ISSN 0009-2940
CHBEAM 124
1991 (1) 1-250, A l - A XVII
Chemische
Berichte
Contents
Inhalt
Teil A : Anorganische und elementorganische Chemie/Part A : Inorganic and Organometallic Chemistry
Kreiter. C . G „ L e h r , K . ,
Leyendecker, M . , Sheldrick, W . S.,
Exner, R.
3
•
Photochemische Reaktionen von Ü b e r gangsmetall-Organyl-Komplexen m i t O l e finen, 3. — [4 + 5]-Cycloaddition konjugierter Diene an T r i c a r b o n y K r i ^ ^ - d i m e thyl-2,4-pentadienyl)mangan
Photochemical Reactions of T r a n s i t i o n
M e t a l O r g a n y l Complexes with Olefines,
3. — [4 + 5] C y c l o a d d i t i o n of Conjugated
Dienes to Tricarbonyl(r) -2,4-dimethyl2,4-pentadienyl)manganese
5
Westermann, H . , Nieger, M . ,
Niecke, E.
13
•
Synthese und Struktur von Bis[bis(diisopropylamino)phosphino]chalkogeniden
Synthesis and Structure of Bis[bis(diisopropylamino)phosphino]chalcogenides
Herberich, G . E., Englert, U . ,
Hostalek, M . , L a v e n , R.
17
•
Derivate des Borols, X V I . nickel-Komplexe
Derivatives of Borole, X V I . — Bis(borol)nickel Complexes
Herberich, G . E„ Negele, ML,
Ohst, H .
25
•
Derivate des Borols, X V I I . - f r | - [ l - ( D i isopropylamino)borol]}metall-Komplexe:
Synthesen, Protonierung, interne R o t a t i o n
Derivatives of Borole, X V I I . - ( n , - [ l - D i isopropylamino)borole]J metal Complexes:
Syntheses, P r o t o n a t i o n , Internal R o t a t i o n
Erhart, M . , M e w s , R., Pauer, F.,
Stalke, D . , Sheldrick, G . M .
31
•
(Perfluoralkyl)(dimethylamino)sulfoniumhexafluoroarsenate
(Perfluoroalkyl)(dimethylamino)sulfonium
Hexafluoroarsenates
M a g g i u l l i , R., M e w s , R.,
Noltemeyer, M . , Offermann, W . ,
Paape, R., Stohrer, W . - D .
39
•
A d d i t i o n von A l k e n e n an
thyl)-l,3,2,4,6-dithiatriazin
5-(Trifluorme-
A d d i t i o n of Alkenes to 5-(Trifluoromethyl)-l,3,2,4,6-dithiatriazine
H a b b e n , C . D . , Heine, A . ,
Sheldrick, G . M . , Stalke, D . ,
B ü h l , M . , von R. Schleyer, P .
47
•
Synthese und Eigenschaften von 1.2.4.3Thiadiazaborctidincn. K r i s t a l l s t r u k t u r des
2,4-Di-ferr-butyl-3-phenyl-1,2,4,3-thiadiazaboretidins
Synthesis and Properties of 1,2,4,3-Thiadiazaboretidines. C r y s t a l Structure of 2,4Di-f(?r/-butyl-3-phenyl-1,2,4,3-thiadiazaboretidine
Boese, R., Haas, A . ,
Spehr, M .
51
•
Darstellung von (Perfluoralkyl)halogeno1,3-diselenetanen aus entsprechenden Selenocarbonylfluoriden und U m s e t z u n g mit
Bortrichlorid sowie Arsenpentafluorid
Preparation of (Perfluoroalkyl)halogcno1,3-diselenetanes from the Corresponding
Selenocarbonyl Fluorides and Reactions
with B o r o n T r i c h l o r i d e or Arsenic Pentafluoride
P i a n a , H . , Wagner, H . ,
Schubert, U .
63
•
Ü b e r g a n g s m e t a l l - S i l y l - K o m p l e x e , 36. —
Z u r Frage von G o l d - G o l d - W e c h s e l w i r kungen bei P h P [ C H ] P P h - v e r b r ü c k ten zweikernigen G o l d - S i l y l - K o m p l e x e n
T r a n s i t i o n - M e t a l Silyl Complexes, 36. —
O n the Question of G o l d - G o l d Interactions in P h P [ C H ] P P h - B r i d g e d D i n u clear G o l d Silyl Complexes
Beiträge zur Chemie des
Phosphors,
210. Pentaorganyltricyclononaphosphane mit Brexan-Struktur, / ? - P R (R =
M e , Et, iPr)
Contributions to the Chemistry of Phosphorus, 210. — Pentaorganyltricyclononaphosphanes with a Structure Analogous
to Brexane, fr-P R (R = M e , Et, /Pr)
Synthese und Struktur der P o l y c y c l o h e xaphosphane P ( C M e ) und P ( C M e )
Synthesis and Structure of the P o l y c y c l o hexaphosphines P ( C M e ) 4 and P ( C M e )
Untersuchungen ü b e r das P r o d u k t aus
Monobutylzinn(IV)-Verbindungen und Benzoyl(thiobenzoyl)methan: ein 1,3,2^,4^Dithiadistannetan
Investigation on the Product from M o n o butyltin(IV) C o m p o u n d s and Benzoyl(thiobenzoyl)methane: a 1.3,2A\4>v -Dithiadistannetane
69
•
2
l { 2 )
2
9
Jutzi, P., K r o o s , R.,
M ü l l e r , A . , Bögge, H . ,
Penk, M .
75
•
5
5
2
Baudler, M . , A r n d t , V .
Bis(borol)-
6
5
5
4
6
2
5
5
5
2
9
2
1 ( 2 )
2
5
6
5
5
6
5
5
2
Notizen / Notes
Seth, N . , G u p t a , V . D . ,
Linti, G., Nöth, H .
Bittner, J., Seppelt, K .
83
5
M o l e k ü l s t r u k t u r von H g [ C ( C O F ) = = S F , =
87
• Molecular
SF = 0]
O]:
•
Publikationssprache
Fortsetzung: bitte u m b l ä t t e r n / C o n t i n u e d : please turn over
2
•
Structure
2
Language of Publication
of H g [ C ( C O F ) =
K u h n , N . , Jendral, K . ,
Boese, R., Bläser, D .
89
Wjberg, N . , Schuster, H .
93
•
•
Inhalt (Fortsetzung)
Contents (Continued)
Heterocyclen als L i g a n d e n , X . — 2,2',5,5'Tetra-ferf-butyl-U'-diazaferrocen — Stabilisierung der Diheterometallocen-Struktur durch sterische A b s c h i r m u n g
Heterocycles as L i g a n d s , X . — 2,2',5,5'T e t r a - f 6 f / Y / - b u t y l - l , l '-diazaferrocene —
Stabilization of the Diheterometallocene
Structure by Steric S h i e l d i n g
Z u r K e n n t n i s des „ S i l a n p h o s p h i m i n s "
(Phosphasilaethens) tBu Si = P S i f B u
O n the Knowledge of the " S i l a n e p h o s p h i mine" (Phosphasilaethene) f B u S i = P S i f B u
2
,
3
2
3
Kurzmitteilung / Short Communication
S o m m o v i g o , M . , Pasquali, M . ,
L e o n i , P., Braga, D . ,
Sabatino, P .
4
97
P — C - B i n d u n g s a k t i v i e r u n g und r ) - K o o r dinierung von A r e n : R ö n t g e n - K r i s t a l l struktur eines zweikernigen u-Phosphidou - T ) : r| -Phenoxo-Zwitterionenkomplexes
von P a l l a d i u m , der ein Aggregat von drei
Wasserstoff-verbrückten Phenol-Molekülen a b f ä n g t
•
Massenspektrometrie und M a t r i x - I s o l i e rung einiger 9-Silaanthracene
•
2
4
P — C B o n d A c t i v a t i o n and r | - C o o r d i n a tion of Arene: X - r a y C r y s t a l Structure of
a Dinuclear u - P h o s p h i d o u-n, : r p - P h e n o x o Zwitterionic C o m p l e x of P a l l a d i u m
T r a p p i n g an Aggregate of Three H y d r o gen-Bonded Phenol M o l e c u l e s
2
2
Querverweise /Cross References
B i c k e l h a u p t , F . , M a i e r , G . et al.
E i l b r a c h t , P . et
A u m a n n , R. et
B
185
M a s s Spectrometry a n d M a t r i x Isolation
of Some 9-Silaanthracenes
al.
191
•
U m w a n d l u n g e n des ( + )-2- und ( + )-3-Carens in optisch aktive Siebenring-Systeme
Conversions of ( + )-2- a n d ( + )-3-Carene
into Optically A c t i v e S e v e n - M e m b e r e d
R i n g Systems
al.
213
•
Organische Synthesen mit Ü b e r g a n g s m e t a l l - K o m p l e x e n , 50
O r g a n i c Syntheses via T r a n s i t i o n
Complexes, 50
Metal
Teil B: Organische Chemie/Part B: Organic Chemistry
Hoffmann, V . T., M u s s o f , H .
103
•
Asterane, X X I I . — Synthese eines doppelten Tetraasterans: Nonacyclo[10.8.0.0 .
Asteranes, X X I I . — Synthesis of a D o u b l e
Tetraasterane: N o n a c y c l o [ 1 0 . 8 . 0 . 0 . 0 ' .
211
0
4.9 6.17_ 7.l6
0
0
0
9.l4 14.19
0
2n
] e i c o s a n
0
4 , 9 6 j 7 7.,6 9 . l 4
0
0
0
> 0
l4 19
t
4
9
] e i c o s a n e
K o r b o n i t s , D . , Simon, K . ,
Kolonits, P.
111
Synthese v o n 4 - A m i n o p y r i m i d i n e n aus
1,2,4-Oxodiazolen, III. — Eine neuartige
B i l d u n g von Olefinen aus A m i n e n
•
Synthesis of 4 - A m i n o p y r i m i d i n e s from
1,2,4-Oxadiazoles, III. — A N o v e l T y p e of
F o r m a t i o n of Olefins from A m i n e s
Reißig, H . - U . , Hippeli, C .
115
Lithiicrte 5,6-Dihydro-4tf-l,2-oxazine: Synthese, hoch diastereoselektive Reaktionen
mit E l e k t r o p h i l e n u n d nachfolgende U m wandlungen
•
Lithiated 5,6-Dihydro-4//-l,2-oxazines: Synthesis, H i g h l y Diastereoselective Reactions
with Electrophiles, and Subsequent T r a n s formations
Schulz, A . , K a i m , W .
129
P r ü s s e , T., Czekay, G . ,
Schwarz, H .
141
G o d t , A . , Schlüter, A . - D .
149
•
C y c l o b u t e n - R i n g ö f f n u n g : Eine nützliche
R e a k t i o n zur Synthese d o p p e l s t r ä n g i g e r
Moleküle
Cyclobutene Ring O p e n i n g : A Useful R e action for the Synthesis of D o u b l e Stranded Molecules
Effenberger, F., Streicher, W .
157
•
Darstellung aromatischer F l u o r - V e r b i n dungen durch nucleophilen Austausch von
N i t r o - G r u p p e n gegen F l u o r i d
Synthesis of A r o m a t i c F l u o r o C o m p o u n d s
by Nucleophilic Exchange of N i t r o G r o u p s
by Fluoride
Effenberger, F . , K o c h , M ,
Streicher, W .
163
•
N u c l e o p h i l e Substitution von N i t r i t i n N i trobenzolen, N i t r o b i p h e n y l e n und N i t r o naphthalinen
N u c l e o p h i l i c Substitution of N i t r i t e in N i trobenzenes, N i t r o b i p h e n y l s , a n d N i t r o naphthalenes
Ohler, E., Zbiral, E.
175
•
Z u r R e a k t i o n von D i a l k y l p h o s p h i t e n mit
a-Enonen, I. — Synthese und A l l y l - U m lagerung v o n ( l - H y d r o x y - 2 - a l k e n y l ) - und
(l-Hydroxy-2-cycloalkenyl)phosphonsäuredimethylestern
Reaction of D i a l k y l Phosphites w i t h a - E n ones, I. — Synthesis a n d A l l y l i c Rearrangement of D i m e t h y l ( l - H y d r o x y - 2 - a l kenyl)- and ( l - H y d r o x y - 2 - c y c l o a l k e n y l ) phosphonates
van den W i n k e l , Y . ,
van Baar, B . L . M . ,
Bickelhaupt, F . , K u l i k , W . ,
Sierakowski, C , M a i e r , G .
185
•
Elektrochemische u n d
spektroskopische
Charakterisierung v o n N , W - D i a l k y l c h i noxalinium-Redoxsystemen
W i r d die F e '-induzierte C - H / C - C - B i n dungsaktivierung von a,a)-Alkandinitrilen
durch bifunktionelle Wechselwirkungen
beeinflußt?
Neutralisations-Reionisations-Massenspektrometrie u n d M a t r i x - I s o l i e r u n g einiger 9-Silaanthracene
•
Publikalionssprache
Fortsetzung: g e g e n ü b e r l i e g e n d e Seite / C o n t i n u e d : opposite page
Electrochemical and Spectroscopic C h a r acterization
of N , W - D i a l k y l q u i n o x a l i n i u m Redox Systems
•
Isthe F e M n d u c e d C - H / C - C B o n d A c tivation of a,co-Alkanedinitriles Affected
by Bifunctional Interactions?
•
N e u t r a l i z a t i o n - R e i o n i z a t i o n M a s s Spectrometry and M a t r i x Isolation of S o m e 9Silaanthracenes
•
Language of Publication
Inhalt (Fortsetzung)
Contents (Continued)
E i l b r a c h t , P., W i n k e l s , I.
191
•
Stereospezifische U m w a n d l u n g e n des ( + )2- und (+ )-3-Carcns in optisch aktive Siebe nring-Sy steine
Stereospecific Conversions of ( + )-2- and
( + )-3-Carene into O p t i c a l l y Active SevenMembered R i n g Systems
Bestmann, H . J., R ö d e r , T.,
Bremer, M . , Low, D .
199
•
Bororganyle, II. — Darstellung, Struktur
und
Reaktionen
von
Lithium-[cyan(trip henyiphosphoranyliden)methyl]trihydroborat( - 1 )
O r g a n o b o r o n C o m p o u n d s , II. — Preparation, Structure, and Reactions of L i t h i u m
[Cyano(triphenyl)phosphoranylidene)methyl]trihydroborate(— 1)
M a y r , H . , Heilmann, W.,
Bäuml, E., Vorbrüggen, H .
203
Synthese von 2,2,5,5-Tetramethylcyclop e n t a c a r b o n s ä u r e — E i n Baustein eines
Süßstoffes auf A m i n o s ä u r e - B a s i s
•
Synthesis of 2,2,5,5-Tetramethylcyclopentanecarboxylic A c i d — A Building Block
of an A m i n o A c i d Bascd Sweetener
V i c t o r y , P., A l v a r e z - L a r e n a , A . ,
Beti, C , Borreil, J . I.,
Batllori, X., C ö r d o b a , C.
207
Trioxypcntafulvene, 2. — Synthese 1-substituierter 2,3.6-Trioxypentafulvene
•
Trioxypentafulvenes. 2. — Synthesis of 1Substituted 2,3,6-Trioxypentafulvenes
A u m a n n , R., H i n t e r d i n g , P.
213
Enders, D . , N a k a i , S.
219
Regio-, diastcreo- und enantioselektive
Synthese von u/c-Diolen ü b e r a-Silylketone nach der S A M P / R A M P - H y d r a z o n Methode
•
Regio-, Distereo-, and Enantioselcctive
Synthesis of w'c-Diols via a-Silyl K e t o n e s
A c c o r d i n g to the S A M P / R A M P H y d r a zone M e t h o d
A d a m , W . , Hadjiarapoglou, L . ,
Smerz, A .
227
D i o x i r a n - E p o x i d i e r u n g von a , ß - u n g e s ä t tigten Kctonen
•
Dioxirane E p o x i d a t i o n
rated Ketones
•
Organische Synthesen mit Ü b e r g a n g s m e tall-Komplexen, 50. 2//-Pyrrol-Komplexc durch stufenweise Insertion von A l kinen und lsocyaniden in M = C - B i n d u n gen von C h r o m - und W o l f r a m - C a r b e n komplexen
O r g a n i c Syntheses via Transition M e t a l
Complexes, 50. — 2f/-Pyrrole Complexes
by a Stepwise Insertion of A l k y n e s and
Isocyanides into M = C Bonds of Carbene
C h r o m i u m or Tungsten Complexes
of a , ß - U n s a t u -
Notizen / Notes
G a s t , A . , Breitmaier, E .
233
•
Neue 0 - M a k r o c y c l e n mit 2,2-Bis(2-furyl)propan-Einheiten
New 0 Macrocycles with 2,2-Bis(2-furyl)propane Units
Kirmse, W., M ö n c h , D .
237
•
Umlagerungen von 1,4,4- und 2,2,5-Trimethylbicyclo[3.2.1]oct-6-yl-Kationen
Rearrangements of 1,4,4- and 2,2,5-Trimethylbicyclo[3.2.1 ]oct-6-yl Cations
Kirmse, W , Mrotzeck, U.,
Siegfried, R.
241
•
Umlagerungen von
norbornyl-Kationen
Rearrangements of
norbornyl Cations
6
6
5,5,6,6-Tetraalkyl-2-
5,5,6,6-Tetraalkyl-2-
Kurzmitteilung / Short Communication
Schinzer, D . , Ruppelt, M .
247
S ä u t c - k a t a l y s i c r t e und
Lewis-Säure-beschleunigte Synthese von 6 - H y d r o x y b i c y cl o [4.3.0] n o n a n - 3 - o nen
•
A c i d - C a t a l y z e d and Lewis A c i d - P r o m o t c d
Synthesis of 6-Hydroxybicyclo[4.3.0]nonan-3-ones
Querverweise / Cross References
K r e i t e r , C . G . et al.
M e w s , R. et al.
3
•
Photochemische Reaktionen von Ü b e r gangsmetall-Organyl-Komplexen mit Olefinen, 3
Photochemical Reactions of T r a n s i t i o n
Metal O r g a n y l Complexes with Olefines, 3
39
•
A d d i t i o n von Alkenen an 5-(Trifluormethyi)-l ,3,2.4,6-dithiatriazin
A d d i t i o n of Alkenes to 5-(Trifluoromethyl)-l ,3,2,4,6-dithiatriazine
•
A I Richtlinien für Autoren
•
Instructions for Authors
Publikationsspraclie
•
Language of Publication
B
H. M a y r , W . Heilmann, E. Bäuml, H . Vorbrüggen
203
A Building
Synthesis of 2,2,5,5-Tetramethylcyclopentanecarboxylic Acid
Block of an Amino Acid Based Sweetener
a
3
3
Herbert Mayr* , Werner Heilmann , Englbert Bäuml , and Helmut Vorbrüggen
b
3
Institut für Chemie, M e d i z i n i s c h e U n i v e r s i t ä t zu L ü b e c k ,
Ratzeburger Allee 160, D - 2 4 0 0 L ü b e c k 1
Schering
b
AG ,
Postfach 650311, D - 1 0 0 0 B e r l i n 65
Received M a y 29, 1990
Key Words: Sweetener / Electrophilic addition / Cycloalkanecarboxylic acid
The title Compound 2 is synthesized in three Steps from readily
available 2 5-dichloro-2 5-dimethylhexane (8) and vinylidene
Chloride (9). The key steps are carbocationic addition and
cyclization reactions.
A^-L-Aspartyl-A^'^alkylcarbonyl^ljl-diaminoethanes 1 have
been reported to be thermally stable, water-soluble sweeteners without bitter after-taste *. The sweetness of 1 strongly
depends on the nature of the acyl group R, and among 14
tested Compounds (1), the maximal taste intensity has been
foundforR = 2,2,5,5-tetramethylcyclopentylcarbonyl (1000fold sweetness relative to sucrose).
For the synthesis of precursors of 3, two different approaches, indicated by the disconnections a and b in formula
3, have been considered.
(
(
1
HC
3
H
HN
3
-
CH—
I *
CO,
e
C -
NH—
C -
C
H
NH—
R
CH
3
R = - C -
3
H C
CH
3
D i s c o n n e c t i o n a: The aldehyde 6 has previously been prepared in 88% yield from the anion of isobutyraldehyde (5)
and prenyl bromide . Since in this procedure, the enolate
anion is generated with potassium hydride in THF, we have
preferred to combine Compounds 4 and 5 under phase-transfer conditions as shown in Scheme 2, making use of a procedure previously described for the synthesis of similar
Compounds^. Treatment of 6 with triphenylphosphine/
tetrachloromethane gives the diene 7 in good yield.
4)
6)
3
1
The incorporated carboxylic acid 2 has previously been
synthesized by permethylation of the a positions of cyclopentanone, Wittig reaction, hydroboration, and Cr(VI) oxidation as shown in Scheme l .
50 % aq. NaOH,
Toluene, Phase transfer ^
H
85 %
l a )
CCl /PPh
4
3
78 - 83 %
Scheme 1
D i s c o n n e c t i o n b yields a Q fragment, which is technically
produced from acetylene and acetone. The commercially
available 2,5-dimethyl-2,5-hexanediol is quantitatively converted into the dichloride 8 by treatment with hydrochloric
acid. Attempts to produce the five-membered ring in a onepot reaction from 8 have not been successful. While reactions of 8 with vinylsilanes have not been considered for
economic reasons, the reaction of 8 with propyne gives complex mixtures of products under a variety of conditions .
When 8 and 9 are combined in sulfuric acid (Bott-Hellmann
conditions ), a diacid is formed from 8 and two equivalents
of vinylidene chloride 9.
7)
3b)
Since Compounds with quaternary carbons are often readily accessible via carbocationic addition reactions , we have
attempted to improve the synthesis of 2 by employing the
carbocationic cyclization of 3 as the key step .
2)
8)
3)
R =
-CH=CX
- c = cx
2
Since 8 incorporates two isolated equivalent functional
groups, we have not succeeded in selectively engaging a Single C — C l bond in the reaction with vinylidene chloride.
M i l d Lewis acids (ZnCl ) do not initiate the reaction of 8
with 9, while A1C1 , EtAlCL, or FeCh produce mixtures of
2
3
Chem. Ber. 124 (1991) 2 0 3 - 2 0 6
© VCH
Verlagsgesellschaft m b H , D-6940 Weinheim, 1991
0009-2940/91/0101 - 0 2 0 3 $ 3.50 + .25/0
B
H . Mayr, W. Heilmann, E. Bäuml, H . Vorbrüggen
204
the 1:1 adduct 10 and the 2:1 adduct 11. Among these Lewis
acids, A1C1 gives rise to the highest yields of 10.
3
heating, pure 13 is formed in 79% yield. Since the cyclization
of 13 appears to be easier than the cyclization of 12, no
efforts have been made to selectively produce 12.
9)
C y c l i z a t i o n s : In analogy to investigations by B o t t and
G a l l o , we tried to achieve the conversion of 13 into 2 in
sulfuric acid. Compound 2 is obtained under these conditions, but generally only in low yield (<30%). Therefore,
the cyclization has been carried out in boiling formic acid,
conditions previously employed by Lansbury for analogous
conversions . In this medium, like in 70 — 95% aqueous
acetic acid, 7 as well as 13 are cyclized to give 50 — 60% of
2, but we have not found conditions which avoid ihc concomitant formation of the six-membered ring Compounds
14 and or 15.
!0)
u)
;
2 (68 %)
Though vinylidene chloride is usually employed as the
solvent, the AlCl -initiated reactions terminate after a certain degree of conversion due to deactivation of the Lewis
acid. In accord with this rationalization, a progress of the
reactions can be achieved by adding more aluminum chloride. The degree of conversion thus depends on the percentage of Lewis acid, and Figure 1 shows that optimal
yields of 10 are obtained with 8 — 10% of A1C1 . Larger
amounts of the Lewis acid give rise to the formation of a
higher percentage of 11 and of unidentified nonvolatile Compounds. Since the ratio of 10/11 decreases with increasing
degree of conversion, one can improve the yield of the process by using a smaller amount of Lewis acid and recovering
the nonconverted reactants 8 and 9.
3
15 (7 %)
Compound 15 is formed in 95% yield, however, when 7
is treated with FeCl in CH C1 . Possibly, this conversion is
due to proton catalysis (traces of moisture) since the selective
rearrangement of 7 to 15 is also catalyzed by F S 0 H .
The mechanism of these reactions has not been elucidated,
and Scheme 3, which is self-explanatory, only represents a
rationalization of the isolated produets. Probably, thermodynamic product control is responsible for the exclusive formation of 15 from 7 in the absence of water: Under these
3
F i g u r e 1. P r o d u c t c o m p o s i t i o n d u r i n g the A l C l ^ - p r o m o t e d reaction
of 8 (50.0 mmol) with 9 (325 m m o l ) at 0 ° C . Since the reaction takes
place only w i t h i n the first few minutes after the addition of the
catalyst, this figure refers to a Single experiment, in which the AICI3
portions have been added at 30-min intervals.
14 (17 %)
2
2
3
Scheme 3
' > o <
J!'
> y <
CO.H
Cl
3
C1
C1
>/~V
1
0
NaOH/CH Cl
Aliquat 336
2
2
^
^
CH
II
C
4
Cl
Cl
12
>/~V
X
o
r
C
cM
ci
13
Treatment of 10 with a base under phase-transfer conditions ( N a O H / C H C l ) gives mixtures of 12 and 13; on
2
2
22
14
23
C h e m . Ber. 124 (1991) 2 0 3 - 2 0 6
B
205
Synthesis of 2,2,5,5-Tetramethylcyclopentanecarboxylic A c i d
conditions, irreversible trapping of the cyclopentyl-substituted carbenium ion 18 is not possible, so that the less
straäned six-membered ring Compound 15 is produced selectively. It is remarkable that Compound 15 is also generated from 13 in formic acid; thus, one has to assume the
presence of an ion pair [20 C l ] which collapses to give the
dichloride 15.
The dependence of the product composition on the reaction conditions indicates the occurrence of mutual rearrangements of the intermediate carbenium ions, so that the product
ratio 2/(14 + 15) does not provide information on the relative
rates of the cyclization Steps (6-endo or 5 - e x o ) .
C o n c l u s i o n : The sequence 8 — > 1 0 — » 1 3 — > 2 leads to the
title Compound 2 in a three-step synthesis in 32% overall
yield. Since only inexpensive reagents are needed, which are
combined under convenient reaction conditions, the carbocationic approach to 2 is superior to the carbanionic route
described in Scheme 1. Alternative routes , which have been
published after the Submission of our first report , also employ 2,2,5,5-tetramethylcyclopentanone as starting Compound and, in our opinion, are less straightforward than the
procedures reported in this article.
e
]2)
later on the precipitation of crystalline 8 takes place. T h e product
is extracted with 600 m l o f petroleum ether (b.p. 40 —60°C) and
dried with C a C l . E v a p o r a t i o n of the solvent yields 81.9 g (89%) of
2
an N M R - s p e c t r o s c o p i c a l l y pure solid, which is recrystallized from
7)
petroleum ether: m.p. 6 8 - 6 8 . 5 ° C (ref. : 64°C). 3
' H N M R (CC1 ):
4
1 3
5 = 1.55 (s, 1 2 H , C H ) , 1.86 (s, 4 H , C H ) . 2
C N M R (CDC1 ):
3
5 = 32.51 (q), 41.11 (t), 70.22 (s).
Reaction o f 8 with Vinylidene
C h l o r i d e (9): A l u m i n u m chloride
(3.75 g, 28.0 m m o l ) is added i n portions d u r i n g 45 m i n to a wellstirred Suspension of 8 (54.9 g, 300 m m o l ) i n 9 (135 m l , 1.70 mol)
C
at 0 C . After stirring for another 100 m i n at 0 ° C , 10 m l of water
and 20 g of C a C l are added successively, and the mixture is filtered.
2
E v a p o r a t i o n of 9 leaves 88.4 g of a dark viscous residue from which
17.5 g (95.6 m m o l ) of 8 are recovered by distillation. Distillation of
the residue yields 34.3 g of 10 (60% with respect to consumed 8)
and 26.2 g of 11 (34% with respect to consumed 8) which solidifies
at - 2 0 ° C .
lJJ 6-Tetrachloro-3J,6-trimethylheptane
(10): B . p . 7 9 - 8 0 ° C /
t
l3)
3a)
0.5 mbar. CH ),
3
1.59 (s, 6 H ,
3
1.59- 1.83 (m, 4 H , C H - C H ) , 2.81 (s, 2 H , C H - C C 1 ) .
3
, 3
' H N M R ( C D C 1 ) : 5 = 1.20 (s, 6 H , C H ) ,
2
2
2
3
-
C N M R (CDCI3): 5 = 27.80 (q), 32.43 (q), 35.69 (s), 38.38 (t), 39.97
(t), 63.25 (t), 70.74 (s), 98.60 (s). -
I R (neat): v = 2961, 2931, 2870,
1
1470,
1452, 1387, 1370, 1100, 896, 790, 726, 703, 605 c m " . - M S
(70 eV):
m/z (%) = 229, 227 (0.9, 1.3) [ M
+
-
HCl -
C H ] , 171
3
(4), 147 (7), 137 (13), 123 (10), 111 (50), 77 (64), 69 (83), 31 (100).
Experimental
NMR:
C H C1
1 0
I 8
4
(280.1)
X L 200 (Varian), internal Standard T M S . — M a s s spec-
tra: 7 0 - 2 5 0 E (VG-Instruments). -
I R : IR-435 (Shimadzu).
(6): A Solution of 4 (13.6 g, 130 mmol)
2,2,5-Trimethyl-4-hexenal
1,1,1
t
C a l c d . C 42.89 H 6.48
F o u n d C 43.06 H 6.54
8,8,8-Hexachloro-3,3,6,6-tetramethyloctane
(11): Colorless
needles with m . p . 5 2 . 5 - 5 3 . 5 C (petroleum ether). -
'H NMR
and 5 (7.21 g, 100 mmol) in toluene (10 ml) is added dropwise (10
(CDCI3): 5 = 1.18 (s, 1 2 H , C H ) , 1.46 (s, 4 H , C H - C H ) , 2.81 (s,
min)
4H, CH -CC1 ). -
to a vigorously stirred mixture of 5 0 % aqueous N a O H (30 g),
toluene (70 ml), a n d t e t r a b u t y l a m m o n i u m iodide (1.4 g, 3.8 mmol)
3
2
1 3
3
1472,
2
C N M R ( C D C 1 ) : 5 = 27.79 (q), 35.91 (s), 37.16
3
(t), 63.32 (t), 98.67 (s). -
at 80 C . T h e mixture is stirred for 4.5 h (80 C), cooled a n d poured
2
I R ( K B r ) : v = 2976, 2953, 2904, 2870,
1465,1390, 1373, 1337, 1255, 1188, 1154, 1123, 1042, 903, 784,
onto water. T h e product is extracted with ether, and the ethereal
717,
extract dried with N a S 0 . D i s t i l l a t i o n over a Vigreux c o l u m n
0.18, 0.29, 0.18) [ M
yields 6 (11.9 g, 85%) as a colorless liquid with b.p. 8 9 - 9 2 C / 7 1
(1.2), 173 (3), 171 (7), 149 (23), 147 (70), 137 (19), 111 (81), 77 (100),
2
608 cm '. -
M S (70 eV): m / z (%) = 344, 342, 340, 338, (0.07,
f
-
H C l ] , 229, (1.3), 227 (1.4), 193 (1.0), 191
4
141
mbar (ref. : 6 5 - 6 6 C / 2 0 T o r r ; purity 9 4 % by G C ) . Spectral data
6 9
36
' >-
C H C 1 (377.0)
1 2
2 0
6
14)
are given in ref. .
/,/'-Dichloro-3,3,6-trimethyl-1,5-heptadiene
(7): A Solution of 6
C a l c d . C 38.23 H 5.35
F o u n d C 38.38 H 5.37
J,6-Dichloro-3J,6-trimethyl-l-heptyne
(13): C o m p o u n d 10 (25.2 g,
(5.00 g, 35.7 mmol) i n C C 1 (5 ml) is added dropwise (5 min) with
90.0 mmol) a n d 0.60 g o f t r i c a p r y l m e t h y l a m m o n i u m chloride (Ali-
stirring to a mixture of triphenylphosphine (21.0 g, 80.0 mmol) i n
quat 336) are stirred vigorously with 4 0 % aqueous N a O H (50 ml)
CC1
at 8 0 C for 22 h. After c o o l i n g , 60 m l of C H C 1
4
(40 ml) at 80 C ( N atmosphere). After 3.5 h, the mixture is
4
2
2
2
is added, and the
cooled and poured onto 300 m l of hexane to precipitate triphen-
organic layer is dried with C a C l . T h e solvent is evaporated, and
ylphosphine and triphenylphosphine oxide. T h e Suspension is f i l -
the residue isdistilled to give 14.7 g ( 7 9 % ) of 13 with b.p. 3 9 - 4 3 C /
2
tered over silica gel a n d the resulting Solution evaporated to give
1 mbar. -
7 (6.12 g, 83%), as a colorless o i l , which is used without further
1.53-1.93 (m, 1 0 H i n c l u d i n g the s at 5 1.59, C H - C H ) .
purification. B u l b - t o - b u l b distillation [ 3 4 - 3 7 ' C (bath)/0.15 m b a r ]
!
H N M R ( C D C 1 ) : 5 = 1.21 (s, 6 H , C H ) , 1.59 (s, C H ) ,
3
3
3
2
, 3
2
yields an analytically pure product. - ' H N M R ( C D C 1 ) : ö = 1.16
(t), 57.90 (s), 70.66 (s), 75.80 (s). -
(s, 6 H , 3-CH3), 1.62, 1.73 (2 br. s, 6 H , 6-CH3, 7-H), 2.14 (br. d, 7 =
2220, 1465, 1450, 1385, 1370, 1267, 1098, 989, 788 c m - . -
3
7.6 H z , 2 H , 4-H), 5.13 (br. t, J = 7.6 H z , 1 H , 5-H), 5.87 (s, 1 H , 2H).
-
, 3
C N M R (CDCI3): 5 = 17.95, 26.04 (2 q, 6-CH3, C-7), 26.70
(q, 3-CH3), 37.66 (s, C-3), 40.52 (t, C-4), 118.83 (s, C - l ) , 120.21 (d,
134.10 (s, C-6), 137.93 (d, C-2). -
I R (neat): v = 2956, 2917,
I R (neat): v = 2967, 2920, 2864,
1
eV):
m/z (%) = 208, 206 (0.4, 0.6) [ M
+
M S (70
], 155 (28), 135 (20), 115
(15), 103 (33), 101 (100), 77 (16), 69 (74), 65 (28).
C H C 1 (207.1)
1 0
C-5),
-
N M R (CDCI3): 5 = 28.98 (q), 31.26 (s), 32.49 (q), 38.25 (t), 41.48
C
1 6
2
C a l c d . C 57.98 H 7.79
F o u n d C 58.29 H 7.67
1
1606,1466, 1450, 1383, 1376, 879 c m - . - M S (70 e V ) : m/z (%) =
208,
+
206 (0.1, 0.15) [ M ] , 141, 139, 137 (3, 17, 26), 118, 116 (6, 8),
C
1 0
H Cl
l 6
C y c l i z a t i o n o f 13: C o m p o u n d 13 (8.29 g, 40.0 m m o l ) is added
dropwise with stirring to 80 m l o f refluxing 9 0 % aqueous formic
69 (100), 41 (47).
2
(207.1)
C a l c d . C 57.98 H 7.79
F o u n d C 57.97 H 7.84
2,5-Dichloro-2,5-dimethylhexane
acid (30 min) a n d heated under reflux for 6 h. W a t e r (300 ml) is
added after cooling, a n d the mixture is extracted with two 50-ml
portions of petroleum ether. T h e c o m b i n e d organic layers are ex-
(8): 2,5-Dimethyl-2,5-hexanediol
tracted with five 30-ml portions o f 1 0 % aqueous N a C 0 Solution.
(73.1 g, 0.500 mol) is stirred with 3 7 % aqueous H C l (250 ml) for
T h e aqueous layers are c o m b i n e d a n d acidified w i t h conc. H C l to
1 h The initially biphasic mixture first becomes homogeneous, a n d
precipitate 4.63 g (68%) o f spectroscopically
Chem. Ber. 124 (1991) 2 0 3 - 2 0 6
2
3
N M R ) pure 2.
B
H . Mayr, W . Heilmann, E. BäumL H . V o r b r ü g g e n
206
The
remaining petroleum ether Solution is dried with C a C k and
4,5),
47.00 (s, C-3,6), 155.06 (s, C - l , 2 ) . -
IR (neat): v = 2987, 2950,
the solvent is evaporated to give 2.07 g of a b r o w n liquid residue
2864, 1604, 1588, 1458, 1363, 1216, 1145, 1007, 907, 866, 847, 778
which is separated by c h r o m a t o g r a p h y (silica gel, petroleum ether/
cm- .
C H C 1 ) to give 574 m g (7%) of 15 and 1.02 g (17%) of 14.
191 (13), 173 (17), 171 (52), 150 (58), 135 (18), 115 (59), 91 (12), 83
2
2
2.2.5.5- T e t r a m e t h y l c y c l o p e m a n e c a r b o x y l i c
l
129°C (petroleum ether). -
Acid
(2):
M . p . 128 —
H N M R (CDC1 ): 5 =
1.15 (s, 6 H ,
3
1
-
M S (70 eV):
(100), 77 (21), 55 (18).
C H C 1 (207.1)
1 0
1 6
2
3
1 3
c
C N M R (CDCI3): 8 = 25.42, 31.41, (2 q, C H ) ,
3
40.80
(t, C-3,4), 42.56 (s, C-2,5), 64.20 (d, C - l ) , 179.26 (s, C 0 H ) . 2
IR
( K B r ) : v = 2938, 2860, 2724, 2325, 1691, 1459, 1409, 1379, 1362,
1274,
1
1253, 1230, 1204, 935, 730 c m - . -
M S (70 eV): m / z (%) =
+
170 (0.21) [ M ] , 155 (1.8), 137 (1.5), 114 (2.4), 110(4), 109 (10), 102
(5), 101 (100), 83 (8), 70 (32), 55 (17).
C
1 0
H
1 8
O
2
(170.3)
C a l c d . C 57.98 H 7.79
F o u n d C 58.14 H 7.78
2,5-CHO, 1.16 (s, 6 H , 2 , 5 - C H ) , 1 . 5 1 - 1 . 6 3 (m , 4 H , 3,4-H), 2.26 (s,
1 H , 1-H). -
H
m / z (%) = 208, 206 (9, 14) [ M ] , 193 (8),
CAS
Registry N u m b e r s
2: 96188-82-8 / 4: 503-60-6 / 5: 78-84-2 / 6: 1000-30-2 / 7: 12860084- 0 / 8: 6223-78-5 / 9: 75-35-4 / 10: 109749-69-1 / 11: 12860085- 1 / 13: 109749-70-4 / 14: 53343-33-2 / 15: 128600-86-2 / 2,5dimethyl-2,5-hexanediol: 110-03-2
C a l c d . C 70.55 H 10.66
F o u n d C 70.32 H 10.51
2.3.6.6- T e t r a m e t h y l - 2 - c y c l o h e x e n - l - o n e
(bath)/0.6 mbar. -
(14):
' H N M R (CDC1 ): 8 =
3
B.p. 3 0 - 4 0 C
1.04 (s, 6 H , 6-CH3),
11
1.69 (t, J = 1 A H z , 2 H , 5-H), 1.85 (br. s, 3 H , 2 - C H ) , 2.24 (t, J =
3
2 H z , 3 H , 3-CH3), 2.50 (m , 2 H , 4-H). c
C N M R (CDC1 ): 5 =
3
20.41 (q), 24.07 (q, 6-CH3), 24.43 (q), 25.27, 34.77 (2 t, C-4,5), 46.48
2)
I R (neat): v =
2951,
2850, 1706 (s, C = 0 ) . 1631 (s, C = C), 1450, 1378, 1364, 1270,
1192,
1114, 989, 849, 786, 762 c m " . -
1 0
H
1 6
O (152.2)
2 a )
2 b )
M S (70 eV): m / z (%) =
+
152 (78) [ M ], 137 (93), 109 (25), 96 (31), 81 (12), 68 (100), 67 (36).
C
C u m b e r l a n d P a c k i n e C o r p o r a t i o n ( M . S. V e r l a n d e r , W . D .
Füller, M . G o o d m a n , Inv.) E u r o p e a n P a t . A p p l . 0128654 (1984)
[ C h e m . A b s t r . 102 (1985) 185492 c ] . W . D . Füller, M .
G o o d m a n , M . S. Verlander, J . A m . C h e m . Soc. 107 (1985) 5821.
Reviews:
M . T. Reetz, Angew.
C h e m . 94 (1982) 97;
Angew.
C h e m . I n t . Ed. E n g l . 21 (1982) 96. H . M a y r in S e l e c t i v i t i e s
i n L e w i s A c i d - P r o m o t e d R e a c t i o n s , N A T O A S I Series C , ( D .
Schinzer, Ed.), vol. 289, p. 21, K l u w e r A c a d e m i c P u b l i s h e r s , D o d recht 1989.
Schering A G ( H . V o r b r ü g g e n , H . M a y r , W . H e i l m a n n , Inv.)
DOS
3534613.2 (24.09.86) [ C h e m . A b s t r . 107 (1987) 115282
p]. - > W . H e i l m a n n , H . M a y r , H . V o r b r ü g g e n F O C U S M H L
4 (1987) 94 [ C h e m . A b s t r . III (1989) 57078 w].
P . Groenewegen, H . K a l l e n b e r g , A . van der G e n , T e t r a h e d r o n
L e u . 1978, 491.
H . K . Dietl, K . C . Brannock, T e t r a h e d r o n L e u . 1973, 1273.
R. A p p e l , Angew.
C h e m . 87 (1975) 863; Angew.
C h e m . I n t . Ed.
E n g l . 14 (1975) 801.
L . R. C . Barclay, E . E . Betts, J . A m . C h e m . Soc. 11 (1955) 5735.
K . Bott, Angew.
C h e m . 92 (1980) 169; Angew.
C h e m . I n t . Ed.
E n g l . 19 (1980) 171.
K . Bott, H . H e l l m a n n , Angew.
C h e m . 78 (1966) 932;
Angew.
C h e m . I n t . Ed. E n g l 5 (1966) 870.
S. Randriamahefa, P . Deschamps, R. G a l l o , H . Grangette, Synthesis
1985, 493.
P. T. Lansbury, R. C . Stewart, T e t r a h e d r o n L e u . 1973, 1569.
J. E . B a l d w i n , J . C h e m . Soc. C h e m . C o m m u n . 1976, 734.
K y o w a H a k k o K o g y o C o . (T. Y a m a u c h i , K . H a t t o r i , S. Ikeda,
K . T a m a k i , Invs.) European Pat. A p p l . 0196461 (1986) [ C h e m .
A b s t r . 110 (1989) 172746 d].
P . Cresson, B u l l . Soc. C h i m . F r . 1964, 2618.
[184/90]
, b )
1 3
(s, C-6), 130.12, 148.28 (2s, C-2,3), 211.22 (s, C - l ) . 1
l a )
3)
C a l c d . C 78.90 H 10.59
3 a )
3b
F o u n d C 79.50 H 10.75
C y c l i z a t i o n o f l i n F o r m i c A c i d : C o m p o u n d 7 (1.0 g, 4.8 mmol)
is added dropwise within 10 m i n to a refluxing mixture of 9 8 %
formic acid (10 ml) and B F
3
—ether (1 ml). T h e mixture is heated
4)
5)
6)
under reflux for 6 h and w o r k e d up as described above to yield
7>
0.40 g (49%) of 2 and 0.20 g (20%) of 15.
8)
1 2 - D i c h l o r o - 3 , 3 , 6 , 6 - t e t r a m e t h y l - 1 - c y c l o h e x e n e (15): A Solution of
7 (210 mg, 1.01 m m o l ) in 3 m l of a n h y d r o u s C H C 1
2
2
is added to a
Suspension of F e C l (40 mg, 0.25 m m o l ) in 5 m l of C H C 1 . D ü r i n g
3
2
2
9)
10)
stirring, the mixture adopts a deep red c o l o r after approximately
5 m i n . Pentane (20 ml) is added after 2.5 h, and the mixture is
passed through 2.0 g of silica gel. After elution with pentane (ca.
n )
,2)
13)
50 ml), the pentane Solutions are concentrated to give 200 m g (95%)
of spectroscopically ( ' H N M R ) pure 15; b.p. 2 0 - 3 0 C (bath)/0.5
mbar. CH ).
2
-
' H N M R ( C D C 1 ) : 8 = 1.27 (s, 1 2 H , C H ) , 1.63 (s, 4 H ,
3
1 3
3
C N M R (CDCI3): 5 = 26.13 (q, 3 , 6 - C H ) , 41.00 (t, C 3
,4)
C h e m . Ber. 124 (1991) 2 0 3 - 2 0 6