dichloromethane (2 × 50 ml). The organic fractions were com-
bined and the solvent was removed to leave a viscous yellow oil.
The product was purified via silica gel chromatography (the
eluent being 9:1, EtOAc–n-hexane) yielding diol 9 as a colour-
less viscous oil (7.65 g, 76%), which was identical to that
added in small portions in benzene over 45 minutes whilst azeo-
tropically removing water. The distillation apparatus was then
removed and replaced by a reflux condenser so that refluxing
could continue overnight. The benzene was then removed and
replaced by a mixture of water (5 ml) and dichloromethane (5
ml) the latter of which was removed and the water layer was
washed again with dichloromethane (5 ml). The organic frac-
tions were pooled and the solvent removed to leave colourless
16
reported in the literature.
Preparation of dimesylate 10
Ϫ1
oil 7d (52 mg, 37%): νmax(thin film)/cm inter alia 1039 (P–O-
Diol 9 (2.00 g, 5.76 mmol) and triethylamine (7.00 g, 69.19
mmol) were dissolved in dichloromethane (60 ml) and stirred.
To this solution methanesulfonyl chloride (1.78 g, 15.56 mmol)
was added dropwise over a period of about 10 minutes. The
reaction mixture was allowed to stir for 2 hours after which time
TLC (8:2, EtOAc–n-hexane) indicated that the reaction had
gone to completion. The reaction mixture was then washed
with 1 M HCl (100 ml), and the organic layer was removed and
the solvent removed under reduced pressure. The resulting
viscous oil was purified via column chromatography using the
above solvent system yielding 10 as a pale yellow oil (2.32 g,
alkyl), 1226 (P᎐O); δ (200 MHz; CDCl ) 1.31 (18H, t, J 7.1,
᎐
H
3
6
3
6
× CH ), 2.93 (12H, t, J 5.7, 6 × NCH CH ), 3.00 (6H, d, J 9.5,
3
2
2
× PCH ), 3.53 (12H, t, J 5.7, 6 × OCH CH ), 4.12 (12H, m,
2
2
2
× CH CH ); δ (75.5 MHz; CDCl ) 16.37 (6 × CH ), 50.54 (d,
2
3
C
3
3
J 158.9, 3 × CH P), 55.16 (6 × NCH CH ), 61.76 (2 × OCH -
2
2
2
2
CH ), 69.44 (2 × POCH ); m/z (FAB)ϩ inter alia 298
2
2
ϩ
(
(
M Ϫ 3PO(OEt) ) , 436 (M Ϫ 2PO(OEt) ) , 574 (M Ϫ PO-
2 2
ϩ ϩ ϩ
OEt) ) , 712 (M ϩ H) , 734 (M ϩ Na) [Found: M, 712.3477.
Calc. for C H N O P , M: 712.3468].
2
ϩ
3
27
61
3
12
Preparation of cyclic triphosphonic acid 2b
27
8
0%), which was identical to that reported in the literature.
Cyclic triamine 5 (1.00 g, 1.98 mmol) and phosphorous acid
(
0.49 g, 5.95 mmol) were dissolved in a mixture of concentrated
Preparation of cyclic tritosylamide 7a
HCl (5 ml) and water (5 ml) and stirred. The mixture was then
heated to reflux (~115 ЊC) and paraformaldehyde (0.36 g, 11.90
mmol) was then added in small portions over 45 minutes. After
this was added, refluxing continued for a further 48 hours at
which point the reaction mixture was cooled and the solvent
removed. On adding ethanol (30 ml) with swirling, a white
precipitate formed which could be separated from the liquid
via centrifugation. The white solid was then dried in vacuo to
Ditosylamide 11 (4.92 g, 11.93 mmol) and dimesylate 10 (6.00
g, 11.93 mmol) were added to a suspension of caesium carbon-
ate (15.55 g, 47.72 mmol) in N,N-dimethylformamide (300 ml).
The reaction was heated to 100 ЊC and stirred for 20 hours, after
which the N,N-dimethylformamide was removed under reduced
pressure, and to the remaining slurry dichloromethane (100 ml)
was added. The milky mixture was then filtered through Celite
which was subsequently washed with dichloromethane (50 ml),
the organic fractions were pooled and the solvent was removed
under reduced pressure. To the resulting syrup, methanol
Ϫ1
yield the tri-HCl salt of 2b (0.75 g, 58%): νmax(KBr)/cm inter
alia 1135 (P᎐O); δ (200 MHz; D O) 3.54 (6H, d, J 12.5, 3 ×
᎐
H
2
PCH ), 3.68–3.85 (12H, m, 6 × NCH CH ), 3.96–4.10 (12H, m,
2
2
2
(
200 ml) was added to induce precipitation of the product
6
× OCH CH ); δ (75.5 MHz; D O) 49.80 (d, J 139.0, 3 ×
2 2 C 2
which was then filtered and washed with methanol (100 ml)
PCH ), 55.54 (6 × NCH CH ), 64.82 (6 × OCH ); δ (81 MHz;
2
2
2
2
P
16
leaving 7a as a white crystalline solid (6.40 g, 74%); mp 130–
ϩ
D O) 8.55 (3 × P); m/z (FAB) inter alia 544 (M ϩ H) , 562
M ϩ H O) [Found: M, 544.1581. Calc. for C H N O P ,
2
Ϫ3
Ϫ1
Ϫ1
1
(
32 ЊC; λmax/nm (ε/dm mol cm ) 205.1 (26209), 231.0
ϩ
(
2 15 37 3 12 3
Ϫ1
27613); νmax/(KBr)/cm inter alia 1330 (asym SO ), 1155 (sym
2
M: 544.1590].
SO ); δ (300 MHz; CDCl ) 2.41 (9H, s, 3 × CH ), 3.31 (12H, t,
2
H
3
3
Solutions of sodium salt 2a were prepared prior to use by
direct neutralisation of an aqueous solution of acid derivative.
J 5.8, 6 × NCH ), 3.55 (12H, t, J 5.8, 6 × OCH ), 7.29 (6H, d,
2
2
J 8.1, 6 × CH CCH), 7.66 (6H, d, J 8.1, 6 × SO CCH); δ (75.5
3
2
C
MHz; CDCl ) 21.42 (3 × CH ), 49.52 (6 × NCH ), 70.61
3
3
2
Preparation of ettringite
(
6 × OCH ), 126.96 (12 × CH CCH), 129.68 (12 × SO CCH),
2
3
2
A stirring slurry of calcium hydroxide (0.50 g, 6.75 mmol) in
water (40 ml) was heated to 70 ЊC in a jacketed vessel, to which
a solution of aluminium hydroxide (0.71 g, 1.13 mmol) in water
1
36.40 (3 × CH C), 143.37 (3 × SO C); m/z (FAB) inter alia 414
3 2
ϩ ϩ ϩ
(
M Ϫ 2 × ArSO ϩ H) , 568 (M Ϫ ArSO ) , 724 (M ϩ H)
2 2
ϩ
[Found: M, 724.2404. Calc. for C H N O S , M: 724.2459].
33 45 3 9 3
(
60 ml), also at 70 ЊC, was added in under 5 seconds. The result-
ing mixture was then allowed to stir for 30 minutes after which
time the mixture was centrifuged and the mother liquors
removed. The resulting amorphous material was then washed
three times with distilled water (40 ml), after each wash the
water was removed after centrifugation. The product was then
dried in vacuo leaving pure ettringite. In experiments where
ettringite was grown in the presence of the additives, these were
dissolved in the aluminium sulfate solution, in a known con-
centration, prior to the mixing with the calcium hydroxide
solution. All other experimental details were identical to that
when preparing pure ettringite. The ettringite crystals were
then mounted on 2.5 cm circular stubs, using ethanol which was
then allowed to evaporate, before observation under a scanning
electron microscope with fitted camera.
Preparation of cyclic triamine 5
Cyclic tritosylamide 7a (9.71 g, 13.40 mmol) and phenol (11.38
g, 0.12 mol) were dissolved in 33% HBr/AcOH (400 ml) and
stirred. The reaction mixture was then heated to 80 ЊC and left
for 60 h. After this time the reaction was cooled and the solvent
was removed to a volume of 20 ml, when 100 ml acetone was
then added to precipitate the HBr salt of 6. This was then fil-
tered, washed with acetone (3 × 50 ml) and dried under vacuum
to yield the tri-HBr salt of triamine 5 (5.75 g, 85%). This could
be easily neutralised to its basic form by dissolving it in water
and adding portions of anionic exchange resin (IRA 400) until
the pH of the solution remained constant. The water was then
removed to yield a white solid which was recrystallised from
hexane to form triamine 5 as long white crystals and which was
28
24
identical to that reported in the literature: mp 134–136 ЊC
Preparation of cement
10
(
lit. 135–136 ЊC).
To class G cement (80 g), water (35.2 ml) was added with vigor-
ous stirring. The slurry was allowed to stir for 20 seconds and
then transferred to a calorimeter cell noting the exact weight of
the slurry used. The cell was then sealed and placed in a calor-
imeter which measured the heat given out over a period of
time, and left for 24 hours during monitoring. In experiments
in the presence of the additives, these were added to the
Preparation of cyclic triphosphonic ester 7d
Cyclic triamine 5 (0.10 g, 0.20 mmol), diethyl phosphite (0.08
ml, 0.70 mmol) and triethylamine (0.17 ml, 1.19 mmol) were
dissolved in benzene (5 ml) which was then heated to reflux and
left for 10 min. Then paraformaldehyde (27 mg, 0.90 mmol) was
1
980
J. Chem. Soc., Perkin Trans. 2, 1999, 1973–1981