Novel syntheses of α,β-unsaturated esters, α,β-unsaturated γ-lactones, and 2-alkoxypyrroles via 1,2,4-triazole-stabilized allenic anions

Article abstract of DOI:10.1021/jo961397l

The dianion 12 (?13) of 1-(1,2,4-triazol-1-yl)phenylpropargyl ethyl ether 11 (readily prepared from phenylpropargylaldehyde diethyl acetal 8 and 1,2,4-triazole) reacts with alkyl halides, aldehydes, ketones, and α,β-unsaturated ketones to give exclusively γ-substituted allenic products of type 10. These adducts underwent mild in situ hydrolysis enabling convenient syntheses of α,β-unsaturated esters 9a-c and α,β-unsaturated γ-lactones 16, 18, 20, and 22. Reactions of dianion 13 with imines generated the 1,3,4-trisubstituted 2-alkoxypyrroles 27, 30, and 31 in high yields. The alkylsubstituted analog 34 underwent similar reactions to give predominantly the γ-products 39, 40, and 42 along with a small proportion of α-analogs.

Full text of DOI:10.1021/jo961397l

J . Org. Chem. 1997, 62, 715-720
715
Novel Syn th eses of r,â-Un sa tu r a ted Ester s, r,â-Un sa tu r a ted
γ-La cton es, a n d 2-Alk oxyp yr r oles via 1,2,4-Tr ia zole-Sta bilized
Allen ic An ion s
Alan R. Katritzky,* Daming Feng, and Hengyuan Lang
Center for Heterocyclic Compounds, Department of Chemistry, University of Florida,
Gainesville, Florida 32611-7200
Received J uly 23, 1996X
The dianion 12 (h 13) of 1-(1,2,4-triazol-1-yl)phenylpropargyl ethyl ether 11 (readily prepared from
phenylpropargylaldehyde diethyl acetal 8 and 1,2,4-triazole) reacts with alkyl halides, aldehydes,
ketones, and R,â-unsaturated ketones to give exclusively γ-substituted allenic products of type 10.
These adducts underwent mild in situ hydrolysis enabling convenient syntheses of R,â-unsaturated
esters 9a -c and R,â-unsaturated γ-lactones 16, 18, 20, and 22. Reactions of dianion 13 with imines
generated the 1,3,4-trisubstituted 2-alkoxypyrroles 27, 30, and 31 in high yields. The alkyl-
substituted analog 34 underwent similar reactions to give predominantly the γ-products 39, 40,
and 42 along with a small proportion of R-analogs.
We have recently reported convenient benzotriazole
acyl anion methodologies for the synthesis of a wide
variety of simple and functionalized alkenyl,1-4 aryl/
heteroaryl,5 and alkynyl6 ketones and of alkenoyl-,
alkynoyl-, aroyl-, and heteroaroylsilanes.7 We utilized
benzotriazole-stabilized carbanions derived from 1-3
which share the following features: (i) convenient avail-
ability of starting materials; (ii) adequate reactivity
toward various electrophiles including alkyl halides,
aldehydes, ketones, and imines; and (iii) the intermedi-
ates can be hydrolyzed under mild conditions. Reactions
with electrophiles are also regiospecific. Thus, 1-(benzo-
triazol-1-yl)propargyl ethyl ethers 3, readily accessible
from propargyl diethyl acetals and benzotriazole, undergo
smooth lithiation at the methine proton and subsequent
reactions with a wide range of electrophiles to give
regioselective R-substituted derivatives 4.6 We now find
that use of the 1,2,4-triazole group instead of benzotri-
azole in 3 changes the regiochemistry of electrophilic
attack and directs the alkylation to occur exlusively at
the γ-position in the case of the phenyl-substituted
1-(triazol-1-yl)propargyl ethyl ether 11 and mainly at the
γ-position in the case of the alkyl-substituted 1-(triazol-
1-yl)propargyl ethyl ether 33, forming synthetically use-
ful allene derivatives of types 10 and 37.
less work has been done on the generation, reactivity,
and synthetic utility of substituted allenes of type 6 with
two hetero substituents. Clinet and Linstrumelle13 depro-
tonated methoxyallene (5, X ) MeO, R ) H) and
subsequently reacted it with trimethylsilyl chloride to
produce 1-methoxy-1-(trimethylsilyl)allene (6a ) which,
upon treatment with an alkyllithium reagent, undergoes
regioselective γ-alkylation. Treatment with LDA of
species 6a (R ) H) gives the lithium acetylide of 1-(tri-
methylsilyl)propargyl ether.14 An alternative route for
the synthesis of allenes 6 is from acetylene derivatives
7. However, such transformations are quite limited;
while for R ) Me3Si, the species 7b,c in most cases
undergo mainly regioselective R-lithiation and alkyl-
ations, variable amount of γ-alkylated 6b,c can be
generated depending on the electrophiles used,15,16 which
limits their generality and wide application. Deproton-
ated acetylene 7d (R ) SMe) was reported to react with
alkyl halides, aldehydes, and ketones to furnish selec-
tively allene derivatives, which were then hydrolyzed to
yield â-keto esters and â-(methylthio)-R,â-unsaturated
γ-lactones.17
Allenes are very useful intermediates in organic syn-
thesis due to their diverse transformations via metal-
ations and facile additions and cyclizations.8,9 The regio-
selectivity of mono- and dilithiation in allenes of type 5
with one hetero substituent has been extensively inves-
tigated and been found to depend both on the substrate
and on the electrophile introduced.10-12 However, much
X Abstract published in Advance ACS Abstracts, November 1, 1996.
(1) Katritzky, A. R.; J iang, J . J . Org. Chem. 1995, 60, 6.
(2) Katritzky, A. R.; Zhang, G.; J iang, J . J . Org. Chem. 1995, 60,
7589.
(3) Katritzky, A. R.; J iang, J . J . Org. Chem. 1995, 60, 7597.
(4) Katritzky, A. R.; Zhang, G.; J iang, J . J . Org. Chem. 1995, 60,
7605.
(5) Katritzky, A. R.; Lang, H.; Wang, Z.; Zhang, Z.; Song, H. J . Org.
Chem. 1995, 60, 7619.
(6) Katritzky, A. R.; Lang, H. J . Org. Chem. 1995, 60, 7612.
(7) Katritzky, A. R.; Wang, Z.; Lang, H. Organometallics 1996, 15,
486.
(8) Schuster, H. F.; Coppola, G. M. In Allenes in Organic Synthesis;
J ohn Wiley & Sons: New York, 1984; p 212.
(9) Zimmer, R. Synthesis 1993, 165.
(10) Leroux, Y.; Roman, C. Tetrahedron Lett. 1973, 2585.
(11) Leroux, Y.; Mantione, R. Tetrahedron Lett. 1971, 591.
(12) Mantione, R.; Leroux, Y. Tetrahedron Lett. 1971, 593.
(13) Clinet, J .-C.; Linstrumelle, G. Tetrahedron Lett. 1980, 21, 3987.
(14) Kuwajima, I.; Sugahara, S.; Enda, J . Tetrahedron Lett. 1983,
24, 1061.
(15) Kruithof, K. J . H.; Schmitz, R. F.; Klumpp, G. W. Tetrahedron
1983, 39, 3073.
(16) Andersen, N. H.; Denniston, A. D.; McCrae, D. A. J . Org. Chem.
1983, 47, 1145.
S0022-3263(96)01397-7 CCC: $14.00 © 1997 American Chemical Society

716 J . Org. Chem., Vol. 62, No. 3, 1997
Katritzky et al.
Sch em e 1
characterized by comparing their NMR spectra with
those reported in the literature.20
The less reactive electrophiles ethyl bromide, pentyl
bromide, and allyl bromide generated only the monoalkyl-
ated allenes 14b-d . Analysis of the reaction products
1
by H NMR spectra showed the presence of two charac-
teristic triazole protons and of one alkyl group (ethyl or
pentyl). Accordingly, for the preparation of 9b-d , only
1 equiv of the electrophile was used. Compounds 9b-d
were obtained in 79-93% yields when the intermediates
14b-d were subjected to direct hydrolysis without isola-
tion under similar conditions to those developed for 9a .
The ratios of the E and Z stereoisomers for 9b,c are ca.
1:3 as determined by comparing their NMR spectra with
literature.20 For 9d the assignment of E and Z isomers
(ratio, 1:2) was accomplished by NMR (NOE technique).
The present results on the selective alkylation of the
triazole ring with different electrophiles are consistent
with those reported in the literature,18,19 which indicated
that the deprotonated 1-[(dialkyamino)methyl]-1,2,4-
triazole reacts only with those reactive electrophiles (such
as MeI, RCHO, or RCOR) to give the triazole-alkylated
products. Independent of whether the triazole is alkyl-
ated or not, the triazole moiety, as a leaving group in
the present work, will finally be hydrolyzed off and can
be easily removed from the reaction mixture by washing
with water during workup.
Synthesis of R,â-unsaturated esters is generally achieved
by CdC bond formation from carbonyl compounds by
Wittig-Horner,21-23 Wadsworth-Emmons,24 or Peterson
reactions25,26 or by reaction of mercaptoacetate deriva-
tives including dianions20,27,28 or of alkoxyacetylide an-
ions.29 Other available methods for their synthesis
include oxidation of the corresponding R,â-unsaturated
aldehydes30 and addition of an organocopper reagent
(nucleophile) to acetylenic esters.31 The present ap-
proach, utilizing various electrophiles, readily affords â,â-
disubstituted R,â-unsaturated esters of type 9.
Resu lts a n d Discu ssion
Heating phenylpropargyl aldehyde diethyl acetal (8)
with triazole in toluene for 2 days gave 1-(triazol-1-yl)-
3-phenylproparyl ethyl ether (11) stable on storage at 20
°C for at least 3 months in 76% yield (Scheme 1). The
structure of 11 was confirmed spectrally and by elemen-
tal analysis.
Syn th esis of r,â-Un sa tu r a ted Ester s. Unlike the
benzotriazole analog 3, triazole derivative 11 bears two
acidic protons on the molecule, one on the methine group
and the another at the 5-position of the triazole ring:
1-substituted 1,2,4-triazoles are known to undergo easy
lithiation at the 5-position of the triazole ring.18,19 Treat-
ment of compound 11 with 1 equiv of butyllithium
followed by reaction with methyl iodide or benzaldehyde
led to a complex mixture including the R-, γ-, and triazole-
alkylated products, as we observed from TLC and crude
1H and 13C NMR spectra.
Treatment of 11 with 2 equiv of butyllithium at -78
°C for a few minutes formed a dilithio derivative, which
may have structure 12 or 13 or exists as a mixture of
both. Subsequent reaction with 2 equiv of methyl iodide
at the same temperature for a few minutes gave only 10
(>95% from NMR) in quantitative yield. The structure
of 10 was determined by NMR spectra and the further
analysis of the hydrolyzed product 9a . 13C NMR clearly
showed the characteristic allene carbon (185 ppm) and
the absence of signals for the triple bond and the
quarternary carbon which would have been in the range
80-110 ppm. Attempted preparation of the analytically
pure sample by column chromatography on silica gel
resulted in partial hydrolysis to give rise to the expected
R,â-unsaturated ester 9a . Therefore, in a further experi-
ment, intermediate 10 generated after lithiation of 11
and reaction with methyl iodide was directly hydrolyzed
in a 50% aqueous ethanol containing a small amount of
hydrochloric acid at 20 °C for 4 h without isolation. Two
stereoisomers (E, and Z) of 9a were isolated in yields of
17% and 70%, respectively. These E and- Z isomers were
Syn th esis of r,â-Un sa tu r a ted γ-La cton es. When
anions 13 (h 12) were reacted with an aldehyde or a
ketone followed by hydrolysis, the expected lactones of
type 16a -c, 18, and 20 were easily prepared in 51-78%
yields (Scheme 2). Under the acidic conditions, the
hydroxyalkyl-substituted allenes 15a -c, 17, and 19
formed after lithiation and reactions with the carbonyl
compounds underwent ready cyclization to give the five-
membered cyclic products 16a -c, 18, and 20. Thus,
treatment of 11 with 2 equiv of butyllithium at -78 °C
for 2 min, followed by reactions with the 2 equiv of
cyclohexanone at this temperature for another 5 min,
(20) Matsui, S. Bull. Chem. Soc. J pn. 1984, 57, 426.
(21) Gallagher, G., J r.; Webb, R. L. Synthesis 1974, 122.
(22) Wittig, G.; Haag, W. Chem. Ber. 1955, 235, 1654.
(23) McKenna, E. G.; Walker, B. J . J . Chem. Soc., Chem. Commun.
1989, 568.
(24) Wadsworth, W. S., J r.; Emmons, W. D. J . Am. Chem. Soc. 1961,
82, 1733.
(25) Shimoji, K.; Taguchi, H.; Oshima, K.; Yamamoto, H.; Nozaki,
H. J . Am. Chem. Soc. 1974, 96, 1620.
(26) Hartzell. S. L.; Sullivan, D. F.; Rathke, M. W. Tetrahedron Lett.
1974, 1403.
(27) Tanaka, K.; Uneme, H.; Ono, N.; Kaji, A. Chem. Lett. 1979,
1039.
(28) Matui, S.; Tanaka, K.; Kaji, A. Synthesis 1983, 127.
(29) Olah, G. A.; Wu, A.-h.; Farooq, O.; Prakash, G. K. S. Synthesis
1988, 537.
(30) Corey, E. J .; Gilman, N. W.; Ganem, B. E. J . Am. Chem. Soc.
1968, 90, 5616.
(17) Carlson, R. M.; Isidor, J . L. Tetrahedron Lett. 1973, 4819.
(18) Katritzky, A. R.; Lue, P.; Yannakopoulou, K. Tetrahedron 1990,
46, 641.
(19) Rewcastle, G. W.; Katritzky, A. R. In Advances in Heterocyclic
Chemistry; Katritzky, A. R., Ed.; Academic Press: New York, 1993;
Vol. 56, p 155.
(31) Anderson, R. J .; Corbin, V. L.; Cotterrell, G.; Cox, G. R.;
Henrick, C. A.; Schaub, F.; Siddall, J . B. J . Am. Chem. Soc. 1975, 97,
1197.

Triazole-Stabilized Allenic Anions
J . Org. Chem., Vol. 62, No. 3, 1997 717
Sch em e 2
straints. The reason for the cis hydrolysis in the present
cases is still not clear.
R,â-Unsaturated butenolide moieties exists in many
biologically important natural products, and a number
of methods are available for its construction.32 Transi-
tion-metal-catalyzed cyclizations (Pd,33 Mn,34 Zr,35 Rh36
)
of various acetylene or olefin derivatives have been
frequently employed. However, such reactions often
require expensive catalysts. Methods closely related to
the present approach for the synthesis of R,â-unsaturated
butenolides comprise the lithiation of 3-sulfur-function-
alized (PhSO or PhSO2) acid derivatives37,38 or equiva-
lents39 and subsequent reactions with carbonyl com-
pounds followed by elimination of the sulfur functional
group. However, only the butenolides without R- or â-
substituents were prepared by these methods. Iwai et
al.40 reported a similar procedure utilizing the reactions
of the dianions of 2-phenylthiocarboxy acids with ep-
oxides to prepare R- or â-substituted R,â-unsaturated
butenolides. Further methods used include treatment of
3-chloroacrylate successively with (i) a Grignard reagent,
(ii) metal lithium, and (iii) carbon dioxide;41 oxidation of
cyclobutenones;42 cyclocondensation of 4-oxo carboxylic
acids43 and cross-aldol condensation of an R-keto dimethyl
acetal and a ketone enolate, followed by acid-promoted
cyclization.44 However, all these methods are limited by
the availability of the starting materials or require
multisteps operations. Our method commences with
readily available starting materials and is a simple and
high yielding procedure.
Syn th esis of 1,3,5-Tr isu bstitu ted 2-Eth oxyp yr -
r oles. When N-benzylidineaniline was used as an elec-
trophile to react with anion 13 (h 12) under similar
conditions as in the cases 16a -c, only γ-phenylamino-
substituted (Z)-R,â-unsaturated ester 24 was generated
in 70% yield (the Z configuation of 24 was assigned by
NOE technique) (Scheme 3). No cyclized lactam was
detected from the reaction. Further treatment of 24 in
refluxing ethanol containing 20% 2 M sulfuric acid still
does not produce any R,â-unsaturated γ-lactam. The
reason for the trans hydrolysis of 23 is still unclear.
However, carrying out the reaction at -78 °C for 15 h
and then quenching with water resulted in the formation
of 5-ethoxy-1,2,3-triphenylpyrrole 27a presumably via
the intermediate 26a and subsequent intramolecular
displacement of the triazole moiety. When we used N-(4-
gave the intermediate 19 in 62% yield. Subsequent
treatment of 19 with 2 M hydrochloric acid in ethanol
under reflux for 4 h gave the expected spirolactone 20 in
98% yield. Compounds 16a -c and 18 were similarly
prepared in 61-78% overall yields without isolation of
the intermediates 15a -c and 17.
As mentioned previously, the triazole anion formed can
also react with the relatively reactive electrophiles.
Therefore in the cases of 16a -c and 20, 2 equiv of
aldehydes was used in the reactions. Otherwise, low
yields were achieved. However, in the case of 18 with
benzophenone as electrophile, we found that only 1 equiv
of benzophenone was consumed in the reaction. This can
be rationalized by the the steric effect of benzophenone
which prevents its reaction with triazole anion.
We have also used the reaction of 13 (h 12) with
cyclohexenone to prepare lactone 22. Interestingly, no
1,4-addition product was observed from the crude NMR
spectra, which would give a ketone carbonyl signal in the
range of 190-220 ppm. Normally, reactions of lithium
agents with an R,â-unsaturated ketones produce mixture
of 1,2- and 1,4-addition products. Exclusive formation
of the 1,2-addition product probably involved the six-
membered ring species I.
(32) Rao, Y. S. Chem. Rev. 1976, 76, 625.
(33) (a) Larock, R. C.; Stinn, D. E.; Kuo, M.-Y. Tetrahedron Lett.
1990, 31, 17. (b) Arcadi, A.; Bernocchi, E.; Burini, A.; Cacchi, S.;
Marinelli, F.; Pietroni, B. Tetrahedron 1988, 44, 481. (c) Cowell, A.;
Stille, J . K. J . Am. Chem. Soc. 1980, 102, 4193. (d) Kasahara, A.; Izumi,
T.; Sato, K.; Maemura, M.; Hayasaka, T. Bull. Chem. Soc. J pn. 1977,
50, 1899.
(34) DeShong, P.; Sidler, D. R.; Rybczynski, P. J .; Slough, G. A.;
Rheingold, A. L. J . Am. Chem. Soc. 1988, 110, 2575.
(35) Buchwald, S. L.; Fang, Q.; King, S. M. Tetrahedron Lett. 1988,
29, 3445.
(36) Hong, P.; Mise, T.; Yamazaki, H. Chem. Lett. 1981, 989.
(37) Iwai, K.; Kosugi, H.; Miyazaki, A.; Uda, H. Synth. Commun.
1976, 6, 357.
(38) Tanaka, K.; Wakita, H.; Yoda, H.; Kaji, A. Chem. Lett. 1984,
1359.
(39) Carretero, J . C.; De Lombaert, S.; Ghosez, L. Tetrahedron Lett.
1987, 28, 2135.
(40) Iwai, K.; Kosugi, H.; Uda, H.; Kawai, M. Bull. Chem. Soc. J pn.
1977, 50, 242.
(41) Barluenga, J .; Ferna´ndez, J . R.; Yus, M. J . Chem. Soc., Chem.
Commun. 1986, 183.
(42) Schmit, C.; Sahraoui-Taleb, S.; Differding, E.; Dehasse-De
Lombaert, C. G.; Ghosez, L. Tetrahedron Lett. 1984, 25, 5043.
(43) Metz, G.; Schwenker, G. Synthesis 1980, 394.
(44) Tanabe, Y.; Ohno, N. J . Org. Chem. 1988, 53, 1560.
In the present reactions, formation of cyclic products
16, 18, 20, and 22 relied on the cis hydrolyses of 15, 17,
19, and 21. The trans hydrolysis would not result in the
cyclic products due to the difficult geometrical con-

718 J . Org. Chem., Vol. 62, No. 3, 1997
Katritzky et al.
Sch em e 3
Sch em e 4
Sch em e 5
chlorobenzylidine)aniline and N-(4-methylbenzylidine)-
aniline as electrophiles, the corresponding pyrroles 27b,c
were similarly prepared in 83% and 86% yields, respec-
tively.
formation of major γ-alkylated product 40 (49%) along
with R-alkylated product 41 (16%) (Scheme 5). When we
used N-benzylidineaniline as the electrophile, the ex-
pected pyrrole derivative 42 was obtained exclusively.
The structures for the final products and the isolated
intermediates were confirmed by 1H and 13C NMR
spectra and elemental analyses. The data for known
compounds are consistent with those reported in litera-
ture.
When an alkyl imine (obtained from benzaldehyde and
primary alkylamine) was used as an electrophile to react
with dianion 13 at -78 °C for a few minutes, two pyrrole
derivatives 30 and 31 were obtained from the reaction.
This is because the amido anion 29 formed is strongly
nucleophilic and immediately attacks these R-carbon
adjacent to triazolyl and ethoxy groups to generate the
cyclized products 30 and 31. In this reaction, both
triazole and ethoxy have been used as leaving groups,
which is different from previous cases. To the best of
our knowledge, compounds of type 27, 30, and 31 were
previously unknown.
3-Alk yl-1-(tr ia zol-1-yl)p r op a r gyl Eth yl Eth er 33 a s
Sta r tin g Ma ter ia l Lea d in g to Ma in ly γ-P r od u cts.
Reaction of acetal 32 with triazole in refluxing toluene
for 20 h produced 1-(triazol-1-yl)-3-hexylpropargyl ethyl
ether (33) in 70% yield (Scheme 4). When compound 33
was treated with 2 equiv of butyllithium at -78 °C for a
few minutes, dianion 34 (h 35) was formed similarly to
the previous case. Subsequent reaction with hexyl
bromide for ca. 10 min at the same temperature followed
by hydrolysis with 2 M sulfuric acid gave R,â-unsaturated
ester 39 and alkynyl ketone 38 in 65% and 15% yields,
respectively, which is different from the phenyl-substi-
tuted case (11) where the γ-products are exclusive. The
reason for this is not clear.
Con clu sion s
Novel 1,2,4-triazole-stabilized allenic anions have been
developed for the generation of R,â-unsaturated esters,
γ-lactones, and 1,2,3,5-tetrasubstituted pyrroles. The
simplicity and convenient availibility of the starting
materials give these methods considerable potential
importance in organic synthesis.
Exp er im en ta l Section
Gen er a l Com m en ts. Melting points were determined on
a hot stage apparatus without correction. 1H (300 MHz) and
13C NMR (75 MHz) spectra were recorded in CDCl3 with TMS
or CDCl3, respectively, as the internal reference. Column
chromatography was carried out on MCB silica gel (230-400
mesh). Tetrahydrofuran (THF) was freshly distilled from
sodium-benzophenone. Lithiation reactions were carried out
under the protection of dry nitrogen.
P r ep a r a tion of 1-(1,2,4-Tr ia zol-1-yl)p r op a r gyl Eth yl
Eth er s 11 a n d 33. Gen er a l P r oced u r e. Propargyl alde-
hyde acetals 7 or 32 (30 mmol) and 1,2,4-triazole (36 mmol)
Use of benzophenone as an electrophile in the reaction
with anion 34 (h 35) produced similar results with

Triazole-Stabilized Allenic Anions
J . Org. Chem., Vol. 62, No. 3, 1997 719
were heated under reflux in toluene (30 mL) for 30 h. The
solvent was evaporated under reduced pressure, and the
residues were chromatographed on silica gel (hexane/ethyl
acetate 5 :1).
1-(1,2,4-Tr ia zol-1-yl)-3-p h en ylp r op a r gyl et h yl et h er
(11): obtained as a brown oil; yield 82%; 1H NMR δ 1.25 (t, 3
H, J ) 7.0 Hz), 3.63-3.80 (m, 2 H), 6.47 (s, 1 H), 7.34-7.41
(m, 3 H), 7.51-7.54 (m, 2 H), 8.02 (s, 1 H), 8.59 (s, 1 H); 13C
NMR δ 14.6, 63.9, 78.4, 80.9, 88.3, 120.5, 128.4, 129.6, 131.9,
142.6, 152.0. Anal. Calcd for C13H13N3O: C, 68.71; H, 5.77;
N, 18.49. Found: C, 68.50; H, 5.69; N, 18.50.
appropriate electrophile (EtBr, C5H11Br, allyl bromide or
N-benzylidineaniline; 5 mmol; for C6H13I, 10 mmol) was then
added. After the solution was stirred at -78 °C for an
additional 5 to 10 min, the reaction was quenched at this
temperature with water (50 mL). The mixture was extracted
with diethyl ether (3 × 100 mL). Evaporation of the solvent
gave a residue, which was hydrolyzed in a mixture of ethanol
(15 mL), water (15 mL), and HCl (2 mL) at room temperature
for 2 h. The resulting solution was extracted with diether (3
× 100 mL), washed with water (100 mL), and dried over
anhydrous MgSO4. Evaporation of the solvent gave a residue
which was separated by column chromatography (hexane/ethyl
acetate, 25:1).
1-(1,2,4-Tr ia zol-1-yl)-2-n on yn yl eth yl eth er (33): ob-
1
tained as a colorless oil; yield 86%; H NMR δ 0.91 (t, 3 H, J
Eth yl 3-p h en yl-2-p en ten oa te (9b): Obtained as two
) 7.2 Hz), 1.21 (t, 3 H, J ) 7.1 Hz), 1.28-1.44 (m, 6 H), 1.53-
1.63 (m, 2 H), 2.31-2.36 (m, 2 H), 3.52-3.60 (m, 1 H), 3.62-
3.72 (m, 1 H), 6.24 (t, 1 H, J ) 1.9 Hz), 7.98 (s, 1 H), 8.51 (s,
1 H); 13C NMR δ 13.8, 14.6, 18.5, 22.3, 27.8, 28.4, 31.1, 63.4,
72.7, 78.1, 90.1, 142.4, 151.8. Anal. Calcd for C13H21N3O: C,
66.35; H, 8.99; N, 17.86. Found: C, 66.60; H, 9.20; N, 18.00.
Gen er a l P r oced u r e for th e P r ep a r a tion of Allen es 10
a n d 19, r,â-Un sa tu r a ted Ester 9a , a n d Bu ten olid e 20. To
a solution of 1-(1,2,4-triazol-1-yl)propargyl ethyl ether (11) (5
mmol) in THF (70 mL) at -78 °C was added n-butyllithium
(2.5 M in cyclohexane, 4 mL, 10 mmol). The solution was
stirred at this temperature for 5 min, and the appropriate
electrophile (MeI or cyclohexanone; 10 mmol) was then added.
After the solution was stirred at -78 °C for an additional 5 to
10 min, the reaction was quenched at this temperature with
water (50 mL) and the solution was extracted with diethyl
ether (3 × 100 mL). Evaporation of the solvent gave a residue.
In the case of 10. The pure (>95%) compound was obtained.
In the case of 19, pure compound was obtained after column
chromatography (hexane/ethyl acetate 20:1). Hyd r olysis. In
the case of 9a , the compound 10 was dissolved in a mixture of
ethanol (15 mL), water (15 mL), and HCl (2 mL) and kept for
2 h. In the case of 20, compound 19 was dissolved in a mixture
of ethanol (15 mL), water (15 mL), and HCl (2 mL) and heated
under reflux for 2 h. The resulting solution was extracted with
diether (3 × 100 mL), washed with water (100 mL), and dried
over anhydrous MgSO4. Evaporation of the solvent gave a
residue which was separated by column chromatography
(hexane/ethyl acetate 25:1).
diastereoisomers. E-isom er : a colorless oil, lit.20 bp 91-94.5
1
°C/1 mmHg; yield 23%; H NMR δ 1.08 (t, 3 H, J ) 7.5 Hz),
1.32 (t, 3 H, J ) 7.1 Hz), 3.11 (q, 2 H, J ) 7.5 Hz), 4.21 (q, 2
H, J ) 7.1 Hz), 6.02 (s, 1 H), 7.35-7.39 (m, 3 H), 7.42-7.46
(m, 2 H); 13C NMR δ 13.5, 14.3, 24.3, 59.8, 116.8, 128.6, 128.8,
1
141.2, 162.0, 166.4. Z-isom er : a colorless oil; yield 70%; H
NMR δ 1.03-1.09 (m, 6 H), 2.45 (q, 2 H, J ) 7.2 Hz), 3.98 (q,
2 H, J ) 7.1 Hz), 5.88 (s, 1 H), 7.13-7.17 (m, 2 H), 7.29-7.36
(m, 3 H); 13C NMR δ 12.0, 13.9, 33.3, 59.6, 116.3, 126.9, 127.4,
127.7, 140.4, 160.8, 166.1.
Eth yl 3-p h en yl-2-octen oa te (9c): obtained as two dia-
stereoisomers. E isom er : a colorless oil; yield 15%; 1H NMR
δ 0.86 (t, 3 H, J ) 7.1 Hz), 1.25-1.50 (m, 9 H), 3.10 (t, 2 H, J
) 7.4 Hz), 4.22 (q, 2 H, J ) 7.1 Hz), 6.03 (s, 1 H), 7.34-7.48
(m, 5 H); 13C NMR δ 14.0, 14.3, 22.4, 28.7, 31.0, 31.9, 59.8,
117.3, 126.7, 128.5, 128.7, 141.5, 160.8, 166.5. Z isom er : a
1
colorless oil; yield 64%; H NMR δ 0.85 (t, 3 H, J ) 7.1 Hz),
1.05 (t, 3 H, J ) 7.2 Hz), 1.24-1.30 (m, 4 H), 1.31-1.41 (m, 2
H), 2.42 (t, 2 H, J ) 6.9 Hz), 3.97 (q, 2 H, J ) 7.2 Hz), 5.87 (s,
1 H), 7.12-7.18 (m, 2 H), 7.28-7.36 (m, 3 H); 13C NMR δ 13.9,
22.3, 26.9, 31.2, 40.3, 59.6, 117.1, 127.0, 127.4, 127.7, 140.3,
159.7, 166.0. Anal. Calcd for C16H22O2: C, 78.01; H, 9.00.
Found: C, 77.89; H, 9.36.
Eth yl 3-p h en yl-2,5-h exa d ien oa te (9d ): obtained as two
diastereoisomers. E isom er : a colorless oil; yield 28%; 1H
NMR δ 1.31 (t, 3 H, J ) 7.1 Hz), 3.87-3.90 (m, 2 H), 4.21 (q,
2 H, J ) 7.1 Hz), 4.99-5.14 (m, 2 H), 5.83-5.92 (m, 1 H), 6.15
(s, 1 H), 7.33-7.36 (m, 3 H), 7.44-7.49 (m, 2H); 13C NMR δ
14.2, 35.3, 59.8, 116.1, 117.9, 126.7, 128.4, 128.9, 135.2, 141.0,
156.7, 166.1. Anal. Calcd for C14H16O2: C, 77.75; H, 7.46.
Found: C, 78.13; H, 7.66. Z isom er : a colorless oil; yield 52%;
1H NMR δ 1.07 (t, 3 H, J ) 7.2 Hz), 3.16-3.19 (m, 2 H), 3.99
(q, 2 H, J ) 7.2 Hz), 5.07-5.13 (m, 2 H), 5.76-5.85 (m, 1 H),
5.90 (s, 1 H), 7.17-7.20 (m, 2 H), 7.30-7.37 (m, 3 H); 13C NMR
δ 13.8, 44.1, 59.6, 117.9, 118.0, 127.0, 127.5, 127.7, 133.6, 140.0,
157.0, 165.8. Anal. Calcd for C14H16O2: C, 77.75; H, 7.46.
Found: C, 78.03; H, 7.64.
E t h yl (Z)-3,4-d ip h en yl-4-(p h en yla m in o)-2-b u t en oa t e
(24): yield 70%; mp 128-130 °C; 1H NMR δ 1.03 (t, 3 H, J )
7.1 Hz), 3.96 (q, 2 H, J ) 7.1 Hz), 4.14 (d, 1 H, J ) 4.1 Hz),
5.08 (d, 1 H, J ) 4.1 Hz), 6.41 (s, 1 H), 6.67 (d, 2 H, J ) 8.5
Hz), 6.77 (t, 1 H, J ) 7.2 Hz), 6.98-7.02 (m, 2 H), 7.18-7.30
(m, 10 H); 13C NMR δ 13.8, 59.9, 65.8, 113.4, 118.2, 118.5,
127.6, 127.7, 127.9, 128.1, 128.8, 129.2, 138.1, 139.1, 146.5,
156.8, 166.1. Anal. Calcd for C24H23NO2: C, 80.64; H, 6.49;
N, 3.92. Found: C, 81.03; H, 6.62; N, 3.84.
1-E t h oxy-1-[5-m e t h yl-1,2,4-t r ia zol-1-yl]-3-m e t h yl-3-
p h en yla llen e (10): obtained as a colorless oil; yield 100%; 1H
NMR δ 1.40 (t, 3 H, J ) 7.1 Hz), 2.39 (s, 3 H), 2.50 (s, 3 H),
3.88 (q, 2 H, J ) 7.1 Hz), 7.30-7.42 (m, 3 H), 7.56-7.60 (m, 2
H), 7.89 (s, 1 H); 13C NMR δ 12.8, 14.2, 19.7, 64.9, 120.4, 126.5,
128.4, 128.6, 128.7, 135.7, 151.0, 152.9, 185.0.
1-Eth oxy-1-[5-(1-h yd r oxycycloh exyl)-1,2,4-tr ia zol-1-yl]-
3-(1-h yd r oxycycloh exyl)-3-p h en yla llen e (19): yield 52%;
mp 127-129 °C; 1H NMR δ 1.10-2.15 (m, 23 H), 3.55 (s, 1 H),
3.86-4.00 (m, 3 H), 7.30-7.45 (m, 5 H), 7.34 (s, 1 H); 13C NMR
δ 14.4, 21.4, 21.5, 21.6, 21.7, 25.0, 25.1, 36.2, 36.8, 65.2, 71.1,
74.2, 127.8, 128.1, 128.6, 130.5, 134.0, 135.6, 149.9, 160.7,
185.1. Anal. Calcd for C25H33N3O3: C, 70.89; H, 7.85; N, 9.92.
Found: C, 71.12; H, 8.10; N, 10.13.
Eth yl 3-p h en yl-2-bu ten oa te (9a ): obtained as two dia-
stereoisomers. E isom er : a colorless oil, lit.20 bp 115-116 °C/5
mmHg; yield 17%; 1H NMR δ 1.34 (t, 3 H, J ) 7.1 Hz), 2.61 (s,
3 H), 4.23 (q, 2 H, J ) 7.1 Hz), 6.16-6.17 (m, 1 H), 7.37-7.40
(m, 3 H), 7.47-7.51 (m, 2 H); 13C NMR δ 14.3, 17.9, 59.7, 117.1,
Eth yl 3-h exyl-2-n on en oa te (39): obtained as a colorless
1
126.2, 128.4, 128.6, 128.9, 133.0, 142.2, 155.4, 166.8.
Z
oil; yield 65%; H NMR δ 0.88-0.97 (m, 6 H), 1.26-1.50 (m,
isom er : a colorless oil; yield 70%; 1H NMR δ 1.07 (t, 3 H, J )
7.1 Hz), 2.17 (s, 3 H), 3.99 (q, 2 H, J ) 7.1 Hz), 5.90 (s, 1 H),
7.18-7.21 (m, 2 H), 7.29-7.34 (m, 3 H); 13C NMR δ 13.9, 27.1,
59.7, 117.8, 126.8, 127.6, 127.8, 140.8, 155.2, 165.9.
19 H), 2.14 (t, 2 H, J ) 7.4 Hz), 2.60 (t, 2 H, J ) 7.4 Hz), 4.15
(q, 2 H, J ) 7.1 Hz), 5.63 (s, 1 H); 13C NMR δ 14.0, 14.3, 22.5,
22.6, 27.6, 28.7, 29.0, 29.6, 31.6, 31.7, 32.2, 38.4, 59.4, 115.0,
164.8, 166.6. Anal. Calcd for C17H32O2: C, 76.06; H, 12.02.
Found: C, 75.89; H, 12.21.
3′-P h en ylcycloh exa n espir o-4′-r,â-bu ten olid e (20): yield
98%; mp 77-79 °C; 1H NMR δ 1.22-2.07 (m, 10 H), 6.17 (s, 1
H), 7.45-7.55 (m, 5 H); 13C NMR δ 22.0, 24.4, 34.4, 89.3, 115.5,
127.4, 128.8, 130.2, 130.8, 171.6, 172.7. Anal. Calcd for
C15H16O2: C, 78.92; H, 7.06. Found: C, 78.95; H, 7.30.
Gen er a l P r oced u r e for th e P r ep a r a tion of 9b-d , 24,
a n d 39. To a solution of 1-(1,2,4-triazol-1-yl)propargyl ethyl
ethers 11 or 33 (5 mmol) in THF (70 mL) at -78 °C was added
n-butyllithium (2.5 M in cyclohexane, 4 mL, 10 mmol). The
solution was stirred at this temperature for 5 min, and the
Gen er a l P r oced u r e for th e P r ep a r a tion of 16a -c. To
a solution of 1-(1,2,4-triazol-1-yl)propargyl ethyl ethers 11 (5
mmol) in THF (70 mL) at -78 °C was added n-butyllithium
(2.5 M in cyclohexane, 2 mL, 10 mmol). The solution was
stirred at this temperature for 5 min, and the appropriate
electrophile (benzaldehyde, 4-tolualdehyde, or octanal; 10
mmol) was then added. After the solution was stirred at -78
°C for an additional 5 to 10 min, the reaction was quenched
at this temperature with water (50 mL). HCl (2 M, 8 mL) was

720 J . Org. Chem., Vol. 62, No. 3, 1997
Katritzky et al.
added, and the mixture was kept for 4 h at room temperature.
The resulting solution was extracted with diether (3 × 100
mL), washed with water (100 mL), and dried over anhydrous
MgSO4. Evaporation of the solvent gave a residue which was
separated by column chromatography (hexane/ethyl acetate
25:1).
3,4-Dip h en yl-r,â-bu ten olid e (16a ): yield 67%; mp 151-
153 °C; (lit.45 mp 149 °C); 1H NMR δ 6.34 (d, 1 H, J ) 1.6 Hz),
5.56 (d, 1 H, J ) 1.5 Hz), 7.31-7.44 (m, 10 H); 13C NMR δ
84.3, 114.6, 127.5, 127.8, 128.9, 129.1, 129.5, 129.6, 131.2,
134.9, 165.8.
4-(4-Meth ylp h en yl)-3-p h en yl-r,â-bu ten olid e (16b): yield
61%; mp 129-131 °C; 1H NMR δ 2.31 (s, 3 H), 6.32 (d, 1 H, J
) 1.6 Hz), 6.56 (d, 1 H, J ) 1.6 Hz), 7.13-7.23 (m, 4 H), 7.3-
7.44 (m, 5 H); 13C NMR δ 21.1, 84.1, 114.4, 127.4, 127.7, 128.8,
129.7, 131.1, 131.8, 139.5, 165.7, 172.6. Anal. Calcd for
C17H14O2: C, 81.58; H, 5.64. Found: C, 81.54; H, 5.69.
4-Hep tyl-3-p h en yl-r,â-bu ten olid e (16c): obtained as a
colorless oil: yield 70%; 1H NMR 0.87 (t, 3 H, J ) 6.6 Hz),
1.19-1.66 (m, 11 H), 1.97-2.07 (m, 1 H), 5.50-5.55 (m, 1 H),
6.29 (d, 1 H, J ) 1.5 Hz), 7.30-7.53 (m, 5 H); 13C NMR δ 13.9,
22.5, 24.4, 28.9, 29.0, 31.5, 33.4, 82.2, 114.2, 127.0, 129.1, 130.1,
131.2, 167.8, 172.8. Anal. Calcd for C17H22O2: C, 79.03; H,
8.58. Found: C, 79.03; H, 9.01.
Gen er a l P r oced u r e for th e P r ep a r a tion of 18, 22, 24,
40, a n d 41. To a solution of 1-(1,2,4-triazol-1-yl)propargyl
ethyl ethers 11 or 33 (5 mmol) in THF (70 mL) at -78 °C was
added n-butyllithium (2.5 M in cyclohexane, 2 mL, 10 mmol).
The solution was stirred at this temperature for 5 min, and
the appropriate electrophile (benzophenone, 5 mmol; cyclo-
hexenone, 10 mmol) was then added. After the solution was
stirred at -78 °C for an additional 5 to 10 min, the reaction
was quenched at this temperature with water (50 mL). The
mixture was extracted with diethyl ether (3 × 100 mL).
Evaporation of the solvent gave a residue, which was hydro-
lyzed in a mixture of ethanol (15 mL), water (15 mL), and HCl
(2 mL) under reflux for 4 h. The resulting solution was
extracted with diether (3 × 100 mL), washed with water (100
mL), and dried over anhydrous MgSO4. Evaporation of the
solvent gave a residue which was separated by column
chromatography (hexane/ethyl acetate, 25:1).
3,4,4-Tr ip h en yl-r,â-bu ten olid e (18): yield 78%; mp 203-
205 °C; 1H NMR δ 6.50 (s, 1 H), 7.28-7.40 (m, 15 H); 13C NMR
δ 93.4, 116.6, 128.2, 128.4, 128.7, 128.8, 130.8, 138.0, 170.0,
171.4. Anal. Calcd for C22H16O2: C, 84.59; H, 5.16. Found:
C, 84.56; H, 5.07.
3′-P h en yl-2-cycloh exen esp ir o-4′-r,â-b u t en olid e (22):
yield 64%; mp 90-92 °C; 1H NMR δ 1.81-2.36 (m, 6 H), 5.70
(dd, 1 H, J ) 9.8, 1.5 Hz), 6.32-6.38 (m, 2 H), 7.42-7.49 (m,
3 H), 7.62-7.68 (m, 2 H); 13C NMR δ 18.4, 24.1, 33.2, 85.0,
114.6, 125.0, 127.4, 128.7, 129.8, 130.7, 134.9, 170.0, 171.3.
Anal. Calcd for C15H14O2: C, 79.62; H, 6.24. Found: C, 79.96;
H, 6.35.
1.30 (m, 6 H), 1.37-1.45 (m, 2 H), 2.29 (t, 2 H, J ) 7.0 Hz),
4.73 (s, 1 H), 7.32-7.39 (m, 6 H), 7.45-7.50 (m, 4 H); 13C NMR
δ 13.9, 19.3, 22.3, 27.1, 28.3, 31.1, 79.0, 85.6, 104.6, 127.6,
128.0, 128.1, 141.0, 187.8. Anal. Calcd for C22H24O2: C, 82.46;
H, 7.55. Found: C, 82.44; H, 7.89.
Gen er a l P r oced u r e for th e P r ep a r a tion of 27a -c, 30,
31, a n d 42. To a solution of 1-(1,2,4-triazol-1-yl)propargyl
ethyl ethers 11 or 33 (5 mmol) in THF (70 mL) at -78 °C was
added n-butyllithium (2.5 M in cyclohexane, 2 mL, 10 mmol).
The solution was stirred at this temperature for 5 min, and
the appropriate electrophile (N-benzylidineaniline, N-(4-chlo-
robenzylidine)aniline, N-(4-methylbenzylidine)aniline, or N-
benzylidinehexylamine; 5 mmol) was then added. After the
solution was stirred at -78 °C for an additional 15 h, the
reaction was quenched at this temperature with water (50
mL). The mixture was extracted with diethyl ether (3 × 100
mL) and dried over anhydrous MgSO4. Evaporation of the
solvent gave a residue, which was chromatographed on silica
gel (hexane/ethyl acetate 25:1).
2-E t h oxy-N,4,5-t r ip h en ylp yr r ole (27a ): yield 82%; mp
1
99-101 °C; H NMR δ 1.33 (t, 3 H, J ) 7.1 Hz), 4.09 (q, 2 H,
J ) 7.1 Hz), 5.67 (s, 1 H), 6.98-7.28 (m, 15 H); 13C NMR δ
14.7, 66.8, 86.0, 120.7, 122.5, 125.3, 126.2, 126.6, 127.8, 128.0,
128.3, 130.9, 132.4, 136.6, 136.8, 148.1. Anal. Calcd for
C24H21NO: C, 84.92; H, 6.24; N, 4.13. Found: C, 84.49; H,
6.24; N, 3.94.
2-Eth oxy-N,4-diph en yl-5-(4-ch lor oph en yl)pyr r ole (27b):
1
yield 83%; mp 137-139 °C; H NMR δ 1.32 (t, 3 H, J ) 7.1
Hz), 4.08 (q, 2 H, J ) 7.1 Hz), 5.64 (s, 1 H), 6.89 (d, 1 H, J )
8.2 Hz), 7.02-7.30 (m, 12 H); 13C NMR δ 14.7, 66.8, 86.3, 121.1,
121.5, 125.6, 126.9, 128.1, 128.2, 128.3, 128.4, 130.9, 132.0,
136.4, 136.6, 148.3. Anal. Calcd for C24H20NOCl: C, 77.10;
H, 5.39; N, 3.75. Found: C, 77.36; H, 5.35; N, 3.62.
2-Eth oxy-N,4-diph en yl-5-(4-m eth ylph en yl)pyr r ole (27c):
1
yield 86%; mp 107-109 °C; H NMR δ 1.31 (t, 3 H, J ) 7.1
Hz), 2.22 (s, 1 H), 4.07 (q, 2 H, J ) 7.1 Hz), 5.65 (s, 1 H), 6.88
(s, 4 H), 7.09-7.27 (m, 10 H); 13C NMR δ 14.7, 21.1, 66.8, 85.9,
113.2, 120.4, 122.6, 125.2, 126.6, 128.0, 128.2, 128.4, 128.6,
130.8, 135.8, 136.8, 136.9, 147.9. Anal. Calcd for C25H23NO:
C, 84.95; H, 6.56; N, 3.96. Found: C, 85.29; H, 6.73; N, 3.88.
2-Eth oxy-N-h exyl-4,5-d ip h en ylp yr r ole (30): obtained as
a colorless oil; yield 41%; 1H NMR δ 0.83 (t, 3 H, J ) 7.1 Hz),
1.10-1.28 (m, 6 H), 1.42-1.60 (m, 5 H), 3.70 (t, 2 H, J ) 7.5
Hz), 4.13 (q, 2 H, J ) 7.1 Hz), 5.55 (s, 1 H), 7.00-7.18 (m, 5
H), 7.26-7.37 (m, 5 H); 13C NMR δ 13.9, 14.9, 22.4, 26.2, 30.3,
31.2, 42.2, 66.0, 83.8, 119.2, 122.1, 124.7, 127.1, 127.6, 127.9,
128.4, 133.3, 136.9, 147.8. Anal. Calcd for C24H29NO: C,
82.95; H, 8.41; N, 4.03. Found: C, 82.68; H, 8.61; N, 4.09.
N-Hexyl-2,5-d ip h en yl-5-(1,2,4-tr ia zol-1-yl)p yr r ole (31):
yield 40%; mp 87-89 °C; 1H NMR δ 0.76 (t, 3 H, J ) 7.2 Hz),
0.90-1.00 (m, 4 H), 1.02-1.15 (m, 2 H), 1.25-1.35 (m, 2 H),
3.74 (t, 2 H, J ) 7.7 Hz), 6.53 (s, 1 H), 7.03-7.20 (m, 5 H),
7.30-7.40 (m, 5 H), 8.16 (s, 1 H), 8.35 (s, 1 H); 13C NMR δ
13.5, 21.9, 25.7, 30.2, 30.5, 43.9, 105.1, 121.3, 124.4, 125.3,
127.4, 127.9, 128.0, 128.4, 130.3, 103.8, 131.8, 134.9, 145.6,
152.5. Anal. Calcd for C24H26N4: C, 77.80; H, 7.07; N, 15.12.
Found: C, 77.82; H, 7.00; N, 15.20.
4,4-Dip h en yl-3-h exyl-r,â-bu ten olid e (40): yield 49%; mp
58-60 °C; 1H NMR δ 0.85 (t, 3 H, J ) 7.2 Hz), 1.18-1.32 (m,
6 H), 1.45-1.55 (m, 2 H), 2.33 (t, 2 H, J ) 7.1 Hz), 6.00 (s, 1
H), 7.26-7.39 (m, 10 H); 13C NMR δ 13.6, 22.1, 26.9, 28.3, 28.4,
31.0, 93.8, 115.4, 127.3, 128.2, 128.4, 138.4, 171.9, 175.6. Anal.
Calcd for C22H24O2: C, 82.46; H, 7.55. Found: C, 82.10; H,
7.73.
2-Eth oxy-4-h exyl-N,5-d ip h en ylp yr r ole (42): yield 83%;
mp 57-59 °C; 1H NMR δ 0.87 (t, 3 H, J ) 7.0 Hz), 1.22-1.40
(m, 11 H), 1.55-1.65 (m, 2 H), 2.52 (t, 2 H, J ) 7.5 Hz), 3.99
(q, 2 H, J ) 7.1 Hz), 5.39 (s, 1 H), 7.00-7.22 (m, 10 H); 13C
NMR δ 14.1, 14.7, 22.6, 22.7, 29.3, 31.3, 31.7, 66.5, 85.8, 121.4,
122.3, 125.4, 125.9, 127.6, 127.8, 128.1, 130.0, 132.9, 137.7,
147.7. Anal. Calcd for C24H29NO: C, 82.95; H, 8.41; N, 4.03.
Found: C, 82.72; H, 8.58; N, 3.97.
1-Hyd r oxy-1,1-d ip h en yl-3-d ecyn -2-on e (41): obtained as
1
an oil; yield 16%; H NMR δ 0.86 (t, 3 H, J ) 7.0 Hz), 1.17-
(45) Bestmann, H. J .; Schmid, G.; Sandmeier, D.; Schade, G.;
Oechsner, H. Chem. Ber. 1985, 118, 1709.
J O961397L