Synthesis of aromatic triynes as precursors to helicene derivatives

Article abstract of DOI:10.1135/cccc20000577

A general and versatile synthetic approach to a broad series of aromatic triynes as precursors to helicene derivatives has been developed. Employing a set of simple tools, triynes comprising the (phenylethynyl)benzene, 1-(phenylethynyl)naphthalene, and 1-(1-naphthylethynyl)-naphthalene moiety have been prepared in good to excellent yields throughout the whole reaction sequence. The methodology allows constructing various types of a junction between the central diarylacetylene moiety and the attached acetylene units to get the target triynes of general formula R-C≡C-CH₂-X-CH₂-Ar-C≡C-Ar-CH ₂-X-CH₂-C≡C-R or R-C≡C-CH₂CH₂-Ar-C=C-Ar-CH₂CH ₂-C≡C-R (R = H, CH₃, TMS, or TIPS; X = O, NTs, or C(CO₂CH₃)₂; Ar/Ar = 2-phenylene or 2-naphthylene).

Full text of DOI:10.1135/cccc20000577

Synthesis of Aromatic Triynes
577
SYNTHESIS OF AROMATIC TRIYNES AS PRECURSORS TO HELICENE
DERIVATIVES
1,
2
3
4,
Irena G. STARÁ *, Adrian KOLLÁROVIČ , Filip TEPLÝ , Ivo STARÝ *,
5
David ŠAMAN and Pavel FIEDLER
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic,
1
Flemingovo nám. 2, 166 10 Prague 6, Czech Republic; e-mail: stara@uochb.cas.cz,
2
3
4
5
adrian@uochb.cas.cz, fteply@natur.cuni.cz, stary@uochb.cas.cz, saman@uochb.cas.cz
Received March 17, 2000
Accepted April 21, 2000
Dedicated to Professor Otakar Červinka on the occasion of his 75th birthday.
A gen eral an d versatile syn th etic approach to a broad series of arom atic triyn es as precursors
to h elicen e derivatives h as been developed. Em ployin g a set of sim ple tools, triyn es com pris-
in g th e (ph en yleth yn yl)ben zen e, 1-(ph en yleth yn yl)n aph th alen e, an d 1-(1-n aph th yleth yn yl)-
n aph th alen e m oiety h ave been prepared in good to excellen t yields th rough out th e wh ole
reaction sequen ce. Th e m eth odology allows con structin g various types of a jun ction be-
tween th e cen tral diarylacetylen e m oiety an d th e attach ed acetylen e un its to get th e target
triyn es of gen eral form ula R–C≡C–CH2–X–CH2–Ar–C≡C–Ar′–CH2–X–CH2–C≡C–R or
R–C≡C–CH2CH2–Ar–C≡C–Ar′–CH2CH2–C≡C–R (R = H, CH3, TMS, or TIPS; X = O, NTs, or
C(CO2CH3)2; Ar/Ar′ = 2-ph en ylen e or 2-n aph th ylen e).
Key w ord s: Acetylen es; Alkyn es; Aren es; Eth ers; Helicen es; Son ogash ira reaction ; Triyn es;
Cyclotrim erization s; Cross-couplin g reaction s.
Durin g th e last decade, a growin g atten tion h as been paid to h elicen e
ch em istry bein g in duced by a gen eral in terest in artificial ch iral m olecules1
an d th eir exploitation 2. However, fascin atin g h elicen es3 h ad earn ed a bad
reputation in th e past as h ardly attain able m olecules. Th e situation dram at-
ically ch an ged in th e n in eties n am ely due to a breakth rough in th eir syn -
th esis m ade by Katz in 1990 (ref.4). His origin al m eth odology in volvin g
Diels–Alder cycloaddition of 1,4-ben zoquin on e to divin yl arom atics, wh ich
is surprisin gly easy an d gen eral, h as gradually becom e th e first practical
m eth od for m ultigram -scale preparation of various substituted carbo-
h elicen es5 as well as h eteroh elicen es6.
Th e discovery of Katz h as in spired oth er groups to search for altern ative
n on ph otoch em ical strategies to syn th esize h elicen es7. Recen tly, we h ave
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

578
Stará, Kollárovič, Teplý, Starý, Šaman, Fiedler:
publish ed a n ovel organometallic approach to h elicen e-like m olecules as well
as paren t carboh elicen es based on in tram olecular [2+2+2] cyclotri-
m erization of arom atic triyn es un der Co(I) or Ni(0) catalysis8 (Sch em e 1).
We h ave sh own th at our de novo con struction of a h elical scaffold exh ibits
rem arkable flexibility allowin g syn th esis of a series of products with five,
six, an d seven ortho-fused carbo- an d/or h eterocycles. However, th e success
of th is m eth odology depen ds on th e facile accessibility of th e key arom atic
triyn es. Herein , we report sim ple an d versatile m eth ods for an assem bly of
th e various arom atic triyn es as precursors to h elicen e derivatives. To diver-
sify th e skeleton of target h elices, we h ave altered arom atic parts, lin kers,
an d term in al alkyn e substituen ts at th e arom atic triyn es.
O
O
CpCo(CO)2
PPh3
O
O
SCHEME 1
RESULTS AND DISCUSSION
Synthesis of Triynes Containing the (Phenylethynyl)benzene Moiety
Triyn es com prisin g th e (ph en yleth yn yl)ben zen e m oiety with two teth ered
acetylen e un its are design ed as precursors of pen tacyclic h elical m olecules.
All triyn e variation s m ay be derived from th ree substituted (ph en yleth y-
n yl)ben zen es 1–3 th at are readily available from com m ercial ch em icals9
(Sch em e 2).
In order to attach th e acetylen e un its to th e (ph en yleth yn yl)ben zen e
m oiety by an oxygen -con tain in g th ree-atom ester-type teth er, diester 1 was
treated with excess of prop-2-yn -1-ol un der basic con dition s. Alth ough
som e tran sesterification proceeded, th e desired triyn e 5 was obtain ed in
low yield alon g with th e m in or diyn e 4 (Sch em e 2). Sim ilarly, th e attem pt
to con n ect th e acetylen e un its by a com plem en tary ester-type teth er pro-
vided discouragin g results because con den sation of diol 2 with propiolic acid
led on ly to a sm all am oun t of triyn e 7 beside th e m ajor diyn e 6.
By con trast, a th ree-atom eth er-type teth er could be prepared m ore effec-
tively. It m ay be con structed by alkylation of dialkoxide derived from diol 2
or, altern atively, by displacem en t of brom in e atom s in dibrom ide 3 with
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Synthesis of Aromatic Triynes
579
alkoxides. To pursue th e form er approach , deproton ation of diol 2 with so-
dium h ydride h ad to be carried out in THF at 0 °C oth erwise, at h igh er tem -
perature, th e addition of an in tern al alkoxide n ucleoph ile across th e triple
bon d yielded th e un desirable en ol eth er 11 (ref.13). Th e subsequen t
alkylation with prop-2-yn -1-yl brom ide afforded triyn e 8 in excellen t yield
but th e sam e reaction with 1-brom obut-2-yn e furn ish ed triyn e 9 in un satis-
factory yield (Sch em e 2). In a com plem en tary approach , ben zylic substitu-
O
Br
Br
CO2CH3
CO2CH3
O
O
(iii)
OR
4, R = CH3
1
3
5, R = CH2C≡CH
(i)
(ii)
(vii) or (viii)
R
R
O
O
OH
OH
O
(iv)
(v) or (vi)
OR
O
8, R = H ((v) or (vii))
9, R = CH3 ((vi) or (viii))
10, R = TMS
2
6, R = H
7, R = COC≡CH
(x)
(ix)
(i) Na[AlH2(OCH2CH2OCH3)2] (1.2 equiv.), toluene, 0 oC, 15 min, 87%
(ii) PBr3 (1.0 equiv.), THF, 0 oC, 30 min, 87%
(iii) HOCH2C≡CH (95 equiv.), K2CO3 (1.2 equiv.), 50 oC, overnight, 12% of 4, 21% of 5
(iv) HC≡CCO2H (2.0 equiv.), DCC (2.0 equiv.), DMAP (28 mole %), ether-THF (5 : 1), rt,
overnight, 31% of 6, 12% of 7
(v) NaH (2.7 equiv.), THF, 0 oC, 30 min, then BrCH2C≡CH (4.3 equiv.), 0 oC to rt, overnight, 91%
(vi) NaH (2.4 equiv.), THF, 0 oC, 1 h, then BrCH2C≡CCH3 (4.1 equiv.), 0 oC to rt, overnight, 24%
(vii) NaOCH2C≡CH (2.4 equiv.), DMF, rt, 15 min, 79%
(viii) NaOCH2C≡CCH3 (2.2 equiv.), DMF, rt, overnight, 69% of 9, 5% of 14
(ix) BuLi (2.1 equiv.), THF, -78 oC, 10 min, then CH3I (3.0 equiv.), -78 oC to rt, overnight, 62%
(x) BuLi (2.1 equiv.), THF, -78 oC, 10 min, then TMSCl (2.4 equiv.), -78 oC to rt, overnight, 71%
SCHEME 2
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580
Stará, Kollárovič, Teplý, Starý, Šaman, Fiedler:
tion in dibrom ide 3 with sodium alkoxides derived from prop-2-yn -1-ol as
well as but-2-yn -1-ol resulted in th e form ation of th e desired triyn es 8 an d
9, respectively, in good an d com parable yields14 (Sch em e 2).
O
OTMS
OTMS
OH
R
O
O
Br
Br
11
12, R = OH
13, R = H
14
15
Triyn e 8 with th e term in al acetylen e un its h as been sh own to be a suit-
able substrate for furth er m odification s. Gen eratin g th e double lith ium
acetylide from 8 with butyllith ium , th e followin g reaction with m eth yl io-
dide or trim eth ylsilyl ch loride gave rise to triyn es 9 an d 10 with th e m eth yl
or trim eth ylsilyl groups at th e alkyn e term in i16 (Sch em e 2).
Owin g to an in creased susceptibility of th e fluorin ated diol 16 (ref.10b) to
n ucleoph ilic addition across th e triple bon d, th e gen eration of dialkoxide
from 16 was n ot possible (Sch em e 3). Th erefore, dibrom ide 17 was prepared
an d tran sform ed in good yield by reaction with sodium prop-2-yn -1-olate
to th e fluorin ated triyn e 18.
F
F
F
OH
OH
Br
Br
O
O
(i)
(ii)
17
16
18
(i) CBr4 (2.3 equiv.), PPh3 (2.1 equiv.), acetonitrile, rt, overnight, 80%
(ii) NaOCH2C≡CH (2.2 equiv.), DMF, rt, 10 min, 78%
SCHEME 3
In order to attach acetylen e un its to th e (ph en yleth yn yl)ben zen e m oiety
by a n itrogen -con tain in g th ree-atom am ide-type teth er, dibrom ide 3 was
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Synthesis of Aromatic Triynes
581
treated with sodium salt of N-(prop-2-yn -1-yl)sulfon am ide 21 (ref.17) as well
as N-(but-2-yn -1-yl)sulfon am ide18 (22) (Sch em e 4). Th e reaction s gave
triyn e 23 in low yield an d triyn e 24 in m oderate yield. Th e latter com -
poun d was prepared altern atively by th e Mitsun obu reaction from diol 2
an d N-(but-2-yn -1-yl)sulfon am ide (22) in better yield.
Boc
OH
N
Ts
HN Ts
(i) or (ii)
(iii) or (iv)
R
R
R
19, R = H (i)
20, R = CH3 (ii)
21, R = H (iii)
22, R = CH3 (iv)
R = H, CH3
Ts
N
R
Br
Br
OH
OH
(v) or (vi)
(vii)
N
Ts
R
3
2
23, R = H (v)
24, R = CH3 (vi) or (vii)
(i) BocNHTs (1.5 equiv.), DEAD (2.5 equiv.), PPh3(3.0 equiv.), THF, rt, overnight, 76%
(ii) BocNHTs (1.4 equiv.), DEAD (2.4 equiv.), PPh3(2.9 equiv.), THF, rt, overnight, 78%
(iii) CF3CO2H (3.0 equiv.), CH2Cl2, rt, 45 min, 87%
(iv) CF3CO2H (3.3 equiv.), CH2Cl2, rt, 4 h, 88%
(v) 21 (2.0 equiv.), NaH (2.1 equiv.), DMF, 0 oC to rt, overnight, 27%
(vi) 22 (2.0 equiv.), NaH (2.6 equiv.), THF-DMF (6 : 1), 65 oC, 20 min, 63%
(vii) 22 (2.0 equiv.), DEAD (2.6 equiv.), PPh3 (3.0 equiv.), THF, rt, 1 h, 72%
SCHEME 4
Th e teth ers in triyn es 8 an d 9 called for th e Wittig rearran gem en t21 to
con tract th e th ree-atom jun ction to th e two-atom jun ction an d, th erefore,
to diversify furth er th e fam ily of triyn es. Th erefore triyn es 8 an d 9 were
treated with a stron g base an d subsequen tly with an electroph ile (Sch em e 5).
In th e case of triyn e 8 with th e term in al acetylen e un its, a sin gle [1,2] rear-
ran gem en t proceeded bein g in itialized by deproton ation un iform ly at th e
ben zylic position . Triyn es 25–27 bearin g on ly on e con tracted teth er were
isolated in low or m odest yield. By con trast, triyn e 9 with th e m eth ylated
acetylen e un its exh ibited a differen t beh avior. Th e proton abstraction also
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

582
Stará, Kollárovič, Teplý, Starý, Šaman, Fiedler:
took place at th e ben zylic position but th e rearran gem en t proceeded in a
[1,4] fash ion in volvin g th e propargylic sh ift. Hen ce, a 2 : 1 m ixture of
bisallen e 29 an d m on oallen e 28 was obtain ed in m oderate yield. Un der dif-
feren t con dition s, bisallen e 29 was form ed as th e m ain product in m odest
yield.
TMS
TMS
O
O
(ii)
OH
TMS
O
10
+
O
O
TMS
TMS
26
(i)
O
O
(iii)
8
OH
OTMS
TMS
27
25
O
(v)
(iv)
OH
OH
OH
29
+
O
O
29
9
28
(i) BuLi (2.4 equiv.), THF, -78 oC, 40 min, then TMSCl (2.6 equiv.), -78 oC to rt, overnight,
48% of 10, 22% of 25, 22% recovery of 8
(ii) BuLi (4.9 equiv.), THF, -78 oC, 1.5 h, then TMSCl (5.1 equiv.), -78 oC to rt, overnight, 23%
(iii) BuLi (5.0 equiv.), THF, -78 oC, 30 min, then CH3I (5.6 equiv.), -78 oC to rt, 3 h, 31%
(iv) BuLi (2.6 equiv.), THF, -78 oC, 30 min, then CH3I (3.4 equiv.), -78 oC to rt, 3 h, 14% of 28,
28% of 29 as a 1 : 1 mixture of the (R*,R*) and (R*,S*) diastereoisomers (1H NMR)
(v) tert-BuLi (2.5 equiv.), THF, -78 oC, 2 h, then H2O (excess), -78 oC to rt, overnight, 31%,
a 1 : 1 mixture of the (R*,R*) and (R*,S*) diastereoisomers (1H NMR)
SCHEME 5
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Synthesis of Aromatic Triynes
583
As th e attem pt to prepare triyn es with all-carbon -atom teth ers via th e
Wittig rearran gem en t failed due to in sufficien t yields, altern ative an d m ore
efficien t approach es to th e con struction of an eth an e or propan e jun ction
were developed (Sch em e 6). Con cern in g a two-carbon -atom teth er,
displacem ent of brom ine in dibrom ide 3 with LiCH2C≡CTMS (generated in
situ from trimethyl(prop-1-yn-1-yl)silane and butyllithium) proceeded smoothly
to build up a triyne framework, however, with partially desilylated terminal
alkyne units. Therefore, the reaction mixture was instantly treated with an ex-
cess of Bu4NF an d th is on e-pot procedure afforded triyn e 30 with th e term i-
n al acetylen e un its in good yield8c. Deproton ation of 30 with butyllith ium
an d th e subsequen t reaction s of th e double lith ium acetylide with
electroph iles clean ly provided triyn es 31 an d 32 with th e m eth yl or
trim eth ylsilyl groups at th e acetylen e term in i. Sim ilarly, th e reaction s of
dibrom ide 3 with stabilized carbon n ucleoph iles gen erated in situ from
dim eth yl 2-(prop-2-yn -1-yl)m alon ate22 or dim eth yl 2-(but-2-yn -1-yl)-
m alon ate23 by sodium h ydride led to triyn es 33 an d 34 in good or h igh
yield to dem on strate an efficien t approach to a th ree-carbon -atom teth er.
CO2CH3
R
Br
(i)
(iv) or (v)
CO2CH3
CO2CH3
Br
R
CO2CH3
30
3
33, R = H (iv)
34, R = CH3 (v)
(ii) or (iii)
R
R
31, R = CH3 (ii)
31, R = TMS (iii)
(i) LiCH2C≡CTMS (2.1 equiv.), THF, -78 oC, 1 h, then Bu4NF (8.0 equiv.) in THF, rt, 16 h, 67%
(ii) BuLi (2.2 equiv.), THF, -78 oC, 10 min, then CH3I (2.2 equiv.), -78 oC, 15 min, 91%
(iii) BuLi (2.1 equiv.), THF, -78 oC, 10 min, then TMSCl (2.1 equiv.), -78 oC, 15 min, 98%
(iv) (HC≡CCH2)NaC(CO2CH3)2 (2.1 equiv.), THF, rt, 30 h, 60%
(v) (CH3C≡CCH2)NaC(CO2CH3)2 (2.2 equiv.), THF, rt, 1 h, 86%
SCHEME 6
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584
Stará, Kollárovič, Teplý, Starý, Šaman, Fiedler:
Synthesis of Triynes Containing the 1-(Phenylethynyl)naphthalene Moiety
Triyn es com prisin g th e 1-(ph en yleth yn yl)n aph th alen e m oiety with two
teth ered acetylen e un its are design ed as precursors to th e h exacyclic h elical
m olecules. Th e ch em istry of th e 1-(ph en yleth yn yl)n aph th alen e-derived
triyn es 38–43 exh ibits alm ost th e sam e features as th e ch em istry of th eir
(ph en yleth yn yl)ben zen e coun terparts (Sch em e 7). Accordin gly, th e syn th e-
sis started with diester 35 wh ich is available from th e correspon din g aro-
m atic buildin g blocks by em ployin g th e aryl-alkyn yl couplin g m eth od-
ology11. Diester 35 was routin ely reduced to diol 36 an d th en con verted to
dibrom ide 37 th at was a com m on substrate for all bran ch es of th e un iform
reaction sch em e.
OH
Br
Br
CO2CH3
CO2CH3
(i)
(ii)
OH
(iii)
35
36
37
(iv)
(v)
Ts
N
O
O
R
R
N
Ts
38
39
40, R = TIPS
41, R = H
42, R = CH3
43, R = TMS
(vi)
(vii)
(viii)
(i) Na[AlH2(OCH2CH2OCH3)2] (5.0 equiv.), toluene, 0 oC, 1 h, 82%
(ii) PBr3 (1.4 equiv.), THF, 0 oC, 2 h, 65%
(iii) 21 (2.6 equiv.), NaH (2.8 equiv.), DMF, 0 oC to rt, overnight, 99%
(iv) NaOCH2C≡CCH3 (2.2 equiv.), DMF, rt, 2 h, 68%
(v) LiCH2C≡CTIPS (2.3 equiv.), THF, -78 oC, 1 h, 74%
(vi) Bu4NF (4.9 equiv.), THF, rt, 1 h, 97%
(vii) BuLi (2.2 equiv.), THF, -78 oC, 10 min, then CH3I (2.5 equiv.), -78 oC, 20 min, 93%
(viii) BuLi (2.2 equiv.), THF, -78 oC, 10 min, then TMSCl (2.7 equiv.), -78 oC, 20 min, 93%
SCHEME 7
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Synthesis of Aromatic Triynes
585
Dibrom ide 37 allowed buildin g up th e triyn e fram ework in on e step re-
gardless of th e teth er type th at it com prised. Reaction with N-(prop-2-yn -
1-yl)sulfon am ide (21) in th e presen ce of a base afforded triyn e 38 with th e
th ree-atom n itrogen -con tain in g teth ers in excellen t yield. Th e
base-m ediated alcoh olysis with but-2-yn -1-ol furn ish ed triyn e 39 with th e
th ree-atom oxygen -con tain in g teth ers in good yield. On treatm en t with
LiCH2C≡CTIPS (gen erated in situ from triisopropyl(prop-1-yn -1-yl)silan e
an d butyllith ium ), th e bis-silylated triyn e 40 con tain in g th e
two-carbon -atom teth ers was obtain ed in good yield8c. Th e stable TIPS
groups, bein g un touch ed by th e lith ium reagen t, were easily rem oved by
Bu4NF to get triyn e 41 with th e term in al acetylen e un its in n early quan tita-
tive yield8c. Th e latter com poun d was furth er m odified at th e alkyn e ter-
m in i by deproton ation followed by a quen ch with an electroph ile to afford
triyn es 42 an d 43 in excellen t yields.
Synthesis of Triynes Containing the 1-(1-Naphthylethynyl)naphthalene
Moiety
Triyn es com prisin g th e 1-(1-n aph th yleth yn yl)n aph th alen e m oiety with
two teth ered acetylen e un its are design ed as precursors to th e h eptacyclic
h elical m olecules. Th e syn th esis of triyn es 47 an d 48 relied on a sligh tly
differen t strategy (Sch em e 8). Th e readily available alcoh ol 44 (ref.11) was
I
I
Br
OH
(i)
45
44
(ii)
I
TIPS
R
R
(iii)
(iv)
47, R = TIPS
48, R = H
46
(i) PBr3 (0.5 equiv.), THF, 0 oC, 1 h, 94%
(ii) LiCH2C≡CTIPS (1.2 equiv.), THF, -78 oC, 2.5 h, 69%
(iii) HC≡CH(g), Pd(PPh3)4 (6 mole %), CuI (10 mole %), piperidine, 80 oC, 2 h, 77%
(iv) Bu4NF (4.3 equiv.), THF, rt, 1 h, 70%
SCHEME 8
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586
Stará, Kollárovič, Teplý, Starý, Šaman, Fiedler:
con verted to brom ide 45 wh ich on reaction with LiCH2C≡CTIPS allowed
th e attach m en t of a side arm with a protected alkyn e un it to obtain iodide
46 in good yield. Th e n aph th alen e buildin g block was coupled with gas-
eous acetylen e un der Pd(0)/Cu(I) catalysis to give triyn e 47 with th e
two-carbon -atom teth ers in good yield. Desilylation with Bu4NF gave triyn e
48 in good yield as well.
CONCLUSION
Em ployin g a set of sim ple syn th etic tools, a broad series of triyn es derived
from th e (ph en yleth yn yl)ben zen e, 1-(ph en yleth yn yl)n aph th alen e, an d
1-(1-n aph th yleth yn yl)n aph th alen e m oiety h as been prepared. Effective
m eth ods h ave been developed to con struct various types of a jun ction be-
tween th e cen tral diarylacetylen e m oiety an d th e attach ed acetylen e un its
com prisin g th e th ree-atom oxygen -, n itrogen -, an d all-carbon -con tain in g
teth ers as well as th e two-carbon -atom teth er. Th e target triyn es h ave been
obtain ed in good to excellen t yields th rough out th e wh ole reaction se-
quen ce en ablin g also a m ultigram -scale preparation .
EXPERIMENTAL
Gen eral
Meltin g poin ts were determ in ed on a Kofler h ot-stage apparatus an d are un corrected.
1H NMR spectra were m easured at 499.8 or 200.0 MHz, 13C NMR spectra at 125.7 MHz, in
CDCl3 with TMS as an in tern al stan dard or in aceton e-d6 (referen ced to aceton e). 19F NMR
spectra were m easured at 470.3 MHz in CDCl3 with CFCl3 as an in tern al stan dard. Ch em ical
sh ifts are given in δ-scale, couplin g con stan ts J are given in Hz (Fig. 1). HMBC experim en ts
were setup for JC-H = 5 Hz. For correct assign m en t of both 1H an d 13C NMR spectra of key
com poun ds, th e HCOSY an d HMQC experim en ts were perform ed. For all th e oth er com -
poun ds, th e gen eral sem iem pirical equation s were applied to th e ch em ical sh ift assign m en ts.
IR spectra were m easured in CHCl3 or CCl4. EI MS spectra were determ in ed at an ion izin g
voltage of 70 eV. FAB MS spectra were m easured usin g th e th ioglycerol–glycerol 3 : 1, dith io-
th reitol–dith ioeryth ritol 5 : 1 or bis(2-h ydroxyeth yl)disulfide m atrix. HR MS spectra were
obtained by the EI or FAB technique. GC MS analyses were carried out on a DB-5 column (0.25 ×
30 m × 0.25 µm ). All reaction s were perform ed un der argon . Reagen t grade m aterials pur-
ch ased from Sigm a–Aldrich , Fluka, Merck, an d Avocado were used as received. THF an d
eth er were fresh ly distilled from sodium /ben zoph en on e un der n itrogen ; piperidin e was dis-
tilled from calcium h ydride un der argon an d degassed by th ree freeze-pum p-th aw cycles be-
fore use; toluen e was fresh ly distilled from ph osph orus pen toxide un der argon ; dich loro-
m eth an e was fresh ly distilled from calcium h ydride un der argon ; aceton itrile was distilled
from calcium h ydride un der argon an d stored over 4Å m olecular sieves; DMF was distilled
from calcium h ydride un der reduced pressure an d stored over 4Å m olecular sieves. Th e reac-
tion s with gaseous acetylen e un der 1 atm pressure were perform ed in a vessel con n ected to a
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

Synthesis of Aromatic Triynes
587
rubber balloon filled with acetylen e directly from a cylin der. TLC was perform ed on Silica
gel 60 F254-coated alum in ium sh eets (Merck) an d spots were detected by th e solution of
Ce(SO4)2·4H2O (1%) an d H3P(Mo3O10
) (2%) in sulfuric acid (10%). Flash ch rom atograph y
4
was perform ed on Silpearl silica gel (Kavalier Votice, Czech Republic) or Silica gel 60
(0.040–0.063 m m or <0.063 m m , Merck). Sem ipreparative HPLC was carried out on a silica
gel colum n (Partisil M9, Wh atm an 10/50, 500 m m × 10 m m ; sam ple in jection s on a 10–20
m g scale) usin g a refractom etric detector.
[Eth yn ediylbis(2,1-ph en ylen e)]dim eth an ol (2)
Na[AlH2(OCH2CH2OCH3)2] (3.5 M solution in toluen e, 3.5 m l, 12.25 m m ol, 1.2 equivalen t) was
added dropwise durin g a 5 m in period to a solution of diester 1 (ref.10) (1.5 g, 5.097 m m ol) in
dry toluen e (15 m l) un der argon at 0 °C. After stirrin g at room tem perature for 15 m in , th e
un reacted h ydride reagen t was carefully decom posed by addin g saturated aqueous solution
of Na2SO4. Th e reaction m ixture was filtered th rough a sh ort pad of silica gel usin g aceton e,
th e solven ts were evaporated in vacuo an d th e residue was crystallized from petroleum
eth er–aceton e to get diol 2 (1.05 g, 87%). 1H NMR (200 MHz, aceton e-d6) spectrum was in
accord with th e literature data11
.
Bis[2-(brom om eth yl)ph en yl]acetylen e (3)
Ph osph orus tribrom ide (280 µl, 2.95 m m ol, 1.0 equivalen t) was added to diol 2 (ref.11) (703 m g,
2.95 m m ol) in dry THF (5 m l) at 0 °C un der n itrogen . After stirrin g at 0 °C for 30 m in , th e
solven t was rem oved in vacuo. Flash ch rom atograph y on silica gel (petroleum
R
R
2'
2
3
3'
5'
In compounds:
1'
4
1
4 (2-CO2CH3, 2'-CO2CH2C≡CH),
5, 17 (2-CH2Br, 4-F, 2'-CH2Br),
18 (2-CH2OCH2C≡CH, 4-F, 2'-CH2OCH2C≡CH)
4'
R
6'
6
5
In compounds:
R
R
1
6
4
2'
6 (1-CH2OCOC≡CH, 2'-CH2OH),
7 - 10, 14 (1-CH2OCH2C≡CCH3, 2'-CHBr2),
15, 23, 24, 25 (1-CH2OCH2C≡CTMS,
2'-CH(OTMS)CH2C≡CTMS), 29 - 34
3'
5'
1'
2
4'
5
6'
3
5
6
4
1
R
3
R
R
R
R
2
2
2
2
2
3
3
6
3
3
2'
O
1'
1
1
1
1
4
4
4
4
7a'
3'
4a
5
8a
8
8a
8
4a
8a
8
4a
6
5
7'
6'
3a'
4'
5
5
6
7
6
7
7
5'
In compounds: 11 -13
In compounds: 36 - 43
In compounds: 47, 48
FIG. 1
Num berin g of arom atics as utilized in 1H an d 13 C NMR spectra sign al assign m en ts
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

588
Stará, Kollárovič, Teplý, Starý, Šaman, Fiedler:
eth er–eth er–aceton e 80 : 10 : 10) gave dibrom ide 3 (929 m g, 87%) as a wh ite solid. 1H NMR
(200 MHz, aceton e-d6) spectrum was in accord with th e literature data12a
Meth yl Prop-2-yn -1-yl 2,2′-Eth yn ediyldiben zoate (4)
.
Dim eth yl ester 1 (ref.10) (53 m g, 0.180 m m ol) an d an h ydrous potassium carbon ate (30 m g,
0.217 m m ol, 1.2 equivalen t) in prop-2-yn -1-ol (1 m l, 17.18 m m ol, 95 equivalen ts) were
stirred in a tigh tly stoppered flask at 50 °C overn igh t. Th e m ixture was cooled to room tem -
perature an d evaporated to dryn ess un der vacuum of th e oil pum p. Th e residue was parti-
tion ed between eth er an d water, th e eth ereal ph ase was separated an d th e aqueous ph ase
was extracted with eth er (4×). Th e eth ereal portion s were com bin ed, wash ed with brin e (1×),
dried over Na2SO4 an d evaporated in vacuo. Repeated preparative HPLC on silica gel
(petroleum eth er–aceton e 85 : 15 an d 87 : 13, respectively) gave m eth yl prop-2-yn -1-yl ester 4
(7 m g, 12%) as an oil an d th e m ore polar di(prop-2-yn -1-yl) ester 5 (13 m g, 21%) as a wh ite
solid. Com poun d 4: IR (CCl4): 3 392 w, 3 313 m , 3 070 w, 3 022 vw, 2 133 vw, 1 735 vs,
1 722 s, 1 597 w, 1 568 w, 1 493 m , 1 448 m , 1 434 w, 1 367 w, 1 291 s, 1 264 m , 1 251 vs,
1 247 vs, 1 191 w, 1 163 w, 1 129 m , 1 078 m , 1 069 m , 700 w, 673 w, 665 w, 632 w.
1H NMR (500 MHz, CDCl3): 2.47 (d, 1 H, J = 2.4, HC≡C); 3.96 (s, 3 H, CH3); 4.97 (d, 2 H, J =
2.4, CH2); 7.40 (ddd, 1 H, J = 7.9, 7.5, 1.3, 4-H); 7.41 (ddd, 1 H, J = 7.9, 7.5, 1.4, 4′-H); 7.51
(dt, 1 H, J = 7.5, 7.5, 1.4, 5-H); 7.54 (dt, 1 H, J = 7.5, 7.5, 1.4, 5′-H); 7.74 (ddd, 1 H, J = 7.7,
1.3, 0.6, 6′-H); 7.78 (ddd, 1 H, J = 7.6, 1.4, 0.6, 6-H); 7.99 (ddd, 1 H, J = 7.9, 1.4, 0.6, 3-H);
8.04 (ddd, 1 H, J = 7.9, 1.3, 0.6, 3′-H). 13C NMR (CDCl3): 52.19 (q, CH3), 52.56 (t, CH2),
75.06 (d, HC≡C), 77.76 (s, HC≡C), 92.87 (s, ArC≡CAr′), 93.54 (s, ArC≡CAr′), 123.80 (s, C-2),
124.21 (s, C-2′), 128.15 (d, C-4′), 128.18 (d, C-4), 130.44 (d, C-3), 130.73 (d, C-3′), 130.90 (s,
C-1′), 131.70 (d, C-5), 131.83 (s, C-1), 132.15 (d, C-5′), 134.42 (d, C-6′), 134.47 (d, C-6),
165.26 (s, CO2CH2), 166.62 (s, CO2CH3). EI MS (m/z, rel.%): 287 ((M – CH3O)+, 3), 279
(100), 264 (27), 248 (11), 235 (5), 220 (17), 180 (8), 176 (7), 163 (10), 152 (5), 132 (3), 88
(5), 39 (5), 28 (8). FAB MS (m/z, th ioglycerol–glycerol m atrix): 319 ((M + H)+), 287, 279, 263,
248, 220, 189, 186, 176, 163, 151, 115, 77. HR FAB MS: calculated for C20H15O4 (M + H)
319.0970, foun d 319.0883.
Di(prop-2-yn-1-yl) 2,2′-ethynediyldibenzoate (5). M.p. 112.5–113.5 °C (m eth an ol). IR (CCl4):
3 392 w, 3 313 m , 3 070 w, 2 133 vw, 1 738 s, 1 724 m , 1 597 w, 1 568 w, 1 493 w, 1 448 w,
1 367 w, 1 287 m , 1 265 w, 1 248 vs, 1 163 w, 1 128 m , 1 072 s, 699 w, 674 w, 632 w.
1H NMR (500 MHz, CDCl3): 2.47 (t, 2 H, J = 2.6, 2 × HC≡); 4.97 (d, 4 H, J = 2.6, 2 × CH2);
7.41 (dt, 2 H, J = 7.6, 7.6, 1.2, 4,4′-H); 7.54 (dt, 2 H, J = 7.6, 7.6, 1.4, 5,5′-H); 7.79 (dd, 2 H,
J = 7.8, 1.2, 6,6′-H); 8.04 (dd, 2 H, J = 7.9, 1.4, 3,3′-H). 13C NMR (CDCl3): 52.57 (t, 2 × CH2),
75.07 (d, 2 × HC≡C), 77.76 (s, 2 × HC≡C), 93.28 (s, ArC≡CAr), 124.11 (s, C-2,2′), 128.20 (d,
C-5,5′), 130.70 (d, C-6,6′), 130.87 (s, C-1,1′), 132.10 (d, C-3,3′), 134.54 (d, C-4,4′), 165.23 (s,
2 × C=O). EI MS (m/z, rel.%): 303 ((M – C3H3)+, 59), 275 (8), 264 (100), 248 (13), 231 (6),
220 (11), 208 (22), 180 (24), 176 (14), 163 (26), 152 (16), 137 (4), 104 (5), 88 (8), 76 (8), 63
(5), 39 (18). FAB MS (m/z, th ioglycerol–glycerol m atrix): 343 ((M + H)+), 303, 287, 265, 249,
179, 165, 147, 91, 87, 73, 61, 57. HR FAB MS: calculated for C22H15O4 (M + H) 343.0970,
foun d 343.1022.
2-{[2-(Hydroxym eth yl)ph en yl]eth yn yl}ben zyl Propiolate (6)
N,N-Dim eth ylpyridin -4-am in e (7 m g, 0.057 m m ol, 28 m ole %) in dry eth er (1 m l) was
added to propiolic acid (27 µl, 0.433 m m ol, 2.0 equivalen ts) in dry eth er (1 m l) at room
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Synthesis of Aromatic Triynes
589
tem perature un der argon . Th e yellowish suspen sion was form ed an d th en diol 2 (ref.11) (50 m g,
0.210 m m ol) in a m ixture of dry eth er–THF (3 m l, 2 : 1) an d N,N′-dicycloh exylcarbodiim ide
(87 m g, 0.420 m m ol, 2.0 equivalen ts) in dry eth er (1 m l) were added. Th e reaction m ixture
was stirred at room tem perature overn igh t. Th e oran ge precipitate was filtered off, th e fil-
trate was evaporated to dryn ess an d th e residue was passed th rough a sh ort pad of silica gel
(petroleum eth er–aceton e 75 : 25). Th e crude product was purified by preparative HPLC
(petroleum eth er–aceton e 75 : 25) to get diester 7 (8 m g, 12%) an d m ore polar m on oester 6
(19 m g, 31%) as am orph ous solids. Com poun d 6: IR (CCl4): 3 617 w, 3 463 vw, 3 306 w,
3 069 w, 3 027 w, 2 942 m , 2 928 w (sh ), 2 859 w, 2 125 w, 1 722 m , 1 687 m , 1 612 s,
1 575 vw, 1 491 w, 1 460 vw, 1 377 w, 1 338 w, 1 230 w (sh ), 1 221 m , 1 151 m , 1 114 m ,
1 019 w, 690 vw, 655 vw. 1H NMR (500 MHz, CDCl3): 2.17 (brs, 1 H, OH); 2.91 (s, 1 H,
HC≡C); 4.92 (brs, 2 H, CH2Ar′); 5.48 (s, 2 H, CH2Ar); 7.31 (dt, 1 H, J = 7.6, 7.6, 1.5, 5′-H);
7.37 (brdt, 1 H, J = 7.6, 7.6, 2.0, 4′-H); 7.37–7.41 (m , 2 H, 4,5-H); 7.47–7.49 (m , 1 H, 6-H);
7.50 (brd, 1 H, J = 7.7, 6′-H); 7.57 (dt, 1 H, J = 7.6, 7.6, 1.5, 3′-H); 7.58–7.60 (m , 1 H, 3-H).
13C NMR (CDCl3): 63.96 (t, CH2Ar′), 66.42 (t, CH2Ar), 75.27 (d, HC≡C), 90.88 (s, ArC≡CAr′),
92.06 (s, ArC≡CAr′), 121.15 (s, C-1′), 122.91 (s, C-2), 127.56 (d, C-3′), 127.59 (d, C-5′),
128.74 (d, C-4), 128.83 (d, C-6), 129.09 (d, C-4′, 5), 132.46 (d, C-3), 132.47 (d, C-6′), 135.85
(s, C-1), 142.51 (s, C-2′), 152.57 (s, CO); sign al of HC≡C was n ot iden tified. EI MS (m/z,
rel.%): 290 (M+• , 15), 259 (6), 237 (11), 220 (100), 202 (19), 191 (84), 178 (29), 165 (34), 119
(15), 115 (34), 105 (13), 94 (29), 77 (26), 69 (15), 63 (14), 53 (56), 43 (24). FAB MS (m/z,
th ioglycerol–glycerol m atrix): 291 ((M + H)+), 273, 253, 245, 221, 219, 203, 191, 178, 165,
149, 135, 115, 105. HR EI MS: calculated for C19H14O3 290.0943, foun d 290.0893.
2-({2-[(Propioloyloxy)methyl]phenyl}ethynyl)benzyl propiolate (7). IR (CCl4): 3 306 w, 3 254 w,
3 070 vw, 3 030 vw, 2 929 m , 2 855 w, 2 123 w, 2 115 w (sh ), 1 722 vs, 1 613 w, 1 491 w,
1 371 w, 1 337 vw, 1 216 vs, 1 150 w, 1 115 w, 999 w, 965 w, 713 w, 690 w, 655 w. 1H NMR
(500 MHz, CDCl3): 2.89 (s, 2 H, 2 × HC≡C); 5.49 (s, 4 H, 2 × CH2); 7.37–7.39 (m , 4 H,
4,4′,5,5′-H); 7.52–7.54 (m , 2 H, 3′,6-H); 7.58–7.60 (m , 2 H, 3,6′-H). 13C NMR (CDCl3): 66.22
(t, 2 × CH2), 75.16 (d, 2 × HC≡C), 91.40 (s, ArC≡CAr′), 94.78 (s, 2 × HC≡C), 122.62 (s, C-1′,2),
128.70 (d, C-4,5′), 128.89 (d, C-3′,6), 128.95 (d, C-4′,5), 132.61 (d, C-3,6′), 137.17 (s, C-1,2′),
152.49 (s, 2 × CO). EI MS (m/z, rel.%): 342 (M+• , 8), 243 (21), 219 (37), 215 (55), 204 (34),
202 (38), 191 (38), 189 (50), 178 (37), 165 (42), 152 (15), 139 (11), 115 (31), 101 (8), 91
(18), 77 (15), 63 (11), 53 (100), 39 (10). FAB MS (m/z, th ioglycerol–glycerol m atrix): 329,
253, 225, 205, 179, 147, 105. HR EI MS: calculated for C22H14O4 342.0891, foun d 342.1034.
Bis(2-{[(prop-2-yn -1-yl)oxy]m eth yl}ph en yl)acetylen e (8)
Method A. Diol 2 (ref.11) (258 m g, 1.08 m m ol) in dry THF (2 m l) was added dropwise to
sodium h ydride (80% suspen sion in m in eral oil, 89 m g, 2.97 m m ol, 2.7 equivalen ts) in dry
THF (6 m l) at 0 °C un der argon . After stirrin g at 0 °C for 30 m in , prop-2-yn -1-yl brom ide
(350 µl, 4.61 m m ol, 4.3 equivalen ts) was added an d th e m ixture was stirred at 0 °C to room
tem perature overn igh t. Th e solven t was rem oved in vacuo an d th e crude product was puri-
fied by flash ch rom atograph y on silica gel (petroleum eth er–aceton e 90 : 10) to obtain triyn e
8 (311 m g, 91%) as a wh ite solid.
Method B. Prop-2-yn -1-ol (430 µl, 7.39 m m ol, 2.4 equivalen ts) was added dropwise to so-
dium h ydride (80% suspen sion in m in eral oil, 230 m g, 7.67 m m ol, 2.4 equivalen ts) in dry
DMF (5 m l) un der argon an d th e m ixture was stirred at room tem perature for 15 m in .
Dibrom ide 3 (ref.12) (1.14 g, 3.14 m m ol) in dry DMF (10 m l) was added. After stirrin g at
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

590
Stará, Kollárovič, Teplý, Starý, Šaman, Fiedler:
room tem perature for 15 m in , th e reaction m ixture was partition ed between eth er an d wa-
ter. Th e eth ereal layer was separated an d th e aqueous ph ase was extracted with eth er (2×).
Th e eth ereal portion s were com bin ed, wash ed with water (2×), dried over Na2SO4 an d evap-
orated in vacuo to dryn ess. Flash ch rom atograph y on silica gel (petroleum eth er–eth er
90 : 10) afforded triyn e 8 (776 m g, 79%) as a wh ite solid, m .p. 51–53 °C (petroleum
eth er–eth er). IR (CHCl3): 3 303 m , 2 862 w, 2 120 vw, 1 606 w, 1 483 m , 1 355 m , 1 079 s,
948 w, 672 vs, 636 m . 1H NMR (500 MHz, CDCl3): 2.46 (t, 2 H, J = 2.4, 2 × HC≡C); 4.28 (d,
4 H, J = 2.4, 2 × HC≡CCH2); 4.88 (s, 4 H, CH2Ar, CH2Ar′); 7.30 (dt, 2 H, J = 7.5, 7.5, 1.4,
4′,5-H); 7.37 (dt, 2 H, J = 7.5, 7.5, 1.5, 4,5′-H); 7.52 (brd, 2 H, J = 7.7, 3,6′-H); 7.56 (dd, 2 H,
J = 7.5, 1.3, 3′,6-H). 13C NMR (CDCl3): 57.99 (t, 2 × HC≡CCH2), 70.15 (t, CH2Ar, CH2Ar′),
74.97 (d, 2 × HC≡C), 79.47 (s, 2 × HC≡C), 91.72 (s, ArC≡CAr′), 122.29 (s, C-1′,2), 127.86 (d,
C-4,5′), 128.20 (d, C-4′,5), 128.94 (d, C-3′,6), 132.50 (d, C-3,6′), 139.38 (s, C-1,2′). EI MS
(m/z, rel.%): 314 (M+• , 8), 257 (11), 245 (15), 229 (29), 219 (100), 215 (29), 203 (32), 189
(37), 178 (32), 165 (29), 115 (14), 91 (10), 71 (11), 57 (16), 43 (14). FAB MS (m/z,
dith ioth reitol–dith ioeryth ritol m atrix): 315 ((M + H)+), 276, 258, 244, 229, 215, 202, 191,
178, 165, 149, 115, 86, 71. HR FAB MS: calculated for C22H19O2 (M + H) 315.1385, foun d
315.1579.
Bis(2-{[(but-2-yn -1-yl)oxy]m eth yl}ph en yl)acetylen e (9)
Method A. Diol 2 (ref.11) (80 m g, 0.336 m m ol) in dry THF (2 m l) was added to sodium
h ydride (80% suspen sion in m in eral oil, 23 m g, 0.800 m m ol, 2.4 equivalen ts) in dry THF
(4 m l) at 0 °C un der argon . After stirrin g at 0 °C for 1 h , 1-brom obut-2-yn e (120 µl, 1.37
m m ol, 4.1 equivalen ts) was added an d th e m ixture was stirred at 0 °C to room tem perature
overn igh t. Th e solven t was rem oved in vacuo an d th e crude product was subsequen tly puri-
fied by flash ch rom atograph y on silica gel (petroleum eth er–eth er 90 : 10) an d preparative
HPLC on silica gel (petroleum eth er–aceton e 95 : 5) to obtain triyn e 9 (28 m g, 24%) as an
oil.
Method B. But-2-yn -1-ol (1.34 m l, 17.91 m m ol, 2.2 equivalen ts) was added dropwise over a
30 m in period to sodium h ydride (80% suspen sion in m in eral oil, 534 m g, 17.80 m m ol, 2.2
equivalen ts) in dry DMF (12 m l) un der stirrin g wh ile tem perature was kept below 15 °C. Th e
yellowish suspen sion was stirred at room tem perature for 1.5 h . Dibrom ide 3 (ref.12) (3.0 g,
8.24 m m ol) in dry DMF (10 m l) was added dropwise over a 10 m in period an d th e resultin g
green solution was left at room tem perature overn igh t. Th e reaction m ixture was partition ed
between eth er an d water. Th e eth ereal layer was separated an d th e aqueous ph ase was ex-
tracted with eth er (2×). Th e eth ereal portion s were com bin ed, wash ed with water (2×), dried
over Na2SO4 an d evaporated in vacuo. Flash ch rom atograph y on silica gel (petroleum
eth er–eth er 90 : 10) afforded rearran ged dibrom ide 14 (191 m g, 5%) an d m ore polar triyn e 9
(1.97 g, 69%) as oils.
Method C. Butyllith ium (1.6 M solution in h exan es, 420 µl, 0.672 m m ol, 2.1 equivalen ts)
was added dropwise to term in al alkyn e 8 (100 m g, 0.318 m m ol) in dry THF (2 m l) at –78 °C
un der argon . After stirrin g at –78 °C for 10 m in , m eth yl iodide (60 µl, 0.964 m m ol, 3.0
equivalen ts) was added an d th e m ixture was stirred at –78 °C to room tem perature over-
n igh t. Th e solven ts were rem oved in vacuo. Flash ch rom atograph y on silica gel (petroleum
eth er–eth er 98 : 2 to 95 : 5) afforded dim eth ylated triyn e 9 (67 m g, 62%) as an oil. IR
(CHCl3): 3 070 w, 2 944 w, 2 922 m , 2 893 w, 2 856 m , 2 243 w, 2 225 w, 1 601 w, 1 572 w,
1 492 m , 1 452 m , 1 386 m , 1 356 m , 1 107 m (sh ), 1 101 m , 1 074 vs, 1 021 m , 951 m .
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

Synthesis of Aromatic Triynes
591
1H NMR (500 MHz, CDCl3): 1.83 (t,
6
H, J = 2.3, 2 × CH3); 4.24 (q,
4
H, J = 2.3,
2 × CH3C≡CCH2); 4.85 (brs, 4 H, CH2Ar, CH2Ar′); 7.28 (dt, 2 H, J = 7.6, 7.6, 1.5, 4,5′-H); 7.36
(dt, 2 H, J = 7.6, 7.6, 1.5, 4′,5-H); 7.52 (brdd, 2 H, J = 7.8, 1.4, 3′,6-H); 7.55 (dd, 2 H, J = 7.6,
1.5, 3,6′-H). 13C NMR (CDCl3): 3.56 (q, 2 × CH3), 58.35 (t, 2 × CH3C≡CCH2), 69.72 (t,
CH2Ar, CH2Ar′), 75.14 (s, 2 × CH3C≡C), 82.78 (s, 2 × CH3C≡C), 91.47 (s, ArC≡CAr′), 121.97
(s, C-1′,2), 127.43 (d, C-4,5′), 127.87 (d, C-4′,5), 128.63 (d, C-3′,6), 132.13 (d, C-3,6′), 139.54
(s, C-1,2′). EI MS (m/z, rel.%): 342 (M+• , 28), 309 (8), 289 (22), 271 (11), 259 (17), 235 (48),
219 (79), 203 (48), 178 (57), 165 (35), 149 (30), 133 (46), 97 (46), 91 (22), 83 (48), 69 (100),
57 (90), 43 (57), 29 (11). FAB MS (m/z, dith ioth reitol–dith ioeryth ritol m atrix): 343
((M + H)+), 289, 243, 228, 219, 191, 165, 115. HR EI MS: calculated for C24H22O2 342.1619,
foun d 342.1567.
Bis[({[3-(trim eth ylsilyl)prop-2-yn -1-yl]oxy}m eth yl)ph en yl]acetylen e (10)
Butyllith ium (1.6 M solution in h exan es, 420 µl, 0.672 m m ol, 2.1 equivalen ts) was added
dropwise to term in al alkyn e 8 (100 m g, 0.318 m m ol) in dry THF (2 m l) at –78 °C un der ar-
gon . After stirrin g at –78 °C for 10 m in , trim eth ylsilyl ch loride (100 µl, 0.788 m m ol, 2.5
equivalen ts) was added an d th e m ixture was stirred at –78 °C to room tem perature over-
n igh t. Th e solven ts were rem oved in vacuo. Flash ch rom atograph y on silica gel (petroleum
eth er–eth er 90 : 10) afforded disilylated triyn e 10 (103 m g, 71%) as an oil. IR (CHCl3):
3 068 vw, 2 960 m , 2 926 m , 2 901 w, 2 854 w, 2 173 w, 1 601 w, 1492 w, 1 453 w, 1 408 w,
1 351 w, 1 252 s, 1 113 w, 1 102 w, 1 079 s, 1 028 w, 949 vw, 847 vs, 654 w. 1H NMR (500
MHz, CDCl3): 0.16 (s, 18 H, 6 × CH3); 4.28 (s, 4 H, 2 × (CH3)3SiC≡CCH2); 4.86 (brs, 4 H,
CH2Ar, CH2Ar′); 7.29 (dt, 2 H, J = 7.4, 7.4, 1.5, 4,5′-H); 7.36 (dt, 2 H, J = 7.6, 7.6, 1.4, 4′,5-H);
7.52 (ddd, 2 H, J = 7.6, 1.4, 0.7, 3′,6-H); 7.55 (dd, 2 H, J = 7.7, 1.4, 3,6′-H). 13C NMR (CDCl3):
–0.24 (q, 6 × CH3), 58.61 (t, 2 × (CH3)3SiC≡CCH2), 69.95 (t, CH2Ar, CH2Ar′), 91.49 (s,
ArC≡CAr′), 96.69 (s, 2 × (CH3)3SiC≡CCH2), 101.53 (s, 2 × (CH3)3SiC≡CCH2), 121.99 (s,
C-1′,2), 127.51 (d, C-4,5′), 127.98 (d, C-4′,5), 128.63 (d, C-3′,6), 139.36 (s, C-1,2′). EI MS
(m/z, rel.%): 458 (M+• , 2), 419 (13), 347 (27), 317 (11), 219 (41), 204 (27), 191 (11), 111 (13),
83 (25), 73 (100), 43 (9). HR EI MS: calculated for C25H31O2Si2 (M – C3H3) 419.1863, foun d
419.1830.
(Z)-{2-[((1H,3H)-2-Ben zofuran -1-yliden e)m eth yl]ph en yl}m eth an ol (11)
Dry THF (5 m l) was added to diol 2 (ref.11) (30 m g, 0.126 m m ol) an d sodium h ydride (80%
suspen sion in m in eral oil, 10 m g, 0.333 m m ol, 2.6 equivalen ts) un der argon an d th e yellow-
ish suspen sion was stirred at 50 °C for 1.5 h . Th e excess of sodium h ydride was decom posed
with water an d th e m ixture was evaporated in vacuo to dryn ess. Th e residue was dissolved in
aceton e an d quickly passed th rough a sh ort pad of silica gel to get en ol eth er 11 (29 m g,
97%) as a wh ite solid, m .p. 103–105 °C (petroleum eth er–aceton e). IR (CHCl3): 3 606 w,
3 066 w, 2 942 w, 2 932 w, 2 877 m , 1 654 m , 1 612 w, 1 599 m , 1 488 m , 1 468 m , 1 460 m ,
1 452 m , 1 376 m , 1 332 w, 1 297 m , 1 236 m , 1 183 m , 1 097 m , 1 062 m , 1 039 vs, 1 005 m
(sh ), 996 s, 946 w, 604 w, 584 w, 528 w, 462 w. 1H NMR (500 MHz, aceton e-d6): 4.24 (t, 1 H,
J = 3.6, OH); 4.86 (d, 2 H, J = 3.6, HOCH2); 5.62 (s, 2 H, 3′-H); 6.40 (s, 1 H, -CH=); 7.19 (dt,
1 H, J = 7.6, 7.6, 1.4, 5-H); 7.32 (dt, 1 H, J = 7.8, 7.8, 1.7, 4-H); 7.47–7.58 (m , 4 H,
4′,5′,6′,7′-H); 7.82 (brd, 1 H, J = 8.3, 3-H); 8.27 (dd, 1 H, J = 7.8, 1.4, 6-H). 13C NMR (ace-
ton e-d6): 63.33 (t, HOCH2), 75.52 (t, C-3′), 92.52 (d, -CH=), 120.96 (d, C-3), 122.44 (d, C-6′),
125.92 (d, C-5), 127.64 (d, C-4), 128.31 (d, C-5′), 128.96 (d, C-4′), 129.12 (d, C-6), 129.84 (d,
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Stará, Kollárovič, Teplý, Starý, Šaman, Fiedler:
C-7′), 135.01 (s, C-2), 135.69 (s, C-7a′), 139.05 (s, C-3a′), 140.54 (s, C-1), 157.45 (s, C-1′). EI MS
(m/z, rel.%): 238 (M+• , 30), 181 (10), 161 (10), 135 (24), 119 (27), 104 (100), 91 (16), 77 (15),
69 (35), 57 (27), 43 (20). HR EI MS: calculated for C16H14O2 238.0993, foun d 238.1003.
{2-[((1H,3H)-2-Ben zofuran -1-yl)m eth yl]ph en yl}m eth an ol (12) an d
1-(2-Meth ylben zyl)-(1H,3H)-2-ben zofuran (13)
En ol eth er 11 (30 m g, 0.126 m m ol) in eth an ol (8 m l) was h ydrogen ated (1 atm ) over palla-
dium on ch arcoal (10% Pd/C, 5 m g) at room tem perature for 22 h . Th e catalyst was filtered
off an d th e filtrate was evaporated to dryn ess. Flash ch rom atograph y on silica gel (petroleum
eth er–eth er–aceton e–m eth an ol 80 : 10 : 10 : 0 to 50 : 30 : 17 : 3) afforded th e deoxygen ated
product 13 (9 m g, 33%) an d th e m ore polar alcoh ol 12 (9 m g, 31%) as oils. Com poun d 12:
1H NMR (200 MHz, CDCl3): 3.12 (dd, 1 H, J = 14.0, 7.9, CH2); 3.33 (dd, 1 H, J = 14.0, 3.7,
CH2); 3.85 (brs, 1 H, OH); 4.55 (dd, 1 H, J = 11.6, 3.2, 3′-H); 4.70 (d, 1 H, J = 11.6, 3′-H); 4.98
(s, 2 H, CH2OH); 5.48 (ddd, 1 H, J = 7.9, 3.7, 3.2, 1′-H); 7.12–7.40 (m , 8 H, 3,4,4′,5,5′,6,6′,7′-H).
Com poun d 13: IR (CHCl3): 3 077 m , 1 604 w, 1 493 m , 1 480 m , 1 462 s, 1 380 w, 1 364 m,
1 289 w, 1 254 m, 1 156 w, 1 132 w, 1 110 m, 1 036 vs, 1 018 s (sh), 942 m, 864 w, 562 w, 557 w,
459 m. 1H NMR (500 MHz, CDCl3): 2.32 (s, 3 H, CH3); 3.06 (dd, 1 H, J = 14.2, 7.6, CH2); 3.10
(dd, 1 H, J = 14.2, 5.6, CH2); 5.04 (brd, 1 H, J = 12.2, 3′-H); 5.12 (dd, 1 H, J = 12.2, 2.7, 3′-H);
5.49 (brddd, 1 H, J = 7.6, 5.6, 2.7, 1′-H); 7.14–7.29 (m , 8 H, 3,4,4′,5,5′,6,6′,7′-H). 13C NMR
(CDCl3): 19.76 (q, CH3), 39.94 (t, CH2), 72.41 (t, C-3′), 83.87 (d, C-1′), 120.98 (d, C-3),
121.59 (d, C-6′), 125.84 (d, C-5), 126.53 (d, C-4′), 127.07 (d, C-5′), 127.54 (d, C-4), 130.10
(d, C-6), 130.25 (d, C-7′), 136.16 (s, C-3a′), 136.73 (s, C-1), 139.42 (s, C-7a′), 141.75 (s, C-2).
EI MS (m/z, rel.%): 223 ((M – 1)+, 13), 178 (7), 151 (10), 133 (63), 105 (100), 91 (17), 77 (35),
65 (9), 51 (19), 39 (10). FAB MS (m/z, th ioglycerol–glycerol m atrix): 223 ((M – H)+), 221, 205,
193, 178, 165, 131, 115, 105, 91, 77, 65. HR EI MS: calculated for C16H15O (M – H)
223.1123, foun d 223.1124.
But-2-yn -1-yl 2-{[2-(Dibrom om eth yl)ph en yl]eth yn yl}ben zyl Eth er (14)
For preparation , see 9 (Meth od B). IR (CHCl3): 3 097 w, 3 071 m , 2 947 m , 2 922 s, 2 856 s,
2 294 w, 2 243 w, 2 215 m , 1 601 m , 1 567 m , 1 491 vs, 1 476 m , 1 450 s, 1 386 m , 1 356 s,
1 151 s, 1 138 s, 1 108 s, 1 074 vs, 1 021 m , 951 m , 867 m , 830 w, 633 s, 595 m , 570 vs (sh ).
1H NMR (500 MHz, CDCl3): 1.83 (t, 3 H, J = 2.3, CH3); 4.26 (q, 2 H, J = 2.3, CH3C≡CCH2);
4.87 (s, 2 H, CH2Ar); 7.31 (dt, 1 H, J = 7.5, 7.5, 1.2, 5′-H); 7.32 (dt, 1 H, J = 7.6, 7.6, 1.4,
5-H); 7.35 (s, 1 H, CHAr′); 7.39 (dt, 1 H, J = 7.7, 7.7, 1.5, 4-H); 7.44 (dt, 1 H, J = 7.8, 7.8, 1.3,
4′-H); 7.48 (dd, 1 H, J = 7.7, 1.3, 6′-H); 7.53 (brd, 1 H, J = 7.6, 3-H); 7.59 (dd, 1 H, J = 7.6,
1.4, 6-H); 7.98 (brdd, 1 H, J = 7.9, 1.2, 3′-H). 13C NMR (CDCl3): 3.38 (q, CH3), 38.89 (d,
CHAr′), 58.38 (t, CH3C≡CCH2), 69.80 (t, CH2Ar), 75.06 (s, CH3C≡CCH2), 82.89 (s,
CH3C≡CCH2), 89.45 (s, ArC≡CAr′), 94.16 (s, ArC≡CAr′), 119.15 (s, C-1′), 121.42 (s, C-2),
127.65 (d, C-6), 128.28 (d, C-4), 129.14 (d, C-5), 129.14 (d, C-3′), 129.44 (d, C-5′), 129.47 (d,
C-4′), 132.34 (d, C-3), 139.70 (s, C-1), 142.55 (s, C-2′). EI MS (m/z, rel.%): 434 (M+• with
81Br, 0.7), 432 (M+• with 81Br/79Br, 1.4), 430 (M+• with 79Br, 0.7), 323 (6), 299 (10), 272 (34),
257 (11), 242 (39), 219 (100), 204 (91), 189 (75), 165 (19), 101 (30), 69 (15), 63 (26).
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Synthesis of Aromatic Triynes
593
Bis(2-{[(trim eth ylsilyl)oxy]m eth yl}ph en yl)acetylen e (15)
Diol 2 (ref.11) (80 m g, 0.336 m m ol) in dry THF (4 m l) was added to sodium h ydride (80%
suspen sion in m in eral oil, 23 m g, 0.800 m m ol, 2.4 equivalen ts) in dry THF (2 m l) un der ar-
gon at 0 °C an d th e m ixture was stirred for 1 h . (3-Brom oprop-1-yn -1-yl)trim eth ylsilan e
(120 µl, 0.848 m m ol, 2.5 equivalen ts) was added an d th e suspen sion was stirred at 0 °C to
room tem perature overn igh t. Th e reaction m ixture was evaporated in vacuo to dryn ess an d
th e crude product was purified by flash ch rom atograph y on silica gel (petroleum eth er) to
provide disilylated diol 15 (48 m g, 37%) as an oil. 1H NMR (200 MHz, CDCl3): 0.19 (s, 18 H,
6 × CH3); 4.96 (s, 4 H, 2 × CH2); 7.25 (ddd, 2 H, J = 7.6, 7.3, 1.5, 4′,5-H); 7.38 (dt, 2 H, J =
7.6, 7.6, 1.2, 4,5′-H); 7.50 (dd, 2 H, J = 7.3, 1.2, 3′,6-H); 7.58 (brdd, 2 H, J = 7.6, 1.5, 3,6′-H).
[2-(Brom om eth yl)ph en yl][2-(brom om eth yl)-4-fluoroph en yl]acetylen e (17)
Triph en ylph osph in e (45 m g, 0.172 m m ol, 2.1 equivalen ts) in dry aceton itrile (1 m l) an d
tetrabrom om eth an e (62 m g, 0.187 m m ol, 2.3 equivalen ts) in dry aceton itrile (1 m l) were
subsequen tly added to a solution of diol 16 (ref.10b) (21 m g, 0.082 m m ol) in dry aceton itrile
(1 m l) un der argon . Th e reaction m ixture was strirred at room tem perature overn igh t. After
rem oval of th e solven t in vacuo, th e crude product was purified by flash ch rom atograph y
(h exan e–eth er 90 : 10) to provide dibrom ide 17 (25 m g, 80%) as a wh ite am orph ous solid.
IR (CHCl3): 3 068 w, 1 609 m , 1 598 w, 1 582 m , 1 570 w, 1 497 vs, 148 3 w (sh ), 1 451 w,
1 438 w, 1 419 w, 1 292 w, 1 277 s, 1 233 s, 1 159 m , 1 125 w, 1 039 vw, 951 w, 875 w, 825 s,
609 m , 583 w, 555 m , 416 w. 1H NMR (500 MHz, CDCl3): 4.76 (s, 2 H, CH2Ar); 4.79 (s, 2 H,
CH2Ar′); 7.04 (dt, 1 H, J = 8.4, 8.4, 2.7, 5-H); 7.19 (dd, 1 H, J = 9.0, 2.7, 3-H); 7.33 (ddd, 1 H,
J = 7.8, 7.5, 1.4, 5′-H); 7.35 (ddd, 1 H, J = 7.8, 7.5, 1.4, 4′-H); 7.46 (ddd, 1 H, J = 7.8, 1.4, 0.5,
3′-H); 7.59 (dd, 1 H, J = 8.6, 5.9, 6-H); 7.59 (ddd, 1 H, J = 7.8, 1.4, 0.5, 6′-H). 13C NMR
(CDCl3): 31.17 (t, CH2Ar′), 32.17 (t, CH2Ar), 91.07 (s, ArC≡CAr′), 91.72 (s, ArC≡CAr′), 116.00
(dd, JC-F = 22.0, C-3), 116.91 (dd, JC-F = 22.9, C-5), 119.05 (d, JC-F = 2.9, C-1), 122.87 (s,
C-1′), 128.62 (d, C-5′), 129.20 (d, C-4′), 129.83 (d, C-3′), 132.80 (d, C-6′), 134.65 (dd, JC-F
=
9.2, C-6), 139.12 (s, C-2′), 141.57 (d, JC-F = 7.3, C-2), 162.44 (d, JC-F = 250.9, C-4). 19F NMR
(CDCl3): –109.77 (dt, JF-H = 8.5, 8.5, 5.9). EI MS (m/z, rel.%): 384 (M+• with 81Br, 13), 382
(M+• with 81Br/79Br, 26), 380 (M+• with 79Br, 14), 303 (36), 301 (35), 222 (100), 221 (99), 220
(77), 202 (5), 200 (4), 110 (24), 98 (14), 85 (6), 63 (5), 39 (5). HR EI MS: calculated for
C
16H11F79Br2 379.9212, foun d 379.9189.
[4-Fluoro-2-({[(prop-2-yn -1-yl)oxy]m eth yl}ph en yl)](2-{[(prop-2-yn -1-yl)oxy]-
m eth yl}ph en yl)acetylen e (18)
Prop-2-yn -1-ol (3.5 µl, 0.060 m m ol, 2.4 equivalen ts) in dry DMF (0.5 m l) was added to so-
dium h ydride (80% suspen sion in m in eral oil, 1.6 m g, 0.053 m m ol, 2.2 equivalen ts) in dry
DMF (0.5 m l) un der argon an d th e m ixture was stirred at room tem perature for 5 m in .
Dibrom ide 17 (9.4 m g, 0.025 m m ol) in dry DMF (0.5 m l) was added. After stirrin g at room
tem perature for 10 m in , th e reaction m ixture was partition ed between eth er an d water. Th e
eth ereal layer was separated an d th e aqueous ph ase was extracted with eth er (2×). Th e eth e-
real portion s were com bin ed, wash ed with water (1×), dried over Na2SO4 an d evaporated in
vacuo to afford triyn e 18 (6.4 m g, 78%). 1H NMR (200 MHz, CDCl3): 2.46 (t, 1 H, J = 2.4,
HC≡C); 2.49 (t, 1 H, J = 2.4, HC≡C); 4.28 (d, 2 H, J = 2.4, HC≡CCH2); 4.31 (d, 2 H, J = 2.4,
HC≡CCH2); 4.82 (s, 4 H, CH2Ar, CH2Ar′); 6.95–7.58 (m , 7 H, H-arom .).
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Stará, Kollárovič, Teplý, Starý, Šaman, Fiedler:
tert-Butyl N-Prop-2-yn -1-yl-N-tosylcarbam ate (19)
Dieth yl diazen edicarboxylate (4.84 m l, 30.74 m m ol, 2.5 equivalen ts) was added over a 30
m in period to prop-2-yn -1-ol (720 µl, 12.37 m m ol), tert-butyl N-tosylcarbam ate19 (5.0 g,
18.43 m m ol, 1.5 equivalen t), an d triph en ylph osph in e (9.67 g, 30.87 m m ol, 3.0 equivalen ts)
in dry THF (30 m l) un der argon at 10–15 °C. Th e m ixture was stirred at room tem perature
overn igh t an d th en th e solven t was rem oved in vacuo. Flash ch rom atograph y on silica gel
(petroleum eth er–eth er–aceton e 90 : 10 : 0 to 80 : 10 : 10) gave carbam ate 19 (2.92 g, 76%)
as a wh ite solid. 1H NMR (200 MHz, CDCl3) in accord with th e literature data20
.
tert-Butyl N-But-2-yn -1-yl-N-tosylcarbam ate (20)
Dieth yl diazen edicarboxylate (1.70 m l, 10.80 m m ol, 2.4 equivalen ts) was added over a 15
m in period to but-2-yn -1-ol (320 µl, 4.51 m m ol), tert-butyl N-tosylcarbam ate19 (1.74 g, 6.41
m m ol, 1.4 equivalen t), an d triph en ylph osph in e (3.37 g, 12.85 m m ol, 2.9 equivalen ts) in dry
THF (10 m l) un der argon at 10–15 °C. Th e m ixture was stirred at room tem perature over-
n igh t an d th en th e solven t was rem oved in vacuo. Flash ch rom atograph y on silica gel (petro-
leum eth er–eth er–aceton e 100 : 0 : 0 to 90 : 10 : 0 to 80 : 10 : 10) gave carbam ate 20 (1.14 g,
78%) as a wh ite solid. 1H NMR (200 MHz, CDCl3): 1.34 (s, 9 H, (CH3)3C); 1.83 (t, 3 H, J =
2.4, CH3C≡C); 2.44 (s, 3 H, CH3C6H4); 4.57 (q, 2 H, CH2); 7.30 (d, 2 H, J = 8.5, 3,5-H); 7.91
(d, 2 H, J = 8.5, 2,6-H).
4-Meth yl-N-(prop-2-yn -1-yl)ben zen esulfon am ide (21)
Trifluoroacetic acid (2.2 m l, 28.55 m m ol, 3.0 equivalen ts) was added to tert-butyl
N-tosyl-N-(prop-2-yn -1-yl)carbam ate 19 (ref.20) (2.92 g, 9.44 m m ol) in dry dich lorom eth an e
(5 m l) un der n itrogen . After stirrin g at room tem perature for 45 m in , th e m ixture was parti-
tion ed between brin e an d dich lorom eth an e. Th e organ ic layer was separated an d th e aque-
ous ph ase was extracted with dich lorom eth an e (2×). Th e organ ic portion s were com bin ed,
wash ed with aqueous KHCO3 (2×), dried over Na2SO4 an d evaporated in vacuo to afford
sulfon am ide 21 (1.72 g, 87%) as a wh ite solid. 1H NMR (200 MHz, CDCl3) in accord with
th e literature data17
.
N-But-2-yn -1-yl-4-m eth ylben zen esulfon am ide (22)
Trifluoroacetic acid (380 µl, 4.93 m m ol, 3.3 equivalen ts) was added to tert-butyl
N-but-2-yn -1-yl-N-tosylcarbam ate 20 (480 m g, 1.48 m m ol) in dry dich lorom eth an e (3 m l)
un der n itrogen . After stirrin g at room tem perature for 4 h , th e m ixture was partition ed be-
tween brin e an d dich lorom eth an e. Th e organ ic layer was separated an d th e aqueous ph ase
was extracted with dich lorom eth an e (2×). Th e organ ic portion s were com bin ed, wash ed
with aqueous KHCO3 (2×), dried over Na2SO4 an d evaporated in vacuo to afford sulfon am ide
22 (292 m g, 88%) as a wh ite solid. 1H NMR (200 MHz, CDCl3): 1.60 (t, 3 H, J = 2.4,
CH3C≡C); 2.43 (s, 3 H, CH3C6H4); 3.77 (dq, 2 H, J = 5.5, 2.4, 2.4, 2.4, CH2); 4.51 (t, 1 H, J =
5.5, NH); 7.32 (d, 2 H, J = 8.4, 3,5-H); 7.77 (d, 2 H, J = 8.4, 2,6-H).
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Synthesis of Aromatic Triynes
595
N,N′-Di(prop-2-yn -1-yl)-N,N′-{eth yn ediylbis[(2,1-ph en ylen e)m eth ylen e]}-
diben zen esulfon am ide (23)
4-Meth yl-N-(prop-2-yn -1-yl)ben zen esulfon am ide 21 (115 m g, 0.550 m m ol, 2.0 equivalen ts)
in dry DMF (5 m l) was added at 0 °C to sodium h ydride (80% suspen sion in m in eral oil, 17 m g,
0.567 m m ol, 2.1 equivalen ts) in dry DMF (1 m l) un der argon . After stirrin g at 0 °C for 1 h ,
dibrom ide 3 (ref.12) (100 m g, 0.275 m m ol) in dry DMF (2 m l) was added an d th e m ixture
was stirred at room tem perature overn igh t. Th e resultin g brown solution was partition ed be-
tween eth er an d water. Th e eth ereal layer was separated an d th e aqueous ph ase was ex-
tracted with eth er (2×). Th e eth ereal portion s were com bin ed, wash ed with water (1×), dried
over Na2SO4 an d evaporated in vacuo. Th e crude product was purified by flash ch rom atogra-
ph y on silica gel (petroleum eth er–eth er–aceton e 70 : 20 : 10 to 70 : 0 : 30 to 50 : 0 : 50) an d
th en by preparative HPLC on silica gel (h exan e–aceton e 80 : 20) to get triyn e 23 (45 m g,
27%) as a wh ite solid, m .p. 169.5–170.5 °C (h exan e–aceton e). IR (CHCl3): 3 307 m , 3 066 w,
3 031 m , 3 012 w, 2 926 w, 2 868 w, 2 122 vw, 1 599 m , 1 571 vw, 1 495 m , 1 452 m ,
1 430 m , 1 401 w, 1 349 s, 1 335 s (sh ), 1 306 m , 1 290 w, 1 185 w, 1 162 vs, 1 119 m ,
1 092 s, 1 062 m , 1 041 w, 1 019 w, 959 w, 928 w, 902 s, 864 w, 814 m , 660 s, 636 m , 590 m ,
567 m , 543 m , 504 w. 1H NMR (500 MHz, CDCl3): 1.88 (t, 2 H, J = 2.4, 2 × HC≡C); 2.44 (brs,
6 H, 2 × CH3); 3.99 (d, 4 H, J = 2.4, 2 × HC≡CCH2); 4.65 (s, 4 H, CH2Ar, CH2Ar′); 7.26 (dt,
2 H, J = 7.6, 7.6, 1.5, 4,5′-H); 7.30–7.32 (m , 4 H, 2 × 3,5-H (Ts)); 7.34 (dt, 2 H, J = 7.6, 7.6,
1.5, 4′,5-H); 7.51 (dd, 2 H, J = 7.6, 1.5, 3,6′-H); 7.54 (brd, 2 H, J = 7.8, 3′,6-H); 7.80–7.82 (m ,
4 H, 2 × 2,6-H (Ts)). 13C NMR (CDCl3): 21.55 (q, 2 × CH3), 36.34 (t, 2 × HC≡CCH2), 48.32 (t,
CH2Ar, CH2Ar′), 73.99 (d, 2 × HC≡C), 91.71 (s, ArC≡CAr′), 122.95 (s, C-1′,2), 127.75 (d,
C-4,5′), 127.96 (d, 2 × C-2,6 (Ts)), 128.92 (d, C-4′,5), 128.95 (d, C-3′,6), 129.52 (d, 2 × C-3,5
(Ts)), 132.63 (d, C-3,6′), 136.04 (s, 2 × C-4 (Ts)), 136.79 (s, C-1,2′), 143.66 (2 × C-1 (Ts)); sig-
n al of HC≡CCH2 overlapped with CDCl3 sign als. EI MS (m/z, rel.%): 465 ((M – C7H7SO2)+,
14), 309 (61), 271 (42), 256 (100), 217 (26), 155 (19), 91 (72), 57 (27). FAB MS (m/z,
th ioglycerol–glycerol m atrix): 621 ((M + H)+), 568, 520, 467, 429, 391, 307, 293, 279, 257,
232. HR FAB MS: calculated for C36H33N2O4S2 (M + H) 621.1882, foun d 621.1959.
N,N′-Di(but-2-yn -1-yl)-N,N′-{eth yn ediylbis[(2,1-ph en ylen e)m eth ylen e]}-
diben zen esulfon am ide (24)
Method A. N-(But-2-yn -1-yl)-4-m eth ylben zen esulfon am ide 22 (300 m g, 1.35 m m ol, 2.0
equivalen ts) in dry THF (15 m l) was added at 0 °C to sodium h ydride (80% suspen sion in
m in eral oil, 52 m g, 1.73 m m ol, 2.6 equivalen ts) in dry THF (5 m l) un der argon . After stir-
rin g at 0 °C for 30 m in , dibrom ide 3 (ref.12) (245 m g, 0.673 m m ol) in dry THF (10 m l) an d
dry DMF (5 m l) was added an d th e m ixture was stirred at 65 °C for 20 m in . Th e resultin g
green ish suspen sion was cooled to room tem perature an d th e fin e precipitate was filtered
off. Th e filtrate was con cen trated in vacuo an d th e residue was partition ed between eth er
an d water. Th e eth ereal layer was separated an d th e aqueous ph ase was extracted with eth er
(2×). Th e eth ereal portion s were com bin ed, wash ed with water (2×), dried over Na2SO4 an d
evaporated in vacuo. Th e crude product was purified by flash ch rom atograph y on silica gel
(petroleum eth er–eth er–aceton e 80 : 10 : 10 to 70 : 20 : 10) to get triyn e 24 (275 m g, 63%) as
a wh ite solid.
Method B. Dieth yl diazen edicarboxylate (170 µl, 1.08 m m ol, 2.6 equivalen ts) was added to
diol 2 (ref.11) (100 m g, 0.420 m m ol), N-(but-2-yn-1-yl)-4-m ethylbenzenesulfonam ide 22 (188 m g,
0.842 m m ol, 2.0 equivalen ts), triph en ylph osph in e (329 m g, 1.25 m m ol, 3.0 equivalen ts) in
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Stará, Kollárovič, Teplý, Starý, Šaman, Fiedler:
dry THF (4 m l) un der argon . Th e m ixture was stirred at room tem perature for 1 h an d th en
th e solven t was rem oved in vacuo. Flash ch rom atograph y on silica gel (petroleum
eth er–eth er–aceton e 80 : 10 : 10) gave triyn e 24 (196 m g, 72%) as a wh ite solid, m .p.
146–147.5 °C (CHCl3). IR (CHCl3): 3 068 w, 2 922 m , 2 855 m , 2 222 vw, 1 559 m , 1 495 m ,
1 452 m , 1 434 m , 1 399 w (sh ), 1 348 s, 1 336 s (sh ), 1 306 m , 1 293 w, 1 185 w, 1 161 vs,
1 147 m (sh ), 1 118 m , 1 091 m , 1 087 m (sh ), 1 040 w, 1 019 w, 909 m , 848 w, 814 m ,
702 w, 658 s, 635 vw, 588 w (sh ), 566 m , 547 m , 538 m . 1H NMR (500 MHz, CDCl3):
1.32 (t, 6 H, J = 2.4, 2 × CH3C≡C); 2.44 (s, 6 H, 2 × CH3C6H4); 3.92 (brq, 4 H, J = 2.4,
2 × CH3C≡CCH2); 4.61 (s, 4 H, CH2Ar, CH2Ar′); 7.24 (dt, 2 H, J = 7.5, 7.5, 1.4, 4,5′-H);
7.30–7.32 (m , 4 H, 2 × 3,5-H (Ts)); 7.34 (dt, 2 H, J = 7.6, 7.6, 1.5, 4′,5-H); 7.48 (dd, 2 H, J =
7.9, 1.5, 3,6′-H); 7.58 (brdd, 2 H, J = 7.8, 1.4, 3′,6-H); 7.81–7.83 (m , 4 H, 2 × 2,6-H (Ts)).
13C NMR (CDCl3): 3.04 (q, 2 × CH3C≡C), 21.50 (q, 2 × CH3C6H4), 36.93 (t, 2 × CH3C≡CCH2),
48.20 (t, CH2Ar, CH2Ar′), 71.76 (s, 2 × CH3C≡C), 81.92 (s, 2 × CH3C≡C), 91.54 (s, ArC≡CAr′),
122.88 (s, C-1′,2), 127.57 (d, C-4,5′), 128.07 (d, 2 × C-2,6 (Ts)), 128.92 (d, C-4′,5), 129.07 (d,
C-3′,6), 129.27 (d, 2 × C-3,5 (Ts)), 132.35 (d, C-3,6′), 136.19 (s, 2 × C-4 (Ts)), 137.32 (s,
C-1,2′). EI MS (m/z, rel.%): 648 (M+• , 1), 493 (20), 338 (31), 323 (18), 309 (13), 285 (32), 270
(100), 256 (43), 242 (16), 218 (37), 155 (10), 91 (53), 65 (11), 53 (16). FAB MS (m/z,
2-h ydroxyeth yldisulfide m atrix): 673 ((M + Na)+), 649 ((M + H)+), 493, 426, 339, 270, 256,
243, 228, 218, 203, 115, 91. HR FAB MS: calculated for C38H37N2O4S2 (M + H) 649.2195,
foun d 649.2204.
Trim eth yl[3-({2-[(2-{4-(trim eth ylsilyl)-1-[(trim eth ylsilyl)oxy]-3-butyn yl}ph en yl)
eth yn yl]ben zyl}oxy)-1-propyn yl]silan e (25)
Butyllith ium (1.6 M solution in h exan es, 2.0 m l, 3.20 m m ol, 2.4 equivalen ts) was added
dropwise to triyn e 8 (420 m g, 1.34 m m ol) in dry THF (5 m l) at –78 °C un der argon . After
stirrin g at –78 °C for 40 m in , trim eth ylsilyl ch loride (440 µl, 3.47 m m ol, 2.6 equivalen ts)
was added an d th e m ixture was stirred at –78 °C to room tem perature overn igh t. Th e precip-
itate was filtered off, wash ed with eth er an d filtrate was evaporated in vacuo to dryn ess.
Flash ch rom atograph y on silica gel (petroleum eth er–eth er 90 : 10) provided th e rearran ged
silylated triyn e 25 (156 m g, 22%), th e silylated triyn e 10 (295 m g, 48%), an d th e recovered
triyn e 8 (22%) as oils. Com poun d 25: IR (CHCl3): 2 961 m , 2 900 w, 2 175 m , 1 410 w,
1 252 s, 1 113 m , 1 079 s, 847 vs, 699 w, 648 w. 1H NMR (500 MHz, CDCl3): 0.12 (s, 9 H,
(CH3)3SiO); 0.13 (s, 9 H, (CH3)3SiC≡CCH2CH); 0.16 (s, 9 H, (CH3)3SiC≡CCH2O); 2.55 (dd,
1 H, J = 16.8, 8.7, C≡CCHHCH); 2.78 (dd, 1 H, J = 16.8, 3.6, C≡CCHHCH); 4.29 (s, 2 H,
C≡CCH2O); 4.88 (s, 2 H, CH2Ar); 5.40 (dd, 1 H, J = 8.6, 3.6, (CH3)3SiOCH); 7.24 (dt, 1 H, J =
7.5, 7.5, 1.4, 5′-H); 7.30 (dt, 1 H, J = 7.5, 7.5, 1.4, 4-H); 7.35 (brdt, 1 H, J = 7.6, 7.6, 1.3, 5-H);
7.37 (dt, 1 H, J = 7.4, 7.4, 1.4, 4′-H); 7.49 (ddd, 1 H, J = 7.7, 1.4, 0.5, 6-H); 7.54 (brdd, 1 H,
J = 7.8, 1.5, 0.7, 3-H); 7.59 (brdd, 1 H, J = 7.9, 1.4, 3′-H); 7.60 (brdd, 1 H, J = 7.8, 1.4, 6′-H).
13C NMR (CDCl3): –0.22 (q, (CH3)3SiC≡CCH2O), 0.02 (q, (CH3)3SiC≡CCH2CH), 0.08 (q,
(CH3)3SiO), 31.13 (t, C≡CCH2CH), 58.57 (t, C≡CCH2O), 69.95 (t, CH2Ar), 69.95 (d,
(CH3)3SiOCH), 85.90 (s, C≡CCH2CH), 91.50 (s, ArC≡CAr′), 91.62 (s, ArC≡CAr′), 92.30 (s,
C≡CCH2O), 101.53 (s, C≡CCH2O), 104.67 (s, C≡CCH2CH), 120.20 (s, C-2), 121.99 (s, C-1′),
125.80 (d, C-5′), 127.10 (d, C-3′), 127.54 (d, C-6), 128.00 (d, C-4), 128.63 (d, C-5), 128.71 (d,
C-4′), 131.85 (d, C-6′), 132.38 (d, C-3), 139.22 (s, C-1), 145.79 (s, C-2′). EI MS (m/z, rel.%):
530 (M+• , 0.6), 457 (1), 419 (61), 329 (12), 219 (10), 97 (12), 73 (100), 57 (17), 43 (16). FAB
MS (m/z, th ioglycerol–glycerol m atrix): 419 ((M – C6H11Si)+), 403, 329, 241, 215, 169, 155,
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Synthesis of Aromatic Triynes
597
147, 133, 111, 97. HR EI MS: calculated for C25H31O2Si2 (M – C6H11Si) 419.1863, foun d
419.1875.
4-(Trim eth ylsilyl)-1-(2-{[2-({[3-(trim eth ylsilyl)-2-propyn yl]oxy}m eth yl)ph en yl]
eth yn yl}ph en yl)-3-butyn -1-ol (26)
Butyllith ium (1.6 M solution in h exan es, 1.2 m l, 1.92 m m ol, 4.9 equivalen ts) was added
dropwise to triyn e 8 (122 m g, 0.388 m m ol) in dry THF (3 m l) at –78 °C un der argon . After
stirrin g at –78 °C for 1.5 h , trim eth ylsilyl ch loride (250 µl, 1.97 m m ol, 5.1 equivalen ts) was
added an d th e m ixture was stirred at –78 °C to room tem perature overn igh t. Th e precipitate
was filtered off, wash ed with eth er an d filtrate was evaporated in vacuo to dryn ess. Flash
ch rom atograph y on silica gel (petroleum eth er–eth er 90 : 10) provided th e rearran ged
silylated triyn e 26 (41 m g, 23%) as an oil. 1H NMR (200 MHz, CDCl3): 0.15 (s, 9 H,
(CH3)3SiC≡CCH2CH); 0.16 (s, 9 H, (CH3)3SiC≡CCH2O); 2.68 (dd, 1 H, J = 16.9, 7.8,
C≡CCHHCH); 2.83 (brs, 1 H, OH); 2.95 (dd, 1 H, J = 16.9, 4.4, C≡CCHHCH); 4.27 (s, 2 H,
C≡CCH2O); 4.84 (s, 2 H, CH2Ar′); 5.39 (dd, 1 H, J = 7.8, 4.4, C≡CCH2CH); 7.23–7.63 (m , 8 H,
H-arom .).
1-[2-({2-[(2-Propyn yloxy)m eth yl]ph en yl}eth yn yl)ph en yl]-3-butyn -1-ol (27)
Butyllith ium (1.6 M solution in h exan es, 810 µl, 1.30 m m ol, 5.0 equivalen ts) was added
dropwise to triyn e 8 (81 m g, 0.258 m m ol) in dry THF (2 m l) at –78 °C un der argon . After
stirrin g at –78 °C for 30 m in , m eth yl iodide (90 µl, 1.45 m m ol, 5.6 equivalen ts) was added
an d th e m ixture was stirred at –78 °C to room tem perature for 3 h . Th e solven ts were re-
m oved in vacuo. Flash ch rom atograph y on silica gel (petroleum eth er–eth er–aceton e–m eth a-
n ol 80 : 10 : 10 : 0 to 50 : 30 : 17 : 3) provided th e rearran ged triyn e 27 (25 m g, 31%) as an
oil. 1H NMR (200 MHz, CDCl3): 2.11 (t, 1 H, J = 2.6, HC≡CCH2CH); 2.48 (t, 1 H, J = 2.3, HC
≡CCH2O); 2.67 (ddd, 1 H, J = 16.9, 7.8, 2.6, HC≡CCHHCH); 2.82 (d, 1 H, J = 4.1, OH); 2.91
(ddd, 1 H, J = 16.9, 4.5, 2.6, HC≡CCHHCH); 4.28 (d, 2 H, J = 2.3, HC≡CCH2O); 4.87 (s, 2 H,
CH2Ar′); 5.43 (ddd, 1 H, J = 7.8, 4.5, 4.1, C≡CCH2CH); 7.25–7.64 (m , 8 H, H-arom .).
1-[2-({2-[(2-Butyn yloxy)m eth yl]ph en yl}eth yn yl)ph en yl]-2-m eth yl-2,3-butadien -1-ol (28)
Butyllith ium (1.6 M solution in h exan es, 300 µl, 0.480 m m ol, 2.6 equivalen ts) was added
dropwise to triyn e 9 (64 m g, 0.187 m m ol) in dry THF (2 m l) at –78 °C un der argon . After
stirrin g at –78 °C for 30 m in , m eth yl iodide (40 µl, 0.642 m m ol, 3.4 equivalen ts) was added
an d th e m ixture was stirred at –78 °C to room tem perature for 3 h . Th e solven ts were re-
m oved in vacuo an d products were separated by flash ch rom atograph y on silica gel (petro-
leum eth er–eth er–aceton e–m eth an ol 80 : 10 : 10 : 0 to 50 : 30 : 17 : 3) to provide m on oallen e
28 (9 m g, 14%) an d th e m ore polar diallen e 29 (18 m g, 28%; a 1 : 1 m ixture of th e (R*,R*)
an d (R*,S*) diastereoisom ers accordin g to 1H NMR) as oils. Com poun d 28: 1H NMR (200 MHz,
CDCl3): 1.68 (t, 3 H, J = 3.1, CH2=C=C(CH3)); 1.84 (t, 3 H, J = 2.3, CH3C≡C); 2.57 (d, 1 H, J =
5.2, OH); 4.23 (q, 2 H, J = 2.3, CH3C≡CCH2); 4.82–4.88 (m , 2 H, CH2=C=C); 4.84 (s, 2 H,
CH2Ar′); 5.68–5.70 (m , 1 H, CH(OH)); 7.25–7.59 (m , 8 H, H-arom .).
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1-(2-{[2-(1-Hydroxy-2-m eth yl-2,3-butadien yl)ph en yl]eth yn yl}ph en yl)-
2-m eth yl-2,3-butadien -1-ol (29)
Method A. For preparation , see 28.
Method B. tert-Butyllith ium (1.7 M solution in pen tan e, 300 µl, 0.510 m m ol, 2.5 equiva-
len ts) was added dropwise to triyn e 9 (69 m g, 0.201 m m ol) in dry THF (2 m l) at –78 °C
un der argon . After stirrin g at –78 °C for 2 h , distilled water (300 µl, 16.70 m m ol, 83 equiva-
len ts) was added an d th e m ixture was stirred at –78 °C to room tem perature overn igh t. Th e
solven ts were rem oved in vacuo an d th e crude product was purified by flash ch rom atograph y
on silica gel (petroleum eth er–eth er–aceton e 70 : 20 : 10) to give diallen e 29 (21 m g, 31%; a
1 : 1 m ixture of (R*,R*) an d (R*,S*) diastereoisom ers accordin g to 1H NMR) as an oil. IR
(CHCl3): 3 601 m , 3 559 m , 3 466 w, 3 070 w, 2 987 m , 1 959 s, 1 706 w, 1 442 m , 1 376 s,
1 043 s, 1 016 s, 909 vs, 957 m , 856 s, 620 m . 1H NMR (500 MHz, CDCl3): 1.65 (dt, 3 H, J =
3.2, 3.2, 0.6, 2 × CH3 of on e diastereoisom er); 1.66 (dt, 3 H, J = 3.2, 3.2, 0.6, 2 × CH3 of on e
d.); 2.51 (brs, 2 H, 2 × OH of both d.); 4.82–4.85 (m , 4 H, 2 × CH2 of both d.); 5.65 (t, 2 H,
J = 2.8, 2 × CH(OH) of on e d.); 5.67 (t, 2 H, J = 2.8, 2 × CH(OH) of on e d.); 7.28 (dt, 2 H, J =
7.5, 7.5, 1.3, 4,5′-H of both d.); 7.37 (dt, 2 H, J = 7.4, 7.4, 1.5, 4′,5-H of both d.); 7.51–7.54
(m , 4-H, 3,3′,6,6′-H of both d.). 13C NMR (CDCl3): 15.08 (q, 2 × CH3 of on e diastereoisom er),
15.17 (q, 2 × CH3 of on e d.), 72.39 (d, 2 × CH(OH) of on e d.), 72.41 (d, 2 × CH(OH) of on e d.),
78.02 (t, 2 × CH2=C=C of on e d.), 78.18 (t, 2 × CH2=C=C of on e d.), 92.08 (s, 2 × CH2=C=C
of on e d.), 92.13 (s, 2 × CH2=C=C of on e d.), 102.29 (s, ArC≡CAr′ of on e d.), 102.41 (s,
ArC≡CAr′ of on e d.), 121.82 (s, C-1′,2 of on e d.), 121.83 (s, C-1′,2 of on e d.), 126.59 (d,
C-4,5′ of on e d.), 126.61 (d, C-4,5′ of on e d.), 127.57 (d, C-4′,5 of both d.), 128.74 (d, C-3′,6
of on e d.), 128.76 (d, C-3′,6 of on e d.), 132.39 (d, C-3,6′ of both d.), 143.43 (s, C-1,2′ of on e d.),
143.45 (s, C-1,2′ of on e d.), 204.99 (s, 2 × CH2=C=C of on e d.), 205.12 (s, 2 × CH2=C=C of
on e d.). EI MS (m/z, rel.%): 324 ((M – H2O)+, 10), 309 (24), 295 (22), 281 (16), 266 (18), 228
(55), 215 (20), 202 (16), 171 (31), 129 (18), 115 (18), 83 (100), 69 (16), 57 (25), 43 (34). HR
EI MS: calculated for C24H20O (M – H2O) 324.1515, foun d 324.1446.
Bis[2-(but-3-yn -1-yl)ph en yl]acetylen e (30)
Butyllith ium (1.6 M solution in h exan es, 11.0 m l, 17.60 m m ol, 2.1 equivalen ts) was added
dropwise over a 10 m in period to a solution of trim eth yl(prop-1-yn -1-yl)silan e (2.60 m l,
17.56 m m ol, 2.1 equivalen ts) in THF (50 m l) at –78 °C un der argon . After stirrin g at –78 °C
for 2 h , dibrom ide 3 (ref.12) (3.03 g, 8.31 m m ol) in THF (30 m l) was added dropwise over a
10 m in period. Th e m ixture was stirred at –78 °C for 1 h an d th en warm ed to room tem per-
ature. Tetrabutylam m on ium fluoride (1.3 M solution in THF, 51 m l, 66.30 m m ol, 8.0 equiva-
len ts) was added an d th e m ixture was stirred at room tem perature for 16 h . Th e solution
was evaporated in vacuo to dryn ess an d th e residue was passed th rough a pad of silica gel
(petroleum eth er–eth er 95 : 5 to 0 : 100). Th e crude product was purified by flash ch rom a-
tograph y on silica gel (petroleum eth er–eth er 99 : 1) to get triyn e 30 (1.58 g, 67%) as an
am orph ous solid. IR (CHCl3): 3 309 vs, 3 097 w, 3 070 w, 2 958 m , 2 935 m , 2 864 w,
2 842 w, 2 211 vw, 2 118 w, 1 600 w, 1 569 vw, 1 492 s, 1 452 s, 1 432 m , 1 340 w, 1 160 w,
1 127 vw, 1 104 w, 640 vs, 597 w, 523 w, 495 m , 489 m . 1H NMR (500 MHz, CDCl3): 1.99 (t,
2 H, J = 2.6, 2 × HC≡C); 2.61 (dt, 4 H, J = 7.5, 7.5, 2.6, 2 × HC≡CCH2); 3.11 (t, 4 H, J = 7.5,
CH2Ar, CH2Ar′); 7.22–7.55 (m , 8 H, 3,3′,4,4′,5,5′,6,6′-H). 13C NMR (CDCl3): 19.60 (t,
2 × HC≡CCH2); 33.84 (t, CH2Ar, CH2Ar′); 69.01 (d, 2 × HC≡C); 83.70 (s, 2 × HC≡C); 91.69 (s,
ArC≡CAr′); 122.81 (s, C-1′,2), 126.51 (d, C-4,5′), 128.49 (d, C-4′,5), 129.10 (d, C-3′,6), 132.52
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Synthesis of Aromatic Triynes
599
(d, C-3,6′), 142.02 (s, C-1,2′). EI MS (m/z, rel.%): 282 (M+• , 99), 281 (100), 265 (93), 253 (54),
239 (67), 228 (58), 215 (39), 202 (54), 189 (16), 165 (23), 141 (25), 115 (34), 101 (17), 91
(15), 69 (26), 55 (12). HR EI MS: calculated for C22H18 282.1409, foun d 282.1552.
Bis[2-(pen t-3-yn -1-yl)ph en yl]acetylen e (31)
Butyllith ium (1.6 M solution in h exan es, 1.20 m l, 1.92 m m ol, 2.2 equivalen ts) was added
dropwise over a 3 m in period to triyn e 30 (249 m g, 0.882 m m ol) in dry THF (5 m l) at –78 °C
un der argon . After stirrin g at –78 °C for 10 m in , m eth yl iodide (120 µl, 1.93 m m ol, 2.2
equivalen ts) was added an d th e m ixture was stirred at –78 °C for 15 m in . Th e solven t was
evaporated in vacuo an d th e crude product was purified by flash ch rom atograph y on silica
gel (petroleum eth er–eth er 99 : 1) to afford dim eth ylated triyn e 31 (248 m g, 91%) as an oil.
IR (CCl4): 3 097 w, 3 069 m , 3 026 w, 2 956 m , 2 920 vs, 2 859 m , 2 845 w, 2 232 vvw,
2 211 vvw, 1 601 w, 1 570 vw, 1 491 vs, 1 479 m , 1 452 s, 1 434 m , 1 378 w, 1 160 w,
1 102 w. 1H NMR (500 MHz, CDCl3): 1.77 (t, 6 H, J = 2.5, 2 × CH3); 2.53 (tq, 4 H, J = 7.5,
7.5, 2.5, 2.5, 2.5, 2 × C≡CCH2); 3.06 (t, 4 H, J = 7.5, CH2Ar, CH2Ar′); 7.21 (ddd, 2 H, J = 7.6,
6.4, 2.5, 4,5′-H); 7.27 (ddd, 2 H, J = 7.7, 6.4, 1.3, 4′,5-H); 7.29 (ddd, 2 H, J = 7.7, 2.5, 0.6,
3′,6-H); 7.53 (ddd, 2 H, J = 7.6, 1.3, 0.6, 3,6′-H). 13C NMR (CDCl3): 3.49 (q, 2 × CH3), 19.98
(t, 2 × C≡CCH2), 34.44 (t, CH2Ar, CH2Ar′), 76.28 (s, 2 × C≡CCH2), 78.52 (s, 2 × C≡CCH2),
91.57 (s, ArC≡CAr′), 122.82 (s, C-1′,2), 126.24 (d, C-4,5′), 128.31 (d, C-4′,5), 129.03 (d,
C-3′,6), 132.39 (d, C-3,6′), 142.60 (s, C-1,2′). EI MS (m/z, rel.%): 310 (M+• , 8), 295 (56), 280
(100), 265 (48), 252 (20), 239 (40), 228 (29), 215 (35), 202 (54), 189 (10), 165 (22), 129 (26),
115 (34), 97 (15), 83 (18), 69 (37), 57 (39), 43 (41). HR EI MS: calculated for C24H22
310.1722, foun d 310.1699.
Bis{2-[4-(trim eth ylsilyl)but-3-yn -1-yl]ph en yl}acetylen e (32)
Butyllith ium (1.6 M solution in h exan es, 490 µl, 0.784 m m ol, 2.1 equivalen ts) was added
dropwise over a 3 m in period to triyn e 30 (104 m g, 0.368 m m ol) in dry THF (2 m l) at –78 °C
un der argon . After stirrin g at –78 °C for 10 m in , trim eth ylsilyl ch loride (100 µl, 0.788 m m ol,
2.1 equivalen ts) was added an d th e m ixture was stirred at –78 °C for 15 m in . Th e solven t
was evaporated in vacuo an d th e crude product was purified by flash ch rom atograph y on sil-
ica gel (petroleum eth er–eth er 100 : 0 to 99 : 1) to furn ish disilylated triyn e 32 (154 m g,
98%) as an oil. IR (CCl4): 3 096 vw, 3 070 w, 3 027 w, 2 961 m , 2 935 w, 2 901 w, 2 863 vw,
2 175 m , 1 600 vw, 1 492 w, 1 452 w, 1 427 w, 1 407 vw, 1 338 w, 1 250 s, 1 160 vw,
1 103 w, 843 vs, 698 w, 645 w, 638 w. 1H NMR (500 MHz, CDCl3): 0.13 (s, 18 H, 6 × CH3);
2.63 (t, 4 H, J = 7.5, 2 × C≡CCH2); 3.09 (t, 4 H, J = 7.5, CH2Ar, CH2Ar′); 7.21 (ddd, 2 H, J =
7.5, 7.0, 1.9, 4,5′-H); 7.27 (ddd, 2 H, J = 7.5, 7.0, 1.5, 4′,5-H); 7.30 (ddd, 2 H, J = 7.5, 1.9, 0.6,
3′,6-H); 7.53 (ddd, 2 H, J = 7.5, 1.5, 0.7, 3,6′-H). 13C NMR (CDCl3): 0.08 (q, 6 × CH3), 21.19
(t, 2 × C≡CCH2), 34.05 (t, CH2Ar, CH2Ar′), 85.41 (s, 2 × C≡CCH2), 91.67 (s, ArC≡CAr′),
106.50 (s, 2 × C≡CCH2), 122.78 (s, C-1′,2), 126.39 (d, C-4,5′), 128.29 (d, C-4′,5), 129.33 (d,
C-3′,6), 132.39 (d, C-3,6′), 142.16 (s, C-1,2′). EI MS (m/z, rel.%): 426 (M+• , 14), 411 (6), 395
(13), 354 (32), 337 (18), 323 (100), 295 (8), 279 (75), 265 (12), 253 (18), 239 (16), 228 (11),
215 (15), 205 (22), 185 (10), 149 (16), 137 (22), 109 (16), 97 (37), 73 (67), 41 (8). HR EI MS:
calculated for C28H34Si2 426.2199, foun d 426.2209.
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

600
Stará, Kollárovič, Teplý, Starý, Šaman, Fiedler:
2,2′-Di(prop-2-yn -1-yl)-2,2′-{eth yn ediylbis[(2,1-ph en ylen e)m eth ylen e]}dim alon ate (33)
Dim eth yl 2-(prop-2-yn -1-yl)m alon ate22 (96 m g, 0.564 m m ol, 2.1 equivalen ts) in dry THF (3 m l)
was added to sodium h ydride (80% suspen sion in m in eral oil, 18 m g, 0.587 m m ol, 2.1
equivalen ts) in dry THF (3 m l) at room tem perature un der argon . Th e m ixture was stirred at
room tem perature for 15 m in an d th en dibrom ide 3 (ref.12) (100 m g, 0.274 m m ol) in dry
THF (3 m l) was added. After stirrin g at room tem perature for 30 h , th e precipitate was fil-
tered off an d th e filtrate was evaporated in vacuo to dryn ess. Th e crude product was purified
by flash ch rom atograph y on silica gel (petroleum eth er–eth er–aceton e 80 : 10 : 10 to
80 : 0 : 20 to 50 : 0 : 50) to get triyn e 33 (147 m g, 99%) as an am orph ous solid. IR (CCl4):
3 313 w, 3 070 vw, 3 028 vw, 3 002 vw, 2 953 w, 2 928 w, 2 122 vvw, 1 758 m , 1 740 s,
1 600 vvw, 1 495 w, 1 450 w, 1 437 w, 1 329 w, 1 282 m , 1 243 w, 1 182 m , 1 104 w,
1 068 w, 1 039 w, 853 w, 649 w, 635 w. 1H NMR (500 MHz, CDCl3): 2.07 (t, 2 H, J = 2.7,
2 × HC≡C); 2.79 (d, 4 H, J = 2.7, 2 × HC≡CCH2); 3.69 (s, 12 H, 4 × CH3); 3.73 (s, 4 H, CH2Ar,
CH2Ar′); 7.23 (ddd, 2 H, J = 7.7, 7.4, 1.3, 4,5′-H); 7.25 (ddd, 2 H, J = 7.9, 7.4, 1.4, 4′,5-H);
7.38 (ddd, 2 H, J = 7.9, 1.3, 0.3, 3′,6-H); 7.57 (ddd, 2 H, J = 7.7, 1.4, 0.3, 3,6′-H). 13C NMR
(CDCl3): 23.15 (t, 2 × HC≡CCH2), 35.55 (t, CH2Ar, CH2Ar′), 52.83 (q, 4 × CH3), 58.08 (s,
2 × C(CO2CH3)2), 72.07 (d, 2 × HC≡C), 79.62 (s, 2 × HC≡C), 91.68 (s, ArC≡CAr′), 124.43 (s,
C-1′,2), 127.17 (d, C-4,5′), 128.31 (d, C-4′,5), 130.42 (d, C-3′,6), 132.81 (d, C-3,6′), 137.27 (s,
C-1,2′), 170.24 (s, 4 × CO). EI MS (m/z, rel.%): 541 ((M – H)+, 15), 511 (12), 483 (6), 451 (13),
423 (62), 391 (36), 363 (86), 331 (30), 303 (53), 279 (41), 253 (100), 215 (51), 169 (14), 137
(20), 113 (16), 59 (32). HR EI MS: calculated for C32H30O8 542.1941, foun d 542.1911.
2,2′-Di(but-2-yn -1-yl)-2,2′-{eth yn ediylbis[(2,1-ph en ylen e)m eth ylen e]}dim alon ate (34)
Dim eth yl 2-(but-2-yn -1-yl)m alon ate23 (278 m g, 1.0 m m ol, 2.2 equivalen ts) in dry THF (2 m l)
was added to sodium h ydride (80% suspen sion in m in eral oil, 44 m g, 1.45 m m ol, 3.1 equiv-
alen ts) in dry THF (2 m l) at room tem perature un der argon . Th e m ixture was stirred at room
tem perature for 30 m in an d th en dibrom ide 3 (ref.12) (86 m g, 0.230 m m ol) in dry THF (3
m l) was added. After stirrin g at room tem perature for 1 h , th e precipitate was filtered off
an d th e filtrate was evaporated in vacuo to dryn ess. Th e crude product was purified by flash
ch rom atograph y on silica gel (petroleum eth er–aceton e 85 : 15) to furn ish triyn e 34 (115
m g, 86%) as an oil. IR (CCl4): 3 000 w, 2 953 m , 2 235 vw, 1 756 m , 1 739 vs, 1 601 vw,
1 495 w, 1 450 w, 1 438 m , 1 282 m , 1 244 m , 1 210 s, 1 200 s (sh ), 1 182 m , 1 104 w,
1 067 m , 1 050 w, 1 038 w, 952 w, 859 w, 591 vw. 1H NMR (500 MHz, CDCl3): 1.73 (t, 6 H,
J = 2.5, 2 × CH3C≡C); 2.74 (q, 4 H, J = 2.5, 2 × CH3C≡CCH2); 3.67 (s, 12 H, 4 × CH3O2C);
3.69 (brs, 4 H, CH2Ar, CH2Ar′); 7.24 (dt, 2 H, J = 7.3, 7.3, 1.7, 4′,5-H); 7.27 (dt, 2 H, J = 7.6,
7.6, 2.0, 4,5′-H); 7.39 (dd, 2 H, J = 7.5, 1.9 , 3′,6-H); 7.56 (dd, 2 H, J = 7.5, 1.9, 3,6′-H).
13C NMR (CDCl3): 3.49 (q, 2 × CH3C≡C), 23.42 (t, 2 × CH3C≡CCH2), 35.42 (t, CH2Ar,
CH2Ar′), 52.69 (q, 4 × CH3O2C), 58.31 (s, 2 × C(CO2CH3)2), 74.12 (s, 2 × CH3C≡C), 79.56 (s,
2 × CH3C≡C), 91.54 (s, ArC≡CAr′), 124.42 (s, C-1′,2), 127.04 (d, C-4,5′), 128.18 (d, C-4′,5),
130.52 (d, C-3′,6), 132.75 (d, C-3,6′), 137.61 (s, C-1,2′), 170.63 (s, 4 × CO). EI MS (m/z,
rel.%): 569 (M+• , 65), 495 (41), 451 (80), 391 (87), 331 (55), 253 (100), 215 (98), 183 (27),
151 (68), 113 (25), 83 (30), 59 (57). HR EI MS: calculated for C34H34O8 570.2254, foun d
570.2197.
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

Synthesis of Aromatic Triynes
601
(1-{2-[2-(Hydroxym eth yl)ph en yl]eth yn -1-yl}-2-n aph th yl)m eth an ol (36)
Na[AlH2(OCH2CH2OCH3)2] (Red-Al®, 3.5 M solution in toluen e, 400 µl, 1.40 m m ol, 5.0
equivalen ts) was added to diester 35 (ref.11) (95 m g, 0.276 m m ol) in toluen e (2 m l) at 0 °C
un der argon an d th e m ixture was stirred at 0 °C for 1 h . An h ydrous Na2SO4 was added an d
th e excess of h ydride was decom posed by addin g saturated aqueous solution of Na2SO4. Th e
m ixture was passed th rough a pad of silica gel usin g toluen e to get diol 36 (65 m g, 82%) as
a wh ite solid, m .p. 138–140 °C (petroleum eth er–aceton e). IR (CHCl3): 3 606 m , 3 460 m ,
3 061 m , 2 940 m , 2 882 m , 2 210 vw, 1 600 w, 1 593 w, (sh ), 1 568 w, 1 508 w, 1 486 m ,
1 450 m , 1 026 m , 1 014 s, 868 w, 822 s, 610 w. 1H NMR (500 MHz, CDCl3): 4.92 (brs, 2 H,
CH2Ph ); 5.04 (s, 2 H, CH2Nph ); 7.36 (dt, 1 H, J = 7.7, 7.7, 1.7, 5-H (Ph )); 7.36 (dt, 1 H, J =
7.6, 7.6, 1.7, 4-H (Ph )); 7.47 (dd, 1 H, J = 7.1, 1.8, 3-H (Ph )); 7.53 (ddd, 1 H, J = 8.1, 6.8, 1.2,
6-H (Nph )); 7.58 (d, 1 H, J = 8.3, 3-H (Nph )); 7.61 (ddd, 1 H, J = 8.3, 6.8, 1.2, 7-H); 7.71 (dd,
1 H, J = 8.1, 1.8, 6-H (Ph )); 7.84 (brd, 1 H, J = 8.3, 4-H (Nph )); 7.85 (brd, 1 H, J = 8.2, 5-H
(Nph )); 8.46 (ddt, 1 H, J = 8.4, 1.2, 0.8, 0.8, 8-H). 13C NMR (CDCl3): 64.14 (t, CH2Ph ), 64.39
(t, CH2Nph ), 89.62 (s, Ph C≡CNph ), 97.18 (s, Ph C≡CNph ), 119.07 (s, C-1 (Nph )), 122.14 (s,
C-1 (Ph )), 125.92 (d, C-3 (Nph )), 126.08 (d, C-8), 126.40 (d, C-6 (Nph )), 127.10 (d, C-7),
127.80 (d, C-5 (Ph )), 128.15 (q, C-3 (Ph )), 128.22 (d, C-5 (Nph )), 128.91 (d, C-4 (Nph )),
128.91 (d, C-4 (Ph )), 132.48 (d, C-6 (Ph )), 132.67 (s, C-4a), 133.35 (s, C-8a), 141.35 (s, C-2
(Nph )), 142.29 (s, C-2 (Ph )). EI MS (m/z, rel.%): 288 (M+• , 12), 270 (100), 253 (10), 241 (60),
226 (17), 215 (13), 202 (6), 169 (8), 141 (12), 119 (19), 91 (6), 77 (5). HR EI MS: calculated
for C20H16O2 288.1150, foun d 288.1162.
2-(Brom om eth yl)-1-{2-[2-(brom om eth yl)ph en yl]eth yn -1-yl}n aph th alen e (37)
Ph osph orus tribrom ide (400 µl, 4.21 m m ol, 1.4 equivalen t) was added to diol 36 (847 m g,
2.94 m m ol) in dry THF (20 m l) at 0 °C un der n itrogen . After stirrin g at 0 °C for 2 h , th e
solven t was rem oved in vacuo. Flash ch rom atograph y on silica gel (petroleum eth er–eth er–-
aceton e 80 : 10 : 10 to 70 : 0 : 30) gave th e crude product (1.61 g) th at was recrystallized
from aceton e to afford dibrom ide 37 (797 m g, 65%) as a wh ite solid, m .p. 155–157 °C (pe-
troleum eth er–aceton e). IR (CCl4): 3 060 m , 3 030 w (sh ), 2 973 m , 2 855 w, 1 599 w,
1 593 w, 1 568 w, 1 509 m , 1 488 s, 1 450 s, 1 228 m , 1 086 w, 1 027 w, 949 w, 867 m , 820 vs ,
607 s, 592 m . 1H NMR (500 MHz, CDCl3): 4.89 (s, 2 H, CH2Ph ); 5.04 (s, 2 H, CH2Nph );
7.37–7.42 (m , 2 H, 4,5-H (Ph )); 7.50–7.52 (m , 1 H, 3-H (Ph )); 7.56 (d, 1 H, J = 8.3, 3-H
(Nph )); 7.56 (ddd, 1 H, J = 8.1, 6.9, 1.2, 6-H (Nph )); 7.64 (ddd, 1 H, J = 8.3, 6.8, 1.2, 7-H);
7.74–7.76 (m , 1 H, 6-H (Ph )); 7.85 (brd, 1 H, J = 8.3, 4-H (Nph )); 7.86 (brd, 1 H, J = 8.1, 5-H
(Nph )); 8.53 (brd, 1 H, J = 8.3, 8-H). 13C NMR (CDCl3): 32.17 (t, CH2Ph ), 32.93 (t, CH2Nph ),
90.25 (s, Ph C≡CNph ), 97.56 (s, Ph C≡CNph ), 120.42 (s, C-1 (Nph )), 123.18 (s, C-1 (Ph )),
126.72 (d, C-3 (Nph )), 126.94 (d, C-8), 127.08 (d, C-6 (Nph )), 127.51 (d, C-7), 128.24 (d, C-5
(Ph )), 128.70 (d, C-3 (Ph )), 129.33 (d, C-5 (Nph )), 129.43 (d, C-4 (Nph )), 129.98 (d, C-4
(Ph )), 132.90 (s, C-4a), 133.09 (d, C-6 (Ph )), 133.43 (s, C-8a), 138.04 (s, C-2 (Nph )), 139.18
(s, C-2 (Ph )). EI MS (m/z, rel.%): 416 (M+• , with 81Br, 7), 414 (M+• with 81Br/79Br, 14), 412
(M+• with 79Br, 8), 335 (33), 333 (29), 273 (10), 271 (10), 254 (59), 253 (52), 252 (48), 137
(71), 135 (68), 97 (11), 83 (29), 55 (100), 41 (27). HR EI MS: calculated for C20H1479Br81Br
413.9442, foun d 413.9540.
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

602
Stará, Kollárovič, Teplý, Starý, Šaman, Fiedler:
4-Meth yl-N-(prop-2-en -1-yl)-N-({1-[2-(2-{[N-(prop-2-yn -1-yl)-N-tosylam in o]m eth yl}
ph en yl)eth yn -1-yl]-2-n aph th yl}m eth yl)ben zen esulfon am ide (38)
4-Meth yl-N-(prop-2-yn -1-yl)ben zen esulfon am ide 21 (ref.17) (130 m g, 0.621 m m ol, 2.6 equiv-
alen ts) in dry DMF (2 m l) was added at 0 °C to sodium h ydride (80% suspen sion in m in eral
oil, 20 m g, 0.667 m m ol, 2.8 equivalen ts) in dry DMF (4 m l) un der argon . After stirrin g at 0 °C
for 1 h , dibrom ide 37 (100 m g, 0.241 m m ol) in dry DMF (2 m l) was added an d th e m ixture
was stirred at room tem perature overn igh t. Th e resultin g clear solution was partition ed be-
tween eth er an d water. Th e eth ereal layer was separated an d th e aqueous ph ase was ex-
tracted with eth er (2×). Th e eth ereal portion s were com bin ed, wash ed with water (1×), dried
over Na2SO4 an d evaporated in vacuo. Th e crude product was purified successively by flash
ch rom atograph y on silica gel (petroleum eth er–aceton e 70 : 30) an d preparative HPLC on
silica gel (h exan e–aceton e 80 : 20) to afford triyn e 38 (160 m g, 99%) as a wh ite solid, m .p.
156–158 °C (petroleum eth er–aceton e). IR (CHCl3): 3 307 m , 3 061 w, 3 032 w, 2 957 w,
2 926 w, 2 856 w, 2 123 vw, 1 599 w, 1 570 vw, 1 508 w, 1 495 w, 1 488 w, 1 450 w, 1 431 w,
1 400 w, 1 378 w, 1 349 s, 1 336 m (sh ), 1 307 w, 1 291 w, 1 261 vw, 1 186 w, 1 162 vs,
1 119 w, 1 093 m , 1 072 w, 1 050 w, 1 025 vw, 1 019 w, 960 w, 929 w, 903 m , 869 w, 823 w
(sh ), 814 m , 661 m , 637 w, 590 w (sh ), 573 m , 543 m , 521 w, 510 w. 1H NMR (500 MHz,
CDCl3): 1.77 (t, 1 H, J = 2.4, HC≡C∩Nph ); 1.84 (t, 1 H, J = 2.4, HC≡C∩Ph ); 2.40 (brs, 3 H,
CH3C6H4SO2N∩Nph ); 2.45 (brs, 3 H, CH3C6H4SO2N∩Ph ); 3.99 (d, 2 H, J = 2.4,
HC≡CCH2N∩Ph ); 4.06 (d, 2 H, J = 2.4, HC≡CCH2N∩Nph ); 4.78 (s, 2 H, CH2Ph ); 4.86 (s, 2 H,
CH2Nph ); 7.23–7.25 (m , 2 H, 3,5-H (Ts∩Nph )); 7.28 (dt, 1 H, J = 7.6, 7.6, 1.3, 5-H (Ph ));
7.31–7.33 (m , 2 H, 3,5-H (Ts∩Ph )); 7.37 (ddd, 1 H, J = 8.3, 6.9, 1.4, 7-H); 7.40 (dt, 1 H, J =
7.6, 7.6, 1.3, 4-H (Ph )); 7.51 (ddd, 1 H, J = 8.0, 6.9, 1.2, 6-H (Nph )); 7.53 (dd, 1 H, J = 7.7,
1.3, 3-H (Ph )); 7.63 (brd, 1 H, J = 8.0, 6-H (Ph )); 7.72 (d, 1 H, J = 8.5, 3-H (Nph )); 7.78–7.80
(m , 2 H, 2,6-H (Ts∩Ph )); 7.83–7.85 (m , 2 H, 2,6-H (Ts∩Nph ); 7.86 (brd, 1 H, J = 8.5, 4-H
(Nph )); 7.86 (brd, 1 H, J = 8.0, 5-H (Nph )); 8.28 (dq, 1 H, J = 8.5, 1.0, 1.0, 1.0, 8-H). 13C NMR
(CDCl3): 21.51 (q, CH3C6H4SO2N∩Nph ), 21.57 (q, CH3C6H4SO2N∩Ph ), 36.38 (t,
HC≡CCH2N∩Ph ), 36.59 (t, HC≡CCH2N∩Nph ), 48.46 (t, CH2Ph ), 48.85 (t, CH2Nph ), 74.00 (d,
HC≡CCH2N∩Ph ), 74.29 (d, HC≡CCH2N∩Nph ), 76.50 (s, HC≡CCH2N∩Nph ), 89.97 (s,
Ph C≡CNph ), 96.82 (s, Ph C≡CNph ), 120.25 (s, C-1 (Nph )), 122.59 (s, C-1 (Ph )), 126.17 (d,
C-3 (Nph )), 126.54 (d, C-8), 126.57 (d, C-7), 126.99 (d, C-6 (Nph )), 127.58 (d, C-5 (Ph )),
127.86 (d, C-2,6 (Ts∩Ph )), 128.00 (d, C-2,6 (Ts∩Nph )), 128.14 (d, C-5 (Nph )), 128.26 (d, C-4
(Nph )), 129.23 (d, C-3 (Ph )), 129.23 (d, C-4 (Ph )), 129.57 (d, C-3 (Ts∩Ph )), 129.60 (d, C-3,5
(Ts∩Nph )), 132.66 (d, C-6 (Ph )), 132.71 (s, C-4a), 133.12 (s, C-8a), 136.02 (s, C-2 (Ph )),
136.04 (s, C-5 (Ts∩Ph )), 136.07 (s, C-4 (Ts∩Nph )), 137.07 (s, C-2 (Nph )), 143.69 (s, C-1
(Ts∩Ph )), 143.74 (s, C-1 (Ts∩Nph )); sign al of HC≡CCH2N∩Ph overlapped with CDCl3 sign als.
EI MS (m/z, rel.%): 604 (7), 515 (24), 359 (40), 332 (20), 321 (28), 306 (64), 268 (25), 239
(13), 155 (13), 139 (14), 111 (25), 83 (52), 69 (64), 57 (100), 43 (82). FAB MS (m/z,
dith ioth reitol–dith ioeryth ritol m atrix): 671 ((M + H)+), 633, 616, 515, 462, 424, 361, 307,
268, 155, 85. HR FAB MS (th ioglycerol–glycerol m atrix): calculated for C40H35N2O4S2
(M + H) 671.2038, foun d 671.2161.
2-[(But-2-yn -1-yloxy)m eth yl]-1-(2-{2-[(but-2-yn -1-yloxy)m eth yl]ph en yl}eth yn -1-yl)
n aph th alen e (39)
But-2-yn -1-ol (320 µl, 4.23 m m ol, 2.2 equivalen ts) in dry DMF (1 m l) was added to sodium
h ydride (80% suspen sion in m in eral oil, 157 m g, 5.23 m m ol, 2.7 equivalen ts) in dry DMF
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

Synthesis of Aromatic Triynes
603
(2 m l) un der argon an d th e m ixture was stirred at room tem perature for 20 m in . Th en
dibrom ide 37 (794 m g, 1.92 m m ol) in dry DMF (15 m l) was added. After stirrin g at room
tem perature for 2 h , th e reaction m ixture was partition ed between eth er an d water. Th e
eth ereal layer was separated an d th e aqueous ph ase was extracted with eth er (3×). Th e eth e-
real portion s were com bin ed, wash ed with water (1×), dried over Na2SO4 an d evaporated in
vacuo. Flash ch rom atograph y on silica gel (petroleum eth er–eth er 90 : 10) afforded triyn e 39
(514 m g, 68%) as an oil. IR (CCl4): 3 061 m , 3 020 w (sh ), 2 944 m , 2 922 s, 2 855 s, 2 294 w,
2 249 w, 2 225 w, 1 621 w, 1599 w, 1 593 vw, 1 570 w, 1 509 m , 1 486 m , 1 467 m , 1 450 s,
1 387 m , 1 355 s, 1 081 vs, 866 m , 819 s. 1H NMR (500 MHz, CDCl3): 1.78 (t, 3 H, J = 2.3,
CH3∩Nph ); 1.82 (t, 3 H, J = 2.5, CH3∩Ph ); 4.26 (q, 2 H, J = 2.3, C≡CCH2O∩Nph ); 4.27 (q,
2 H, J = 2.5, C≡CCH2O∩Ph ); 4.96 (s, 2 H, CH2Nph ); 5.08 (s, 2 H, CH2Ph ); 7.34 (dt, 1 H, J =
7.6, 7.6, 1.5, 5-H (Ph )); 7.40 (dt, 1 H, J = 7.6, 7.6, 1.5, 4-H (Ph )); 7.52 (ddd, 1 H, J = 8.1, 6.9,
1.2, 6-H (Nph )); 7.57 (brd, 1 H, J = 7.6, 3-H (Ph )); 7.60 (ddd, 1 H, J = 8.3, 6.9, 1.2, 7-H); 7.67
(d, 1 H, J = 8.6, 3-H (Nph )); 7.69 (dd, 1 H, J = 7.6, 1.4, 6-H (Ph )); 7.85 (brd, 1 H, J = 8.1, 5-H
(Nph )); 7.86 (brd, 1 H, J = 8.5, 4-H (Nph )); 8.48 (dq, 1 H, J = 8.3, 0.9, 0.9, 0.9, 8-H). 13C NMR
(CDCl3): 3.51 (q, CH3∩Nph ), 3.54 (q, CH3∩Ph ), 58.29 (t, CH2O∩Nph ), 58.39 (t, CH2O∩Ph ),
69.91 (t, CH2Nph ), 70.10 (t, CH2Ph ), 75.06 (s, C≡CCH2∩Nph ), 75.21 (s, C≡CCH2∩Ph ), 82.79
(s, C≡CCH2∩Nph ), 82.87 (s, C≡CCH2∩Ph ), 89.55 (s, Nph C≡CPh ), 97.08 (s, Nph C≡CPh ),
119.15 (s, C-1 (Nph )), 122.12 (s, C-1 (Ph )), 125.53 (d, C-3 (Nph )), 126.33 (d, C-3 (Ph )),
126.33 (d, C-8), 126.99 (d, C-6 (Nph )), 127.51 (d, C-7), 127.96 (d, C-5 (Ph )), 128.17 (d, C-5
(Nph )), 128.74 (d, C-4 (Nph )), 128.74 (d, C-4 (Ph )), 132.31 (d, C-6 (Ph )), 132.63 (s, C-4a),
133.26 (s, C-8a), 138.55 (s, C-2 (Ph )), 139.49 (s, C-2 (Nph )). EI MS (m/z, rel.%): 392 (M+• , 8),
339 (22), 321 (7), 309 (13), 293 (16), 269 (92), 254 (48), 239 (100), 228 (46), 202 (16), 165
(17), 119 (15), 84 (38), 53 (53). HR EI MS: calculated for C28H24O2 392.1776, foun d 392.1899.
2-[4-(Triisopropylsilyl)but-3-yn -1-yl]-1-(2-{2-[4-(triisopropylsilyl)but-3-yn -1-yl]ph en yl}
eth yn -1-yl)n aph th alen e (40)
Butyllith ium (1.6 M solution in h exan es, 340 µl, 0.544 m m ol, 2.3 equivalen ts) was added
dropwise over a 10 m in period to a solution of triisopropyl(prop-1-yn -1-yl)silan e (130 µl,
0.543 m m ol, 2.3 equivalen ts) in THF (2 m l) at –78 °C un der argon . After stirrin g at –78 °C
for 2 h , dibrom ide 37 (100 m g, 0.241 m m ol) in THF (5 m l) was added dropwise over a 10
m in period. Th e m ixture was stirred at –78 °C for 1 h th en warm ed to room tem perature
an d evaporated in vacuo to dryn ess. Flash ch rom atograph y on silica gel (petroleum
eth er–eth er 90 : 10) gave triyn e 40 (115 m g, 74%) as an am orph ous solid. IR (CCl4):
3 059 w, 2 958 s, 2 944 s, 2 925 s (sh ), 2 891 s, 2 866 vs, 2 171 m , 1 621 vw, 1 599 vw,
1 569 vw, 1 509 w, 1 487 w, 1 463 w, 1 452 w, 1 429 w, 1 383 w, 1 366 w, 1 324 w, 1 290 w,
1 252 w, 1 146 vw, 1 102 vw, 1 073 w, 1 024 m , 996 m , 884 s, 865 w, 678 s, 661 s, 617 m ,
523 w. 1H NMR (500 MHz, CDCl3): 1.01–1.04 (m , 42 H, 6 × (CH3)2CH); 2.76 (t, 4 H, J = 7.3,
2 × C≡CCH2); 3.21 (t, 2 H, J = 7.3, CH2Ph ); 3.32 (t, 2 H, J = 7.3, CH2Nph ); 7.25 (dt, 1 H, J =
7.4, 7.4, 1.4, 5-H (Ph )); 7.29 (dt, 1 H, J = 7.4, 7.4, 1.5, 4-H (Ph )); 7.39 (brdd, 1 H, J = 7.4, 1.4,
3-H (Ph )); 7.48 (d, 1 H, J = 8.4, 3-H (Nph )); 7.48 (ddd, 1 H, J = 8.1, 6.8, 1.2, 6-H (Nph )); 7.58
(ddd, 1 H, J = 8.3, 6.9, 1.3, 7-H); 7.67 (brdd, 1 H, J = 7.4, 1.5, 6-H (Ph )); 7.76 (brd, 1 H, J =
8.4, 4-H (Nph )); 7.83 (brd, 1 H, J = 8.1, 5-H (Nph )); 8.43 (dq, 1 H, J = 8.3, 1.0, 1.0, 1.0, 8-H).
13C NMR (CDCl3): 11.31 (d, 6 × (CH3)2CH), 18.59 (q, 6 × (CH3)2CH), 21.24 (t,
C≡CCH2∩Nph ), 21.32 (t, C≡CCH2∩Ph ), 34.36 (t, CH2Nph ), 35.02 (t, CH2Ph ), 81.20 (s,
C≡CCH2∩Nph ), 81.22 (s, C≡CCH2∩Ph ), 89.75 (s, Ph C≡CNph ), 97.35 (s, Ph C≡CNph ), 107.84
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

604
Stará, Kollárovič, Teplý, Starý, Šaman, Fiedler:
(s, C≡CCH2∩Nph ), 107.96 (s, C≡CCH2Ph ), 113.41 (s, C-1 (Nph )), 122.90 (s, C-1 (Ph )), 125.75
(d, C-8), 126.02 (d, C-3 (Nph )), 126.41 (d, C-5 (Ph )), 126.87 (d, C-6 (Nph )), 127.53 (d, C-7),
128.10 (d, C-5 (Nph )), 128.28 (d, C-4 (Ph )), 128.41 (d, C-4 (Nph )), 129.53 (d, C-3 (Ph )),
132.03 (s, C-4a), 132.62 (d, C-6 (Ph )), 133.56 (s, C-8a), 141.53 (s, C-2 (Nph )), 141.98 (s, C-2
(Ph )). EI MS (m/z, rel.%): 644 (M+• , 7), 601 (18), 486 (5), 443 (11), 329 (5), 291 (9), 157 (83),
129 (19), 115 (100), 101 (15), 87 (46), 73 (49), 59 (63), 43 (17). HR EI MS: calculated for
C
44H60Si2 644.4234, foun d 644.4183.
2-(But-3-yn -1-yl)-1-{2-[2-(but-3-yn -1-yl)ph en yl]eth yn -1-yl}n aph th alen e (41)
Tetrabutylam m on ium fluoride (1.0 M solution in THF, 7.0 m l, 7.00 m m ol, 4.9 equivalen ts)
was added to silylated triyn e 40 (930 m g, 1.44 m m ol) in dry THF (15 m l) an d th e m ixture
was stirred un der argon at room tem perature for 1 h . Th e solution was evaporated in vacuo
to dryn ess an d th e crude product was purified by flash ch rom atograph y on alum in a (petro-
leum eth er–eth er 100 : 0 to 99 : 1) to get triyn e 41 (466 m g, 97%) as an am orph ous solid. IR
(CHCl3): 3 308 vs, 3 060 w, 2205 vw, 2 118 w, 1 620 w, 1597 w, 1 594 w, 1 567 w, 1 507 m ,
1487 m , 1 451 m , 1 431 w, 1 259 w, 1 102 w, 1 041 vw, 1 025 w, 867 w, 820 m , 640 vs, 495 w.
1H NMR (500 MHz, CDCl3): 2.01 (t, 1 H, J = 2.6, HC≡C∩Ph ); 2.03 (t, 1 H, J = 2.7,
HC≡C∩Nph ); 2.68 (dt, 2 H, J = 7.6, 7.6, 2.7, HC≡CCH2∩Ph ); 2.69 (dt, 2 H, J = 7.6, 7.6, 2.7,
HC≡CCH2∩Nph ); 3.23 (t, 2 H, J = 7.6, CH2Ph ); 3.33 (t, 2 H, J = 7.6, CH2Nph ); 7.29 (dt, 1 H,
J = 7.3, 7.3, 1.9, 5-H (Ph )); 7.33 (dt, 1 H, J = 7.6, 7.6, 1.5, 4-H (Ph )); 7.36 (dd, 1 H, J = 7.2,
1.9, 3-H (Ph )); 7.45 (d, 1 H, J = 8.4, 3-H (Nph )); 7.50 (ddd, 1 H, J = 8.1, 6.8, 1.3, 6-H (Nph ));
7.60 (ddd, 1 H, J = 8.3, 6.7, 1.3, 7-H); 7.68 (dd, 1 H, J = 7.3, 1.5, 6-H (Ph )); 7.80 (brd, 1 H, J =
8.4, 4-H (Nph )); 7.84 (brd, 1 H, J = 8.1, 5-H (Nph )); 8.45 (dq, 1 H, J = 8.3, 1.0, 1.0, 1.0, 8-H).
13C NMR (CDCl3): 19.81 (t, HC≡CCH2∩Nph ), 19.86 (t, HC≡CCH2∩Ph ), 34.07 (t, CH2Nph ),
34.55 (t, CH2Ph ), 69.12 (d, HC≡CCH2∩Nph ), 69.15 (d, HC≡CCH2∩Ph ), 83.66 (s, Ph C≡CNph ),
83.69 (s, Ph C≡CNph ), 89.69 (s, HC≡CCH2∩Nph ), 97.15 (s, HC≡CCH2∩Ph ), 119.44 (s, C-1
(Nph )), 122.94 (s, C-1 (Ph )), 125.91 (d, C-8), 126.10 (d, C-3 (Nph )), 126.61 (d, C-5 (Ph )),
127.01 (d, C-6 (Nph )), 127.28 (d, C-7), 128.16 (d, C-5 (Nph )), 128.49 (d, C-4 (Ph )), 128.61
(d, C-4 (Nph )), 129.19 (d, C-3 (Ph )), 132.03 (s, C-4a), 132.68 (d, C-6 (Ph )), 133.56 (s, C-8a),
141.22 (s, C-2 (Nph )), 141.84 (s, C-2 (Ph )). EI MS (m/z, rel.%): 332 (M+• , 37), 315 (30), 303
(20), 289 (22), 276 (29), 265 (12), 252 (27), 239 (12), 202 (12), 191 (100), 165 (16), 141 (15),
138 (14), 126 (13), 115 (12), 91 (12). HR EI MS: calculated for C26H20 332.1565, foun d
332.1580.
2-(Pen t-3-yn -1-yl)-1-{2-[2-(pen t-3-yn -1-yl)ph en yl]eth yn -1-yl}n aph th alen e (42)
Butyllith ium (1.6 M solution in h exan es, 1.60 m l, 2.56 m m ol, 2.2 equivalen ts) was added
dropwise over a 5 m in period to triyn e 41 (385 m g, 1.16 m m ol) in dry THF (12 m l) at –78 °C
un der argon . After stirrin g at –78 °C for 10 m in , m eth yl iodide (180 µl, 2.89 m m ol, 2.5
equivalen ts) was added an d th e m ixture was stirred at –78 °C for 20 m in . Th e solven ts were
rem oved in vacuo an d th e crude product was purified by flash ch rom atograph y on silica gel
(petroleum eth er–eth er 96 : 4) to furn ish dim eth ylated triyn e 42 (387 m g, 93%) as an oil. IR
(CCl4): 3 094 vw, 3 059 m , 3 032 w, 2 956 m , 2 931 m , 2 920 s, 2 859 w, 2 845 w, 2 235 vvw,
2 198 vvw, 1 621 vw, 1 599 w, 1 569 w, 1 508 m , 1 487 m , 1 451 m , 1 434 m , 1 341 w,
1 326 w, 1 259 vw, 1 163 w, 1 102 w, 1 025 w, 865 w. 1H NMR (500 MHz, CDCl3): 1.77 (t,
3 H, J = 2.6, CH3∩Ph ); 1.79 (t, 3 H, J = 2.6, CH3∩Nph ); 2.61 (tq, 4 H, J = 7.6, 7.6, 2.6, 2.6, 2.6,
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

Synthesis of Aromatic Triynes
605
C≡CCH2∩Ph , C≡CCH2∩Nph ); 3.18 (t, 2 H, J = 7.6, CH2Nph ); 3.28 (t, 2 H, J = 7.6, CH2Ph );
7.26–7.31 (m , 2 H, 4,5-H (Ph )); 7.33 (dd, 1 H, J = 6.8, 1.6, 3-H (Ph )); 7.44 (d, 1 H, J = 8.4, 3-H
(Nph )); 7.49 (ddd, 1 H, J = 8.1, 6.8, 1.2, 6-H (Nph )); 7.58 (ddd, 1 H, J = 8.3, 6.8, 1.3, 7-H);
7.68 (ddd, 1 H, J = 7.5, 1.5, 0.8, 6-H (Ph )); 7.78 (dt, 1 H, J = 8.4, 0.6, 0.6, 4-H (Nph )); 7.83
(ddt, 1 H, J = 8.1, 1.3, 0.7, 0.7, 5-H (Nph )); 8.46 (ddt, 1 H, J = 8.3, 1.2, 0.8, 0.8, 8-H)).
13C NMR (CDCl3): 3.50 (q, CH3∩Ph ), 3.53 (q, CH3∩Nph ), 20.18 (t, C≡CCH2∩Nph ), 20.25 (t,
C≡CCH2∩Ph ), 34.69 (t, CH2Nph ), 35.17 (t, CH2Ph ), 76.35 (s, C≡CCH2∩Nph ), 76.42 (s,
C≡CCH2∩Ph ), 78.49 (s, C≡CCH2∩Nph ), 78.54 (s, C≡CCH2∩Ph ), 89.64 (s, Ph C≡CNph ), 97.11
(s, Ph C≡CNph ), 119.47 (s, C-1 (Nph )), 123.06 (s, C-1 (Ph )), 125.76 (d, C-8), 126.21 (d, C-3
(Nph )), 126.36 (d, C-5 (Ph )), 126.86 (d, C-6 (Nph )), 127.40 (d, C-7), 128.09 (d, C-5 (Nph )),
128.27 (d, C-4 (Ph )), 128.45 (d, C-4 (Nph )), 129.13 (d, C-3 (Ph )), 131.97 (s, C-4a), 132.61 (d,
C-6 (Ph )), 133.61 (s, C-8a), 141.88 (s, C-2 (Nph )), 142.50 (s, C-2 (Ph )). EI MS (m/z, rel.%):
360 (M+• , 46), 345 (40), 330 (88), 315 (53), 303 (25), 291 (52), 289 (69), 265 (41), 252 (100),
239 (29), 216 (22), 202 (21), 189 (18), 165 (33), 141 (20), 126 (15), 115 (24), 91 (33), 69
(43), 57 (40), 43 (34). HR EI MS: calculated for C28H24 360.1878, foun d 360.1862.
2-[4-(Trim eth ylsilyl)but-3-yn -1-yl]-1-(2-{2-[4-(trim eth ylsilyl)but-3-yn -1yl]ph en yl}eth yn -1-yl)-
n aph th alen e (43)
Butyllith ium (1.6 M solution in h exan es, 400 µl, 0.640 m m ol, 2.2 equivalen ts) was added
dropwise over a 3 m in period to triyn e 41 (97 m g, 0.292 m m ol) in dry THF (3 m l) at –78 °C
un der argon . After stirrin g at –78 °C for 10 m in , trim eth ylsilyl ch loride (100 µl, 0.788 m m ol,
2.7 equivalen ts) was added an d th e m ixture was stirred at –78 °C for 20 m in . Th e solven ts
were rem oved in vacuo an d th e crude product was purified by flash ch rom atograph y on sil-
ica gel (petroleum eth er–eth er 98 : 2) to furn ish disilylated triyn e 43 (129 m g, 93%) as an
oil. IR (CCl4): 3 059 w, 2 960 w, 2 935 w, 2 902 w, 2 864 w, 2 175 w, 1 599 vw, 1 508 w,
1 487 w, 1 451 w, 1 428 vw, 1 407 vw, 1 338 vw, 1 324 vw, 1 250 m , 1 162 vw, 1 102 vw,
1 027 vw (sh ), 844 s, 698 w, 639 w. 1H NMR (500 MHz, CDCl3): 0.128 (s, 9 H (CH3)3Si∩Ph );
0.132 (s, 9 H (CH3)3Si∩Nph ); 2.70 (t, 2 H, J = 7.6, C≡CCH2∩Nph ); 2.71 (t, 2 H, J = 7.6,
C≡CCH2Ph ); 3.20 (t, 2 H, J = 7.6, CH2Nph ); 3.31 (t, 2 H, J = 7.6, CH2Ph ); 7.28 (dt, 1 H, J =
7.5, 7.5, 1.6, 5-H (Ph )); 7.32 (dt, 1 H, J = 7.5, 7.5, 1.7, 4-H (Ph )); 7.35 (ddd, 1 H, J = 7.4, 1.6,
0.8, 3-H (Ph )); 7.45 (d, 1 H, J = 8.4, 3-H (Nph )); 7.50 (ddd, 1 H, J = 8.1, 6.8, 1.2, 6-H (Nph ));
7.60 (ddd, 1 H, J = 8.3, 6.8, 1.4, 7-H); 7.68 (ddd, 1 H, J = 7.3, 1.7, 0.7, 6-H (Ph )); 7.78 (dt,
1 H, J = 8.4, 0.6, 0.6, 4-H (Nph )); 7.84 (ddt, 1 H, J = 8.1, 1.4, 0.7, 0.7, 5-H (Nph )); 8.44 (dq,
1 H, J = 8.4, 0.9, 0.9, 0.9, 8-H). 13C NMR (CDCl3): 0.06 (q, (CH3)3Si∩Nph ), 0.09 (q,
(CH3)3Si∩Ph ), 21.37 (t, 2 × C≡CCH2), 34.23 (t, CH2Nph ), 34.76 (t, CH2Ph ), 85.47 (s,
C≡CCH2∩Nph ), 85.54 (s, C≡CCH2∩Ph ), 89.68 (s, Ph C≡CNph ), 97.20 (s, Ph C≡CNph ), 106.38
(s, C≡CCH2∩Nph ), 106.47 (s, C≡CCH2∩Ph ), 119.46 (s, C-1 (Nph )), 122.97 (s, C-1 (Ph )),
125.81 (d, C-8), 126.10 (d, C-3 (Nph )), 126.49 (d, C-5 (Ph )), 126.93 (d, C-6 (Nph )), 127.57
(d, C-7), 128.12 (d, C-5 (Nph )), 128.25 (d, C-4 (Ph )), 128.43 (d, C-4 (Nph )), 129.42 (d, C-3
(Ph )), 132.01 (s, C-4a), 132.61 (d, C-6 (Ph )), 133.53 (s, C-8a), 141.46 (s, C-2 (Nph )), 142.01
(s, C-2 (Ph )). EI MS (m/z, rel.%): 476 (M+• , 2), 404 (7), 387 (5), 373 (6), 329 (23), 289 (5), 267
(6), 252 (9), 96 (3), 73 (100), 59 (8), 45 (5), 28 (4). HR EI MS: calculated for C32H36Si2
476.2356, foun d 476.2351.
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

606
Stará, Kollárovič, Teplý, Starý, Šaman, Fiedler:
2-(Brom om eth yl)-1-iodon aph th alen e (45)
Ph osph orus tribrom ide (180 µl, 1.90 m m ol, 0.5 equivalen t) was added to (1-iodo-
2-n aph th yl)m eth an ol 44 (ref.11) (989 m g, 3.48 m m ol) in dry THF (10 m l) at 0 °C un der n i-
trogen . After stirrin g at 0 °C for 1 h , th e solven t was rem oved in vacuo. Flash ch rom atogra-
ph y on silica gel (petroleum eth er–eth er 95 : 5 to 85 : 15) gave brom ide 45 (1.14 g, 94%) as
an am orph ous solid. IR (CCl4): 3 057 w, 3 037 w (sh ), 3 007 vw, 2 974 w, 2 859 vw,
1 607 vw, 1 596 vw, 1 552 m , 1 503 s, 1 462 w, 1 438 m , 1 350 w, 1 322 s, 1 260 m , 1 210 s,
1 032 w, 861 m , 589 m , 523 m . 1H NMR (500 MHz, CDCl3): 4.91 (s, 2 H, CH2); 7.53 (ddd,
1 H, J = 8.1, 6.9, 1.2, 6-H); 7.55 (d, 1 H, J = 8.4, 3-H); 7.60 (ddd, 1 H, J = 8.5, 6.9, 1.4, 7-H);
7.77 (ddt, 1 H, J = 8.1, 1.4, 0.6, 0.6, 5-H); 7.80 (dt, 1 H, J = 8.4, 0.7, 0.7, 4-H); 8.25 (ddt, 1 H,
J = 8.5, 1.3, 0.7, 0.7, 8-H). 13C NMR (CDCl3): 43.03 (t, CH2), 106.27 (s, C-1), 127.13 (d, C-5),
127.20 (d, C-4), 128.23 (d, C-6), 128.28 (d, C-7), 129.43 (d, C-3), 133.16 (d, C-8), 133.52 (s,
C-4a), 135.21 (s, C-8a), 139.36 (s, C-2). EI MS (m/z, rel.%): 348 (M+• with 81Br, 17), 346 (M+•
with 79Br, 18), 267 (100), 140 (96), 127 (7), 113 (8), 79 (8), 63 (10). HR EI MS: calculated for
C
11H879BrI 345.8854, foun d 345.8850.
1-Iodo-2-[4-(triisopropylsilyl)but-3-yn -1-yl]n aph th alen e (46)
Butyllith ium (1.6 M solution in h exan es, 220 µl, 0.352 m m ol, 1.2 equivalen t) was added
dropwise to a solution of triisopropyl(prop-1-yn -1-yl)silan e (85 µl, 0.355 m m ol, 1.2 equiva-
len t) in dry THF (2 m l) at –78 °C un der argon . After stirrin g at –78 °C for 2.5 h , brom ide 45
(103 m g, 0.297 m m ol) in dry THF (1 m l) was added dropwise. Th e m ixture was stirred at –78 °C
for 2.5 h an d th en warm ed to room tem perature. Th e solven ts were rem oved in vacuo. Flash
ch rom atograph y on silica gel (petroleum eth er–eth er 98 : 2) gave alkyn e 46 (95 m g, 69%) as
an oil. IR (CCl4): 3 055 w, 2 866 vs, 2 171 m , 1 621 vw, 1 597 vw, 1 551 w, 1 501 m ,
1 463 m , 1 451 m (sh ), 1 428 w, 1 383 w, 1 366 w, 1 323 w, 1 256 w, 1 073 w, 1 030 m , 996
m , 884 m , 860 w, 678 s, 660 m . 1H NMR (500 MHz, CDCl3): 1.03 (m , 21 H, 3 × (CH3)2CH);
2.66 (t, 2 H, J = 7.3, C≡CCH2); 3.26 (t, 2 H, J = 7.3, CH2Nph ); 7.45 (d, 1 H, J = 8.4, 3-H); 7.47
(ddd, 1 H, J = 8.1, 6.8, 1.2, 6-H); 7.55 (ddd, 1 H, J = 8.4, 6.8, 1.4, 7-H); 7.72 (brd, 1 H, J = 8.4,
4-H); 7.75 (ddq, 1 H, J = 8.1, 1.4, 0.7, 0.7, 0.7, 5-H); 8.23 (brdd, 1 H, J = 8.4, 1.2, 8-H).
13C NMR (CDCl3): 11.28 (d, 3 × (CH3)2CH), 18.60 (q, 3 × (CH3)2CH), 20.68 (t, C≡CCH2),
42.02 (t, CH2Nph ), 81.49 (s, C≡CCH2), 94.78 (s, C≡CCH2), 107.41 (s, C-1), 125.99 (d, C-3),
127.62 (d, C-5), 127.90 (d, C-4), 128.13 (d, C-6), 128.51 (d, C-7), 132.70 (d, C-8), 132.93 (s,
C-4a), 135.07 (s, C-8a), 142.51 (s, C-2). EI MS (m/z, rel.%): 462 (M+• , 7), 419 (100), 391 (10),
377 (11), 349 (5), 293 (10), 267 (10), 249 (17), 235 (5), 221 (24), 207 (22), 179 (8), 140 (11),
59 (5). HR EI MS: calculated for C23H31ISi 462.1240, foun d 462.1235.
Bis{2-[4-(triisopropyl)but-3-yn -1-yl]-1-n aph th yl}acetylen e (47)
A m ixture of n aph th yl iodide 46 (5.60 g, 12.11 m m ol), Pd(PPh 3)4 (771 m g, 0.667 m m ol, 6
m ole %), an d CuI (237 m g, 1.24 m m ol, 10 m ole %) in deoxygen ated piperidin e (40 m l) was
stirred un der 1 atm pressure of acetylen e at 80 °C for 2 h (a rubber balloon filled with acety-
len e was attach ed to th e Sch len k flask). Th e precipitated solid was rem oved by suction ,
wash ed with petroleum eth er, an d th e filtrate was evaporated in vacuo to dryn ess. Flash
ch rom atograph y on silica gel (petroleum eth er–eth er 100 : 0 to 96 : 4) furn ish ed triyn e 47
(3.25 g, 77%) as an oil. IR (CCl4): 3 058 w, 3 012 vw, 2 958 s, 2 944 vs, 2 922 s (sh ), 2 891 m ,
2 866 vs, 2 171 m , 1 621 vw, 1 593 vw, 1 570 vw, 1 509 w, 1 463 m , 1 451 w (sh ), 1 428 w,
Collect. Czech. Chem. Commun. (Vol. 65) (2000)