Organic compounds -- part of the class 532-570 series – Organic compounds – Silicon containing
Patent
1996-01-18
1998-03-17
Shaver, Paul F.
Organic compounds -- part of the class 532-570 series
Organic compounds
Silicon containing
556 10, 546 6, 546 14, C07F 708, C07F 710
Patent
active
057288569
DESCRIPTION:
BRIEF SUMMARY
DESCRIPTION
The invention relates to stable silylenes, processes for producing such silylenes and analog carbenes as well as selected uses of the silylenes in accordance with the invention.
Silylenes, like carbenes, are very reactive owing to the problematic stabilization of divalent silicon compounds with free electron pair and have therefore been very difficult to isolate in substance until now. June 1992, p. 1375-1377) postulated for the first time a silylene as a result of a compound intercepted IR-spectroscopically at temperatures below 77 K. They formulated the silylene, because it could have originated intermediary during a photolysis reaction. A specific allocation of the spectrum in question with the formula "2d" of a silylene as given in the article is not made. The given publication also lacks a production approach for synthesizing the postulated silylene.
Silylenes are highly desired structural elements in the chemical synthesis owing to their reactivity.
It is thus the object of the present invention to provide stabilized, and therefore isolatable silylenes and a process for their production which can also be applied for analog carbon compounds.
This invention achieves this object by the materials as given in the independent claim 1 and by the process as given in the independent claim 7. Uses of the materials in accordance with the invention are obtained from the independent claims 36 to 40. Further advantageous embodiments of the materials and the process in accordance with the invention can be obtained from the dependent claims, the description and the examples.
The invention is based on the general recognition that silylenes can be stabilized by adjacent amido groups and furthermore that divalent silicon and carbon compounds can be prepared from the respective dihalogeno compounds by reduction with metals. The subject matter of the invention is therefore a silylene of the general formula I R.sup.6)!tm (I) R.sup.8 are the same or different and each mean a hydrogen or halogen atom or an alkyl, aryl, alkoxy, aryloxy, amido or heteroaryl residue, and R.sup.7 and R.sup.8 can also represent the residue --ER.sup.1 R.sup.2 R.sup.3 or .sup.- ER.sup.4 R.sup.5 R.sup.6, and E means an element of the fourth main group of the periodic system of elements with the exception of lead and R.sup.7 and R.sup.8 can jointly form with the respective adjacent nitrogen atoms and the central silicon atom an optionally unsaturated heterocyclic ring with at least 4 ring atoms and furthermore a process for producing compounds of the general formula IV R.sup.6)!tm (IV) R.sup.1,R.sup.2,R.sup.3,R.sup.4,R.sup.5,R.sup.6,R.sup.7,R.sup.8 and E have the aforementioned meanings, characterized in that a compound with the general formula (V) R.sup.5 R.sup.6)!tm (V) and E have the aforementioned meanings and X represents a hydrogen or halogen atom, optionally in the presence of a solvent, is converted with a reducing agent.
It has proved to be particularly advantageous in stabilizing the silylene in accordance with the invention to insert the two amido nitrogen atoms into a ring skeleton, preferably a hydrocarbon ring skeleton. In this respect the ring to be formed can consist of at least 4, preferably 4 to 10, particularly 4 to 6, ring atoms. Of particular advantage is the formation of an aromatic under inclusion of the respective free electron pairs on the nitrogen into the 6 (.pi.) electron system. Preferably, an olefinic double bond is sufficient as a bridge-type cross-link between the amido nitrogen atoms. In a five-membered ring thus obtained two hydrogen atoms are preferably located at the olefinic double bond as ring substituent. The formed aromatic heterocycle can preferably also be stabilized by fused benzole or cyclopentadienyl nuclei. Other aromatic nuclei can also be fused. Various other, preferably bulky and electron-pushing groups such as alkyl, aryl, alkoxy, aryloxy, amido or heteroaryl groups can be situated at the nitrogen atom. Alkyl and aryl groups have proved to be advantageous. Particularly advantageous are a
REFERENCES:
patent: 3030745 (1962-07-01), Weber et al.
patent: 3509194 (1970-04-01), Fink
Article: Chemische Berichte, "Spektroskopischer Nachweis eines Bis(amino)silylens", vol. 125, Jun. 1992 (pp. 1375-1377).
Article: Chemische Berichte, "Decamethylsilicocene--The First Stable Silicon(ll) Compound: Synthesis, Structure, and Bonding", P. Jutzi et al, vol. 122, 1989 (pp. 1629-1639).
Article: Journal of the American Chemical Society, "A Stable Crystalline Carbene", A. J. Arduengo, III et al, vol. 113, Jan. 1991 (pp. 361-362). 1,4-Diaminnno-1,3-butadiiiien-2,3-dicarbonsaure-Derivaten", T. Dieck et al, vol. 102, 1987 (pp. 795-801).
Article: Journal of the American Chemical Society "Synthesis and Structure of a Stable Silylene", M. Denk et al, vol. 116, No. 6, Mar. 23, 1994, (pp. 2691-2692).
Article: Journal of the Chemical Society, Chemical Communications "Silylene Complexes from a Stable Silylene . . . Donor-free Bis-silylene Complex", No. 1, Jan. 7, 1994 (pp. 33-34).
Article: Taschenlehrbuch Der Organischen Chemie, Part A: Theoretische Und Allgemeine Gebiete, "Reaktive Zwischenstufen l", Georg Thieme-Verlag Stuttgart, C. Wentrup, vol. 8, 1979 (p. 203).
Article: Journal of the American Chemical Society, No. 53, Aug. 1931 (p. 3045).
Article: Chemikon, 1972 (V/43).
LandOfFree
Silylene, a process for its production and its use does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Silylene, a process for its production and its use, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Silylene, a process for its production and its use will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-959011