..
Introduction
[AcOPdCOOCH3] f C6&C = CH -
AcOPd COOCr-1,
\
/WC’ - C,H,C =CCOOCH, i- Pd k HOAc _
=sH5 ‘ti
I
” : -- -. __.. _.I__
-_.-; ~_ -: ._-: .. -.- ._: ,:‘. .:.1.__.-_.
.-..- ._...:I
260
RC=C- + -
+ R’C=CR + Pd[P(C6&)3]2
Thus, the major limitation of this disubstituted acetylene and enyne prepa-
ration is that halides with strongly electron-donating substituents, or halides
which are otherwise made relatively unreactive in the oxidative reaction with
the palladium(O) catalyst, do not react well. Otherwise, the reaction appears
widely applicable and it will provide a convenient new method for obtaining a
variety of acetylene derivatives.
TAIILE 1. ACETYLENIO SUBSTITUTION REACTIONS (REACTION TPMP, = 100°C)
---I_.-- --_-..-
Orwnlo halldc Acotylanlo rcnctnnt hmlna Cnta- Reaction Product B,p, or m.p, Mel, wt, found NMR spectrum
(mmol) (mmol) (ml) lysta tlmo (h) (yield Ib) (roportcd)% (cnlcd,) (7)
_-“. __--..l.-..I-.---L1.--.-- -----_- --.--_.-,l-.-_l-
Iodobonzcne Phenylncotylcno Triothyl~ A 116 Dlphcnylncctylone
W-N (12,G) nmlno (20) (67, 73 “)
Bromobcnxeno Phonylncctylcnc Tricthyl. A 2,G Dlphcnylaoetylcno
” (10) (20) nmlno (20) (GlP
Bromobcnzeno Phcnylncctylcnc Plpcrldlno A 2,G Dlphonylacatylcnc
(10) (20) (20) (64)”
Iodobcnzcne l.Hcxync Plpcrldlno II 1 l~Phcnyl.l.hcxync
(6) (10) (10) (62)b
E-B-Bromostyronc Phonylncctylonc Triothyl- A 1 &l,l.Dlphcnyb
(10) (20) nmlno (60) l.buton.S.yncd (7o)b
C2~Rromostyrcnc Phcnylucctylcno Trlothyl. C 1 Z.l,l.Dlphcnyl. Idcntlcnl to thnt
(20) (40) nmlno (60) l.buton4wwd (60,9) previously reported ‘d
Iodobcnzono IL.Mcthyl.l-butcn- Trlothyk C 2.Mcthyl.l.pbcnyl. 42.431 142,078 (Neat) 2,34.2,36m
(100) 3wc (200) amino (200) l*butcw3.ync (71) OS36Torr (142,078) (GH), 4,GGm(lH),
4.74m (lH), 8,07s(br)
(3H)
2~IIromoproponc Phcnylncctylcnc Trlcthyl. C 1 2.Mctlryl.4.pbo~ryl.
(10) (1286) umlnc (20) l.butcn.3.ync (38)b
bIIromobcnxnldchydc Phcnylncctylcnc Triothyl. C 1 d.(Phcnylcthynyl). 98.98,6 206,060 [(CD3)2301 0,088 (lH),
(60) (76) nmlnc (100) benznldchydc (6&O) (206,073) 2,OOd(2H), 2,20d (2H)
J = 8 Hz, 2,20_2,7Om
(6H)
2.Bromothlophcnc Phonylncctylcnc Plpcridlnc II 0,G 2~Phcnylcthynyl~ 40.49 3% 184,036 (CCl4) 2,32-2,86m (7H),
(10) (20) (20) thiophcnc (63.0) (48,6-49.6)c (184,036) 3.00,3,06,3.09, 3,14m
% 136.040 (1H)
(186,034)
3(1s 186,034
(186,030)
4rBromonltrobcnzcne t~Butylacctylcnc Tricthyl. II 0,G (CDC13)2,Old (2H),
cl~(t~Butylclhynyl)nItro- 103.104 203,ODl
(20) (30) amlnc (40) bcnrano (38,4)
2JIGd (2H) J = D Hz, (203,096)
8,679 (DH)
Mothyl &Smbromo= t.Butylacctylonc ‘I’rlcthyl. C 2,2G Methyl &2,6,G~trlnrcthyl~ 47~48/ 130,116 (Neut) 3,41q (lH),
Bmcthylpropcnontc (30) ilmlnc (40) hcpt-2.cn.4-ynootc (68.6) 0,45 Torr (180,116) 3,02d (3H) J < 2 Hie,
j c-w 6,308 (3H), 8,736 (WI)
-._-....__“.l_“_........ll-..-..-.”-..--
Y--..<.-.” _._..I _..” _......__ _“_I”...__ . . .-...-.,-_ . . . . _ .,.--.
I”...,-_..-I .,.-......_ .._“,.
....(“.“..I,__.,..I....,_. ,_....._
“.“” ,-.I,.“.....,.,” .. .... ........“.._.._
oh = 1 mol ‘x,Pd(OAc)l, 2 mol % Ph3P: B = 2 mol Z (IJh3P)2Pd(OAc)2:C m 1 mol% (Ph3P)2Pd(OAc)z,bYicld determined by VPC, ‘Rcf, 10. dRef. 11, ‘Ret, 12,
;.
~--
263
Experimental
Methyl E-3-bromo-Z-methylpropenoate _
This material was prepared by the method of Canbere [S].
Z-2-Bromostyiene
This was prepared by the method of Cristol and Norris 191.
4(t-Butyiethynyl)nitrobenzene
CBromonitrobenzene (4.04 g, 20 mmol), t-butylacetylene (2.46 g, 30
mmol) and 40 ml triethylamine were placed in a heavy-walled Pyrex reaction
bottle containing a magnetic stirring bar. (Ph3 P&Pd(OAc), (0.298 g, 0.4 mmol)
was added and the bottle was flushed with argon and capped with a self-sealing
rubber-lined cap. The mixture was then heated with stirring on a Steam bath.
After 30 mm, VPC analysis showed that essentially all of the starting bromide
had reacted. The reaction mixture was diluted with 100 ml ether and filtered
and the residue on the filter was washed several times with ether. The ether and
other volatile materials in the filtrate were removed under reduced pressure
leaving a brown solid which was sublimed at lOO”C/O.2 Torr. Recrystallization
of the sublimate from hexane afforded 3.59 g (88.4%) of 4-(t-butylethynyl)-
nitrobenzene, m-p. 103-104°C.
References
1 R-F. Heck, J. Amer. Chem. Sot-. 94 (1972) 2712.
2 R.F. Heck. J. Amer. Che SOG 91(1969) 6707.
3 R-F. Heck. J. Amer. Chem. Sot. 93 (1971) 6896.
4 R-F_ Heck. J. Amer. Chem. Sot.. SO (1968) 5518.
5 H. Horino. M_ Arai end N. Inoue. Bull Chem. Sot. Japan. 47 (1974) 1683.
6 H-A. Dieck and R-F. Heck. J. Amer. Chem. Sot.. 96 (1974) 1133.
7 L. Cassar. J. Organometal. Chem.. 93 (1975) 253.
8 P. Canbere. BulL Sot Chim. France. <1964) 144.
9 S.J. Cristol and W-P_ Norrir J. Amer. Chem- Sot-. 75 (1953) 2645
10 A.C. Cope. D-S. Smith and R-J- Cotter. Org. Syath_. COIL VoL 4. (1963) 377.
11 A. Schoenberg and R.F. Heck. J- Org. Chem_. 39 (1974) 3327.
12 D. Brown. J-C. Craig. N-H. Dyson and W.C. Westlery. J. Chem. Sot_. (1966) 89.