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Formation of Bis-(-chloro--alkoxyethyl) Sulfoxides by Addition of Thionyl Chloride onto Alkyl Vinyl Ethers.

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sodium hydride. As soon as the evolution or gas has ceased
(after about 2.5 h), 0.75 g (4 mmoles) of p-nitrobenzoyl
chloride is added without interrupting the stirring or reflux.
One hour later the mixture is cooled, a n d t h e cxcess sodium
hydride is decomposed with 0.35 g (2 mnioles) of anhydrous
p-toluenesulfonic acid. The salts precipitated a r e filtered off,
the benzene is distilled off, and the residual oil is refluxed for
onc hour with a mixture of 0.1 g of p-toluenesulfonic acid in
25 ml of glacial acetic acid containing about 2 % (by volume)
of acetic anhydride. The evolution of gas ceases after about
45 min. The mixture is poured o n t o ice, neutralized with
dilute alkali, and the white precipitate is filtered off (0.83 g;
8 1 ';<{ yield). After recrystallization from ethanol, colorless
leaflets are obtained which melt at 74.5 -75 " C .
-4) Diphenylenephenylphosphine [ 1611:
A Schlenk tube is charged under nitrogen with 21.6 g (83
moles) of triphenylphosphine a n d a suspension of phenylsodium (prepared from 8.5 g of chlorobenzene and 3.5 g of
sodium) in 40 ml of benzene, then sealed and shaken for 10 h
at 20 C a n d for 30 h at 70°C. After decomposition of unreacted starting material with methanol and addition of
water, the benzene layer is dried, the solvent is evaporated,
a n d the residue distilled. Thirteen grams of distillate are
collected at 0.05 m m H g and 155-160°C. This is mulled
with aqueous HCI (2 parts conc. HCI, 1 part H l O ) t o extract
10.2 g of triphenylphosphine. After recrystallization from
methanol, the residue melts a t 93-94'C. T h e yield varies
from 8 t o 15 ;,<;. For reasons of safety, larger-scale preparations should be carried out in a three-necked flask with
thorough mixing (Vibrator).
3) Tetraphenylgermane [ 1621:
A mixture of l o g (47 mmoles) of germanium tetrachloride.
100 ml of toluene, 9 g (39 mg-atom) of sodium and 30 g
(190 mmoles) of bromobenzene is carefully heated. As soon
as the reaction has begun, cooling must be applied. When the
reaction has subdued, the mixture is refluxed for 2:nothcr
hour. The hot solution is hydrolysed with hydrochloric acid.
Additional 100 ml of warm toluene are added, and tke
toluene layer is separated off, filtered, a n d concentrated to a
small voiume. T h e dark colored solution yields a pxcipitate
of 9.6 g of purely white crystals (53 "4 yield).
Thp arithor wishes to oxpuess his thanks to Prof: G.
Witiig, Du. V. L. Hansley, Dr. D. C. Foster, and Dr. G.
Kiihricli for lii,lpfiil advice.
R x e i v e d , M a r c h ?5th, 1963
[A 353/153 IE]
G e r m a n version: Angew. Chem. 76, 258 (1964)
T r a n s l a t e d by scripta technica, W a s h i n g t o n
[ l h l ] G. Wittifi a n d G.GeissIer, Liebigs Ann.Chem. 580, 50 (1953).
[I621 D.E.
The o-Nitrophenylsulfenylimine Radical [ 1 ]
sulfenylimine radical (2) t o sulfenylainine (4). Compounds
( 3 ) and ( 4 ) were identified. Dry decomposition of ( I ) gave
rise to (3), Nz, and NH3. Decomposition of ( I ) in acrylonitrile resulted in polymerisation.
By Doz. Dr. Ulrich Schmidt, Dipl.-Chern. K. H. Kabitzke,
and Dipl.-Chem. K. Markau
clicm. Soc. 62, 3267 (1940)
Received, July 18th, 1963
[ Z 712/538 IEI
Publication deferred until n o w a t t h e a u t h o r s ' request
G e r m a n version: Angew. Cheni. 76, 376 (1961)
Chemisches Laboratorium der Universitiit a n d
Institut fur Elektrowerkstoffe der Fraunhofer-Gesellschaft
Freiburg/Brsg. (Germany)
Di-(v-nitrophenylsuIfeny1)hydrazine ( I ) dissociates in toluene
at about 5 0 ° C into o-nitrophenylsulfenyliniine radicals (2).
T h e ESR spectrum shows three lines of equal intensity which
indicates a spin density at the nitrogen. As the equidistant
line-spacing is only about half as great ( I 1 Gauss) a s in the
spectrum of diphenylpicrylhydrazyl (DPPH), one must assume a high spin density a t a n a t o m without nuclear spin, in
this case at the sulfur [formula (2rr)I. Also, the high g-factor
(2.0076) which lies in the region of t h e values found for
I V . w n l / . J . Amer.
[I] Communication No. 7 on Organic Sulfur Radicals. -~Communication No. 6: U . Schmidt, A . Miiller, and K. Mnrknrc, Chcm.
Ber. 97, 405 (1964).
[ 2 ] U . Schmidt, K . H . Krrhitzke. and K . Marknn, Liebigs Ann.
Chem., i n thc prcss.
Formation of Bis-( $-chloro-$-alkoxyethyl)
Sulfoxides by Addition of Thionyl Chloride onto
Alkyl Vinyl Ethers
sulfur radical ions (CH3OC6H4-S -C6H4OCH3: g
By Dr. F. Effenberger a n d cand. chem. J. D a u b
[2]) and away from the g-values of N-radicals ( D P P H : g =
2.0036) indicates a n important participation of resonance
structures with radical sulfur.
lnstitut fur Organische Chernie und Organisch-Chemische
Technologie der Technischen Hochschule Stuttgart (Germany)
On cooling, the signal dies away and appears o n reheating,
indicating a reversible dissociation. Above 80 " C in toluene,
nitrogen is evolved from ( I ) . T h e sulfenylimine radical (2)
probably decomposes into a sulfur radical, which recombines
t o give the disulfide (3), a n d into imene which reduces the
Dediccitrd to Professor H. Bredereck on the occcisioti of his
60th birtli&v
2-Chloro-2-ethoxyethanesulfinyl chloride has been described
[ I ] as the unstable product of the addition of thionyl chloride
o n t o ethyl vinyl ether.
T h e reaction of thionyl chloride a n d alkyl vinyl ethers ( I )
in a molar ratio of 1 : 3 has now yielded bis-(3-chloro-Falkoxyethyl) sulfoxides (2).
2 RO-CH=CHz + SOCl, -+
I J)
When absolute ether was used a s solvent, t h e sulfoxides (2)
crystallized directly a s coloriess compounds that are readily
Atrgew. Cheni. interticit. Edit. 1 Vol. 3 (1964)
No. 5
recrystallizable from CC14 [R = CzH5, 97
yield, m. p.
20‘C (decomp.); R = s - C ~ H 80
~ , ‘i: yield, m.p. 30 -32°C
(decomp.); R = n-C4H9,90 2,yield, m.p.41-43”C(decomp.)].
The action of secondary amines o n (2) yields compounds of
type ( 3 ) [RI-R2 = (CH&, m.p. 78-80“C, RI--R2 =
( C H Z ) ~ - O - ( C H ~ )m.
~ , p. 79-8 I “C], while phenylhydrazine
produces f 4 ) , m. p. 1 18-1 20 “C, which could also be forniulated as ( 5 ) .
\c H = c H - N’
- (2)
dyes therefore yields the series 4-<5-<6-ring for the coupling
capacity of the nitrogen as a function of the ring size; this
corresponds t o the order observed by Lippert and Prigg:, [4]
for the electron-donor capacity of the nitrogen atom in free
cyclic imines.
Further work is in progress, also o n cyanine dyes with longer
[ Z 6461533 1El
Received, January 15th, 1964
German version: Angew. Chem. 76, 187 (1964)
[ I ] S . S. Mdtiotrn and M . C. W/titir1g, J. chem. SOC.(London)
1960, 3812.
[21 D . Grosse, Ph. D. Thesis, Technische Hochschule Munchen,
C H = C H- NH - NH- CGH,
[3] J . ffcifi,Ph. D.Thesis, Technische Hochschule Munchen,1964.
[4] E. Lippert and H . Prigge, Ber. Bunsenges. physik. Chem. 67,
6, 5 5 4 (1963).
Synthesis of Ribodinucleotides with Terminal
3‘-Phosphate Groups
Tertiary amines eliminate hydrogen chloride from (2),
R = C2H5, yielding a product of formula CsH,dO.$S, the
structure of which has not yet been established.
By Dr. D. Sol1 [*I a n d Prof. Dr. H . G . Khorana
Received, January Znd, 1964
[Z 649/474 IE]
Publication deferred until now at the authors’ request
German version: Angew. Chem. 76, 435 (1964)
. -
Institute for Enzyme Research, University of Wisconsin,
Madison, Wis. (U.S.A.)
Dedicated to Professor
[ I ] H . E. Si/nr~ions.D. C. Blomstrorn, and R. D. West, J . Arner.
H. Brerlereck
chem. Soc. 84, 4782 (1962).
Ribodinucleotides with 3’-phosphate end groups can be
polymerized chemically t o give ribopolynucleotides, which
are of importance for the experimental analysis of the amino
acid code.
Using C p U p ( I ) as a n example, we wish t o describe in the
following the simplest and most satisfactory approach yet
discovered t o dinucleotides with 3’-phosphate end groups.
3‘-phosphate (2) (0.1 mmole)
[I] was treated with 0.1 mmole of uridine 2‘(3’)-phosphate ( 3 )
in pyridine in the presence of 1.5 mmoles of dicyclohexylcarbodiimide. Subsequent treatment with Dowex-50 (H form) was used t o decompose the N-phosphorylureas formed [2]. The resultant N,2’,5’-triacetylcytidyl-3’+5’-uridine
3’(2’)-phosphate was treated with dicyclohexylcarbodiimide
in the presence of triethylamine to form the dinucleotide with
the terminal 2’,3‘-cyclophosphate ( 4 ) . Treatment of ( 4 ) with
pancreatic ribonucledse at pH 7.0 leads t o N,Z’,S’-triacetylcytidyl-3’-t5’-uridine 3‘-phosphate. Subsequent removal o f
the ribonuclease on a column of Dowex-SOX2 (pyridinium
form) a n d final deacetylation with 7 N ammonia leads to
C p U p ( I ) , which was isolated pure in 5 3 :< yield by chromatography on DEAE-cellulose. Using the same method, A p U p
Dependence of the Electron Excitation of
Open-Chain Cyanine Dyes on the Valence Angle
of Their Nitrogen Atoms
By Prof. Dr. G . Scheibe, Dipl.-Cheni. D. Grosse, and
Dipl.-lng. J . Heiss
Institut fur physikalische Chemie
der Technischen Hochschule Munchen germa an)^)
In contrast t o the statements of the simple theories on the
light absorption in cyanine dyes, the electron-cxcitation
energy depends not only upon the chain length but also on
the angle imposed on the residual valences of nitrogen by its
incorporation into rings of varying size. The energy ditferences amount t o about 1 kcal/mole and decrease with increasing
Table 1 . Electron-excitation energy Gmax and extinction coefticient
temperature. The values for thecoo-bands, measured in ethanol at - 180 ’C
1 0 - 3 [cm-’1
(I), n
(I),n= 1
(I), n
Jmax 10-3 [cm-’]
23.65 (23.45)
1.45 [ I ]
31.3 (30.6)
31.7 (31.3)
32.2 (31.75)
23.75 (23.5)
24.0 (24.0)
chain length. T h e cause is probably hybridization of the
nitrogen atom, depending o n the angle involved; this alters
the s-portion of the N-C bond and, therefore, the coupling
capacity of the nitrogen. T h e light absorption of the cyanine
of cyanine dyes [2] in ethanol at room
[)I, are shown in brackets
E m a x 10-4
( I ) ,n = 2
ocrnsioii of
h i s 60th h i r t h d ~ i ~ .
oil the
24.35 (24.15)
and I p U p were prepared in 47 ”/, a n d 4 4 74 yields, respectively.
Enzymatic degradation showed that the synthetic dinucleotides contained exclusively the C(3’)-C(5’) internucleotidic
Aiigew. C/ic.m. iritrrritit.
Edit. 1 Vol. 3 (1964)
No. 5
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onto, alkyl, ethers, formation, chloro, vinyl, additional, alkoxyethyl, sulfoxide, bis, chloride, thionyl
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