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N-[(Methylthio)-N-tosylformimidoyl]amino Acids.

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Cyclopentadienylgold(1)and Cyclopentadienyl(triphenylphosphine)gold(r)
By R . Hiittel, U. R a f a y , and H . Reinheimer[*l
Pure cyclopentadienyl-metal compounds involving elements
of the first sub-group have not been described hitherto. Only
(triethylphosphine)cyclopentadienylcopper(I) is known 121.
We have now synthesized cyclopentadienylgold(r). The
success of the method depends on preparing solutions of AuCl
in organic solvents in which it is normally insoluble. This may
be accomplished by means of a loose addition of a cyclic
olefin. Dicyclopentadienylgold(1) chloride [31 and truns,trans,
cis-1,5,9-cyclododecatrienegold(1)chloride [31 are soluble in
tetrahydrofuran (THF) and o n treatment with cyclopentadienylsodium afford the desired C5H5Au.
About 1 g of the olefin-gold(1) chloride is dissolved in 100 ml
of THF/ether (1 :4)and treated at -60 "C under nitrogen with
a solution of CSHSNa (3 molar equiv.) in THF. A yellow
precipitate is a t once formed but dissolves in the excess of
CsHsNa solution to give a colorless solution. The yellow
substance separates again on addition of dry ice. After
centrifugation at -30 "C the precipitate is washed three times
with 96 % alcohol and twice with ether and then taken up in
n-pentane. All solvents are precooled to -70 "C. On evaporation of the pentane under vacuum at -3O'C there remains a
powdery, yellow insoluble substance whose elemental composition corresponds to the formula CsHsAu.
The substance is sensitive to heat and friction. It is stable
for about an hour at room temperature but often deflagrates
o n gentle warming.
The same compound was obtained by treating the olefingold(1) chloride with cyclopentadiene (Cp) and triethylamine
but was then not analytically pure.
Since the insolhbility and instability of CsHsAu prevent its
closer study, the soluble and more stable cyclopentadienyl(triphenylphosphine)gold(r) was prepared.
About 1 g of (triphenylphosphine)gold(I) chloride [41 was
made into a slurry in 20 mi of ether and treated at -3OOC
under nitrogen with an excess of CsH5Na solution in ether
(5x 10-3 mole/liter). The temperature was slowly raised to
0 "C and the mixture was stirred for an hour. The whole was
poured into 200 ml of ice-water with vigorous stirring and
then filtered.Theresidue was washed first withwater,then with
cold acetone, and finally with ether. For purification it was
dissolved in THF/acetone at 0 ° C and treated dropwise with
ice-water. Colorless rhombohedra1 crystals of the composition C23H20A~Pwere obtained; they decompose above
100 OC.
present because the intense bands at about 1100 cm-1 are
missing [GI. The only remaining possibility is a a bond.
The UV spectrum of TPP.AuC5H5 resembles the spectra of
a-cyclopentadienyl(triethylphosphine)copper(I) and di(cyclopentadienyl)mercury(ir) [21. Its maximum lies at 236.6 nm
(E = 33400 in dioxane); TPP and TPP.AuCI give n o maximum
near this wavelength.
Only a few 1H-NMR measurements of a-cyclopentadienylmetal compounds are available[71. For TPP.AuCsH5 we find
only one sharp signal (7 = 3.7)[81 for the protons on the fivemembered ring, corresponding to a a-bonded cyclopentadienyl ligand undergoing rapid exchange of the carbon-metal
bond 191.
The N M R spectrum of(methylcyclopentadieny1)-TPP-gold(r),
which we have so far obtained only in solution - by treating
TPP-ALCI with methylcyclopentadienylsodium or with
niethylcyclopentadiene + NaOCH3 - shows three signals,
namely at i =- 3.9, 4.15, and 7.7 ( 2 : 2 : 3 ) . This indicates that
in this instance the metal IS o-bonded to the carbon atom
carrying the CH3 group [ l o ] .
Received: July 3rd, 1967
[ Z 560 IE]
German version: Angew. Chem. 79, 859 (1967)
['I Prof. Dr. R. Huttel, DipLChem. U. Raffay, and
Dip1.-Chem. H. Reinheimer
Institut fur Organische Chemie der Universitat,
Abteilung fur Technische Chemie
Karlstr. 23
8 Munchen 2 (Germany)
[l] Part 5 of Olefin-Gold Complexes. - Part 4: R. Huttel, H.Reinheimer, and K . Nowak, Tetrahedron Letters 1967, 1019.
[21 G. Wilkinson and T. S. Piper, J. inorg. nuclear Chem. 2, 32
(1956).
[3; R . Huttel, H. Reinheirner, and H . Diet/, Chem. Ber. 99, 462
(1966).
[4] M. Levi-Malvuno, Atti Reale Accad. naz. Lincei, Ser. 5, 17 I,
847 (1908).
[5] s = strong, m = medium, w = weak.
[6] H. P. Fritz in F. G. A . Stone and R. West: Advances in Organometallic Chemistry. Academic Press, New York, London
1964, Vol. 1.
[7] G. Wilkinson and F. A . Cotton, Progr. inorg. Chern. I, 5i
(1959); H . P. Fritz and K . E. Schwarzhans, Chem. Ber. 97, 1390
(1964); H. P. Fritz and C. G. 0-eiter,J. organometallic Chem. 4,
313 (1965).
[Sl Recorded in DCCI3 with a Varian A 60.
[9] T. S . Piper and G . Wilkinson, J. inorg. nuclear Chem. 3, 104
(1956).
[lo] H. P. Fritz and K . E. Schwarzhans, Chern. Ber. 97, 1390
(1964).
The same compound was detected by N M R spectroscopy in
the products of the following reactions:
+
Acids
CsHsAu triphenylphosphine (TPP)
TPP.AuCl+ Cp triethylamine
TPP.AuC1f Cp KOH
TPP.AuCI Cp NaOCH3.
+
+
+ +
The IR spectrum (KBr disc) of cyclopentadienyl(tripheny1phosphine)gold(I) (TPP.AuCsH5) contains the following
bands in addition to those that occur in the spectrum of
TPP.AuCI:
642 w, 734 s, 803 s, 922 w-m, 970 m, 998 m, 1404 m (cm-*)[5]
An ionic cyclopentadienyl-metal bond is excluded because
there are two bands in the region around 1000 cm-1161; it is
questionable whether a n bond of the ferrocene type is
862
N- ((Methy1thio)-N-tosylforrnimidoyl]amino
By J . Gante [*I
Heating the sodium salts of the amino acids (la)-(Id) with
S,S-dimethyl N-tosyldithiocarbonimidate[zl (molar ratio
1:1) in boiling ethanol/water (2: 1) for five to six hours and
then adding a n equivalent amount of 1 N HCI gives the
hitherto unknown N - [(methylthio) - N - tosylformimidoyl]amino acids (2a)-(2d). In the case of ( I d ) (L-glutamic acid
the disodium salt is used.
SCH3
TOS-N=C'
'SCH3
P
H2N-CH-COONa2) ,
1)
HC,
-D
B
Tos-N=C-NH-CH-COOH
(1)
Tos = p-toluenesulfony!
Angew. Chem. internat. Edit.
/ Vol. 6 (1967) 1 No. 10
Optical
rotation
Yield
M.p.
( %)
( "C)
-H
76
173-175
-CH,
61
135-136
-CHz-GHs
85
168-170
R
~
64
95 "/, yield and avoids the high-vacuum distillation necessary
for purification in all previous preparations of these compounds 11-31. 0,O-Dialkyl S-morpholinodithiophosphate ( I )
is treated with a dialkyl phosphite (2) in a stream of anhydrous HCI 141.
s
9
( R O ) ~ P - S - N ~+
O (R'0)zP-H + HC1
-+
u
[cr]g--24.4
( c = I . ethanol)
151-153
Compounds (2a)-(2d) are colorless, crystalline substances
that react weakly acidic and dissolve readily in ethanol but
only slightly in water; they can be readily recrystallized from
mixtures of these two solvents from which they often separate
first as oils.
These compounds are susceptible to aminolysis, ethanolysis,
and hydrolysis. Thus (2a) (as the sodium salt) reacts with
an excess of benzylamine in boiling ethanol/water ( 3 : l )
within 8 h to give N-(N1-benzyl-N~-tosylamidino)glycine(3)
(yield 41 %, m.p. 196-198 "C), and with an excess of hydrazine hydrate o n six hours' heating with water under reflux
to give N-(hydrazino-N-tosylformimidoy1)glycine( 4 ) (yield
50 %, m.p. 146-147 "C).
Yield
( %)
T 06
95
96
(3c)
i3di
1
1
C2H5
i-CdH5
I
1
L-CIHP
CzH,
1
1.4880
I
1.1322
1
1 1 1
1.4870
1.1302
[a] Values i n the literature: For f3a; n:
1.4969 121; for ( 3 5 ) n:; = 1.4920 [31.
~
96.54
96.30
94
96.54
96.33
95
= 1.5008 [I],
1.4964 [31,
n 3 :c
The elemental compositions, molecular refractions, and IR
spectra(maxima at 555, 653,and1270 cm-l,whicb correspond
to P-0-P, P=S, and P=O groups) prove the purity and
structure of the compounds (3a)-(3d).
Experimental:
When the sodium salt of (2a) (obtained by adding a n
equivalent amount of 1 N NaOCzHS) is heated for 30 h in
boiling ethanol, ethanolysis occurs to yield N-(ethoxy-Ntosylformimidoy1)glycine (5) (yield 28 %, m.p. 166-168 "C).
When, however, double the amount (100 % excess) of sodium
ethoxide is used and the mixture is boiled for 15 h, N-(tosylcarbarnoy1)glycine (6) (yield 22 %, m.p. 187-188 "C) is
obtained, probably under the hydrolytic influence of small
amounts of water present in the ethanol.
Received: June 29th, 1967
[ Z 563 IE]
German version: Angew. Chem. 79, 858 (1967)
[*I Dr. J. Gante
Institut fur Oiganische Chemie der Freien Universitat
Thielallee 63-67
1 Berlin 33 (Germany)
[l] This work was supported by the Deutsche Forschungsgemeinschaft.
[2] R. Gompper and W. Hagele, Chem. Ber. 99, 2885 (1966).
Synthesis of Asymmetric O,O,O,O-Tetraalkyl
Dithiopyrophosphates
By L. Almasi and L . PaskuczL*]
We have found a simple process for preparing asymmetrical
O,O,O,O-tetraalkyl dithiopyrophosphates (3) that have
powerful anticholinesterase activity. This method affords a
Angew. Chem. internat. Edit. / Vol. 6 (1967)
/ No. I0
The thioamide ( I ) (0.04 mole) in anhydrous ether (100 ml)
is treated at room temperature with a n equivalent amount
of (2) in a two-necked flask fitted with a CaC12 tube and a
tube for introduction of gas. A stream of anhydrous hydrogen
chloride is passed into the ice-cooled solution. After saturation of the solution with HCl, the precipitated morpholine
hydrochloride is filtered off and the etheral solution is concentrated (at 10 mm) to half its volume, treated with 50 ml
of petroleum ether, and washed successively with 20 ml of
water, 20 ml of sodium hydrogen carbonate solution, and
20 ml of water. The organic layer is dried for 2 h over anhydrous MgS04, and the solvent is removed at room temperature (1 mm, 1 h). The residue (3) is a colorless liquid.
Received: June 26th, 1967
IZ 565 IE]
German vers:on: Angew. Chein. 79, 859 (1967)
[*I Dr. L. Almasi and Dip1.-Chem. L. Paskucz
Academia Republicii Socialiste Romania
Filiala Cluj
Institutul de Chimie
Str. Donath No. 59-65
Cluj (Roumania)
[l] N . N . Melnikcf; K . D . Shevzovn-Schilovskaya, and M . I.
Kagan, i.obSE. Chim. 30, 200 (1960).
[2] W . Lorenz and G. Schrader, German Pat. 1159934; Chem.
Abstr. 60, 11898b (1964).
[3] J. Michalski and J. Wassiuk, J. chem. SOC. (London) 1962,
5056.
[4] The course of the reaction will be discussed in a paper to be
published later.
863
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