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Aromatic Compounds form Leaf Alcohol.

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The IH-NMR spectrum of (11) shows two signals with areas
in the ratio 3 :2 141. In comparison with hexamethyldisilazane
and tetramethylsilane (Table 1) there is little shielding of the
protons in the silyl group, indicating the extinction of the
d,p,-portion of the Si-N bond due to the fact that the free
electron pairs on the nitrogen are used for co-ordination with
aluminum. In the case of (I) this effect is overlapped by the
inductive effect of the two chlorine atoms.
Received, February 21st. 1962
Our compounds had to some extent different properties from
those reported in this paper.
[3] Varian A 60 (60 Mc). All compounds in CC14 solution at concentrations of 1-5 %. Tetramethylsilane as external standard,
hexamethyldisilazane as additional internal standard.
[4]The signal of the protons on nitrogen is not cbnsidered.
IH-NMR Investigation of the tris-Trimethylsiloxy
Compounds of Boron, Aluminum and Gallium [ll
By Dr. H. Schmidbaur and Priv.-Doz. Dr. Max Schmidt
Institut fur Anorganische Chemie der Universitat Miinchen
The reactions of sodium trimethylsiloxide with aluminum or
gallium trichloride in the molar ratio of 3 : 1 according to
+ AICI3 -+
3 (CHj)3SiONa
+ GaCl3
Table 1. Physical Data and Chemical Shift Values 141
[Z 257/89 IE]
[I] Heterosiloxanes VII. CommunicationVI : H. Schmidbaur and
M. Schmidt, J. Amer. chem. Sac. 84, 1069 (1962).
[2] M. Becke-Goehringand H.Krill. Chem. Ber. 94, 1059 (1961).
3 (CH3)aSiONa
sharp resonance singlets with relatively high chemical shift
differences (Table 1) [4], and areas in the ratio of 2: 1. The
astonishingly small shielding of the protons of the bridge
siioxy groups indicates the extinction of the d,p,-portion of
these Si-0 bonds through coordination [ l , 51.
+ 3 NaCl
+ 3 NaCl
afford good yields of the colorless, crystalline, waxlike compounds, (Me3SiO)sAl [2] and (Me3Si0)3Ga, respectively.
Both are high melting, sublimable solids of strikingly low
chemical reactivity, high thermal stability and excellent solubility in all organic solvents. Cryoscopic molecular weight
determinations for both (I) and (11) give the dimeric molecu-
-0.27 5
-0.28 3
In contrast to (I) and (11), the known compound (111) [6] is a
volatile, monomeric substance. As expected, its NMR spectrum, as determined by us, shows only one sharp signal whose
position indicates the presence of Si-0 bonds in which the
portions are only partially cancelled by mesomeric x
bonding between boron and oxygen.
Received, February 2lst. 1962
[Z 258/88 IE]
111 Heterosiloxanes VIII. Communication VII : preceding.
121 We were unable to verify earlier reports concerning these
compounds: K. A. Andrianov, A. A. Zhdanov, and K. Kazakova, Izvestiya Akad. Nauk SSSR, Otdel. Tekh. Nauk 466 (1959);
Chem. Abstr. 53, 17561 (1959).
[3] Cf. C. G. Barraclough, D. C. Bradley, J. Lewis, and J. M .
Thomas, J. chem. SOC.(London) 2601 (1961).
[4] Varian A 60 (60 Mc). All compounds in CC14 solution at
concentrations of 3-5 yo, trimethylsilane as internal standard.
[5] H . Schmidbaur and H. Schmidt, J. Amer. chem. SOC.,in the
[6] W. E. Abeland Apar Singh, J. chem. SOC.(London) 690 (1959),
and references cited therein.
Aromatic Compounds from Leaf Alcohol
By Dr. A. Hatanaka, Prof. Dr. M. Ohno,
and Assist. Prof. Dr. Y.Inoue
Institute for Chemical Research, University of Kyoto (Japan)
In 1935 S. Takei et al. [l] obtained compound (I), b.p. 240 "C,
by heating leaf alcohol (cis-hex-3-en-1-01) with sodium at
160 to 170°C under reflw; the compound has an orange-like
aroma. The structure of (I) was assumed t o be 3-propyl-3since it forms a
nonen-1-01 or 3-propyl-3,5-nonadien-l-ol,
urethane (m.p. 145 "C)and a 3,5-dinitrobenzoate (m.p. 78 "C).
We assume that compound (I) (b.p. 138-139"C/12 mm. Hg;
ng 1.5150; 3,5-dinitrobenzoate, m.p. 78OC [2]) has an
aromatic structure for the following reasons: (1) It does not
absorb hydrogen in the presence of platinum oxide; (2) it
does not decolorize a potassium permanganate solution at
room temperature; (3) it does not react with bromine, and (4)
the infrared spectrum has the sharp bands characteristic of
aromatic compounds. Furthermore, the ultraviolet spectra,of
2,5-dimethylbenzyl alcohol and of compound (I) both show
a strong maximum at 268 mp. Oxidation with potassium
permanganate gives benzene-l,2,4-tricarboxylicacid [3] (m.p.
208°C) in quantitative yield. Compound (I) was obtained
not only from cis-hex-3-en-1-01, but from trans-hex-3-en-,
cis-hex-2-en- and trans-hex-2-en-l-ols, as well as from transhex-2-en-I-a1 (leaf aldehyde); n-hexan-1-01 and n-caproic
acid were obtained as by-products in every case.
The infrared spectra [3] of the compounds (in solution and in
Nujoi mull) are in agreement with this structure, as are the
1H-NMR spectra. Compounds (I) and (11) each show two
The structure of the aromatic compound (I) obtained from
leaf alcohol or leaf aldehyde should therefore be 2-propyl-5ethylbenzyl alcohol, since from cis- and trans-hex-2-en-1-01s
and from trans-hex-2-en-l-al, we obtained (I) and from
trans-but-2-en-1-01 we obtained 2-methylbenzyi alcohol [4]
(b.p. 115-117 "(317 mm. Hg; nB 1.5082; 3,5-dinitrobenzoate
Angew. Chem. internat. Edit.
Vol. I (1962) I No. 6
m.p. 128-129 "C). An aromatic compound, presumably 2ethyl-5-methylbenzyl alcohol (b.p. 110-120 OC/ll 111111. Hg;
ng 1.5080); 3,Sdinitrobenzoate m. p. 76 "C), was obtained
from pent-3-en-1-01.
example, adds on 53 to 62 % of various amines in the m-position [3], it seems that, besides aryne formation, s N 2 reaction
of the carboxylate group can only play a very small part in
the formation of the above products.
Received, February 23rd. 1962 [Z 238/73 IE]
Received, February 23rd. 1962
[I J S. Takei, Y . Sakato, and M . Ohno, J. agric. chem. SOC.Japan
14, 303 (1935).
[2] According to S . Tukei [I], no melting point depression when
mixed with the 3,Sdinitrobenzoate of compound (I).
[3] No melting point depression when mixed with authentic
[4] Identified in the form of o-toluic acid.
A New Route to Benzyne
By Dr. G. Kbbrich [*I
[Z 241/81 IE]
[*I Dedicated in admiration and gratitude to Prof. Dr. G. Wittig
on the occasion of his 65 th. birthday.
[I] Cf. G. Wiftigand R. W.Hoflman, Angew. Chern. 73,435 (1961);
G. Wittig and H . F. Ebel, ibi#. 72,564 (1960); M . Stiles and R. G.
Miller, J. Amer. chem. SOC.82, 3802 (1960).
[2] G. Kobrich, Chern. Ber. 92, 2985 (1959); cf. H. E. Simmons,
J. org. Chemistry, 25, 691 (1960); J. K . Kochi, ibid. 26, 932
(1961); E. I. McNelis, Abstr. Papers Fall Meeting Amer. chem.
SOC. 1961, p. 89.
[3] R. Huisgen and J. Sauer, Chem. Ber. 91, 1453 (1958); Angew.
Chem. 72, 91 (1960); F. Scardiglia and J. D: Roberts, J . org.
Chemistry 23, 629 (1958).
Organisch-Chemisches Institut
der Universitat Heidelberg (Germany)
Ternary Uranium(V) Oxides [I]
Decarboxylation of salts of o-halogenobenzoic acids in
non-alkaline reaction medium should proceed via the intermediate (1) and provide a convenient approach to benzyne
(VIII, R = H) [I]. Although pyrolysis of p o t a s s i u m oc h l o r o b e n z o a t e (11, R = H) produces a 5 2 % yield of
xanthone (111) and a small quantity of phenol [2], pyrolysis
of the p-methyl compound (11, R = CH3) gives some m-cresol
and a mixture of esters (IV) and (V), both containing mcresol as phenol component. This result is in agreement with
the assumption of nucleophilic substitution of the halogen
induced by the carboxylate anion, but not with formation of
a benzyne intermediate.
By Prof. Dr. W. Riidorff, Dip1.-Chem. S. Kemmler,
and Dr. H. Leutner
Laboratorium fur anorganische und analytische Chemie.
Universitat Tiibingen (Germany) [*I
Reaction of uranates (VI) with U02, if necessary in the
presence of U03 or M e W , gave the uranium(V) compounds
shown in Table 1. The reaction between zinc as well as nickel(11)-uranate (VI) and UOZ gave only mixtures of U308,
UO2.25, and Me"0.
Table 1. Ternary qranium(V) Oxides
Liz0.2 UzO5 = LiUz05,5
Na20.Uz05 = NaUO3
The silver s a l t VI (R = H), in which the nucleophilicity
is depressed by increased homopolarity of the bond between
cation and the carboxylate group, pyrolyzes smBothly to give
chlorobenzene and phenyl o-chlorobenzoate (VII, R = H).
Proof for the existence of the intermediate VIII, which
was postulated earlier for this reaction [2], but which could
not be trapped using tetracyclone, is furnished by decarboxylating VI (R = CH3); this produces a mixture of esters
(VII, R = CH3) which have a u n i f o r m acid component and
which on hydrolysis gave m- and p-cresol in a ratio of 61 :
39, determined by infrared spectroscopy. Since 3-toluyne, for
Angew. Chcm. internat. Edit. / Vol. I (1962) No. 6
p: 3 9 %
Lattice Constants
Structure Type
a = 5,901 A
a = 54 "36'
a = 10,70A
a = 5,175 A,
b = 5,905 A
c = 8,25 8,
a = 4,290 A
a = 4,323 8,
a = 5,275 A
a = 5,357A
a = 10,715 A
a = 91 "IS'
a = 11,lsA
Ilmenit or
CaFz Superstructure
CaFz Superstructure
a = 90'18'
In the alkali-uranium (V) oxides series, only the compounds
Li7UO6, Li3UO4, Na3U04 [2], LiUO3, and NaU03 [ I ] were
previously known. The structures of the two latter compounds
have now been determined. The brown-violet compounds
K U 0 3 and RbUO3, which crystallize in a cubic perovskitetype lattice, were prepared for the first time. Furthermore,
the existence of a cubic phase Li20.2 U2O5 in the system
Li20-U205 has been demonstrated. It possesses a CaF2
superstructure with empty spaces in the anion positions. On
further reduction of the Liz0 content, a hexagonal phase
appears in addition to the cubic phase. Its lattice constants
(a = 6.815 A, c = 4.130A) are practically the same as those of
the "U30s" modification which is stable between 400-600 OC
[3]; the oxygen content of the latter, however, is less than
that of this Structure [4]. Since the hexagonal phase was
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forma, compounds, alcohol, aromatic, leaf
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