N
CH2 − O2S NH N OH−
| CH2=CHO2S N N
CH2OSO3Na N
Cl insoluble N
Cl
poorly soluble
H+ OH-
Cl
−
N
CH2=CHO2S N N
Na+
N
Cl
soluble
Scheme 4
This scheme is strongly supported by the work sulphonyl group, would be expected to be more
of Horrobin and others [13,14], who showed acidic. Accordingly, both experimental and
that arylaminodichlorotriazines, devoid of literature evidence support the view that the
water solubilising groups are soluble in dilute two reactive groups responsible for the cross-
sodium hydroxide solution. That this was due linking of Lyocell with Cibatex AE 4425 are
to acidity and not a chemical reaction was vinylsulphone and dichlorotriazine.
confirmed by measurement of the dissociation
constants of water soluble derivatives, e.g.
dichloro-p-sulphoanilino-s-triazine has a pKa =
10.5 at 25°C. Compound (2), which has a p-
56
Lenzinger Berichte, 82 (2003) 49-57
57