Sinn H, Hinck H, Bandermann F, Grützmacher H-F. Formation of Polymethyl(methylene)aluminum. Angewandte Chemie, International Edition in English. 1968;7(3):217

Bandermann, F.

Grützmacher, Hans-Friedrich

Hinck, H.

Sinn, H.

English

Publications at Bielefeld University

to the conclusion that an asymmetric synthesis of the poly- mer has in fact been achieved. These results demonstrate a new method for the synthesis of optically active polymers. Experimental: Polyvinylacetophenone was prepared according to  Kenyon (61, and (+)-a-methylbenzyl alcohol according to  eervinka [31 with = +19.5" (homogeneous), in 45-48 % optical yield. (+)-Poly-[4-(2-hydroxyethyl)styrene] (2) : LiAIH4 (2.112 g, 0.0553 mole) was suspended in tetrahydro- furan (250 mi), quinine ([a]D = -172'; 16.2 g, 0.05 mole) was added, and the mixture was boiled for 10 min. A solution of ( I )  (4 g, 0.0274 unit mole) in tetrahydrofuran (50 ml) was added dropwise during 10 min and the whole boiled under reflux for 6 h. The polymer was precipitated by pouring the mixture into 3 % sulfuric acid and was reprecipitated from tetrahydrofuran by 3 % sulfuric acid and then from tetra- hydrofuran by saturated sodium hydrogen carbonate solution and water. Yield 2.5 g. Received: December 1 1 ,  1967 [Z 690 IE] German version: Angew. Chem. 80, 236 (1968) [*I Prof. Dr. Rolf C. Schulz and DipLChem. H. Mayerhofer Organisch-chemisches Institut der Universitat 65 Mainz, Johann-Joachim-Becher-Weg 18-20 (Germany) I**] Part of the dissertation by H.  Mayerhofer, Mainz D 77. [***I We are grateful to the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie for financial support. [I] J .  A. Reid and E. E. Turner, J. chem. SOC. (London) 1949, 3365; 1950, 3694. [2] [a] S. R.  Landor, B. J .  Miller, and A. R. Tatchell, Proc. chern. SOC. (London) 1964, 227; [b] J. chem. SOC. (London) (C) 1966, 1822, 2280; 1967, 197; S. R. Landor and J.  P .  Regan, ibid. (C) 1967, 1159. [3] 0. fei-vinka, Collect. czechoslov. chem. Commun. 30, 1684 (1 965). [4] W. Bodenheimer and C.  Bruhn, Z .  physik. Chem. (B) 25, 319 (1934). [5] A .  McKenzie and G .  W. Clough, J. chem. SOC. (London) 103, 697 (1913). [6] W. 0. Kenyon and G .  P .  Wuugh, J. Polymer Sci. 32, 83 (1958). Formation of Polymethyl(methylene)aluminum By H. Sinn[*l .  H.  Hinckr*1, F. Bandermann[*J, and H. F. Grutzmacher [* *I Complex formation between biscyclopentadienyltitanium(1v) compounds (CpzTiC12 and CpzTiCICH3) and trimethyl- aluminum has a half-reaction time of < 10-2 seconds even at  -45OC. In both cases the complex formation is accom- panied by a very slow reaction. This is indicated by develop- ment of an  absorption band at  460 nm which is at  first syn- chronous with an evolution of methane. It thus seemed likely that the reaction should be considered as formation of the compounds with CH2 bridges between Ti and A1 that C. Feay " 1  had isolated. However, we observed that further methane was evolved after the band at  460 nm had developed; the reaction was therefore studied without use of a solvent and with a large excess of AI(CH&. The rate of initial evolution of methane followed the rate law: If the initial molar ratio CpzTiC12/AI(CH& was 1: 100, the evolution of methane increased after ca. 100 hours at  room temperature. The viscosity of the mixture increased from 0.9 cp to  > 100 cp; after 350 hours the reaction mass solidified, yet slowly evolved more methane. In sum, almost 1 mole of methane was liberated per mole of Al(CH3)3. The solidified mass does not dissolve in petroleum ether, and swells in benzene; components of low molecular weight and products formed from the titanium compound are removed by extraction in a glass Soxhlet apparatus with benzene. The residue is a pale greyish powder with the composition C2HSA1. It reacts quantitatively with deuterium chloride: CZHSAI+ 3 DCI + AlCI3+ DzCHzf DCH3 We therefore propose formula ( I ) ,  where n is probably about 100. (If this were not so, more DCH3, would be formed by reaction with the end groups.) [ - g - C H 2 - ]  " In this connection the compound (2) that was obtained by H.  Lehrnkuhl and R .  Schaeferf21 by a quite different route should be noted. Before the extraction, the reaction mass evolves only traces of A1(CH3)3 in a high vacuum. It dissolves in tetrahydrofuran. Viscosity determination (on the basis of the Staudinger relation that is valid for polystyrene) gave a mean degree of polymerization P,, = 1/(1 - p )  = 20, corresponding to  a degree of reaction p = 0.95, whereas we expected p = 0.85 to  0.90 on the basis of the amount of methane evolved. The extraction residue, swollen and suspended in benzene, reacts with titanium tetrachloride with formation of a voluminous, almost black, mass. A suspension of this com- pound in hydrocarbons is an  efficient catalyst for the poly- reaction of ethylene and cc-olefins. Received: December 13, 1967 IZ 689 IEI German version: Angew. Chem. 80, 190 (1968) [*I Prof. H. Sinn, DipLChem. H. Hinck, and Dr. F. Bandermann Lehrstuhl fur Angewandte Chemie, Institut fur Anorganische Chemie, Chemisches Staatsinstitut 2 Hamburg, Papendamm 6 (Germany) Institut fur Organische Chemie, Chemisches Staatsinstitut 2 Hamburg, Papendamm 6 (Germany) 111 D. C. Feay, Belg. Pat. 635987 (Feb. 10, 1964); Belg. Pat. 635988 (Feb. 10, 1964); D.  C. Feay and G .  S .  Fujioka, Lecture, 10th International Conference on Coordination Chemistry, Sept. 1967. [2] H.  Lehmkuhl and R. Schiifer, Tetrahedron Letters 1966, 231 5. [**I Doz. Dr. H. F. Griitzmacher N-(Fluoroformy1)iminosulf ur Dichloride and N-(Chloroformy1)iminosulfur Dichloride By H. W .  Roesky and R.  M e w s [ * ]  As part of our study of sulfur-nitrogen compounds[ll we have prepared iminosulfur dichlorides -N= SClz from the corresponding fluoro derivatives. N-(Fluoroformy1)imino- sulfur difluoride ( I )  (21 reacts with phosphorus pentachloride at  room temperature, giving N-(fluoroformyl)iminosulfur dichloride (2) and phosphorus pentafluoride. 33 g of (i) is added dropwise with ice cooling to 23.1 g of PC15. The mixture is then stirred for 2 h at  0 "C and for 24 h at room temperature. The volatile products are removed in a Angew. Chem. internat. Edit. 1 Vol. 7 (1968) No. 3 217 

Formation of Polymethyl(methylene)aluminum

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Formation of Polymethyl(methylene)aluminum

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