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Bis-(p-hydroxyphenyl)alkylphosphonic Acid Esters and Derived Polycarbonates.

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Bis-(phydroxypheny1)alkylphosphonic Acid Esters
and Derived Polycarbonates
Synthesis of N,N'-Bis(chlorodimethylsily1)tetramethylcyclodisilazane [l]
By Dr. M. I. Iliopulos [l] and Dip].-Chem. H. Wieder
By Dr. P. Geymayer and Prof. Dr. E. G.Rochow
lnstitut fur Organische Chemie
der Technischen Hochschule Stuttgart (Germany)
Department of Chemistry,
Harvard University, Cambridge, Mass. (U.S.A.)
Dialkyl I-bis-Cp-hydroxypheny1)alkylphosphonates( 3 ) are
made by condensation of the adduct obtained from the phenol
( I ) and BF3 with dialkyl acylphosphonates (2) in a molar
ratio of 3:1 to 6:1,cooling being applied to maintain the
reaction temperature at 30-40 'C. The same products are also
obtained under similar conditions by passing BF3 into a mixture of ( I ) and (2). When the condensation is complete,
the reaction mixture is diluted with acetic acid and poured
into water. The crude product crystallizes out and can be
recrystallized from methanol/water.
1,3-Dichlorotetramethyldisilazane (2) [2,3] was hitherto
obtainable only in unsatisfactory yields but can now be
by refluxing octaconveniently prepared in yields of 80
methylcyclotetrasilazane ( I ) with an excess of dimethyldichlorosilane (molar ratio 1 : 5 ) for 24 h. The product is isolated by subsequent distillation.
+
[ -S~(CH~)Z-NH-]~4 (CH3)zSiCL
--f
4 [CI(CH~)ZS~J-NH-[S~(CH~)ZCI]
(2)
(1)
Compound (2) reacts with sodium bistrimethylsilylamide 141
with substitution of one or both chlorine atoms. The products
formed are not stabIe but decompose even at room temperature to hexamethyldisilazane and N,N'-bis(ch1orodimethylsily1)tetramethylcyclodisilazane ( 3 ) or N,N'-bis(trimethylsily1)tetramethylcyclodisilazane (4) [ 5 ] , respectively.
(3a)
(3b)
(3~)
(3d)
(3e)
H
C1
C1
H
C1
CH3
CH3
CH3
C6Hs
C6HS
CH3
CH3
C2Hs
CH3
CH3
217
213
143.5
270
259-260
70
49
64
89
70
When a solution of sodium bistrimethylsilylamide in ether
is added dropwise to a vigorously stirred solution of ( I ) in
petroleum ether at room temperature (molar ratio of the
components = 1 : l), (3) can be secured in yields of up to
70 %. Compound (3) forms beautiful colorless crystals, m. p.
7OoC, which can be purified by recrystallization from petroleum ether and sublimation at 55 OC/O.O3 mm. The N M R
spectrum of a 20 % solution of (3) in CC14 has only a single
sharp proton signal (8 = 0.33 ppm). In benzene, on the other
hand, two signals are observed. It appears that the two types
of protons present in (3) happen to have the same chemical
shifts in CC14. The structure of (3) was proved by elemental
analysis, ebullioscopic molecular-weight determipations and
by its infrared and mass spectra.
We consider (3) to be a potential starting material for the
synthesis of polymers containing cyclodisilazane structures.
[Z 953/778 IEI
Received: March 29th, 1965
German version: Angew. Chem. 77, 618 (1965)
r
H3
1
(4)
Sheets of (4) 0.085-0.090 mm thick ignite when held in a Bunsen burner pilot flame 5-6 cm long but cease to burn irnmediately upon removal from the flame. Films made from the
polycarbonate produced from phosgene and 2,2-bis-(p-hydroxypheny1)propane burn out completely under the same
conditions.
The phosphorus content of the polycarbonates can be reduced
by copolycondensation of (3) and 2,2-bis-(p-hydroxyphenyl)propane, but the fire-resistance of the products is reduced
[I] This work was supported by the National Science Foundation,
Washington, D.C. (U.S.A.).
[2] H. Kriegsmann and G . Engelhardt, Z . anorg. allg. Chem. 310,
100, 320 (1961).
[3] U.Wannagat, P. Geymayer, and E . Eogusch, Mh. Chem. 95,
801 (1964).
[4] U.Wannagat and H . Niederpriim, Chem. Ber. 94, 1540 (1961).
[51 W. Fink, Chem. Ber. 96, 1071 (1963).
1,6-Anhydroidose Derivatives with Rings
Containing Nitrogen [l]
By Priv.-Doz. Dr. H. Paulsen and Dipl.-Chem. K. Todt
Chemisches Staatsinstitut, Institut fur Organische Chemie,
Universitlt Hamburg (Germany)
correspondingly.
Received: February 24th, 1965 [Z 994/819 IEI
German version: Angew. Chem. 77, 618 (1965)
Publication deferred until now at the authors' request
[I 1 University Exchange Fellow of the Alexander-von-Humboldt
Stiftung 1965.
592
In acidic solution, the piperidinoses obtained from 5-amino
sugars are always spontaneously dehydrated to form 3hydroxypyridine derivatives [2]. We have found that free
piperidinoses - in contrast to all other monosaccharides A n g e w . C h e m . internat. Edit.
/
Vol. 4 (1965) / No. 7
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acid, esters, bis, derived, polycarbonate, hydroxyphenyl, alkylphosphonic
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