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Detection of Atomic Sulfur and Phenylphos-phinidene (C6H5P ) in Solution.

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of the inlet system 125 'C; temperature of the ion source
250°C) of the pairs of valence isomers (/)/(2) have approximately equal abundances of the various fragments 171. The
carbanion ( 3 ~ ) formed from (2n) with sodium methoxide
reacts with methanol to yield at leist four products in
proportioils of about 68: 18: I3 : 1 ; their structures are at
present being investigated.
The carbanion (3n) can be formulated as a non-classical
bishomocyclopentadienyl anion (4a) 181. Compounds of
type (2) are therefore representatives of a system which
permits the study of such non-classical anions.
Received: Marcb 19th, 1965
[Z 9491780 I€]
German version: Angew. Chem. 77, 454 (1965)
[ I ] Unsubstituted tetracyclo[3,3,0,02~8,04.6]octane( 2 a ) , R' = H ,
and its 7-methoxycarbonyl derivative cannot be obtained directly
by irradiation of the corresponding exo-tricycl0[3,2,1,02,4]octene
compounds [2].The possibility of photosensitized energy transfer is currently being examined.
[2] G.von Vel7, Ph. D. Thesis, Universitiit Freiburg/Breisgau
1965; R. R. Sauers and P . E. Sonnet, Chem. and Ind. 1963, 786;
Tetrahedron 20, 1029 (1964).
[3] lrradiation of 1 g of ester in 300 ml of ether at 5 "C for 3 h.
[4] Irradiation of 1 g of acid in 300 ml of water at 5 "C for 6.5 h.
[5] It is remarkable that the photoisomerization in water of the
endo-compounds corresponding to ( I b ) and ( I d ) is much less
specific; in addition to the tetracycles epimeric with f 2 j in the
7-position, comparable yields of a second, as yet unidentified
product are obtained.
[ 6 ] The mass spectra were kindly measured by Dr. W. B e m ,
Badische Aniliii- & Soda-Fabrik. Ludwigshafen (Germany).
[7] Z.DofejSek, V. HnnuS, and H . P ~ i n z b a c hAngew.
,
Chem. 74,
902 (1962);Angew. Chem. internat. Edit. I , 598 (1962).
IS] S.Winstein, P. Bruck, P . Radfick, and R. Baker, J. Amer.
chem. SOC.86, 1867 (1964); N . A. Le Bel, A. G . Phillips, and
N. N . Lieseiner, J . Amer. chcm. SOC.86, 1876 (1964).
Detection of Atomic Sulfur and Phenylphosphinidene (C6H5P:) in Solution
By Prof. Dr. Ulrich Schmidt and cand. chem. Ch. Osterroht
Chemisches Labol-dtorium
der Universitiit Freiburg/Breisgau (Germany)
While searching for electronic states of elements of the second
group of the periodic table corresponding t o those of the
carbenes and imenes (nitrenes, azenes), we have succeeded in
detecting both atomic (electrophilic) sulfur and phenylphos) their solutions.
phinidene ( C ~ H S P :in
Procedure: Nine grams of phenyldichlorophosphine are
stirred for 2 h at 25 "C with 10 ml of tetrahydrofuran, 50 ml
of diethyl disulfide, and 4 g of zinc dust. After extraction of
the reaction mixture with water, distillation of the organic
phase yields 7 g of diethyl phenylphosphonodilhioite.
Received: March 23rd, 1965
[Z 9461772 IE]
German version: Angew. Chern. 7 7 , 455 (1965)
[ I ] The formstion of atomic sulfur in the gaseous state on
irradiation of COS is described by A . R. Knight, 0. P . Strausz,
and H . E. Gunning, J. Amer. chem. SOC.85,2349 (1963).
[Z] U . Schmidt and K . H . Kabhitzke, Angew. Chem. 76, 687
(1964);Angew. Chem. internat. Edit. 3, 641 (1964).
[3] Unsuccessful attempts to detect phenylphosphinidene by
addition onto olefins, dienes, and tolane are mentioned by
W. Henderson, M . Epstein, and F. S. Seichter, J. Amer. chem.
SOC.85, 2462 ( I 963) in reference 10).
[4] A . Schonberg, 0.Schutz, and J . Peter, Ber. dtsch. chem. Ges.
62, 440 (1929).
Synthesis and Polymerization
of 1,5-Dioxaspiro[2,4]heptane
By Dr. E. Steininger
Battelle-Institut Frankfurt/Main (Germany)
On heating 4,4-bis(chlormethyl)-rn-dioxane ( I ) [ l ] with 5
by weight of conc. H2S04 in ethanol in a sealed tube at
120 "C for 5 hours, 3-chlormethyl-3-hydroxytetrahydrofuran
(2), b.p. 109,s "C, n:; = 1,4868, is formed in 73 % yield. Another synthesis of (2) is the transformation of ( I ) withlacetic
anhydride [molar ratio 1 :7 in the presence of 10 % by weight
referred t o ( I ) of conc. H2S04, 2 hours at 100 "C, addition of
sodium acetate, filtration and distillation] into 3,3-bis(chloromethyl)-l,5-diacetoxy-2-oxapentane ( 3 ) , b. p. 135
to I37 OC/0.9 mm, yield 83 %. On alcoholysis (refluxing for
12 hours in excess ethanol with addition of small amounts of
HzS04) this gives in 76 P;; yield 4-chloro-3-chloromethylbutane-I,%diol ( 4 ) , b.p. 90°C/10-3 m m (molecular distillation), which on heating to 160°C is quantitatively converted into (2). It was not possible t o obtain ( 4 ) directly
from ( I ) .
Atomic sulfur [I] is formed during the photochemical
formation of isonitriles 121 from isothiocyanates with light
of 254 m p wavelength and was detected by its addition onto
cyclohexene t o form cyclohexene episulfide.
Phenylphosphinidene [31 is produced on heating tetraphenylcyclotetraphosphine (C&-P)4
above 160 " C , or from
phenyldichlorophosphine and zinc dust at 25"C, or o n
oxidation of phenylphosphine with iodine in the presence
of triethylamine. It was trapped by insertion into the p,-d,
double bond of disulfides, a reaction leading to phenylphosphonodithioites. This reaction is analogous to the
formation of mercaptals o n trapping of carbenes with disulfides 141.
Ph-PH2
f 12
Treatment of (2) with NaOH or sodium t-butoxide (molar
ratio 1: 1.1) in ether at 20-30°C gives 1,5-dioxaspiro[2,4]heptane ( 5 ) , b. p. 46 % C/14 mm, n?," 1,4423, with a yield of
over 80 %. With catalysts conventionally used in epoxide
polymerization [ e .g. BF3.(CzH5)20], ( 5 ) polymerizes in
CHzC12 to give a polyglycol (6), which is a viscous oil or a
low-melting resin, depending o n i t s molecular weight.
-
/
Phenylphoshinidene made from phenyldichlorophosphine
reacts with benzil to yield the I,l'-spirobis(phosphadioxo1e)
0).
A n g e n . Clwiii. intermit. Edit. 1 Vol. 4 (1965)
1 No. 5
437
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phinidene, solutions, c6h5p, phenylphos, detection, sulfur, atomic
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