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Elimination of Hydrogen Halide from Benzo- and Naphtho-thiazolium Halides.

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is removed in a vacuum and the residue is taken up in 200 ml
of 0.1 % aqueous hydrocyanic acid and added t o a column
(40 mm diameter by 100 mm) of carboxymethylcellulose.
Most of the unchanged cyanocobinamide runs through the
column; the rest is eluted with 2 % acetic acid, and immediately thereafter the cobyric ester (3) of 1-aminopropan-2-01
is eluted with a 1 : l mixture of 2 % acetic acid and 2 %
ammonium acetate solution. This ester is purified by extraction with phenol[3J, taken up in 100 ml of water, and acetylated by slow, dropwise addition to 5 ml of acetic anhydride
at 0 to 2 ° C with stirring. After an hour the product is
washed twice with 10 ml of chloroform, and the corrinoid
is purified by extraction with phenol. For cleavage, the ester
is kept at 0 ° C for 2 h in 200 ml of 1 M aqueous piperidine
solution. The mixture is washed three times with 30 ml of
2:1 isopropyl ether/l-butanol and brought to p H 5.5 by
dilute hydrochloric acid. After a further phenol extraction
and cellulose-column-chromatography with sec-butanoli
water (10: 3) the cobyric acid is obtained in pure form; yield
20-22 %.
Received: October 7th, 1965
[Z 83/917 IE]
German version: Angew. Chem. 78, 143 (1966)
Publication delayed at the authors' request
[I] K. Bernhauer, H . Dellweg, W . Friedrich, G. Gross, F. Wagner,
and P. ZeNer, Helv. chim. Acta 43, 693 ,696 (1960).
[2] H . C. Heinrich and E. E. Gabbe in: Vitamin B12 und Intrinsic
Factor, 2. Europ. Symp., Hamburg 1961. Enke-Verlag, Stuttgart
1962; H . C. Heinrich, W. Friedrich, and P. Riedel, Biochem. Z .
334, 284 (1961); W. Friedrich, H . C . Heinrich, E. Konigk, and
P. Schulze in: Conference on Bl2-Coenzymes, New York Academy of Sciences, New York 1963.
[3] W . Friedrich u. K. Bernhauer, Z. Naturforsch. 96, 755 (1954).
Trans-Selective Olefin Syntheses
By Dr. M. Schlosser and K. F. Christmann
1-Phenyl-1 -propene
1 -Phenyl- 1-hexene
1 -Phenyl-1,3-pentadiene
99: 1
96: 4
98: 2
99: 1
97: 3
96: 4
97: 3
[a] Determined gas-chromatographically.
[bl Isolated in substance.
[c] With acetophenone as carbonyl component, i.e., R
with CH3 in place of H.
G H s and
The phosphonium salt (30 mmole) is suspended in 50 ml of
tetrahydrofuran and 30 ml of ether and stirred with 30 mmole
of ethereal phenyl-lithium solution until the Gilman test is
negative (about 10 min). The solution is cooled to -70 OC
and 30 mmole of aldehyde (dissolved in 20 ml of ether) is
added; the mixture is stirred vigorously. As soon as decolorization is complete (5 min at -70 to -4OoC), a further
30 mmole of phenyllithium solution is added and the whole
kept at -30 "C until the Gilman test is again negative (about
5 min). This solution is treated with 33 mmole of ethereal
hydrogen chloride and with 45 mmole of potassium t-butoxide (as 1 : l complex with t-butyl alcohol). The mixture
is stirred at room temperature for 2 h, centrifuged, and the
clear supernatant liquor is poured off, washed with water
until neutral, and dried. After evaporation of the solvent,
the olefin is fractionated in a vacuum.
For comparison the olefins listed were prepared in parallel
experiments by the conventional Wittig reaction. The trans:cis
ratio (determined gas-chromatographically) varied between
75: 25 (phenylhexene) and 20: 80 (2-octene).
Received: October 14th, 1965
[Z 91/922 IE]
German version: Angew. Chem. 78, 115 (1966)
Organisch-Chemisches Institut
der Universitat Heidelberg (Germany)
Usually only mixtures of trans- and cis-olefins can be obtained by the Wittig reaction. A few examples are known
yielding predominantly trans- [ I ] or cis- [21 olefins. transSelective olefination can be expected if equilibration of the
erythro- and threo-betaines ( 1 ) [ I d can be accelerated.
We have now found that interconversion of the diastereoisomeric betaine ylides (2) [31 is extremely rapid [4J. These
ylides are formed if the betaine-LiX adduct ( I ) is treated
with phenyl-lithium or n-butyl-lithium in ether/tetrahydrofuran (1 : 1) at -30 "C, and with proton donors ( e . g . , hydrogen
chloride or t-butyl alcohol) they regenerate the betaine-LiX
adducts ( I ) .
(I). erythro
[I] a) H . 0.House and G. R. Rasmusson, J. org. Chemistry 24,
4278 (1961). - b) H . J. Bestmann and 0. Kratzer, Chem. Ber. 95,
1894 (1962). - c) M . Schlosser and K . F. Christmann, Angew.
Chem. 77, 682 (1965); Angew. Chem. internat. Edit. 4, 689
[2] H . Pommer, Angew. Chem. 72, 811 (1960), particularly p.
817; L. D. Bergelson, V. A. Vaver, L. I. Barsukov, and M . M .
Shemyakin, Tetrahedron Letters 1964, 2669; H . Machleidt and
R. Wessendorf, Liebigs Ann. Chem. 674, 1 (1964); P. A . Chopard,
R. F. Hudson, and R . J. G. Searle, Tetrahedron Letters 1965,2357.
[3] It is uncertain whether the betaine ylides actually have the
conformation shown. This representation is used merely for
[4] Cf. the rapid racemization of optically active organolithium
compounds: R . L. Letsinger, J. Amer. chem. SOC.72,4842 (1950).
Elimination of Hydrogen Halide from Benzo- and
Naphtho-thiazolium Halides ['I
By Prof. Dr. H.-W. Wanzlick, Dr. H.-J. Kleiner,
Dip1.-Ing. I. Lasch, and Dipl.-Chem. H. U. Fiildner
Organisch-Chemisches Institut
der Technischen Universitat Berlin (Germany)
The equilibrium between the diastereoisomeric betaine ylides
lies far to the side of form (2b), so that protonation gives
mainly the threo-betaine [threo-(I)]. Subsequent treatment
with potassium t-butoxide then liberates almost pure transolefin (cf. Table).
Hydrogen halide can be removed from benzothiazolium
halides by heating them with triethylamine [*I or by treating
them with triethylamine (or other tertiary amine) in polar
solvents at room temperature[3,41, with sodium in dioxane [41,
or with triethylamine in boiling acetone [51. This leads to
dimers (2), of as yet unknown configuration, by way of the
short-lived nucleophilic carbenes ( I ) 161. Contrary to our preAngew. Chem. internot. Edit. ! Vol. 5 (1966)
i No. I
vious assumption[31, the cdrbene moieties ( I ) cannot be isolated in substance.
N-Methylnaphtho[2,1-d]thiazolium iodide (obtained from
naphtho[2,1-d]thiazole and methyl iodide in dimethylformamide in 92 % yield, m.p. 203-204 "C), when treated with
triethylamine in dimethylformamide (preferably under
nitrogen) gives the brilliant red dimer (3) (87 %; decomp.
above cu. 195 OC; configuration not yet known) within a few
seconds even at 0 'C.
If the reaction is carried out with a n excess (3 moles or more)
of the alkyl-lithium (alkyl = ethyl or butyl) for 15-20 h at
20°C, the t-butylsulfonyl group is removed from ( I ) and
the 2-alkyl-1,3-dilithiobenzene is formed, which can be
recognized by formation of the previously unknown 2-alkylisophthalic acids (5) on carbonation. The acids (5) are
Like (2) and related systems, the compound ( 3 ) reacts as a
"half-molecule'' (cf. [I]). Thus with diazo compounds they
give azines.
Whereas the compounds of type (2) studied so far d o not
show evidence of dissociation in mass spectroscopy "1, the
mass spectrum of the dimer (3) shows the peak due to the
half-molecule (m/e = 199) as well as the comparably intense
peak of the molecule-ion (m/e = 398)rgI.
Received: October 19th. 1965
[Z 90/921 IE]
German version: Angew. Chern. 78, 115 (1966)
[l] Part 9 of Chemistry of Nucleophilic Carbenes. - Part 8:
H.- W. Wanzlick, B. Lachmann, and E. Schikora, Chem. Ber. 98,
3170 (1965).
[2] J . 4 . Vorsanger, Bull. SOC. chim. France 1964, 119.
[3] H.- W. Wanzlick and H.-J. Kleiner, Angew. Chem. 75, 1204
(1963); Angew. Chem. internat. Edit. 3, 65 (1964).
141 H . Quast and S. Hunig, Angew. Chem. 76,989 (1964); Angew. Chem. internat. Edit. 3, 800 (1964); cf. also H . Quast and
E. Frankenfeld, Angew. Chem. 77, 680 (1965); Angew. Chem.
internat. Edit. 4,691 (1965).
[5] J. Metzger, H. LarivP, R . Dennilauler, R . Baralle, and C . Gaurat, Bull. SOC. chim. France 1964,2857.
[6] H.Balli, Angew. Chem. 70,442 (1958), formula V; 76,995
(1964); Angew. Chem. internat. Edit. 3, 809 (1964).
[7] We thank Dr. H. Rehling (Farbwerke Hoechst) for these
[8] Cf. H . Prinzbach, H. Berger, and A . Luttringhaus, Angew.
Chem. 77,453(1965); Angew. Chem. internat. Edit. 4,435(1965).
R = CzH5, F p = 247-249'C, 42%
(56). R = CIHs, F p = 201-203"C, 44%
very stable and can be recrystallized from hot concentrated
HNO3 and sublimed without decomposition at 200-220 "C/
1 mm. Their structure is proved by oxidation of (Sa) with
concentrated HNO3 (sealed tube, 16O-18O0C, 5 h) to
hemimellitic acid [I].
The formation of the acids (5) can be explained by nucleophilic substitution of the t-butylsulfonyl group (route A) o r
intermediate occurrence of 3-lithiobenzyne (route B).
Received: October 20th. 1965
IZ 92/926 IE]
German version: Angew. Chem. 78, 116 (1966)
[l] C. Graebe and M . Leonhardt, Liebigs Ann. Chem. 290, 217
Synthesis of Bicyclo[3.1.llheptane
By Prof. Dr. H. Musso and Dip1.-Chem. K. Naumann
Synthesis of 2-Alkyl-l,3-dilithiobenzenesand
2-Alkylisophthalic Acids
Chemisches Institut der Universitat Marburg and
Chemisches Institut der Ruhr-Universitat Bochum [I]
N. D. Zelinskii Institute for Organic Chemistry of the
Academy of Sciences of the U.S.S.R., Moscow
Attempts to synthesise bicyclo[3.1. llheptane (norpinane)
(14) have previously failed [*I. We have now prepared this
compound by the following method, in order to study the 1,4
interaction in the boat form of cyclohexane.
When t-butyl phenyl sulfone ( I ) is metalated in ether/tetrahydrofuran (1 : I ) at -60 "C for 8-10 h with a n excess of an
alkyl-lithium or at -10°C for 3 h with 1 mole of the alkyllithium and then carbonated, o-(t-buty1sulfonyl)benzoic
acid (2) is formed in 40-45 % yield. The structure of the
acid was proved by synthesis from thiosalicylic acid (3).
Ethyl (methoxymethy1)malonate was reduced with LiA1H4
to 2-methoxymethyl-1,3-propanediol(1)(b.p. 139 OC/12 mm,
59 %), whose di-p-toluenesulfonate (2) (m.p. 166OC, 8 1 %)
was condensed with ethyl malonate by Buchtu's method [31,
giving diethyl (3-rnethoxymethyl)-l1l-cyclobutanedicarboxylate (3) (b.p. 97-99'C/0.7 mm, 63 %). The acid (4) (m.p.
123 " C , 100 %) obtained therefrom on hydrolysis was de-
By Dr. F. M. Stoyanovich and Prof. Dr. B. P. Fedorov
Atrgew. Chmi. iiiterrrrit.
Edit. f Vol. 5 (1966) / No. I
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elimination, hydrogen, benz, halide, naphthol, thiazolium
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