Notes
J . Org. Chem., Vol. 62, No. 3, 1997 751
recorded on a FT-IR Nicolet 320 spectrometer with self-sup-
ported wafer of the solids outgassed under vacuum.
P r ep a r a tion of Mesop or ou s MCM-41 Typ e Silica MTS
Ch a r a cter istics of 5. IR: 3650, 3375, 3306, 2960 (intense),
-1
13
2935, 2868, 1974, 1866 cm
.
3 3
C CP-MAS-NMR δ (ppm) (CH ) -
R
â
γ
Si: 0.2 (intense signal); C 8.9; C 26.4; C 43.3. Anal. C, 9.79;
1
.
MTS-silica 1 was prepared by addition of Zeosil 175 MP
N, 1.98; Si, 36.89. Thermogravimetry: % organic weight/dry
2
-1
precipitated silica (Rh oˆ ne-Poulenc, 0.17 weight % Al) (21 g, 0.34
mol) to a stirred solution of cetyltrimethylammonium bromide
mineral weight: 12.5. Surface area: 516 m g ; mesoporous
-
1
volume: 0.32 mL g
.
(
Aldrich) (11 g, 0.034 mol) and sodium hydroxide (4 g, 0.1 mol)
Ch a r a cter istics of 6. IR: 3655, 2960, 2941, 2862, 2803,
-
1
13
in deionized water (200 mL). The reagents were mixed under
stirring at 343 K and then heated in a stirred autoclave at 393
K for 16 h. After filtration and washing with deionized water
to pH 9 and then with ethanol, the solid phase was dried at 353
K in air. The occluded organic template was decomposed by
calcination at 823 K in flowing air for 7 h.
1974, 1866 cm
.
3 3
C CP-MAS-NMR δ (ppm) (CH ) Si: 0.3
(intense signal); 10; 23.8; 40-70 (broad signal). Anal. C, 13.32;
N, 1.36; Cl, 1.02; Si, 37.08. Thermogravimetry: % organic
weight/dry mineral weight: 18.1. Surface area: 515 m
mesoporous volume: 0.26 mL g
2
-1
g ;
-
1
.
Ad sor p tion of Glycid ol on Sila n ol Gr ou p s of MTS 1. The
MTS 1 sample was analyzed after adsorption of glycidol followed
X-ray powder diffraction patterns matched well with those
1
3
by washing with ether-CH Cl2 and vacuum evacuation. IR:
reported for the monodispersed mesoporous system with d100
)
Å.
2
-
1
40.0 Å. The hexagonal lattice parameter was equal to 46.2
3500 (broad), 2920, 2875, 1974, 1866 cm . No signal at 3742
-
1
cm
.
Thermogravimetry: % organic weight/dry mineral
weight: 60.
The nitrogen sorption isotherm of MTS is a type IV isotherm,
An a lysis of th e Oligom er ic Solid Obta in ed d u r in g th e
Rea ction of Glycid ol Solu tion on Solid 3. After dissolution
in methanol, filtration of the functionalized silica, and elimina-
tion of the solvent, the solid was analyzed by GPC using
dimethylacetamide as liquid phase. The estimated mass average
showing monolayer and multilayer adsorptions on a very high
area mesoporous surface and a sharp, reversible step at P/P
0
0
.38 characteristic of capillary condensation within a regular
1
3
mesoporous system.
mesoporous volume Vol
The BET surface area (S
m
) and the
2
-1
-1
m
are 941 m
g
and 0.73 mL g ,
(M
w
) and number average (M
n
) molecular weights are 1500 and
respectively. The average pore diameter d of the mesoporous
/S was equal to
8
00, respectively, with poly(methyl methacrylate) (PMMA) used
channels estimated by the relation d ) 4Vol
m
m
1
3
as a standard. C NMR (CDCl
63.4; CH O, 71.0, 71.6, 72.9; CHOH, 69.6, 70,0, 71.2; CHO, 78.7,
3 2
) δ (ppm): CH OH, 61.5, 61.8,
3
1 Å. Composition: Al/(Al + Si): 0.003; Na/(Al + Si): 0.0014.
-
1 14
IR: 3742, 3536, 1974, 1866 cm
.
2
7
9.3, 80.2, 81.9. Anal. Calcd C, 48.64; H, 8.10; O, 43.24.
F u n ct ion a liza t ion P r oced u r e. (3-Am in op r op yl)silyl-
MTS 2 a n d 3-ch lor op r op ylsilyl-MTS 3. 2 and 3 were
prepared by addition of the 3-amino- and and (3-chloropropyl)-
trialkoxysilane (3 g) to a suspension of freshly activated MTS
silica (3 g) in refluxing toluene (50 mL) and then stirred for 1.5
h. After distillation of a toluene fraction containing ethanol, the
heating and distillation sequences were repeated two times. The
modified solid was filtered, washed in a Soxhlet apparatus with
diethyl ether and dichloromethane, and then dried at 393 K.
Ch a r a cter istics of 2. IR: 3732, 3650,3375,3306, 2979,2936,
Found: C, 47.78; H, 8.61; O, 43.66.
Gen er a l P r oced u r e for th e Ca ta lyzed Ad d ition of La u -
r ic Acid to Glycid ol. The reactions were performed in a glass
flask under vigorous stirring. A 2 g (0.01 mmol) amount of lauric
acid were added to a suspension of 1 g of solid catalyst in toluene
(25 mL). A 750 mg (0.01 mmol) amount of glycidol were added
when the temperature of the reaction mixture reached 393 K.
The reaction mixture sample was analyzed after filtration using
GC-MS (Hewlett Packard, GC series 5890, MS series 5970,
Chem Station, windows series G 1034 C; column CP Sil-5CB
(Chrompack), 25 m × 0.25 mm, gas: He) and GC (Delsi 30; FID,
-
1
13
R
â
γ
2
2
CH
867, 1974, 1836 cm
.
C CP-MAS-NMR δ (ppm) Si CH
2
CH
-
R
â
γ
2
NH
2
:
C 8.9; C 26.4; C 43.3. Anal. C, 6.90; N, 2.36; Si,
column Optima 1 (Macherey-Nagel), 25 m × 0.25 mm, gas: H
2
)
3
1
g
9.69. Thermogravimetry: % organic weight/dry mineral weight:
2
-1
using dodecane as internal standard.
2.0. Surface area: 693 m
g
; mesoporous volume: 0.45 mL
-
1
Selective P r ep a r a tion of Mon ola u r ic Glycer id e. After
two runs, the catalyst 6 was washed with toluene and methanol
and then evacuated at 423 K under vacuum. Lauric acid (2.32
g, 0.012 mol) and glycidol (1.12 g, 0.015 mol) were added to a
stirred suspension of 6 (290 mg) in toluene (29 mL) heated at
293 K during 24 h. After separation of the solid by filtration,
the solvent was distilled and the crude solid (3.15 g) was
recrystallized in hexane. The pure lauric glyceride (2.25 g) was
.
Ch a r a cter istics of 3. IR: 3732, 3650, 2970, 2940, 1974,
-
1
13
R
â
1
CH
836 cm
.
C CP-MAS-NMR δ (ppm) Si (OCH
2
CH
3
) CH
2
-
γ
R
â
γ
2
CH
2
Cl: OCH
2
CH
3
58.7; OCH
2
CH
3
16.3; C 8.9; C 26.3; C
4
6.3. Anal. C, 7.22; Cl, 5.23; Si, 38.43. Thermogravimetry: %
2
organic weight/dry mineral weight: 12.9. Surface area: 872 m
g
-
1
; mesoporous volume: 0.53 mL g-1
.
(
3-P ip er id in op r op yl)silyl-MTS 4. A suspension of acti-
3
obtained in 69% yield. IR (CHCl ): 3580, 3450, 2928, 2855, 1730
vated 3 (3 g) in toluene (30 L) was refluxed and stirred in an
excess of piperidine (1 g) for 6 h. The modified solid was then
washed with water and then extracted with diethyl ether-
-
1
γ
â
R
1
2
3
cm . NMR (CDCl
3
): CH
2
(OH) CH(OH) CHO C(O) CH
2
CH
2
-
2
1
2
1
12
3
(
1
CH
2
)
8
CH
2
3
.
H NMR δ (ppm): CH
2.35; CH 3.65; CH 3.95; CH
3
R
0.88; (CH
2
)
8
1.26; CH
2
γ
â
13
.65; CH
2
4.18.
C NMR δ
dichloromethane mixture in a Soxhlet apparatus overnight. IR:
(ppm): 12CH
14; (CH
)
8
3
2
γ
731, 3649, 2945, 2892, 2867, 2818, 1974, 1866 cm- . Anal. C,
1
3
2
2 2 2
22.5-29.5; CH 31.8; CH 34; CH
3
R
â
1
6
3.2; CH
2
65; CH 70; C(O) 174. MS m/e 257, M - OH; 243,
OH; 214, M - C ; 201, M - C ; 183, M -
; 134, M - C10 20; 98, M - C ; 74, M - C12
. Anal. Calcd: C, 65.69; H, 10.95; O, 23.36. Found:
C, 65.78; H, 11.09; O, 23.55.
1
0.89; N, 1.45; Cl, 1.73; Si, 34.60. Thermogravimetry: % organic
weight/dry mineral weight: 18.1. Surface area: 733 m2
-1
M - CH
2
2
H
4
O
2
3 5 2
H O
g
;
-
1
C
3
H
7
O
3
H
9
H
20
O
3
24 2
H O ;
mesoporous volume: 0.43 mL g
.
4
3 7
3, C H
Tr im eth ylsilyla tion of 2 a n d 4 Solid s w ith Hexa m eth -
yld isila za n e (HMDS). The silylation procedure was a CVD
P r ep a r a tion of Un d ecylen ic Mon oglycer id e. The crude
solid (2 g) obtained during entry 10 and according to the same
procedure used previously produced recrystallized undecylenic
monoglyceride (1.5 g) in 56% yield. IR: 3570, 3420, 2930, 2855,
1
5
method using dynamic vacuum. The sample 2 or 3 (2 g) was
laid on a glass scinter inside a vertical glass tube heated with
an electric furnace. The solid was evacuated at 453 K for 2 h
-
1
under reduced pressure (10 Torr). The organic silane vapor
HMDS) was then admitted through the heated solid under
-
1
γ
â
R
1
2
1
733 cm
.
NMR δ (CDCl
3
): CH
.
2
(OH) CH(OH) CHO C(O) -
1.27-1.59;
(
3
10
11
1
CH
2
CH
2
2
(CH
2; CH
2
)
6
CHd CH
2
H NMR (ppm) (CH
2
)
6
dynamic vacuum (1 Torr) by means of a heated connection with
the reservoir containing the liquid silylating agent (6 g) heated
at 308 K. After all the silazane compound was consumed (4 h),
3
γ
â
R
10
CH
2
2
2.31; CH 3.70; CH 3.87; CH
2
4.10;. CH 5.78;
1
1
13
3
2
CH
4; CH
2
4.95. C NMR δ (ppm): (CH
2
)
6
24-29.1; CH
2
33.6; CH
2
γ
R
â
11
10
1
3
1
6
2
63.3; CH
2
64.9; CH 70.1; CH
2
114; CH 139; C(O)
-
2
the solid was reevacuated (10 Torr) for 1 h.
74.2. Anal. Calcd: C, 65.11; H, 10.08; O, 24.81. Found: C,
4.66; H, 9.13; O, 24.48.
(13) (a) Beck, J . S.; Vartuli, J . C.; Roth, W. J .; Leonowicz, M. E.;
Kresge, C. T.; Schmitt, K. D.; Chu, C. T.-W.; Olson, D. H.; Sheppard,
E. W.; McCullen, S. B.; Higgins, J . B.; Schlenker, J . L. J . Am. Chem.
Soc. 1992, 114, 10834. (b) Chen, C.-Y.; Li, H.-X.; Davis, M. E.
Microporous Mater. 1993, 2, 17. (c) Ortlan, A.; Rathousky, J .; Schulz,
G.; Zukal, A. Microporous mater. 1996, 2, 117.
Ack n ow led gm en t. The authors thank Annie Finiels
1
13
for the H and C NMR measurements in CDCl3
solution. They are grateful to Francesco Di Renzo for
fruitful discussions on the characterization of the solid
materials. One of us (A.C.) is indebted to Ademe for a
postgraduate grant.
(14) Characterization and chemical modification of the silica surface;
Vansant, E. F., Van Der Voort, P., Vrancken, K. C., Eds.; Elsevier:
New York. Stud. Surf. Sci. Catal. 1995, 93, 65.
(15) Chamoumi, M.; Brunel, D.; Fajula, F.; Geneste, P.; Moreau, P.;
Solofo, J . Zeolites 1994, 14, 282.
J O9614001