Benzotriazole- and 1,2,4-triazole-stabilized allylic anions: Applications in syntheses of functionalized α,β-unsaturated ketones, γ-lactones, γ-lactams, and β-substituted esters

Article abstract of DOI:10.1021/jo961396t

Deprotonated 1-(benzotriazol-1-yl)-1-ethoxy-2-hexene (7) reacted with alkyl halides, aldehydes, ketones, imines, and α,β-unsaturated esters to give exclusively the α-alkylated products 8a-c, 10a,b, 12, 14, 16, and 18a,b, respectively. Without isolation, these products were hydrolyzed under mild conditions to generate the corresponding simple or functionalized α,β-unsaturated ketenes 9a-c, 11a,b, 13, 15, 17, and 19a,b. Similar reactions with the phenyl-substituted analog 3-(benzotriazol-1-yl)-3-ethoxy-1-phenyl-1-propene (21) also gave the analogous α-products, but they were accompanied by small amounts of the γ-products in most cases. By contrast, deprotonation of the corresponding triazole derivative 29 with butyllithium followed by reactions with alkyl halides, aldehydes, ketones, or imines yielded exclusively γ-alkylated adducts 32, 34, 36, 38, 40, and 42. Intermediates 32, 34, 36, 38, 40, and 42 were readily converted into β-substituted esters 33a-c, γ-lactones 35a,b, 39, 41, and 43, and γ-lactams 37a-c on hydrolysis.

Full text of DOI:10.1021/jo961396t

706
J . Org. Chem. 1997, 62, 706-714
Ben zotr ia zole- a n d 1,2,4-Tr ia zole-Sta bilized Allylic An ion s:
Ap p lica tion s in Syn th eses of F u n ction a lized r,â-Un sa tu r a ted
Keton es, γ-La cton es, γ-La cta m s, a n d â-Su bstitu ted Ester 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
Deprotonated 1-(benzotriazol-1-yl)-1-ethoxy-2-hexene (7) reacted with alkyl halides, aldehydes,
ketones, imines, and R,â-unsaturated esters to give exclusively the R-alkylated products 8a -c,
10a ,b, 12, 14, 16, and 18a ,b, respectively. Without isolation, these products were hydrolyzed under
mild conditions to generate the corresponding simple or functionalized R,â-unsaturated ketones
9a -c, 11a ,b, 13, 15, 17, and 19a ,b. Similar reactions with the phenyl-substituted analog
3-(benzotriazol-1-yl)-3-ethoxy-1-phenyl-1-propene (21) also gave the analogous R-products, but they
were accompanied by small amount of the γ-products in most cases. By contrast, deprotonation of
the corresponding triazole derivative 29 with butyllithium followed by reactions with alkyl halides,
aldehydes, ketones, or imines yielded exclusively γ-alkylated adducts 32, 34, 36, 38, 40, and 42.
Intermediates 32, 34, 36, 38, 40, and 42 were readily converted into â-substituted esters 33a -c,
γ-lactones 35a ,b, 39, 41, and 43, and γ-lactams 37a -c on hydrolysis.
Over recent decades, the chemistry of heteroatom-
alkyl halide, an aldehyde, or a ketone. Their synthetic
applications have been summarized in our recent
publications.23-25
stabilized allylic anions has been intensively investigated
and has led to the development of many new synthetically
useful methods.1-4 Deprotonated systems 1 provide the
reversed polarity equivalents 2 and homoenolate anion
synthon equivalents 3 through removal of the hetero-
atoms by hydrolysis. Among the most common precur-
sors of 1,1-diheterostabilized allylic anions are R,â-
unsaturated S,S-acetals 1a ,5-8 R,â-Unsaturated O,S-
acetals 1b,9 R,â-unsaturated O-alkyl- or O-(trimethylsilyl)-
protected cyanohydrins 1c,10-15 2-(dialkylamino)-3-
butenenitriles 1d ,16,17 and allylic phosphorus compounds
1e (phosphites,18 phosphonamides,19 and phosphine
oxides20-22). In most cases, these precursors are treated
with butyllithium or LDA to generate the allylic anions,
which are then reacted with an electrophile, such as an
As discussed in our previous papers,24,25 the synthetic
utility of allylic anions 1 depends on (i) the degree of
regioselectivity in their reactions with electrophiles, (ii)
the availability of their precursors, and (iii) the ease of
removal of the heteroatoms at the end of the reaction
sequence. Among these, the regioselectivity is crucial to
the practical application of the ambident anions 1.
Regioselectivity is influenced in a complicated manner
by the substituents on the vinyl groups, the nature of
the incoming electrophile, the nature of the hetero moiety
(i.e., X/Y groups in 1), and the reaction.3,4,15,21 There
seems to be no known general rule for the prediction of
the ratio of R-/γ-products: in rare cases R-attack is
favored at low temperature under kinetic control and
γ-attack at higher temperature under thermodynamic
control.14,15
Recently we described the advantageous use of readily
available N-(R-ethoxyallyl)benzotriazole (4) for the syn-
theses of functionalized vinyl ketones,24 cyclopropanes,25
γ-lactones,25 â,γ-unsaturated carboxylic acids,25 ketones,26
1,4-diketones,26 2-cyclopentenones,26 and R-keto enam-
ines.26 Deprotonated 4 reacted with a variety of electro-
philes (RX, RCHO, ketone and R,â-unsaturated esters)
X Abstract published in Advance ACS Abstracts, November 1, 1996.
(1) Yamamoto, Y.; Asao, N. Chem. Rev. 1993, 93, 2207.
(2) Altenbach, H.-J . In Comprehensive Organic Synthesis; Trost, B.
M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 6, p 829.
(3) Yamamoto, Y. In Comprehensive Organic Synthesis; Trost, B.
M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 2, p 55.
(4) Hoppe, D. Angew. Chem., Int. Ed. Engl. 1984, 23, 932.
(5) Fang, J .-M.; Hong, B.-C.; Liao, L.-F. J . Org. Chem. 1987, 52, 855.
(6) Fang, J .-M.; Chen, M.-Y.; Yang, W.-J . Tetrahedron Lett. 1988,
29, 5937.
(7) Fang, J .-M.; Chen, M.-Y. Tetrahedron Lett. 1988, 29, 5939.
(8) Corey, E. J .; Kozikowski, A. P. Tetrahedron Lett. 1975, 925.
(9) Mandai, T.; Takeshita, M.; Kawada, M.; Otera, J . Chem. Lett.
1984, 1259.
(10) Albright, J . D. Tetrahedron 1983, 39, 3207.
(11) Ahlbrecht, H.; Vonderheid, C. Synthesis 1975, 512.
(12) J acobson, R. M.; Lahm, G. P. J . Org. Chem. 1979, 44, 462.
(13) Stork, G.; Maldonado, L. J . Am. Chem. Soc. 1971, 93, 5286.
(14) J acobson, R. M.; Clader, J . W. Tetrahedron Lett. 1980, 21, 1205.
(15) J acobson, R. M.; Lahm, G. P.; Clader, J . W. J . Org. Chem. 1980,
45, 395.
(16) Takahashi, K.; Honma, A.; Ogura, K.; IIda, H. Chem. Lett. 1982,
1263.
(17) Lesur, B.; Toye, J .; Chantrenne, M.; Ghosez, L. Tetrahedron
Lett. 1979, 2835.
(18) Hata, T.; Nakajima, M.; Sekine, M. Tetrahedron Lett. 1979,
2047.
(19) Evans, D. A.; Takacs, J . M.; Hurst, K. M. J . Am. Chem. Soc.
1979, 101, 371.
(20) Ironside, M. D.; Murray, A. W. Tetrahedron Lett. 1989, 30, 1691.
(21) Birse, E. F.; McKenzie, A.; Murray, A. W. J . Chem. Soc., Perkin
Trans. 1 1988, 1039.
(23) Katritzky, A. R.; J iang, J . J . Org. Chem. 1995, 60, 6.
(24) Katritzky, A. R.; Zhang, G.; J iang, J . J . Org. Chem. 1995, 60,
7589.
(25) Katritzky, A. R.; J iang, J . J . Org. Chem. 1995, 60, 7597.
(26) Katritzky, A. R.; Zhang, G.; J iang, J . J . Org. Chem. 1995, 60,
7605.
(22) Maleki, M.; Miller, J . A. Tetrahedron Lett. 1981, 22, 3789.
S0022-3263(96)01396-5 CCC: $14.00 © 1997 American Chemical Society

Triazole-Stabilized Allylic Anions
J . Org. Chem., Vol. 62, No. 3, 1997 707
Sch em e 1
characterized by NMR spectroscopy and by C,H,N analy-
sis. 13C NMR showed a chemical shift of 88.0 ppm for
the methine carbon. Compound 6 is sensitive to acid but
relatively stable in basic and neutral media, and can be
stored at 0 °C for many days.
Treatment of 6 with 1 equiv of butyllithium at -78 °C
results in formation of dark-blue intermediate 7. Sub-
sequent reaction with 3-phenylpropyl bromide for 2-5
min at the same temperature yielded regioselectively
R-alkylated product 8b, isolated in 41% yield for char-
acterization purposes by column chromatography. No
γ-product was observed from the crude NMR spectra. The
relatively low yield is due to partial decomposition
(hydrolysis) catalyzed by the weakly acidic silica gel.
Treatment of pure 8b with dilute HCl in ethanol at rt
for 4 h gave the expected ketone 9b in 98% yield. In
practice, the intermediate 8b was directly subjected to
hydrolysis without isolation by adding H2O-HCl into the
reaction solutions to give, after keeping the solution at
room temperature for 4 h, the expected R,â-unsaturated
ketone 9b in 61% overall yield. NMR spectra clearly
showed a characteristic carbonyl signal at 202 ppm and
absence of the benzotriazolyl and the ethoxy group.
Compounds 9a and 9c were similarly prepared in 70-
82% yields without isolation of the intermediates 8a and
8c. It is worth mentioning that previously R-alkylated
4 had to be hydrolzed by the weakly acidic H2O-H2C2O4-
SiO2 system to avoid the Michael addition reaction of the
benzotriazole eliminated in the hydrolysis to the ketones
obtained under the HCl hydrolysis conditions.24 In the
present cases, no such addition reactions occurred under
HCl hydrolysis conditions, obviously due to the presence
of the n-propyl group.
R,â-Unsaturated ketones of type 9 were previously
synthesized via (i) construction of the CdC double bond
with Wittig-Hornes reactions27 or Peterson reactions,28
(ii) formation of the bond between CdC and CdO groups
by reaction of vinyl metallic compounds with an acyl
chloride or anhydride29,30 or by palladium-catalyzed car-
bonylative coupling reaction of 1-halo-1-alkene with
9-alkyl-9-borabicyclo[3.3.1]nonanes,31 or (iii) three-carbon
homologation by oxidation of the corresponding hydroxy
compounds32,33 or by alkylation of an allenic anion
followed by hydrolysis.34 A closely related approach for
the synthesis of R,â-unsaturated ketones of type 9
involves the use of alkenoyl anion equivalents of 1c and
1d .13,15,16 However, the need to prepare the cyanohydrins
and dealing with HCN during both stages of the prepara-
tion of the synthon equivalents and the hydrolysis are
problematic on a large scale. The present three-carbon
homologation combines simple procedure, readily acces-
sible reagents, and mild hydrolysis conditions and com-
pares favorably with the previous methodology.
to give either exclusive R-products (in most cases) or
exclusive γ-alkylated products with sterically hindered
electrophiles (bulky ketones). We have since studied the
reactions of representative alkyl- (6) and aryl-substituted
(21) analogs, investigated the reactions of anion 29
stabilized by a 1,2,4-triazolyl group instead of benzotri-
azole, and now disclose the details which are of synthetic
and mechanistic interest.
Resu lts a n d Discu ssion
Ben zotr ia zole-Sta bilized Allylic An ion 7 for th e
Syn th esis of Sim p le a n d F u n ction a lized r,â-Un sa t-
u r a ted Keton es. Heating acetal 5 with 1.3-1.5 equiv
of benzotriazole in hexane for 6 h (or in benzene for 4 h)
followed by normal workup (washing the excess benzo-
triazole with sodium carbonate solution and evaporation
of the solvent) gave 1-(benzotriazol-1-yl)-1-ethoxy-2-hex-
ene (6) and a very small proportion of benzotriazol-2-yl
isomer (ca. 5-10%) in 95% total yield (Scheme 1). As
the benzotriazol-2-yl isomer undergoes similar transfor-
mations, the crude mixture of the 1- and 2-isomers could
be directly used in the subsequent reactions. An analyti-
cally pure sample of 1-isomer was obtained (85% yield)
by column chromatography on silica gel and was fully
When synthon 7 was reacted with benzaldehyde,
octanal, acetone, cyclohexanone, and N-benzylidene-
aniline, as expected the corresponding hydroxy- and
(27) Kanemasa, S.; Otsuka, T.; Doi, K.; Tsuge, O.; Wada, E.
Synthesis 1990, 1167.
(28) Matsuda, I.; Okada, H.; Sato, S.; Izumi, Y. Tetrahedron Lett.
1984, 25, 3879.
(29) Martin, G. Ann. Chim. 1959, 35.
(30) J abri, N.; Alexakis, A.; Normant, J . F. Tetrahedron 1986, 42,
1369.
(31) Ishiyama, T.; Miyaura, N.; Suzuki, A. Bull. Chem. Soc. J pn.
1991, 64, 1999.
(32) Byrne, B.; Karras, M. Tetrahedron Lett. 1987, 28, 769.
(33) Hirao, T.; Misu, D.; Agawa, T. J . Am. Chem. Soc. 1985, 107,
7179.
(34) Clinet, J . C.; Linstrumelle, G. Tetrahedron Lett. 1978, 1137.

708 J . Org. Chem., Vol. 62, No. 3, 1997
Katritzky et al.
Sch em e 2
amino-functionalized R,â-substituted ketones 11a ,b, 13,
15, and 17 were prepared in isolated yields of 71-81%
without separation of the intermediates 10a ,b, 12, 14,
and 16. The reactions all proceeded regioselectively, and
no γ-products were observed in the NMR spectra of the
crude product mixtures. The structures for compounds
11a ,b, 13, 15, and 17 were confirmed by 1H and 13C NMR
spectroscopy and by elemental analysis or high-resolution
mass spectroscopy. The characteristic 13C carbonyl sig-
nals for the ketones 11a ,b, 13, 15, and 17 appear in the
range 200-210 ppm. Interestingly, a similar procedure
allows the convenient preparation of â-alkenoyl-substi-
tuted esters of type 19. Only 1,4-addition was observed,
as judged from the NMR spectra of the crude product.
These results are similar to those obtained with the
unsubstituted benzotriazole derivative 4.24
R′-Hydroxy-R,â-unsaturated ketones of types 11, 13,
and 15 are useful intermediates for the cyclopentenone
annelation12,14,15 and for the synthesis of 3-tetrahydro-
furanone.15,35 Perhaps the most convenient previous
synthesis is by using the ethyl vinyl ether protected
cyanohydrin or trimethylsilyl-protected cyanohydrin 1c.
However, as mentioned earlier, this involves dealing with
HCN.
Although imines have been employed as electrophiles
in reactions with acyl anion equivalents for the synthesis
of R-arylamino-substituted alkynyl, aryl, and dialkyl
ketones in our recent publications,36-38 no report has been
found for the synthesis of R-arylamino-R,â-unsaturated
ketones of type 17 using acyl anion equivalent methodol-
ogy.
characterized by NMR spectroscopy and elemental analy-
ses. Compounds 25b-g were similarly prepared in 45-
73% isolated yields by this procedure. In the case of 25g,
the γ-alkylated product 24g was also isolated and its
structure confirmed by NMR spectra and elemental
analysis. In the cases of 25b-f, the amounts of the
γ-byproducts 24b-f were determined by NMR and GC
of the crude product mixture.
When benzyl bromide was used as the electrophile, the
γ-product 24h was obtained predominantly (86%) along
with minor R-product 25h (13%). This is possibly con-
trolled by the hard and soft acids and bases principle.40
Benzyl bromide is softer than other alkyl bromides, and
it appears that the R-position prefers hard electrophiles
and the γ-position favors the soft electrophile. Conse-
quently, benzyl bromide predominantly reacted at the
γ-position. Murphy and Wattanasin41 observed similar
behavior when they reacted [2-((E)-R-styrenyl)-1,3-dithian-
2-yl]lithium with alkyl halides and found that benzyl
halides behave differently from normal halide compounds
to give predominantly γ-products. The R:γ ratio has been
correlated with the hardness of both the leaving group
and the alkyl group of the alkylating agent. Compound
24h was further hydrolyzed in refluxing EtOH-H2O-
H2SO4 to give ethyl 3,4-diphenylbutanoate (26).
As previously mentioned, the regioselectivity of the
reactions of ambident allylic anions with electrophiles is
strongly affected both by substrates and by the nature
of the electrophile introduced. In the rare cases reported
for γ-phenyl-substituted analogs 1, alkylation of depro-
tonated 1d (NR2 ) morpholino) bearing a γ-phenyl
substituent with alkyl halides (MeI or EtBr) gave 75-
80% of R-products along with 13-20% of γ-products16
(when isopropyl bromide was used as the electrophile,
30% R-product and 30% γ-product were formed during
the reaction16). Ahlbrecht and Vonderheid11 studied
similar systems and found that the regioselectivity also
depended on the NR2 group; however, when an aldehyde
or ketone was used as the electrophile, it gave exclusively
γ-products. Reactions of dithio-substituted cinnamyl-
Syntheses of δ-ene γ-keto esters of type 19 were rarely
reported. Ronald and Wheeler39 prepared a δ-(triphenyl-
phosphoranylidene)-γ-keto ester by condensation of meth-
ylenetriphenylphosphorane with 3-carbomethoxypro-
pionyl chloride in THF or by condensation of triphenyl-
phosphine with methyl 5-bromolevulinate in refluxing
benzene followed by deprotonation. Subsequent Wittig
reaction with an aldehyde formed the δ-ene double bond.
However, this method is limited by the availability of the
starting materials.
Rea ction of P h en yl-Su bstitu ted Allylic An ion 22
w ith Electr op h iles Lea d in g to Both r-Alk yla ted a n d
γ-Alk yla ted P r od u cts. Compound 21 was prepared in
72% yield from cinnamaldehyde (20) according to our
previously developed procedure for the conversion of
aldehydes to the corresponding benzotriazole deriva-
tives.37 Treatment of 3-(benzotriazol-1-yl)-3-ethoxy-1-
phenyl-1-propene (21) with 1 equiv of BuLi at -78 °C
for a few minutes followed by reaction with ethyl bromide
afforded a mixture of 23a and 24a from NMR spectra in
a ratio of ca. 4:1 (Scheme 2). TLC showed that these two
compounds have similar retention times, which hinders
separation by column chromatography. The mixture of
23a and 24a was treated with dilute hydrochloric acid
in aqueous acetone at room temperature for 5 h to
produce the hydrolyzed 25a and unchanged 24a in 79%
and 19% yields, respectively. Compounds 25a and 24a
were separated by column chromatography and fully
(35) Baldwin, J . E.; Thomas, R. C.; Kruse, L. I.; Silberman, L. J .
Org. Chem. 1977, 42, 3846.
(36) Katritzky, A. R.; Lang, H. J . Org. Chem. 1995, 60, 7612.
(37) Katritzky, A. R.; Lang, H.; Wang, Z.; Zhang, Z.; Song, H. J .
Org. Chem. 1995, 60, 7619.
(38) Katritzky, A. R.; Lang, H.; Wang, Z.; Zhu, L. J . Org. Chem.
1996, 61, 7551.
(39) Ronald, R. C.; Wheeler, C. J . J . Org. Chem. 1983, 48, 138.
(40) Ho, T.-L. Tetrahedron 1985, 41, 3.
(41) Murphy, W. S.; Wattanasin, S. J . Chem. Soc., Perkin Trans. 1
1980, 2687.

Triazole-Stabilized Allylic Anions
J . Org. Chem., Vol. 62, No. 3, 1997 709
Sch em e 3
Treatment of 29 with 2 equiv of butyllithium at -78
°C for a few minutes is believed to form dilithio derivative
31 or an isomer with Li attached to the R-rather than
γ-position of the side chain. Subsequent reaction with 1
equiv of ethyl bromide at the same temperature for a few
minutes afforded in 90% yield a mixture of two cis/ trans
isomers of the γ-alkylated product 32a (E and Z; ratio
ca. 1:1 by 1H NMR). The structure of 32a was deter-
mined by NMR spectroscopy. No R-product was observed
from the NMR spectra of the crude product. The R-prod-
uct 13C NMR spectra would give a quaternary carbon
signal in the range 88-100 ppm (the methine carbon of
starting material 29 has a chemical shift of 88 ppm).
Hydrolysis of 32a in a HCl/ethanol/water solution under
reflux for 3 h produced the expected â-alkylated ester 33a
in 84% yield. Ester 33b was similarly prepared in 55%
overall yield.
Even when we used 2 equiv of ethyl bromide in the
reaction with 29, only the monoalkylated product 32a
was generated and no dialkylated product (with γ-posi-
tion and the triazole ring alkylating) was formed. This
is consistent with that reported in the literature,42,43
which indicated that the 5-lithiated 1-[(dialkylamino)-
methyl]-1,2,4-triazole can only react with reactive elec-
trophiles such as MeI, RCHO, or RCOR to generate the
5-alkyltriazoles.
Nucleophilic conjugated addition of organocopper re-
agents to unsaturated esters has been frequently used
in the synthesis of â-alkylated esters 33.44,45 A different
approach for the synthesis of these type of compounds is
via reaction of homoenolate anions 3 with an electrophile,
which has previously been realized by using allylic
phosphorus compounds 1e18-22). However, preparation
of the phosphorus compounds requires relatively com-
plicated manipulation and use of expensive reagents.46
The present triazole-mediated transformation of cinnam-
aldehyde to â-alkylated esters of type 33 is a very
convenient approach. Unfortunately, attempted exten-
sion of this methodology to other â-alkyl- substituted R,â-
unsaturated aldehydes failed as a complex mixtures of
several compounds was formed.
Tr ia zole-Sta bilized Hom oen ola te An ion 31 for th e
Syn th esis of La cton es a n d La cta m s. When aldehydes
or ketones were used as electrophiles to react with
dilithiated species 31 followed by hydrolysis, the expected
γ-lactones 35a ,b, 39, 41, and 43 were easily prepared in
56%-90% yields (Scheme 4). Using imines as electro-
philes similarly gave the lactams 37a -c in 70-83%
yields. A possible mechanistic rationalization is that
under the acidic conditions the substituted triazole
derivatives 34a ,b, 36a -c, 38, 40, and 42 (initially formed
after lithiation and reactions with the carbonyl com-
pounds or imines) underwent hydrolysis to yield the
γ-hydroxy- or γ-arylamino-substituted esters, which in
turn spontaneously cyclized intramolecularly to furnish
the five-membered cyclic products 35a ,b, 37a -c, 39, 41,
and 43. Thus, treatment of compound 29 with 2 equiv
lithium with carbonyl compounds have also been inves-
tigated.6 Little regioselectivity was reported under nor-
mal lithiation conditions; while in the presence of
BF3‚Et2O, the reaction occurred predominantly at the
R-site.
In the present approach, reactions with alkyl halides
gave mainly the R-products in 68-79% yields, and
reactions with aldehydes and ketones still generate the
expected R-functionalized R,â-unsaturated ketones of
types 25d -g in reasonable to good yields. Considering
the convenient availability of the starting materials, the
simple manipulation required, and the easy separation
of the products, this method is still useful in the synthesis
of these types of compounds despite the absence of
regiospecificity.
Tr ia zole-Sta bilized Hom oen ola te An ion s for th e
Syn th esis of â-Alk yla ted Ester s. 3-Ethoxy-1-phenyl-
3-(triazol-1-yl)-1-propene (29) was similarly prepared in
82% yield by reaction of trans-cinnamaldehyde (20) with
1,2,4-triazole and triethyl orthoformate in THF with
sulfuric acid as a catalyst (Scheme 3).
Because of the presence of acidic protons on the triazole
ring, treatment of compound 29 with 1 equiv of butyl-
lithium followed by reaction with methyl iodide gave in
quantitive yield a mixture of 5-methyl- (28) and 3-methyl-
substituted (27) triazole products (ratio, 2.5:1 from NMR).
1H NMR spectra of this mixture clearly showed two
different ring proton signals at 7.82 (H-3) and 8.00 (H-5)
ppm. However, we believe that the 3-methyl isomer 27
is not formed directly, but by isomerization of the
5-alkylated isomer 28, and this is supported by the
finding that keeping the original mixture for ca. 30 days
resulted in the formation of equal amounts of the
3-methyl (27) and 5-methyl (28) isomers. 1-Substituted
1,2,4-triazoles have previously been shown to undergo
easy lithiation at the 5-position of the triazole ring, and
such isomerizations between the 3- and the 5-isomers has
also been previously observed.42,43
(42) Katritzky, A. R.; Lue, P.; Yannakopoulou, K. Tetrahedron 1990,
46, 641.
(43) Rewcastle, G. W.; Katritzky, A. R. In Advances in Heterocyclic
Chemistry; Katritzky, A. R., Ed.; Academic Press: New York, 1993;
Vol. 56, p 155.
(44) Van Heerden, P. S.; Bezuidenhoudt, B. C. B.; Steenkamp, J .
A.; Ferreira, D. Tetrahedron Lett. 1992, 33, 2383.
(45) Behforouz, M.; Curran, T. T.; Bolan, J . L. Tetrahedron Lett.
1986, 27, 3107.
(46) Evans, D. A.; Hurst, K. M.; Takacs, J . M. J . Am. Chem. Soc.
1978, 100, 3467.

710 J . Org. Chem., Vol. 62, No. 3, 1997
Katritzky et al.
Sch em e 4
of a mineral acid. Available methods for the generation
of γ-hydroxy carboxylates include (i) reduction of γ-oxo-
substituted esters,47 (ii) Grignard reaction of γ-oxo-
substituted esters,48 (iii) reaction of â-zinc esters with an
aldehyde,49 (iv) reaction of manganic and other higher
valent metal carboxylates with olefins and carbocylic
acids,50 and (v) direct lactonization of unsaturated car-
boxy acids.51 Reaction of homoenolate anions of types 3
generated from 1a ,52 1c,15 1d ,11 or 1e19 with a carbonyl
compound has also frequently been utilized for the
synthesis of γ-lactones. However, each homoenolate
anion only applies to the synthesis of certain substituted
γ-lactones.
Major methods for γ-lactam syntheses are intramo-
lecular acylation of a γ-amino-functionalized carboxylic
acid or ester.53 These amino acids or amino esters are
frequently generated in situ by reactions such as reduc-
tive amination of keto acids,54 aminolysis of lactones,55
or reduction of nitro esters.56 Takahata reported a novel
synthesis of γ-lactams by a two-step conversion via
γ-hydroxy amides.57 Reactions of a homoenolate anion
or equivalent with an imine analogous to the present
approach for the preparation of γ-lactams were also
previously reported.58
The structures for the final products and the isolated
intermediates were confirmed by 1H and 13C NMR
spectroscopy and by elemental analyses. The data for
known compounds are consistent with those reported in
literature.
Con clu sion s
Novel benzotriazole- and 1,2,4-triazole-stabilized allylic
anions have been developed for the generation of R,â-
unsaturated ketones, γ-lactones, γ-lactams, and â-sub-
stituted esters. The simplicity and convenient availabil-
ity of the starting materials give these methods
considerable potential importance in organic synthesis.
of butyllithium at -78 °C for 5 min followed by reaction
with 1 equiv of N-benzylideneaniline at this temperature
for a few minutes generated the intermediate 36a in 80%
yield. Further acidic treatment of this intermediate in
refluxing ethanol afforded lactam 37a in 95% yield. The
structures for intermediate 36a and product 37a were
fully characterized by NMR spectroscopy and by C,H,N
analyses. Compounds 35a ,b, 37b,c, 39, 41, and 43 were
similarly prepared by this procedure without isolation
of the intermediates 34a ,b, 36b,c, 38, 40, and 42. These
intermediates, 34a ,b, 36a -c, 38, 40 and 42, would be
mixtures of several isomers including regioisomers (E and
Z) and diastereoisomers (three chiral centers), which
would hinder their isolation and characterization.
In the preparations of 35a ,b, 39, and 41, 2 equiv of
the appropriate electrophile was used. Otherwise, low
yields were achieved. In the remaining cases (37a -c,
43), only 1 equiv was consumed. This is because the
triazole anions formed reacted only with the relatively
reactive electrophiles (aldehydes or unhindered ketones)
as mentioned before. Evidently benzophenone behaves
as a hindered electrophile. Formation of the dialkylated
34a ,b, 38, and 40 was determined by the crude NMR
spectra, which indicated the disappearance of one triazole
proton and the presence of two sets of signals from the
substituents introduced.
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 in CDCl3 with TMS or CDCl3,
respectively, as the internal reference. Elemental analyses
and high-resolution mass spectra were performed within the
department. Column chromatography was carried out on
MCB silica gel (230-400 mesh). Tetrahydrofuran (THF) was
freshly distilled from sodium-benzophenone. Lithiation reac-
tions were carried out under the protection of dry nitrogen.
(47) Frenette, R.; Kakushima, M.; Zamboni, R.; Young, R. N.;
Verhoeven, T. R. J . Org. Chem. 1987, 52, 304.
(48) J anowitz, A.; Kunz, T.; Handke, G.; Reissig, H.-U. Synlett 1989,
24.
(49) Ochiai, H.; Nishihara, T.; Tamaru, Y.; Yoshida, Z.-i. J . Org.
Chem. 1988, 53, 1343.
(50) Heiba, E. I.; Dessau, R. M.; Rodewald, P. G. J . Am. Chem. Soc.
1974, 96, 7977.
(51) King, G. S.; Waight, E. S. J . Chem. Soc., Perkin Trans. 1 1974,
1499.
(52) Fang, J .-M.; Liao, L.-F.; Hong, B.-C. J . Org. Chem. 1986, 51,
2828.
(53) Challis, B. C.; Challis, J . A. In Comprehensive Organic Chem-
istry; Sutherland, I. O, Ed.; Pregamon: New York, 1979; Vol. 2, p 956.
(54) Frank, R. L.; Schmitz, W. R.; Zeidman, B. Organic Syntheses;
Wiley: New York, 1955; Collect. Vol. 3, p 328.
(55) Zienty, F. B.; Steahly, G. W. J . Am. Chem. Soc. 1947, 69, 715.
(56) Hill, R. K. J . Org. Chem. 1957, 22, 830.
(57) Takahata, H.; Wang, E.-C.; Yamazaki, T. Synth. Commun.
1988, 18, 1159.
In the present cases, no matter whether the triazole
is alkylated or not, the triazole moiety, as a leaving group
in the present work, will finally be hydrolyzed off and
can easily be removed from the reaction mixture by an
aqueous washing.
Synthesis of γ-lactones was previously accomplished
by cyclization of γ-hydroxy carboxylates in the presence
(58) (a) Fang, J .-M.; Chen. S.-T.; Chen, I-H. J . Organomet. Chem.
1990, 398, 219. (b) Yamamoto, Y.; Komatsu, T.; Maruyama, K. J . Org.
Chem. 1985, 50, 3115.

Triazole-Stabilized Allylic Anions
J . Org. Chem., Vol. 62, No. 3, 1997 711
P r ep a r a tion of tr a n s-1-(Ben zotr ia zol-1yl)-1-eth oxy-2-
h exen e (6). A mixture of 2-hexenal diethyl acetal (5) (3.45
g, 20 mmol) and benzotriazole (3.57 g, 30 mmol) in hexane
(40 mL) was heated under reflux for 6 h. Diethyl ether (300
mL) was then added. The resulting solution was washed with
a saturated sodium carbonate solution (3 × 100 mL) and dried
with anhydrous MgSO4. Evaporation of the solvent gave 4.67
g of oil: yield 95% (contaning 5-10% 2-benzotriazole isomer).
Further separation by column chromatography (hexane/ethyl
acetate 17:1) gave analytically pure compound (4.2 g, 85%):
1H NMR δ 0.86 (t, 3 H, J ) 7.3 Hz), 1.15 (t, 3 H, J ) 7.0 Hz),
1.42 (sixtet, 2 H, J ) 7.4 Hz), 2.04-2.11 (m, 2 H), 3.28-3.38
(m, 1 H), 3.57-3.68 (m, 1 H), 5.85-6.08 (m, 2 H), 6.57-6.60
(m, 1 H), 7.39 (t, 1 H, J ) 7.0 Hz), 7.48 (t, 1 H, J ) 7.0 Hz),
7.77 (d, 1 H, J ) 8.3 Hz), 8.09 (d, 1 H, J ) 8.3 Hz); 13C NMR
δ 13.4, 14.5, 21.6, 33.8, 64.2, 89.1, 111.5, 119.8, 123.9, 124.8,
127.1, 131.1, 136.1, 146.7. Anal. Calcd for C14H19N3O: C,
68.54; H, 7.81; N, 17.13. Found: C, 68.32; H, 7.87; N, 17.34.
by column chromatography (hexane/ethyl acetate 30:1). Com-
pound 9b was obtained by using the above procedure (yield,
61%).
tr a n s-4-Tetr a d ecen -5-on e (9a ): obtained as a colorless
1
oil; yield 70%; H NMR δ 0.89 (t, 3 H, J ) 7.2 Hz), 0.96 (t, 3
H, J ) 7.2 Hz), 1.22-1.38 (m, 10 H), 1.45-1.70 (m, 4 H), 2.27-
2.37 (m, 2 H), 2.54 (t, 2 H, J ) 7.2 Hz), 6.11 (d, 1 H, J ) 15.9
Hz), 6.79-6.90 (m, 1 H); 13C NMR δ 13.6, 14.0, 21.3, 22.5, 24.2,
29.1, 29.2, 29.3, 31.7, 34.3, 40.0, 130.4, 146.8, 200.7; HRMS
calcd for C14H26O M+ ) 210.1983, found M ) 210.1992.
tr a n s-1-P h en yl-3-h ep ten -2-on e (9c): obtained as a color-
less oil; yield 82% (lit.59 mp 76-79 °C/mmHg); 1H NMR δ 0.90
(t, 3 H, J ) 7.4 Hz), 1.46 (sixtet, 2 H, J ) 7.3 Hz), 2.10-2.20
(m, 2 H), 3.81 (s, 2 H), 6.14 (d, 1 H, J ) 15.8 Hz), 6.85-6.96
(m, 1 H), 7.17-7.35 (m, 5 H); 13C NMR δ 13.5, 21.1, 34.3, 47.4,
126.6, 128.5, 129.3, 129.4, 134.5, 148.1, 197.2.
tr a n s-1-Hyd r oxy-1-p h en yl-3-h ep ten -2-on e (11a ): ob-
1
tained as a colorless oil; yield 74%; H NMR δ 0.82 (t, 3 H, J
) 7.4 Hz), 1.32-1.45 (m, 2 H), 2.04-2.15 (m, 2 H), 4.51 (br s,
1 H), 5.20 (s, 1 H), 6.11 (d, 1 H, J ) 15.6 Hz), 6.95-7.10 (m,
1 H), 7.22-7.43 (m, 5 H); 13C NMR δ 13.4, 21.0, 34.5, 78.4,
124.6, 127.6, 128.4, 128.8, 138.2, 150.4, 197.3. Anal. Calcd
for C13H16O2: C, 76.44; H, 7.90. Found: C, 76.83; H, 8.30.
tr a n s-7-Hyd r oxy-4-tetr a d ecen -6-on e (11b): obtained as
a colorless oil; yield 71%; 1H NMR δ 0.87 (t, 3 H, J ) 6.6 Hz),
0.95 (t, 3 H, J ) 7.4 Hz), 1.20-1.60 (m, 13 H), 1.72-1.87 (m,
1 H), 2.20-2.29 (m, 2 H), 3.64 (d, 1 H, J ) 5.4 Hz), 4.32-4.40
(m, 1 H), 6.24 (d, 1 H, J ) 15.7 Hz), 6.96-7.10 (m, 1 H); 13C
NMR δ 13.5, 13.9, 21.1, 22.5, 24.7, 29.0, 29.3, 31.6, 34.3, 34.6,
P r ep a r a tion of In ter m ed ia te 8b a n d Keton e 9b. To a
solution of 1-(benzotriazol-1yl)-1-ethoxy-2-hexene (6) (1.23 g,
5 mmol) in THF (50 mL) at -78 °C was added n-butyllithium
(2.0 M in cyclohexane, 3 mL, 6 mmol). The solution was stirred
at this temperature for 5 min, and 3-phenyl-1-bromopropane
(1.0 g, 5 mmol) was then added. After the solution was stirred
at -78 °C for an additional 5 min, the reaction was quenched
at this temperature with water (50 mL), extracted with diethyl
ether (2 × 100 mL), and dried over anhydrous MgSO4.
Evaporation of the solvent gave a residue which was separated
by column chromatography (hexane/ethyl acetate, 30:1) to give
8b. Compound 8b was disolved in EtOH (20 mL) and cooled
to 0 °C. Water (10 mL) and hydrochloric acid (2 M, 5 mL)
were added at this temperature, and the mixture was stirred
at room temperature for 4 h. The resulting solution was
extracted with diethyl ether (2 × 200 mL) and washed with
saturated sodium carbonate solution (2 × 50 mL). The organic
phase was separated and dried over anhydrous MgSO4.
Evaporation of the solvent gave a residue which was separated
by column chromatography (hexane/ethyl acetate 100:1) to give
ketone 9b.
75.0, 124.9, 149.6, 200.7; HRMS calcd for C14H26O2 M+
226.1932 11, found M ) 226.1919.
)
tr a n s-2-Hyd r oxy-2-m eth yl-4-octen -3-on e (13): obtained
1
as a colorless oil; yield 75%; H NMR δ 0.97 (t, 3 H, J ) 7.4
Hz), 1.40 (s, 6 H), 1.54 (sixtet, 2 H, J ) 7.4 Hz), 2.20-2.30 (m,
2 H), 4.09 (s, 1 H), 6.46 (d, 1 H, J ) 15.4 Hz), 7.10-7.22 (m,
1 H); 13C NMR δ 13.5, 21.1, 26.2, 34.6, 75.0, 122.3, 150.6, 202.2.
Anal. Calcd for C9H16O2: C, 69.19; H, 10.32. Found: C, 69.34;
H, 9.94.
tr a n s-1-(1-Hyd r oxycycloh exyl)-2-h exen -1-on e (15): ob-
1
tained as a colorless oil; yield 81%; H NMR δ 0.96 (t, 3 H, J
t r a n s-4-(B e n z o t r i a z o l-1-y l)-4-e t h o x y -1-p h e n y l-5-
n on en e (8b): obtained as a colorless oil; yield 41%; 1H NMR
δ 0.90 (t, 3 H, J ) 7.4 Hz), 1.10-1.40 (m, 5 H), 1.55-1.84 (m,
2 H), 1.94-2.12 (m, 1 H), 2.13-2.37 (m, 3 H), 2.51 (t, 2 H, J )
7.4 Hz), 3.61-3.82 (m, 2 H), 4.92 (d, 1 H, J ) 9.1 Hz), 5.47 (q,
1 H, J ) 7.4 Hz), 7.08-7.49 (m, 8 H), 8.05 (d, 1 H, J ) 8.3
Hz); 13C NMR δ 13.4, 14.3, 19.4, 28.9, 30.3, 35.2, 38.7, 58.1,
62.4, 96.4, 109.9, 119.9, 123.5, 125.6, 126.6, 128.1, 128.2, 131.7,
141.8, 146.0, 160.4. Anal. Calcd for C23H29N3O: C, 76.00; H,
8.04; N, 11.56. Found: C, 76.32; H, 8.29; N, 11.97.
) 7.3 Hz), 1.21-1.38 (m, 1 H), 1.41-1.60 (m, 4 H), 1.61-1.81
(m, 7 H), 2.20-2.30 (m, 2 H), 3.88 (s, 1 H), 6.56 (d, 1 H, J )
15.2 Hz), 7.07-7.19 (m, 1 H); 13C NMR δ 13.5, 20.9, 21.2, 25.2,
33.5, 34.6, 76.7, 122.6, 150.2, 202.3. Anal. Calcd for
C12H20O2: C, 73.43; H, 10.27. Found: C, 73.31; H, 10.83.
tr a n s-1-P h en yl-1-(p h en yla m in o)-3-h ep ten -2-on e (17):
yield 71%; mp 78-79 °C: 1H NMR δ 0.82 (t, 3 H, J ) 7.4 Hz),
1.32-1.42 (m, 2 H), 2.05 (q, 2 H, J ) 7.1 Hz), 5.11 (s, 1 H),
5.56 (br s, 1 H), 6.23 (d, 1 H, J ) 15.6 Hz), 6.55-6.67 (m, 3
H), 6.96-7.12 (m, 3 H), 7.17-7.35 (m, 3 H), 7.42 (d, 2 H, J )
7.1 Hz); 13C NMR δ 13.4, 20.9, 34.3, 66.2, 113.2, 117.3, 125.7,
127.8, 127.9, 128.8, 128.9, 137.8, 146.0, 149.2, 194.4. Anal.
Calcd for C19H21NO: C, 81.68; H, 7.58; N, 5.01. Found: C,
81.54; H, 7.80; N, 5.04.
tr a n s-1-P h en yl-5-n on en -4-on e (9b): obtained as a color-
1
less oil; yield 98%; H NMR δ 0.92 (t, 3 H, J ) 6.9 Hz), 1.47
(sixtet, 2 H, J ) 7.3 Hz), 1,90-2.02 (m, 2 H), 2.12-2.22 (m, 2
H), 2.53 (t, 2 H, J ) 7.3 Hz), 2.64 (t, 2 H, J ) 7.4 Hz), 6.07 (d,
1 H, J ) 15.1 Hz), 6.71-6.83 (m, 1 H), 7.15-7.35 (m, 5 H); 13
C
Eth yl tr a n s-4-oxa -5-n on en oa te (19a ): obtained as a
1
NMR δ 13.5, 21.2, 25.5, 34.2, 35.0, 39.0, 125.7, 128.2, 128.3,
130.3, 141.6, 146.9, 200.0. Anal. Calcd for C15H20O: C, 83.29;
H, 9.32. Found: C, 82.86; H, 9.35.
colorless oil; yield 47%; H NMR δ 0.96 (t, 3 H, J ) 7.4 Hz),
1.27 (t, 3 H, J ) 7.1 Hz), 1.47-1.60 (m, 2 H), 2.18-2.27 (m, 2
H), 2.63 (t, 2 H, J ) 6.7 Hz), 2.90 (t, 2 H, J ) 6.7 Hz), 4.15 (q,
2 H, J ) 7.1 Hz), 6.14 (d, 1 H, J ) 15.9 Hz), 6.85-6.96 (m, 1
H); 13C NMR δ 13.4, 13.9, 21.1, 27.9, 34.2, 60.3, 129.9, 147.4,
172.7, 198.0. Anal. Calcd for C11H18O3: C, 66.64; H, 9.15.
Found: C, 66.96; H, 9.46.
Gen er a l P r oced u r e for th e P r ep a r a tion of 9a-c, 11a ,b,
13, 15, 17, a n d 19a ,b. To a solution of 1-(benzotriazol-1yl)-
1-ethoxy-2-hexene (6) (1.23 g, 5 mmol) in THF (50 mL) at -78
°C was added n-butyllithium (2.0 M in cyclohexane, 2.5 mL, 5
mmol). The solution was stirred at this temperature for 5 min,
and the appropriate electrophile (C8H17Br, Ph(CH2)3Br,
PhCH2Br, benzaldehyde, octanal, acetone, cyclohexanon, N-
benzylideneaniline, methyl acrylate, or methyl crotonate; 5.5
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). Hydrochloric acid (2
M, 5 mL) was added at this temperature, and the mixture was
stirred at room temperature for 4 h. The resulting solution
was extracted with diethyl ether (2 × 100 mL) and washed
with saturated sodium carbonate solution (2 × 100 mL). The
organic phase was separated and dried over anhydrous MgSO4.
Evaporation of the solvent gave a residue which was separated
Eth yl tr a n s-3-m eth yl-4-oxa -5-n on en oa te (19b): obtained
1
as a colorless oil; yield 50%; H NMR δ 0.95 (t, 3 H, J ) 7.4
Hz), 1.15 (d, 3 H, J ) 7.2 Hz), 1.24 (t, 3 H, J ) 7.1 Hz), 1.46-
1.59 (m, 2 H), 2.18-2.25 (m, 2 H), 2.31 (dd, 1 H, J ) 16.6 and
6.1 Hz), 2.79 (dd, 1 H, J ) 16.6 and 8.2 Hz), 3.20-3.32 (m, 1
H), 4.11 (q, 2 H, J ) 7.1 Hz), 6.19 (d, 1 H, J ) 15.7 Hz), 6.87-
6.98 (m, 1 H); 13C NMR δ 13.5, 14.0, 17.0, 21.2, 34.4, 36.9,
39.6, 60.3, 128.5, 147.8, 172.2, 201.9. Anal. Calcd for
C12H20O3: C, 67.89; H, 9.50. Found: C, 67.49; H, 9.94.
P r ep a r a tion of Ben zotr ia zole a n d Tr ia zole Der iva -
tives 21 a n d 29. A mixture of cinnamaldehyde (16.3 g, 120
(59) Roux, J . L.; Corre, M. L. Tetrahedron Lett. 1990, 31, 2591.

712 J . Org. Chem., Vol. 62, No. 3, 1997
Katritzky et al.
mmol), triazole or benzotriazole (240 mmol), ethanol (8.3 g,
180 mmol), triethyl orthoformate (53.6 g, 360 mmol), and concd
sulfuric acid (0.68 g) in THF (100 mL) was heated under reflux
for 4 h. After cooling, sodium carbonate (15 g) was added the
solution was stirrred for 10 min. Diethyl ether (300 mL) was
added, and the resulting solution was washed with water (2
× 100 mL) and dried with anhydrous magnesium sulfate.
Evaporation of the solvent gave a residure, which was sub-
jected to column chromatography (hexane/ethyl acetate, 20:1
for 21 and 1:1 for 29).
tr a n s-3-(Ben zot r ia zol-1-yl)-3-et h oxy-1-p h en yl-1-p r o-
p en e (21): yield 72%; mp 75-77 °C: 1H NMR δ 1.20 (t, 3 H,
J ) 7.0 Hz), 3.33-3.43 (m, 1 H), 3.61-3.71 (m, 1 H), 6.52 (dd,
1 H, J ) 15.9 and 4.4 Hz), 6.78 (d, 1 H, J ) 4.4 Hz), 6.93 (d,
1 H, J ) 16.0 Hz), 7.20-7.48 (m, 7 H), 7.78 (d, 1 H, J ) 8.1
Hz), 8.10 (d, 1 H, J ) 8.2 Hz); 13C NMR δ 14.5, 64.3, 88.7,
111.3, 119.7, 123.4, 124.0, 126.7, 127.3, 128.4, 128.5, 131.1,
133.8, 135.0, 146.6. Anal. Calcd for C17H17N3O: C, 73.10; H,
6.13; N, 15.04. Found: C, 73.27; H, 6.22; N, 15.07.
1-(Ben zot r ia zol-1-yl)-1-et h oxy-3,4-d ip h en yl-1-b u t en e
(24h ): obtained as a colorless oil; yield 86% (a mixture of E
1
and Z isomers; ratio, ca. 1.5:1 as determined by H NMR); 1H
NMR δ 1.00 (t, J ) 7.1 Hz) and 1.22 (t, J ) 7.1 Hz) (total 3
H), 2.97-3.38(m), 3.51-3.63 (m), 3.78-3.90 (m) and 4.21-4.35
(m) (total 5 H), 5.24 (d, J ) 10.2 Hz) and 5.60 (d, J ) 10.2 Hz)
(total 1 H), 6.80-7.48 (m, 13 H), 8.00 (d, 1 H, J ) 8.2 Hz); 13
C
NMR δ 13.9, 14.3, 43.1, 43.6, 44.1, 64.6, 66.1, 105.1, 110.5,
110.6, 111.9, 119.1, 119.5, 123.8, 124.0, 125.6, 125.9, 126.0,
126.2, 127.0, 127.1, 127.6, 127.7, 127.9, 128.1, 128.3, 128.7,
129.1, 132.0, 132.4, 138.9, 139.4, 142.8, 143.3, 143.5, 143.7,
144.8, 145.2; HRMS calcd for C24H23N3O M ) 369.1763, found
M ) 369.1740.
tr a n s-1-P h en yl-1-p en ten -3-on e (25a ): yield 79%; mp 41-
1
43 °C; H NMR δ 1.17 (t, 3 H, J ) 7.3 Hz), 2.68 (q, 2 H, J )
7.3 Hz), 6.74 (d, 1 H, J ) 16.3 Hz), 7.33-7.42 (m, 3 H), 7.50-
7.60 (m, 3 H); 13C NMR δ 8.0, 33.8, 125.8, 128.0, 128.7, 130.1,
134.4, 141.9, 200.5. Anal. Calcd for C11H12O: C, 82.46; H,
7.55. Found: C, 82.20; H, 7.76.
tr a n s-1-P h en yl-1-octen -3-on e (25b): yield 70%; mp 44-
45 °C; 1H NMR δ 0.91 (t, 3 H, J ) 6.7 Hz), 1.30-1.41 (m, 4 H),
1.62-1.74 (m, 2 H), 2.65 (t, 2 H, J ) 7.5 Hz), 6.75 (d, 1 H, J )
16.2 Hz), 7.33-7.40 (m, 3 H), 7.50-7.59 (m, 3 H); 13C NMR δ
13.8, 22.4, 24.0, 31.4, 40.8, 126.2, 128.1, 128.8, 130.2, 134.5,
142.1, 200.4. Anal. Calcd for C14H18O: C, 83.12; H, 8.97.
Found: C, 83.54; H, 9.28.
tr a n s-1-P h en yl-1-u n d ecen -3-on e (25c): yield 68%; mp
40-42 °C: 1H NMR δ 0.89 (t, 3 H, J ) 7.1 Hz), 1.20-1.43 (m,
10 H), 1.62-1.74 (m, 2 H), 2.65 (t, 2 H, J ) 7.5 Hz), 6.74 (d, 1
H, J ) 16.2 Hz), 7.35-7.42 (m, 3 H), 7.50-7.60 (m, 3 H); 13C
NMR δ 14.0, 22.6, 24.3, 29.1, 29.2, 29.3, 31.7, 40.9, 126.2, 128.1,
128.8, 130.2, 134.5, 142.1, 200.4. Anal. Calcd for C17H24O:
C, 83.55; H, 9.90. Found: C, 83.57; H, 9.82.
t r a n s-3-E t h oxy-1-p h e n yl-3-(t r ia zol-1-yl)-1-p r op e n e
(29): yield 82%; mp 47-49 °C; 1H NMR δ 1.25 (t, 3 H, J ) 7.0
Hz), 3.50-3.70 (m, 2 H), 6.07 (d, 1 H, J ) 5.2 Hz), 6.38 (dd, 1
H, J ) 16.0 and 5.2 Hz), 6.83 (d, 1 H, J ) 16.0 Hz), 7.23-7.55
(m, 5 H), 8.00 (s, 1 H), 8.32 (s, 1 H); 13C NMR δ 14.7, 64.9,
88.6, 123.6, 126.8, 128.5, 128.6, 134.2, 135.0, 141.7, 151.5.
Anal. Calcd for C13H15N3O: C, 68.10; H, 6.59; N, 18.33.
Found: C, 68.52; H, 6.93; N, 18.54.
Gen er a l P r oced u r e for th e P r ep a r a tion of 24a ,g,h a n d
25a -h . To a solution of 3-(benzotriazol-1-yl)-3-ethoxy-1-
phenyl-1-propene (21) (1.40 g, 5 mmol) in THF (50 mL) at -78
°C was added n-butyllithium (2.5 M in cyclohexane, 2 mL, 5
mmol). The solution was stirred at this temperature for 5 min,
and the appropriate electrophile (EtBr, C5H11Br, C8H17Br,
benzaldehyde, 4-methylbenzaldehyde, octanal, acetone, or
benzyl bromide; 5 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 acetone (15 mL), water (15 mL),
and HCl (2 mL) at room temperature for 2 h. The resulting
solution was extracted with diethyl ether (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.
t r a n s-1-P h e n yl-4-h yd r oxy-4-p h e n yl-1-b u t e n -3-on e
1
(25d ): yield 73%; mp 106-108 °C; H NMR δ 4.57 (d, 1 H, J
) 4.6 Hz), 5.32 (d, 1 H, J ) 4.5 Hz), 6.72 (d, 1 H, J ) 15.9 Hz),
7.33-7.47 (m, 10 H), 7.75 (d, 1 H, J ) 15.8 Hz); 13C NMR δ
79.0, 120.3, 127.7, 128.6, 128.7, 128.9, 129.0, 131.0, 133.9,
138.0, 144.9, 197.3. Anal. Calcd for C16H14O2: C, 80.65; H,
5.92. Found: C, 80.80; H, 6.02.
tr a n s-1-P h en yl-4-h yd r oxy-4-(4-m eth ylp h en yl)-1-bu ten -
3-on e (25e): obtained as a colorless oil; yield 65%; 1H NMR δ
2.29 (s, 3 H), 4.71 (br s, 1 H), 5.32 (s, 1 H), 6.75 (d, 1 H, J )
15.9 Hz), 7.16 (d, 2 H, J ) 8.0 Hz), 7.21-7.35 (m, 5 H), 7.37-
7.42 (m, 2 H), 7.75 (d, 1 H, J ) 15.9 Hz); 13C NMR δ 20.8,
78.5, 120.3, 127.4, 128.3, 128.5, 129.4, 130.6, 133.7, 134.9,
138.1, 144.3, 197.4. Anal. Calcd for C17H16O2: C, 80.93; H,
6.39. Found: C, 80.91; H, 6.66.
1-(Be n zot r ia zol-1-yl)-1-e t h oxy-3-p h e n yl-1-p e n t e n e
(24a ): obtained as a colorless oil; yield 19% (a mixture of E
1
and Z isomers; ratio, ca. 4:1 as determined by 1H NMR); H
tr a n s-4-Hyd r oxy-1-p h en yl-1-u n d ecen -3-on e (25f): ob-
1
NMR δ 0.76 (t, J ) 7.2 Hz) and 1.00 (t, J ) 7.4 Hz) (total 3
H), 1.23 (t, J ) 7.1 Hz) and 1.32 (t, J ) 7.1 Hz) (total 3 H),
1.70-1.95 (m, 2 H), 2.98-3.07 (m), 3.51-3.70 (m) and 3.82-
4.03 (m) (total 3 H), 5.25 (d, J ) 10.3 Hz) and 5.60 (d, J )
10.0 Hz) (total 1 H), 7.03-7.55 (m, 7 H), 7.65 (d, 1 H, J ) 8.3
Hz), 8.05 (d, 1 H, J ) 8.5 Hz); 13C NMR δ (11.8, mi), 12.1,
(14.1, mi), 14.6, 29.7, (29.8, mi), 43.3, (43.9, mi), (64.8, mi),
66.5, (106.9, mi), (110.5, mi), 110.8, 111.0, 113.4, (119.6, mi),
119.8, (124.0, mi), 124.2, (126.0, mi), 126.2, 127.0, 127.2, 127.9,
128.1, 128.2, 128.4, 132.2, (132.4, mi), 142.9, 144.3, 145.5. Anal.
Calcd for C19H21N3O: C, 74.24; H, 6.89; N, 13.67. Found: C,
74.25; H, 7.06; N, 14.16.
1-(Ben zot r ia zol-1-yl)-1-et h oxy-4-h yd r oxy-5-m et h yl-3-
p h en yl-1-p en ten e (24g): yield 43%; mp 118-120 °C (a
mixture of E and Z isomers; ratio, ca. 1.8:1 as determined by
1H NMR); 1H NMR δ 1.03 (s), 1.26 (s) and 1.38 (s) (total 6 H),
1.15 (t, J ) 7.1 Hz) and 1.35 (t, J ) 7.1 Hz) (total 3 H), 2.56
(br s, 1 H), 3.15 (d, J ) 10.7 Hz) and 4.01 (d, J ) 10.4 Hz)
(total 1 H), 3.40-3.51 (m, 1 H), 3.60-3.70 (m, 1 H), 4.01-
4.13 (m, 1 H), 5.79 (d, J ) 10.6 Hz) and 6.05 (d, J ) 10.5 Hz)
(total 1 H), 7.05-7.50 (m) and 7.66 (d, J ) 8.3 Hz) (total 8 H),
8.04 (d, 1 H, J ) 8.3 Hz); 13C NMR δ 14.0, 14.5, 27.8, 27.9,
28.4, 52.4, 52.9, 64.8, 66.3, 72.1, 72.2, 102.3, 109.5, 110.5, 110.7,
119.3, 119.6, 124.0, 124.2, 126.3, 126.5, 127.7, 128.0, 128.1,
128.7, 129.0, 132.0, 132.5, 140.9, 141.0, 143.5, 144.4, 144.6,
145.2. Anal. Calcd for C20H23N3O2: C, 71.19; H, 6.87; N,
12.45. Found: C, 71.47; H, 7.04; N, 12.10.
tained as a colorless oil; yield 55%; H NMR δ 0.90 (t, 3 H, J
) 6.2 Hz), 1.21-1.71 (m, 11 H), 1.84-1.99 (m, 1 H), 3.73 (d, 1
H, J ) 5.3 Hz), 4.47-4.54 (m, 1 H), 6.90 (d, 1 H, J ) 16.0 Hz),
7.40-7.50 (m, 3 H), 7.58-7.68 (m, 2 H), 7.78 (d, 1 H, J ) 15.9
Hz); 13C NMR δ 14.0, 22.5, 24.8, 29.0, 29.4, 31.7, 34.2, 75.7,
120.5, 128.5, 128.9, 130.9, 134.0, 144.4, 200.7. Anal. Calcd
for C17H24O2: C, 78.42; H, 9.29. Found: C, 78.08; H, 8.90.
t r a n s-4-H yd r oxy-4-m e t h yl-1-p h e n yl-1-p e n t e n -3-on e
(25g): obtained as a colorless oil; yield 45% (lit.35 mp 39-40
°C); 1H NMR δ 1.50 (s, 6 H), 4.20 (br s, 1 H), 7.16 (d, 1 H, J )
15.7 Hz), 7.38-7.44 (m, 3 H), 7.58-7.62 (m, 2 H), 7.86 (d, 1
H, J ) 15.7 Hz); 1H NMR δ 26.2, 75.4, 118.4, 128.4, 128.7,
130.7, 134.1, 145.1, 202.3.
tr a n s-1,4-Dip h en yl-1-bu ten -3-on e (25h ): yield 13%; mp
79-81 °C; 1H NMR δ 3.94 (s, 2 H), 6.78 (d, 1 H, J ) 16.1 Hz),
7.23-7.40 (m, 8 H), 7.48-7.54 (m, 2 H), 7.63 (d, 1 H, J ) 16.0
Hz); 13C NMR δ 48.3, 125.1, 126.9, 128.3, 128.6, 128.7, 128.9,
129.4, 130.5, 134.4, 143.3, 197.2. Anal. Calcd for C16H14O:
C, 86.45; H, 6.35. Found: C, 86.63; H, 6.61.
P r ep a r a tion of Eth yl 3,4-Dip h en ylbu ta n oa te (26). A
mixture of 1-(benzotriazol-1-yl)-1-ethoxy-3,4-diphenyl-1-butene
(24h ) (1.11 g, 3 mmol), ethanol (15 mL), water (15 mL), and
HCl (2 mL) was heated under reflux for 3 h. The resulting
solution was extracted with diethyl ether (3 × 100 mL),
washed with a saturated Na2CO3 solution (2 × 100 mL), and
dried over anhydrous MgSO4. Evaporation of the solvent gave
a residue which was separated by column chromatography

Triazole-Stabilized Allylic Anions
J . Org. Chem., Vol. 62, No. 3, 1997 713
1
(hexane/ethyl acetate 60:1) to give 0.64 g of colorless oil: yield
80%; 1H NMR δ 1.10 (t, 3 H, J ) 7.1 Hz), 2.66-2.71 (m, 2 H),
2.91 (d, 2 H, J ) 7.2 Hz), 3.37-3.49 (m, 1 H), 3.97 (q, 2 H, J
) 7.1 Hz), 7.05 (d, 2 H, J ) 8.0 Hz), 7.12-7.30 (m, 8 H); 13C
NMR δ 14.0, 40.2, 42.9, 43.9, 60.1, 126.0, 126.4, 127.4, 128.1,
128.2, 129.1, 139.4, 143.3, 172.1. Anal. Calcd for C18H20O2:
C, 80.56; H, 7.51. Found: C, 80.72; H, 7.84.
ca. 1.7:1; major, ma; minor, mi); H NMR δ 2.83-3.08 (m, 2
H), 3.57 (q, ma, J ) 8.6 Hz) and 4.03 (q, mi, J ) 8.0 Hz) (total
1 H), 5.40 (d, ma, J ) 8.6 Hz) and 5.80 (d, mi, J ) 6.9 Hz)
(total 1 H), 6.79-6.90 (m) and 7.04-7.35 (m) (total 10 H); 13
C
NMR δ (34.8, mi), 36.9, (46.6, mi), 50.3, (84.4, mi), 87.2, 125.5,
125.6, 127.1, 127.2, 127.5, 127.6, 127.7, 127.8, 128.0, 128.4,
128.9, 135.4, 136.6, 137.5, 137.8, 175.1, (176.6, mi). Anal.
Calcd for C16H14O2: C, 80.65; H, 5.92. Found: C, 80.62; H,
5.98.
P r ep a r a tion of tr a n s-1-Eth oxy-1-[5(3)-m eth yl(tr ia zol-
1-yl)]-3-p h en yl-2-p r op en e (28). To a solution of trans-3-
ethoxy-1-phenyl-3-(triazol-1-yl)-1-propene (29) (1.15 g, 5 mmol)
in THF (100 mL) at -78 °C was added n-butyllithium (2.5 M
in cyclohexane, 2 mL, 5 mmol). The solution was stirred at
this temperature for 5 min, and MeI (0.85 g, 6 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 (2 × 100 mL). Evaporation of the solvent
gave a residue, which was separated by column chromatog-
raphy (hexane/ethyl acetate 500:3) to give a colorless oil: yield
81% (a mixture of 5-methyl- (28) and 3-methyl- (triazol-1-yl)
(27) isomers); ratio, ca. 2:1; major, ma; minor, mi); 1H NMR δ
1.17-1.28 (m, 3 H), 2.45 (s, 3 H), 3.40-3.69 (m, 2 H), 6.07 (d,
mi, J ) 5.2 Hz) and 6.13 (d, ma, J ) 4.7 Hz) (total 1 H), 6.36
(dd, 1 H, J ) 16.0, 4.7 Hz), 6.72 (d, ma, J ) 15.9 Hz) and 6.82
(d, mi, J ) 15.9 Hz) (total 1 H), 7.24-7.42 (m, 5 H), 7.83 (s,
ma) and 8.00 (s, mi) (total 1 H); 13C NMR δ 12.5, 14.5, (14.6,
mi), 64.1, (64.7, mi), 88.3, (88.4, mi), (123.6, mi), 123.7, 126.7,
(126.8, mi), (128.4, mi), 128.5, 133.4, 134.0, 135.1, 141.6, 150.0,
151.4, 152.1. Anal. Calcd for C14H17N3O: C, 69.11; H, 7.04;
N, 17.27. Found: C, 68.65; H, 7.28; N, 17.33.
Gen er a l P r oced u r e for th e P r ep a r a tion of 32a , 33a ,b,
35a ,b, 37a -c, 39, 41, a n d 43. To a solution of 3-ethoxy-1-
phenyl-3-(triazol-1-yl)-1-propene (29) (1.15 g, 5 mmol) in THF
(100 mL) at -78 °C was added n-butyllithium (2.0 M in
cyclohexane, 5 mL, 10 mmol). The solution was stirred at this
temperature for 5 min, and the appropriate electrophile (EtBr,
benzyl bromide, N-benzylidineaniline, N-(4-chlorophenylidine)-
aniline, N-(4-methylphenylidine)aniline, or benzophenone: each
5.5 mmol; benzaldehyde, 4-methylbenzaldehyde, cyclohex-
anone, or acetone: each 11 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 (2 × 100
mL). Evaporation of the solvent gave a residue (in the case
of 32a , it was isolated by column chromatography), which was
heated under reflux in a mixture of ethanol (15 mL), water
(15 mL), and HCl (2 mL) for the appropriate time (for 33a ,b,
3 h; 35a ,b, 39, 8 h; 37a -c, 43, 6 h; 41, 4 h). The resulting
solution was extracted with diethyl ether (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). Compound 33b prepared is obtained in 55% yield and
has identical spectral data to those of compound 26.
γ-(4-Meth ylp h en yl)-â-p h en ylbu tyr ola cton e (35b): ob-
tained as a colorless oil; yield 88% (a mixture of two dia-
stereomers; ratio, ca. 1.6:1; major, ma; minor, mi): 1H NMR δ
2.17 (s, mi) and 2.29 (s, ma) (total 3 H), 2.80-3.05 (m, 2 H),
3.57 (q, ma, J ) 7.4 Hz) and 3.98 (q, mi, J ) 7.4 Hz) (total 1
H), 5.34 (d, ma, J ) 8.5 Hz) and 5.74 (d, mi, J ) 6.9 Hz) (total
1 H), 6.73-6.92 (m, 2 H), 7.04-7.18 (m, 5 H), 7.20-7.33 (m, 2
H); 13C NMR δ 20.8, 20.9, 34.7, 36.9, 46.5, 50.1, 84.4, 87.2,
125.5, 125.6, 127.0, 127.1, 127.5, 127.8, 128.3, 128.7, 129.0,
132.3, 134.4, 136.7, 137.2, 137.7, 138.2, 175.1, 176.6. Anal.
Calcd for C17H16O2: C, 80.93; H, 6.39. Found: C, 81.41; H,
6.15.
â,γ,N-Tr ip h en yl-γ-bu tyr ola cta m (37a ): yield 70%; mp
119-121 °C (a mixture of two diasteromers; ratio, ca. 3:1;
1
major, ma; minor, mi); H NMR δ 2.75-2.88 (m, 1 H), 3.10-
3.21 (m, 1 H), 3.35-3.46 (m, ma) and 4.04-4.14 (m, mi) (total
1 H), 5.17 (d, ma, J ) 5.0 Hz) and 5.35 (d, mi, J ) 8.0 Hz)
(total 1 H), 6.79-7.60 (m, 15 H); 13C NMR δ (35.7, mi), 38.7,
(44.7, mi), 47.8, (68.5, mi), 71.5, 121.1, 122.3, 124.5, 124.9,
125.9, 126.7, 126.8, 127.0, 127.3, 127.5, 127.7, 127.9, 128.1,
128.5, 128.8, 128.9, 136.1, 136.5, 137.9, 139.8, 141.6, 173.4,
(173.7, mi). Anal. Calcd for C22H19NO: C, 84.31; H, 6.11; N,
4.47. Found: C, 84.40; H, 6.16; N, 4.41.
â,N-Dip h en yl-γ-(4-ch lor op h en yl)-γ-bu tyr ola cta m (37b):
yield 70%; mp 139-140 °C (a mixture of two diasteromers;
ratio, ca. 5:1; major, ma; minor, mi); 1H NMR δ 2.86 (dd, 1 H,
J ) 17.2 and 7.5 Hz), 3.14 (dd, 1 H, J ) 17.2 and 8.8 Hz),
3.32-3.40 (m, 1 H), 5.15 (d, ma, J ) 5.8 Hz) and 5.33 (d, mi,
J ) 5.8 Hz) (total 1 H); 7.03-7.39 (m, 14 H); 13C NMR δ (35.6,
mi), 38.8, (44.7, mi), 48.2, (68.0, mi), 70.9, (121.2, mi), 122.5,
(124.8, mi), 125.2, 127.0, 127.3, 127.5, 128.1, 128.2, 128.4,
128.7, 129.0, 133.6, 137.6, 138.3, 140.9, 173.3. Anal. Calcd
for C22H18NOCl: C, 75.97; H, 5.22; N, 4.03. Found: C, 75.97;
H, 5.22; N, 3.90.
â,N-Diph en yl-γ-(4-m eth ylph en yl)-γ-bu tyr olactam (37c):
yield 83%; mp 154-156 °C (a mixture of two diasteromers;
1
ratio, ca. 6:1; major, ma; minor, mi); H NMR δ 2.19 (s, mi)
and 2.26 (s, ma) (total 3 H), 2.80 (dd, 1 H, J ) 17.2 and 6.6
Hz), 3.14 (dd, 1 H, J ) 17.2 and 8.9 Hz), 3.35-3.48 (m, 1 H),
5.14 (d, ma, J ) 5.0 Hz) and 5.32 (d, mi, J ) 5.0 Hz) (total 1
H), 6.68-7.60 (m, 14 H); 13C NMR δ (20.8, mi), 20.9 (35.8, mi),
38.7 (44.8, mi), 47.9, (68.4, mi), 71.3, 121.0, 122.3, 124.4, 124.8,
125.9, 126.6, 126.8, 126.9, 127.2, 127.9, 128.1, 128.2, 128.5,
128.8, 129.4, 133.0, 136.6, 136.8, 137.1, 137.4, 137.9, 141.8,
173.4, (173.7, mi). Anal. Calcd for C23H21NO: C, 84.37; H,
6.46; N, 4.28. Found: C, 84.33; H, 6.48; N, 4.23.
1-Eth oxy-3-p h en yl-1-(tr ia zol-1-yl)-1-p en ten e (32a ): ob-
tained as a colorless oil; yield 90% (E/ Z isomers, ratio, ca. 1:1).
Isomer I: 1H NMR δ 0.83 (t, 3 H, J ) 7.4 Hz), 1.36 (t, 3 H, J
) 7.0 Hz), 1.76-1.80 (m, 2 H), 3.18-3.28 (m, 1 H), 3.86-4.00
(m, 2 H), 4.93 (d, 1 H, J ) 10.2 Hz), 7.11-7.22 (m, 3 H), 7.25-
7.33 (m, 2 H), 8.06 (s, 1 H), 8.12 (s, 1 H); 13C NMR δ 11.9,
14.2, 30.3, 43.6, 65.0, 103.3, 126.3, 127.0, 128.6, 143.8, 144.4
144.6, 151.9. Isomer II: 1H NMR δ 0.94 (t, 3 H, J ) 7.4 Hz),
1.33 (t, 3 H, J ) 7.1 Hz), 1.72-1.80 (m, 2 H), 3.65-3.75 (m, 1
H), 3.77-3.90 (m, 2 H), 5.65 (d, 1 H, J ) 10.3 Hz), 7.20-7.40
(m, 5 H), 8.00 (s, 1 H), 8.37 (s, 1 H); 13C NMR δ 12.1, 15.0,
30.0, 43.1, 68.5, 109.5, 126.3, 127.2, 128.5, 141.5, 142.4, 144.2,
152.2.
â-P h en yl-γ,γ-d im eth ylbu tyr ola cton e (39): yield 83%; mp
102-104 °C (lit.19 mp 94-102 °C); 1H NMR δ 0.89-1.12 (m, 2
H), 1.42-1.80 (m, 7 H), 1.88-1.98 (m, 1 H), 2.96 (d, 2 H, J )
9.0 Hz), 3.43 (t, 1 H, J ) 8.9 Hz), 7.18-7.23 (m, 2 H), 7.28-
7.40 (m, 3 H); 13C NMR δ 21.5, 22.4, 24.8, 32.2, 34.6, 36.6,
51.0, 88.3, 127.5, 128.0, 128.4, 137.1, 175.5. Anal. Calcd for
C15H18O2: C, 78.23; H, 7.88. Found: C, 78.21; H, 8.04.
â-P h en yl-γ,γ-d im eth ylbu tyr ola cton e (41): yield 56%; mp
94-95 °C; 1H NMR δ 1.05 (s, 3 H), 1.56 (s, 3 H), 2.89 (dd, 1 H,
J ) 17.6 and 8.5 Hz), 3.02 (dd, 1 H, J ) 17.6 and 10.2), 3.53
(dd, 1 H, J ) 10.2 and 8.6 Hz), 7.20-7.27 (m, 2 H), 7.30-7.42
(m, 3 H); 13C NMR δ 23.1, 27.6, 34.4, 51.1, 87.1, 127.6, 127.7,
128.6, 136.7, 175.2. Anal. Calcd for C12H14O2: C, 75.76; H,
7.42. Found: C, 75.96; H, 7.67.
â,γ,γ-Tr ip h en ylbu tyr ola cton e (43): yield 67%; mp 160-
161 °C; H NMR δ 2.79 (dd, 1 H, J ) 17.5 and 4.7 Hz), 2.98
(dd, 1 H, J ) 17.5 and 8.0 Hz), 4.50 (dd, 1 H, J ) 8.0 and 4.7),
6.92-7.47 (m, 13 H), 7.66 (d, 2 H, J ) 7.0 Hz); 13C NMR δ
37.3, 50.9, 92.9, 126.0, 126.2, 127.1, 127.2, 127.6, 128.1, 128.3,
128.5, 128.6, 138.5, 139.9, 143.1, 175.6. Anal. Calcd for
C22H18O2: C, 84.05; H, 5.77. Found: C, 83.96; H, 5.77.
Eth yl 3-p h en ylp en ta n oa te (33a ): obtained as a colorless
1
oil; yield 84%; H NMR δ 0.79 (t, 3 H, J ) 7.4 Hz), 1.22 (t, 3
H, J ) 7.1 Hz), 1.53-1.80 (m, 2 H), 2.50-2.68 (m, 2 H), 2.95-
3.05 (m, 1 H), 4.01 (q, 2 H, J ) 7.1 Hz), 7.13-7.21 (m, 3 H),
7.23-7.32 (m, 2 H); 13C NMR δ 11.8, 14.0, 29.1, 41.4, 43.9,
60.1, 126.3, 127.5, 128.2, 143.8, 172.4. Anal. Calcd for
C13H18O2: C, 75.69; H, 8.80. Found: C, 75.62; H, 9.01.
â,γ-Dip h en ylbu tyr ola cton e (35a ): yield 90%; mp 89-102
°C (lit.19 mp 97-106 °C) (a mixture of two diasteromers; ratio,
1

714 J . Org. Chem., Vol. 62, No. 3, 1997
Katritzky et al.
P r ep a r a tion of 1-Eth oxy-1-(tr ia zol-1-yl)-3,4-d ip h en yl-
4-(p h en yla m in o)-1-bu ten e (36a ). To a solution of 3-ethoxy-
1-phenyl-3-(triazol-1-yl)-1-propene (29) (1.15 g, 5 mmol) in THF
(80 mL) at -78 °C was added n-butyllithium (2.0 M in
cyclohexane, 5 mL, 10 mmol). The solution was stirred at this
temperature for 5 min, and N-benzylidineaniline (0.91 g, 5
mmol) was 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 (2 × 100 mL). Evaporation of the
solvent gave a residue, which was separated by column
chromatography to give 1.65 g of product (80%): mp 127-130
1
°C; H NMR δ 1.35 (t, 3 H, J ) 7.0 Hz), 3.80-3.98 (m, 3 H),
4.54 (dd, 1 H, J ) 9.1 and 6.0 Hz), 5.12 (d, 1 H, J ) 11.0 Hz),
5.52 (d, 1 H, J ) 6.0 Hz), 6.52-6.65 (m, 3 H), 6.88-6.95 (m, 2
H), 7.02-7.20 (m, 10 H), 8.08 (s, 1 H), 8.17 (s, 1 H); 13C NMR
δ 14.2, 49.8, 63.2, 65.2, 99.0, 113.1, 116.9, 126.8, 127.2, 127.9,
128.0, 128.4, 129.0, 140.8, 141.7, 143.6, 145.4, 147.3, 151.6.
Anal. Calcd for C26H26N4O: C, 76.07; H, 6.38; N, 13.65.
Found: C, 76.34; H, 6.51; N, 13.76.
J O961396T