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Angew,. Chem. Int. Ed. Engl. 1993, 32, No. 9, 1306
Angew,. Chem. Int. Ed. Engl. 1993, 32, No. 9, 1306
G1X
sis the generation are prepared by sequential construction of
X I
stepwise branched polymers starting from a polyfunctional X
G2X
core and multiplying the functionalities in each branching
The ideal starburst-type growth is restricted to a X
certain limiting generation,'". ' ' I and when the density of G3X
the functional groups reaches a limit, steric hindrance ac-
counts for incomplete branching reaction and consequently
increased content of structural defects. Furthermore, for the
divergent syntheses large excesses of the reagents must be
used. In contrast, in the convergent synthetic strategy large
dendritic precursors are prepared which are subsequently
coupled.['', 1 3 1 Our research is aimed at the development of
high yield divergent syntheses which d o not require large
excess of reagents and purification.
Vogtle et a1.'21 had first proposed a conceptual approach
involving a branching reaction sequence through cyano-
ethylation of amines with acrylonitrile followed by chemical
reduction to double the amine end group functionality and
stepwise branching the dendritic polyamines, thus forming G4X
poly(trimethy1ene imines). As a consequence of rather low G5X
RNH, - RN:
CH2CH2CN
CH2CH2CN
- RN,
, C H Z C H ~ C H ~H2
N
c n 2 c i i 2 c H 2 NH,
(a)
Scheme 1. Starburst poly(trimethy1eneimine) generations GnX (n = 1-5) with
X = N for nitrile (CN) and X = A for amino (CH,NH,) end groups.
Since acrylonitrile, methanol, and cyanoethylated methanol GIN 3 11 116 - 180 1.02
are readily removed under vacuum, this synthetic route does GlA 3 61 188 - 185 1.05
not require special purification processes. G2N 6 96 506 494 480 1.02
Starting from ammonia as initiator core, it was possible to G2A 6 86 530 - 530 1.07
G3N 12 94 1161 1060 1200 1.02
build five generations of polynitrile- (X = CN) and G3A 12 79 1216 - 1250 1.08
polyamine-functional (X = CH,NH,, Scheme 1) cascade G4N 24 96 2489 2470 2570 1.04
G4A 24 69 2586 - 2480 1.08
[*I
Prof. Dr. R. Mulhdupt, C. Worner G5N 48 93 5133 4880 4810 1.07
Institut fur Makromolekuldre Chemie
Hermann-Staudinger-Haus [a] Determined by vapor pressure osmometry (VPO). [b] Determined by gel
Stefan-Meier-Strasse 31, D-79104 Freiburg (FRG) permeation chromatography (GPC).
Telefax: Jnt. code +(761)276-453
I**]
This work was supported by the Deutsche Forschungsgemeinschaft. Dur-
ing preparation of this manuscript the authors became aware of similar
results from E. M. M. de Brabander-van den Berg. E. W. Meijer, Angew.
For applications of such poly(trimethy1ene imines) cas-
Chnn. 1993.105. 1310-1372; Angew. Chrm. Int. Ed. Engl. 1993.32, 1308- cade molecules it is important to identify structural defects
1311 which may account for changes in the supramolecular archi-
I_
I I I I I I I I I I
200 180 160 140 120 100 80 60 40 20 0
-6
Fig. 3. I 3 C N M R spectrum (100 MHz, CD,CI,) of G5N. Spectrum confirms
structural defects in the Cascade molecule through monosubstitution (sec-
ondary amino end groups).
-1 1- I I
i
I
7 6 5 4 3 2 0
-8
Fig. 2. 'H N M R spectrum (250 MHz, CDCI,) of G4A
Angew Chem. Int. Ed. Engl. 1993, 32, No. 9 0 VCH Verlagsgesellschafr mbH, 0.69451 Weinheim, 1993 0570-0833/93/0909-I307 S l0.00+.25/0 1307
GPC analyses, coupling reactions can be excluded. Interest- 40.7 (CH,NH,). 51.9. 52.3, 52.4, 52.6 (CH,N); IR (neat): i.[cm-'] = 3300,
3260,2910. 2780, 1570. 1450, 1360. 1170. 1070.960-770.
ingly, the solution behavior of poly(ethy1ene oxide), a typical
G5N: The procedure was equivalent to that reported for the synthesis of G4N.
random-coil polymer, is quite different from that of the two From G4A (600 mg. 0.232 mmol) was obtained 1.1 1 g (93%) of the highly
types of highly functional poly(trirnethy1ene imine) cascade viscous substance G5N Correct elemental analysis for C,,,H,,,N,,
molecules prepared by us. As apparent from Figure 5, the (5133.35 gmol-'): ' H N M R (400MHz. CD,CI,): 6 =1.62 (m. 9 0 H ;
polyamine-functional cascade molecules require higher elu- CH,CH,CH,), 2.52 (m. 276H; CH,N), 2.82 (t. J = 7 Hz, 96H; CH,CN); I3C
NMR (100 MHz, CD,CI,): 6 = 17.2 (CH,CN), 23.8.25.1 (CH,CH,CH,), 49.8
tion volumes, which increase with increasing number of gen- (C'H,CH,CN), 51.6, 51.8, 52.1. 52.3 (CH,N). 119.5 (CN); IR (neat):
erations. In agreement with earlier observations,". 'I it ap- i'[cm-'] = 2920.2790, 2220. 1450, 1410. 1350, 1230, 1160, 1120, 1060.
The ' H NMR and "C N M R spectra were measured with a Bruker AC 400
spectrometer with tetramethylsilane as internal standard; CD,CI, was used for
the nitrile-functional and CDCI, for the amine-functional generations. End
group titration was performed in a solution of H,O/Et,O (1 : 1) with 0.1 N HCI
with a Mettler DC 25 titrator. Vapor pressure osmometry wiis carried out with
M
I a Perkin-Elmer Molecular Weight Apparatus Type 115 at 30 C with CHCI, as
solvent. The GPC analysis was performed on a Shimadzu LC-4A at 60JC with
a 0.05 M K,HPO, buffer MeOH/H,O (70: 30) at pH = 11 (HEMA 40 and HE-
MA 100 column (MZ Analysentechnik), flow rate 0.5 m L m i n - ' , UV detector
[g mol- 228 nm, R1 detector. calibrated with the values obtained from vapour pressure
osmometry).
Received: April 1, 1993 [Z 5968 IE]
German version: Angew. Chem. 1993. 105. 1367
12 14 16 18 20 22 24 26
v, [mLI -
Fig. 5. Correlation of molecular weight M and elution volume V, in G P C
D. A. Tomalia. A. M. Naylor. W. A. Goddard 111, Angew. Chem. 1990.
102, 119-157; A n g w . Chem. lnt. Ed. Engl. 1990, 29, 138-175.
analyses of poly(ethy1ene oxide) (o),polynitrile- (A) and polyamine-functional E. Buhleier. W Wehner, F. Vogtle, Sjn//zmir 1978, 155- 158.
poly(trimethylene imines) (*). H.-B. Mekelburger, W. Jaworek, F. Vogtle, Angew. Chem. 1992. 104.
1609-1614; Angeu.. Cl7em. Inr. Ed. Engl. 1992, 31, 1571-1576.
R. G . Denkewalter. J. F. Kolc. W. J. Lukasavage. US-A 4410688, 1983
pears likely that cascade molecules when compared with (Clirm. Absr. 1984, 100. 1 0 3 9 0 7 ~ ) .
conventional random-coil polymers exhibit higher densities, A . M . Naylor. W. A. Goddard 111, G. E. Kiefer, D. A. Tomalia. J. Am.
Cheni. Soc. 1989. 111. 2339-2341.
which increase with increasing molecular weight. The very D. A. Tomalia. H. Baker. J. Dewald, M. Hall. G . Kallos, S . Martin, J.
high elution volumes found for the polynitrile-functional Roeck. J. Ryder. P. Smith, Po/pm. J. 1985, 17. 117-132.
cascade molecules may result from adsorption phenomena, D. A. Tomaha. H. Baker. .I. Dewald. M. Hall, G. Kallos, S. Martin, J.
which d o not interfer with the GPC analysis of the molecular Roeck, J. Ryder, P. Smith, Mucromolecu1e.r 1986, 19, 2466-2468.
G. R. Newkome, G . R. Baker, S. Arai. M. J. Saunders. P. S. Russo, K. J.
weight distributions. In all three polymers there exists a lin- Theriot. C. N. Moorefield. L. E. Rogers. J. E. Miller, T. R. Lieux, M. E.
ear correlation between molecular weight, determined by Murray. B. Phillips, L. Pascal, J. Am. Clwm. Soc. 1990, 112. 8458-8465.
vapor pressure osrnometry, and elution volume. X . Lin. G. R. Newkome, Mucr.omu1et.ule.s 1991. 24. 1443-1444.
In conclusion, the divergent synthesis involving cyano- P. G. de Gennes, H. Hervert. PI7js. L P ! ~1983,
. 44. 351 - 360.
R. L. Lescanec, M. Muthukumar. Mucromulecutes 1990. 23, 2280-2288.
ethylation and catalytic hydrogenation efficiently doubles C. J. Hawker. J. M. 1. Frkchet, J. A m . Clrem. Sot.. 1990. 112. 7638-7647.
the amino groups. With this reaction sequence poly(tri- K. L. Wooley. C. J. Hawker. J. M. J. Frechet,./. A m . Chrrn Soc. 1991. f13.
methylene imine) cascade molecules can be prepared in high 4252- 4261
yields and purity without requiring extensive purifications R. J. Bergeron. J. R. Garlich. Synrhesrs 1984, 782-784.
0. C. Dermer, G. E. Ham. Ethdeneimrnr und other uxridines. Academic
and excess reagent. Press, New York, 1969, p. 334.
S. M. Aharoni. C. R. Crosby, E. K . Walsh, Mat.romo1wrrks 1982, IS,
Experimental Procedure 1093- 1098.
Typical syntheses for the higher generations G4N. G4A, and GSN; the yields
are summarized in Table I .
G4N: To a cold solution of G3A (2.56 g, 2.10 mmol) in methanol (20 mL) were
added acrylonitrile (20.0 mL. 305 mmol) (distilled over CaH, and stabilized
with 0.05 wt% hydroquinonemonomethyl ether) within 90 minutesat 5 - 10 C. Poly(propy1ene imine) Dendrimers: Large-Scale
After stirring 1 h at 10 C and 4 days at 60 'C. the quantitative bis(cyanoethyla-
tion) was obtained. For separation of the stabihzer. the reaction mixture was Synthesis by Hetereogeneously Catalyzed
passed through a neutral AI,O, column and eluted with methanol/ethyl acetate Hydrogenations**
(7:3). and the methanol content was increascd slowly to 100%. The solvent was
evaporated in vacuo to obtain 5.02 g (96%) of the highly viscous G4N. Correct By Ellen M . M . de Brabander-van den Berg*
elemental analysis for C135HLZ2N+h (2489.55 gmol-I); ' H N M R (400 MHz, and E. W Meijer
CD,CI,): /i = 1.62 (q, J = 7 Hz. 4 2 H ; CH,CH,CH,). 2.56 (ni. 132H; CH,N),
2.83 (t. J = 7 Hz, 4 8 H ; CH,CN), " C N M R (100 MHz, CD,CI,): 6 =17.3 Dendritic macromolecules are hyperbranched polymers
(CH,CN), 23.9, 25.1 (CH,CH,CH,), 49.9 (CH,CH,CN), 51.7, 51.9, 52.2, 52.4 that emanate from a central core, have a defined number of
(CH,N), 119.5 (CN); IR (neat). i,[cm-'] = 2920,2800,2220, 1450,1410.1350,
1250, 1160, 1120, 1050. generations and functional end groups, and are synthesized
G4A: The hydrogenation was carried out in a 2 L stainless steel autoclave in a stepwise way by a repetitive reaction sequence."] The
(Biichi AG, UsteriSwitzerland). To 100 m L of a 1.4 M solution of NaOH iu syntheses described so far are either convergent, this is discrete
EtOHjH,O (95:s). G4N (4.20g. 1.69mmol) was added. Under nitrogen the
mixture was treated with Raney-nickel(2.5 g) (slurry in water. Aldrich). and the
[*] Dr. E. M. M. de Brabander-van den Berg, Prof. Dr. E. W Meijer 1''
mixture was hydrogenated at 1000 rpm a t 8 bar H, pressure for 4 days at 25 C.
DSM Research
The catalyst was filtered and washed with EtOHjH,O (95j5). After diluting the
P.O. Box 18, NL-6160 M D Geleen (The Netherlands)
filtrate with H,O (100 mL). EtOH was evaporated and the residue extracted
several times with CH,CI,. Thereby. the NaOH concentration in the aqueous ['I Present address:
phase was increased in every extraction step. The organic layers were dried with Laboratory of Organic Chemistry, Eindhoven University of Technology
Na,SO, and the solvent evaporated in vacuo to give 3.01 g (69%) G4A. Correct P.O. Box 513, NL-5600 M B Eiiidhoven (The Netherlands)
elemental analysis for C,,,H,,,N,, (2586.31 gmol-I); ' H NMR (250 MHz, Telefax: Int. code + (31)40-451036
CDCI,): /i =1.54(m. 138H,CH,CH,CH,, NH,), 2.36(m. 8 4 H ; CH,N), 2.42 [**I We thank many colleagues at DSM Research, especially A. Nijenhuis, J.
(t. J=7Hz.48H;CHzCH,CH,NH,). 2.67(t, J = 7 H z , 4 8 H ; C H 2 N H , ) ; " C Keulen, M. Mure, B. Bosman, F. Vanderbooren, R. Reintjens. and S. van
NMR (100 MHz, CDCI,): ii = 24.6 (NCH,CH,CH,N), 30.9 (CH,CH,NH,). der Wal for their vahxable input.
1308 TI VCH Verlug.~gesell.schufimhH, 0-69451 Weinherm, IYY3 0570-oX33193jo9o9-130n d 10.00+ 2SiO Angeic.. Chem. In!. Ed. Engl. 1993, 32. No. 9