Synthesis of aromatic triynes as precursors to helicene derivatives

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 es³h 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 es⁵as 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

CpCo(CO)₂

PPh₃

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

Collect. Czech. Chem. Commun. (Vol. 65) (2000)

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

CO₂CH₃

O

(iii)

OR

4, R = CH₃

1

3

5, R = CH₂C≡CH

(i)

(ii)

(vii) or (viii)

R

O

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

Collect. Czech. Chem. Commun. (Vol. 65) (2000)

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

OH

R

O

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

OH

Br

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

Collect. Czech. Chem. Commun. (Vol. 65) (2000)

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

19, R = H (i)

20, R = CH₃(ii)

21, R = H (iii)

22, R = CH₃(iv)

R = H, CH₃

Ts

N

R

Br

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 t²¹to

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

O

(ii)

OH

TMS

O

10

+

O

TMS

26

(i)

O

(iii)

8

OH

OTMS

TMS

27

25

O

(v)

(iv)

OH

29

+

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

Collect. Czech. Chem. Commun. (Vol. 65) (2000)

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 yield^8c. 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 ate²²or dim eth yl 2-(but-2-yn -1-yl)-

m alon ate²³by 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

Br

R

CO₂CH₃

30

3

33, R = H (iv)

34, R = CH₃(v)

(ii) or (iii)

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

Collect. Czech. Chem. Commun. (Vol. 65) (2000)

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

CO₂CH₃

(i)

(ii)

OH

(iii)

35

36

37

(iv)

(v)

Ts

N

O

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

Collect. Czech. Chem. Commun. (Vol. 65) (2000)

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 yield^8c. 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 yield^8c. 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

Br

OH

(i)

45

44

(ii)

I

TIPS

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

Collect. Czech. Chem. Commun. (Vol. 65) (2000)

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

CDCl₃with 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 CDCl₃with CFCl₃as 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 J_C-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 CHCl₃or 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

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

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

2

3

6

3

2'

O

1'

1

4

7a'

3'

4a

5

8a

8

8a

8

4a

8a

8

4a

6

5

7'

6'

3a'

4'

5

6

7

6

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 data^12a

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 Na₂SO₄an 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

Collect. Czech. Chem. Commun. (Vol. 65) (2000)

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 C₁₉H₁₄O₃290.0943, 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 C₂₂H₁₄O₄342.0891, 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 Na₂SO₄an 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 Na₂SO₄an 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 C₂₄H₂₂O₂342.1619,

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,

Collect. Czech. Chem. Commun. (Vol. 65) (2000)

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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 C₁₆H₁₄O₂238.0993, 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).

Collect. Czech. Chem. Commun. (Vol. 65) (2000)

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, J_C-F= 22.0, C-3), 116.91 (dd, J_C-F= 22.9, C-5), 119.05 (d, J_C-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, J_C-F

=

9.2, C-6), 139.12 (s, C-2′), 141.57 (d, J_C-F= 7.3, C-2), 162.44 (d, J_C-F= 250.9, C-4). ¹⁹F NMR

(CDCl₃): –109.77 (dt, J_F-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

₁₆H₁₁F⁷⁹Br₂379.9212, 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 Na₂SO₄an 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 Na₂SO₄an 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 Na₂SO₄an 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).

Collect. Czech. Chem. Commun. (Vol. 65) (2000)

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 Na₂SO₄an 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≡CCH₂overlapped with CDCl₃sign 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 Na₂SO₄an 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

Collect. Czech. Chem. Commun. (Vol. 65) (2000)

596

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,

Collect. Czech. Chem. Commun. (Vol. 65) (2000)

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 .).

Collect. Czech. Chem. Commun. (Vol. 65) (2000)

598

Stará, Kollárovič, Teplý, Starý, Šaman, Fiedler:

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 × CH₃of on e diastereoisom er); 1.66 (dt, 3 H, J = 3.2, 3.2, 0.6, 2 × CH₃of on e

d.); 2.51 (brs, 2 H, 2 × OH of both d.); 4.82–4.85 (m , 4 H, 2 × CH₂of 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 × CH₃of on e diastereoisom er),

15.17 (q, 2 × CH₃of 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 C₂₂H₁₈282.1409, 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 C₂₈H₃₄Si₂426.2199, 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 C₃₂H₃₀O₈542.1941, 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 C₃₄H₃₄O₈570.2254, 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 Na₂SO₄was 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 C₂₀H₁₆O₂288.1150, 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 Na₂SO₄an 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 CDCl₃sign 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

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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 Na₂SO₄an 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 C₂₈H₂₄O₂392.1776, 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

₄₄H₆₀Si₂644.4234, 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 C₂₆H₂₀332.1565, 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 C₂₈H₂₄360.1878, 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)

Article Doi

Synthesis of aromatic triynes as precursors to helicene derivatives

DOI: 10.1135/cccc20000577

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Article abstract of DOI:10.1135/cccc20000577

Full text of DOI:10.1135/cccc20000577

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