Beruflich Dokumente
Kultur Dokumente
6 (2007) 461
Full Papers
Received: January 23, 2007, revised version: May 17, 2007; Ms 2007/102
DOI: 10.1002/prep.200700050
CDCl3 or DMSO-d6 as a solvent. IR spectra were recorded heats of formation for the azidoesters in gaseous state
0
on a Perkin-Elmer FT-IR 1605 spectrophotometer either as (Df HðgÞ ) were theoretically predicted by group additivity
neat sample or in KBr pellet. Elemental analyses were method [7]. The azido groupKs contribution to the overall
0
carried out on a Perkin-Elmer Elemental Analyzer EA- Df HðgÞ was extracted from the reported thermochemical
1110. measurements [8]. The sensitivity to impact was determined
Differential scanning calorimetry (DSC) studies were by the Drop Hammer method using 2 kg drop weight. The
carried out on a Perkin-Elmer DSC-7 instrument operating results are reported in terms of height for 50% probability of
at a heating rate of 10 8C min1 in nitrogen atmosphere with explosion (h50%) of the sample. The friction sensitivity of the
1 – 2 mg of sample. Thermal decomposition studies were compounds was measured on a Julius PeterKs apparatus till
also undertaken on a Mettler Toledo TG/SDTA-8551. The there was no explosion/ignition in five consecutive test
Propellants, Explos., Pyrotech. 32, No. 6, 461 – 467 www.pep.wiley-vch.de D 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Synthesis and Characterization of First Generation Dendritic Azidoesters 463
samples at that weight. The results obtained for impact and IR (KBr, cm1): 3325 (OH str), 2941 (CH str), 1730
friction sensitivity were within the uncertainty limits of (C¼O str).
1
5 cm and 0.2 kg, respectively [9]. H NMR (300 MHz, DMSO-d6): d (ppm) ¼ 0.76 (3H, t,
J ¼ 7.2 Hz, CH2CH3), 0.96 (9H, s, CH3), 1.37 (2H, q, J ¼
7.2 Hz, CH2CH3), 3.30 (broad signal, OH and CH2O),
2.2. Synthesis 3.88 (6H, s, CH2O.OC).
[G-1]-(OH)8: White solid, 3.05 g (95.9%).
The steps involved in the synthesis of azido-terminated Elemental analysis: (C25H44O16)n (600.62)n: Calcd. C
dendrimers [G-1]-(N3)6 and [G-1]-(N3)8 are represented in 49.99%, H: 7.38%; Found C 51.50%, H 7.44%.
the schemes above. IR (KBr, cm1): 3325 (OH str), 2941 (CH str), 1730
(C¼O str).
1
H NMR (300 MHz, DMSO-d6/deuterium exchange): d
2.2.1 Preparation of the First Generation Acetonide-Pro- (ppm) ¼ 1.03 (12H, s, CH3), 3.39 (8H, d, Jgem ¼ 10.2 Hz,
tected Dendrimer CHH’OH), 3.47 (8H, d, Jgem ¼ 10.2 Hz, CHH’OH), 4.06
(8H, s, CH2O.OC).
Isopropylidene-2,2-bis(hydroxymethyl)propionic acid
(3.26 g, 18.7 mmol), Tris(hydroxymethyl)propane (TMP)
(0.8 g, 6 mmol) or pentaerythritol (0.61 g, 4.5 mmol), and 2.2.3 Preparation of the First Generation Tosyl-Terminated
DPTS (1.05 g, 3.6 mmol) were mixed in 30 mL of dichloro- Dendrimer
methane (dry). DCC (4.6 g, 22.3 mmol) was added and the
mixture was stirred at 25 8C for 15 h. The side product, Hydroxy-terminated dendrimer (4.14 mmol) was dis-
substituted urea and unused catalyst were filtered off. solved in 20 mL of pyridine. p-Toluene sulfonylchloride
Evaporation of dichloromethane gave crude product, which (1.5 equivalent for each hydroxyl group) was added to the
was purified by column chromatography over silica gel solution at 0 8C. The reaction mixture was stirred at 25 8C for
eluting with ethyl acetate/hexane (25 : 75 v/v) to afford 48 h and then poured into crushed ice, neutralized with 5 N
acetonide-protected dendrimer. HCl, followed by extraction with CH2Cl2. The CH2Cl2
[G-1]-(O2C (CH3)2)3: Colorless oil, 3.32 g (91.8%). extract was washed with saturated aq. NaHCO3 and then
Elemental analysis: (C30H50O12)n (602.71)n: Calcd. C 2 – 3 times with brine followed by drying over Na2SO4.
59.78%, H 8.36%; Found C 59.43%, H 8.64%. Evaporation of solvent yielded tosyl-terminated dendrimer.
IR (Neat, cm1): 2977 (CH str), 1735 (C¼O str). [G-1]-(OTs)6: Colorless thick liquid, 5.04 g (86.4%).
1
H NMR (300 MHz, CDCl3): d (ppm) ¼ 0.93 (3H, t, J ¼ Elemental analysis: (C63H74O24S6)n (1407.65)n: Calcd. C
7.5 Hz, CH2CH3), 1.14 (9H, s, CH3), 1.35 (9H, s, CH3), 53.75%, H 5.30%; Found C 55.00%, H 5.44%.
1.42 (9H, s, CH3), 1.55 (2H, q, J ¼ 7.5 Hz, CH2CH3), 3.63 IR (Neat, cm1): 3035 (Ar CH str), 2957 (CH str), 1741
(6H, d, Jgem ¼ 11.7 Hz, CHH’O), 4.13 (6H, s, CH2O.OC), (C¼O str).
4.17 (6H, d, Jgem ¼ 11.7 Hz, CHH’O). 1
H NMR (300 MHz, CDCl3): d (ppm) ¼ 0.80 (3H, t, J ¼
[G-1]-(O2C (CH3)2)4: White solid, 3.25 g (95.3%). 7.5 Hz, CH2CH3), 1.13 (9H, s, CH3), 1.35 (2H, q, J ¼
Elemental analysis: (C37H60O16)n (760.88)n: Calcd. C 7.5 Hz, CH2CH3), 2.45 (18H, s, ArCH3), 3.96 (6H, s,
58.41%, H 7.95%; Found C 58.74%, H 8.26%. CH2O.OC), 3.97 (6H, d, Jgem ¼ 9.2 Hz, CHH’O), 4.13
IR (Neat, cm1): 2986 (CH str), 1738 (C¼O str). (6H, d, Jgem ¼ 9.2 Hz, CHH’O), 7.34 (12H, d, J ¼ 8.4 Hz,
1
H NMR (300 MHz, CDCl3): d (ppm) ¼ 1.14 (12H, s, ArH), 7.71 (12H, d, J ¼ 8.4 Hz, ArH).
CH3), 1.35 (12H, s, CH3), 1.42 (12H, s CH3), 3.64 (8H, d, [G-1]-(OTs)8: Colorless thick liquid, 6.84 g (90.1%).
Jgem ¼ 12 Hz, CHH’O), 4.17 (8H, d, Jgem ¼ 12 Hz, Elemental analysis: (C81H92O32S8)n (1834.13)n: Calcd. C
CHH’O), 4.26 (8H, s, CH2O.OC). 53.04%, H 5.06%; Found C 53.87%, H 5.32%.
IR (Neat, cm1): 3053 (Ar CH str), 2984 (CH str), 1744
(C¼O str).
1
2.2.2 Preparation of the First Generation Hydroxy-Termi- H NMR (300 MHz, CDCl3): d (ppm) ¼ 1.12 (12H, s,
nated Dendrimer CH3), 2.42 (24H, s, ArCH3), 3.96 (8H, d, Jgem ¼ 9.9 Hz,
CHH’O), 4.07 (8H, s, CH2O.OC), 4.14 (8H, d, Jgem ¼
Acetonide-protected dendrimer (5.3 mmol) was dis- 9.9 Hz, CHH’O), 7.31 (16H, d, J ¼ 8.1 Hz, ArH), 7.69
solved in 30 mL of methanol. Two grams of Amberlite 120 (16H, d, J ¼ 8.1 Hz, ArH).
Hþ resinN was added to the solution and the reaction mixture
was stirred for 3 h at 25 8C. Upon completion of the reaction,
the resin was removed by filtration. The methanol was 2.2.4 Preparation of First Generation Azido-Terminated
evaporated to give hydroxy-terminated dendrimer. Dendrimer
[G-1]-(OH)6: White solid, 2.49 g (97.2%).
Elemental analysis: (C21H38O12)n (482.51)n: Calcd. C Tosyl-terminated dendrimer (3.19 mmol) was dissolved in
52.27%, H 7.94%; Found C 51.77%, H 8.05%. 30 mL of dimethylsulfoxide. NaN3 (1.5 equivalent for each
tosyl group) was added to the solution at 0 8C. The reaction
D 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.pep.wiley-vch.de Propellants, Explos., Pyrotech. 32, No. 6, 461 – 467
464 C. S. Pant, R. M. Wagh, J. K. Nair, G. M. Gore, M. Thekkekara, S. Venugopalan
mixture was warmed to 75 8C and stirred till the completion 3 Results and Discussion
of reaction ( 30 h). The reaction mixture was poured into
iced water and extracted with CH2Cl2. The CH2Cl2 extract The synthesis of [G-1]-(OH)6, as shown in Scheme 1,
was washed 2 – 3 times with brine and dried over Na2SO4. involved protection and deprotection of hydroxyl groups
Evaporation of solvent yielded crude product, which was beginning with the protection of diol group of DMPA by
purified by passage through a small silica gel packed column acetal formation with 2,2-dimethoxy propane and catalytic
eluting with CH2Cl2 to yield azido-terminated dendrimer. p-toluenesulfonic acid. 2,2-Dimethoxypropane was chosen
[G-1]-(N3)6: Colorless liquid, 1.8 g (89.2%). for the protection of the diol because after esterification
Elemental analysis: (C21H32O6N18)n (632.59)n: Calcd. C deprotection is facile in an acid medium, regenerating the
39.87%, H 5.10%, N 39.86%; Found C 39.98%, H 4.50%, N terminal hydroxyl functionality. During esterification, neu-
39.30%. tral conditions are maintained as both the dehydrating agent
IR (Neat, cm1): 2973 (CH str), 2109 (N3 str), 1737 (C¼O DCC and the catalyst 4-(dimethyl amino) pyridinium-p-
str). toluenesulfonate (DPTS) are neutral. All the reactions
1
H NMR (300 MHz, CDCl3): d (ppm) ¼ 0.96 (3H, t, J ¼ involved in the synthesis of [G-1]-(N3)6 and [G-1]-(N3)8 are
7.5 Hz, CH2CH3), 1.24 (9H, s, CH3), 1.52 (2H, q, J ¼ high yielding with minimum impurities.
7.5 Hz, CH2CH3), 3.52 (6H, d, Jgem ¼ 8.1 Hz, CHH’N3), The final products as well as the intermediates involved
3.58 (6H, d, Jgem ¼ 8.1 Hz, CHH’N3), 4.1 (6H, s, CH2 have been fully characterized by elemental analysis, IR, and
O.OC). 1
H NMR. Protection, deprotection, and substitution by N3
[G-1]-(N3)8: White solid, 2.34 g (91.6%). group were monitored by IR. 1H NMR spectra are shown in
Elemental analysis: (C25H36O8N24)n (800.73)n: Calcd. C Figures 1 and 2.
37.50%, H 4.53%, N 41.98%; Found C 38.13%, H 4.72%, N The DSC (Figures 3 and 4) and TGA thermograms
41.48%. showed thermal stability up to 190 8C. DSC revealed
IR (Neat, cm1): 2980 (CH str), 2110 (N3 str), 1734 (C¼O exothermic decomposition with Tmax at 249.3 8C and heat
str). release on the order of 2620 J g1 for [G-1]-(N3)6 and a Tmax
1
H NMR (300 MHz, CDCl3): d (ppm) ¼ 1.25 (12H, s, at 248.2 8C and heat release on the order of 2619 J g1 for[G-
CH3), 3.52 (8H, d, Jgem ¼ 12 Hz, CHH’N3), 3.58 (8H, d, 1]-(N3)8, respectively. The glass transition temperature was
Jgem ¼ 12 Hz, CHH’N3), 4.2 (8H, s, CH2O.OC). found to be 54 to 32 8C, respectively, which is sufficiently
1
Figure 1. H NMR of the azidoester [G-1]-(N3)6.
Propellants, Explos., Pyrotech. 32, No. 6, 461 – 467 www.pep.wiley-vch.de D 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Synthesis and Characterization of First Generation Dendritic Azidoesters 465
1
Figure 2. H NMR of the azidoester [G-1]-(N3)8.
D 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.pep.wiley-vch.de Propellants, Explos., Pyrotech. 32, No. 6, 461 – 467
466 C. S. Pant, R. M. Wagh, J. K. Nair, G. M. Gore, M. Thekkekara, S. Venugopalan
Propellants, Explos., Pyrotech. 32, No. 6, 461 – 467 www.pep.wiley-vch.de D 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Synthesis and Characterization of First Generation Dendritic Azidoesters 467
D 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.pep.wiley-vch.de Propellants, Explos., Pyrotech. 32, No. 6, 461 – 467