RSC Advances
Page 8 of 9
ARTICLE
DOI: 10.1039/C4RA14793F
vacuo. The crude oil was dissolved in dichloromethane and The resulting mixture was stirred for 1 hour at room
extracted with water (2 x 30 mL). The organic phase was dried temperature, then addition of water resulted in the precipitation
with anhydrous CaCl2 and evaporated under reduced pressure of a white powder. The solid was recovered by suction filtration
1
to give the product as colorless oil (0.4 g, 2.15 mmol, 48%). H to give pure
4
(0.45 g, 0.33 mmol, 92%). 1H NMR (CDCl3, 400
NMR (CDCl3, 400 MHz): δ (ppm) = 9.56 (s, 1H, OH), 3.87 (d, MHz): δ (ppm) = 8.15ꢀ8.01 (m, 8H, P(O)ArHo), 7.72ꢀ7.61 (m,
J=33.4 Hz, 2H, NCH2), 2.83 (s, 3H, NCH3), 1.34 (s, 9H, 4H, P(O)ArHp), 7.61ꢀ7.47 (m, 8H, P(O)ArHm), 7.24ꢀ7.13 (m,
C(CH3)3); ESIꢀMS: m/z 190.1 [M+H]+.
4H, ArH), 4.85ꢀ4.72 (m, 4H, ArCH), 4.35ꢀ4.24 (m, 2H,
CH2OC(O)), 3.97 (d, J=36 Hz, 2H, NCH2), 2.90 (s, 3H, NCH3),
2.44ꢀ2.21 (m, 8H, CH2CH2CH3, CH2CH2CH2OC(O)), 2.14 (s,
N-Boc-sarcosine based silyl-cavitand (2)
NꢀBocꢀsarcosine (0.31 g, 1.68 mmol), DCC (0.34 g, 1.68 12H, ArCH3), 1.82ꢀ1.69 (m, 2H, CH2CH2OC(O)), 1.50ꢀ1.21
mmol) and DMAP (0.2 g, 1.68 mmol) were dissolved in dry (m, 15H, C(CH3)3, CH2CH2CH3), 1.12ꢀ0.98 (m, 9H,
1
chloroform under stirring for 15 minutes. Successively, CH2CH2CH3); 31P H NMR (CDCl3, 161.9 MHz): δ (ppm) =
monohydroxy footed silylcavitand
1 (0.8 g, 0.83 mmol) was 8.44 (s, 1P, P=O) 8.34 (s, 3P, P=O); HRꢀESIꢀMS: m/z calcd.
added into the reaction mixture and stirred overnight at room for C76H81NO16P4Na: 1410.4403; found: 1410.4398.
temperature. Saturated NH4Cl solution was added and the
Tiiii[3C3H7, 1 sarcosine salt, CH3, Ph] (5)
organic phase was extracted with water (2 x 20 mL) dried with
anhydrous Na2SO4, filtered and the solvent was removed in Cavitand
4 (20 mg, 0.014 mmol) was treated with 10 equivalent
vacuo. Purification by silica gel column chromatography of trifluoroacetic acid in CHCl3. After 3 hours the solvent was
(hexane:ethyl acetate 85:15) yielded the desired product as removed in vacuo and the crude was dried under reduced
1
1
white solid (0.37 g, 0.33 mmol, 40%). H NMR (CDCl3, 300 pressure (quantitative yield). H NMR (CDCl3, 400 MHz): δ
MHz): δ (ppm) = 7.20 (s, 2H, ArH), 7.18 (s, 2H, ArH), 4.64 (t, (ppm) = 8.17ꢀ7.96 (m, 8H, P(O)ArHo), 7.89ꢀ7.42 (m, 16H,
3J=8 Hz, 4H, ArCH), 4.28ꢀ4.20 (m, 2H, CH2OC(O)), 3.96 (d, P(O)ArHp, P(O)ArHm, ArH), 4.85ꢀ4.61 (m, 4H, ArCH), 4.25 (s,
J= 40 Hz, 2H, NCH2), 2.85 (d, J=10.3 Hz, 3H, NCH3), 2.27ꢀ 2H, CH2OC(O)), 3.30 (s, 2H, NCH2), 2.66ꢀ2.30 (m, 8H,
2.01 (m, 10H, CH2CH2CH2OC(O), CH2CH2CH3), 1.85 (s, 12H, CH2CH2CH3, CH2CH2CH2OC(O)), 2.14 (s, 12H, ArCH3), 1.79ꢀ
ArCH3); 1.67ꢀ1.14 (m, 17H, CH2CH2OC(O), C(CH3)3, 1.59 (m, 2H, CH2CH2OC(O)), 1.51ꢀ1.20 (m, 8H, CH2CH2CH3),
1
CH2CH2CH3), 0.98ꢀ0.82 (m, 9H, CH2CH2CH3), 0.54 (s, 12H, 1.16ꢀ0.81 (m, 9H, CH2CH2CH3), ꢀ0.68 (s, 3H, NCH3); 31P H
SiCH3,out), ꢀ0.64 (s, 12H, SiCH3,in); ESIꢀMS: m/z 1164.1 NMR (CDCl3, 161.9 MHz): δ (ppm) = 11.01 (s, P=O); MALDI
[M+K]+.
TOFꢀTOF: calcd. for C71H74NO14P4 1288.4054 Da, found:
1288.3879 Da.
N-Boc-sarcosine based resorcinarene (3)
Acknowledgements
To a solution of NꢀBocꢀsarcosine based silylꢀcavitand 2 (0.39 g,
We thank the Centro Interfacoltà di Misure “G. Casnati” of the
University of Parma for the use of AFM, MS and NMR
facilities. D. M. thanks the EU through FP7 Project DIRAC
(SECꢀ2009ꢀ242309) for partial support of his scholarship. F.R.
acknowledges financial support from project PRAT
CPDA132473/13 granted by Università degli Studi di Padova.
0.34 mmol) in dry THF, TBAF (1.36 g; 5.2 mmol) was added
under argon atmosphere at 0 °C. After 1 hour the reaction
mixture was quenched by adding saturated NH4Cl solution, the
crude mixture was diluted with ethyl acetate and the organic
phase was extracted with sat. aq. NaHCO3 and water. The
organic phase was dried with anhydrous Na2SO4 and the
solvent removed in vacuo. Purification by silica gel column
chromatography (hexane:ethyl acetate 1:1) afforded the pure
Notes and references
1
a Dipartimento di Chimica and INSTM, UdR Parma, Università di Parma,
Viale delle Scienze 17/A, 43124 Parma, Italy. Eꢀmail:
product as yellow pale solid (0.18 g, 0.2 mmol, 60%). H NMR
((CD3)2CO, 300 MHz): δ (ppm) = 7.84 (s, 2H, OH), 7.46 (s,
3
2H, ArH), 7.44 (s, 2H, ArH), 4.41 (t, J=9 Hz, 4H, ArCH),
b Dipartimento di Chimica “G. Ciamician” and INSTM, UdR Bologna,
Università di Bologna, Via Selmi 2, 40126 Bologna, Italy.
c Dipartimento di Scienze Chimiche, Università degli Studi di Padova,
Via Marzolo 1, 35131 Padova, Italy.
4.24ꢀ4.11 (m, 2H, CH2OC(O)), 3.97 (d, J=14.5 Hz, 2H, NCH2),
2.91 (d, J=9 Hz, 3H, NCH3), 2.45ꢀ2.00 (m, 20H,
CH2CH2CH2OC(O), CH2CH2CH3, ArCH3), 1.71ꢀ1.55 (m, 2H,
CH2CH2OC(O)), 1.50ꢀ1.18 (m, 15H, C(CH3)3, CH2CH2CH3),
0.95 (t, 3J=9 Hz, 9H, CH2CH2CH3); ESIꢀMS: m/z 922.8
[M+Na]+, 939 [M+K]+.
d Dipartimento di Fisica, Università di Parma, Viale delle Scienze 7/A,
43124 Parma, Italy.
e Dipartimento di Chimica e Chimica Industriale and INSTM, UdR
Pisa,Università di Pisa, Via Giuseppe Moruzzi, 3, 56124 Pisa, Italy.
† Electronic Supplementary Information (ESI) available: Homopolymer
Tiiii [3 C3H7, 1 Boc-sarcosine, CH3, Ph] (4)
To a solution of
0.21 mmol)
N
ꢀBocꢀsarcosine based resorcinarene
3
(0.19 g,
characterization, ITC of hostꢀguest complex,
experimental and
in freshly distilled
pyridine,
characterization details of PBMAꢀSarc, DSC and NMR analyses of PSꢀ
Host/PBMAꢀSarc blend. See DOI: 10.1039/b000000x/
dichlorophenylphosphine (0.13 mL, 0.88 mmol) was slowly
added at room temperature under argon atmosphere. After 3
hours of stirring at 75 °C, the solution was allowed to cool at
room temperature and aqueous H2O2 (2 mL, 30%) was added.
‡ Sarcosine methyl ester hydrochloride is soluble in methanol, not soluble
in dichloromethane, chloroform or 1,1,2,2ꢀtetrachloroethane.
8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012