2320 J. Org. Chem., Vol. 37, No.

14, 1972 HECK

AND NOLLEY

nmr (CDC13)7 3.46 (d, J = 3.2 Ha, 1, Cp H), 4.70 (s, 1, NH), slowly over a period of 3 hr and the mixture was further re-
7.14 and 7.32 (m, 2, C? and C1 H), 7.90 (broad s, 1, C B H ) ,8.22 fluxed for 3 hr. The cooled mixture was washed with water
(m, 1, CCH), 8.49 (In, 2, CZand C3 H), and 8.60 (s, 11, CsH and several times and dried over sodium sulfate. Removal of the
CH3) . solvent gave a dark brownish residue (ca. 6 g) which was purified
Anal. Calcd for C14H19NO: C, 77.38; H, 8.81; N, 6.45. on a silica gel column eluting with chloroform-methanol to give
Found: C, 77.12; H , 8.83; K,6.68. N-ethoxycarbonyl-8-aza-6-cyclane (10) as a colorless oil. This
8-Cyano-9-chloro-6-cyclene(3c), ezo-3-Cyano-4-chlorotricyclo- was also obtained by distillation of the crude product: bp 88-
[4.2.1.O * 3 7 nona-3,7-diene (4),and 2-Chloro-3-cyanotric yclo [4.3 .- 90' (0.4 mm); l t z o1.5179;
~ ir (neat) 1700,800, and 770 cm-l.
0.O4lg]nona-2,7-diene (5).-The reaction product of 1 with 2c Anal. Calcd for CllHlaNOz: C, 68.37; H, 7.82; IT,7.23.
could not be extensively pruified by a fractional distillation under Found: C,68.40; H, 7.82; N, 7.22.
reduced pressure, and hence preparative vpc separation was Further elution gave N-ethoxycarbonylamino-5-N-ethoxy-
performed at 150" on a silicone SE-30 column (20 ft x 0.375 in.). carbonylaminomethyltricyclo[2.2.1.024heptane (11) as colorless
The first peak afforded 4 in 6% yield as a colorless oil which on crystals: mp 130-131'; ir (KBr) 3260, 1700, 805, and 782
standing crystallized: mp 36-37'; ir (KBr) 2260 and 1610 cm-'.
cm-'; uv max (EtOH) 228 (infl) and 248 nm (e 1700); mass Anal. Calcd for C I ~ H ~ Z N Z C,
O ~59.55;
: H, 7.85; N, 9.92.
spectrum m/e (re1 intensity) 179 (0.3, M +
2), 177 (1, bl+), Found: C, 59.69; H, 7.84; N, 9.76.
142 (16, M - Cl), 115 (46, M - HCN), 66 (57, cyclopentadiene), Reaction of 1 with Benzalbisurethane .-The reaction was
and 51 (100, cyanoacetylene). carried out as above. Work-up afforded only 3-nortricyclyl-
Anal. Calcd for ClaHsNC1: C, 67.62; H, 4.54; N, 7.88. urethane (12) in ca. 50% yield as colorless crystals, mp 61-64'
Found: C,67.52; H,4.67; N, 7.70. (lit.ILmp 64"); there was no depression of the mixture melting
The second peak afforded 3c in 40% yield as colorless crystals: point with an authentic sample.
mp 40-42'; ir (KBr) 2250 and 1585 cm-'; uv max (EtOH) 240 Reaction of 1 with Anhydrochloralurethane (Qc).-An equi-
nm (e 9100); mass spectrum m/e (re1 intensity) 179 (20, M 2), + molar mixture of 1 and 9cI6 in dry benzene was heated at 80" for
177 (61, >I+), 142 (99, R I - Cl), and 115 (100, &I- HCN). 6 hr. After removal of the solvent, the residue was dissolved in
Anal. Calcd for CloHsNC1: C, 67.62; H, 4.54; N, 7.88. chloroform and was purified on a silica gel column (CHC1,-
Found: C, 67.52; H,4.67; N , 7.70. MeOH). The major product was an adduct of chloralurethane
The third peak was very weak and was not resolved well with to 9c, which was isolated in 23% yield as needles: mp 164-166'
the fourth peak, and therefore, pure material could not be ob- (lit." mp 163-164'); nmr (CDCI,) 7 3.95-4.70 (broad m, 4,
tained. two -NHCH), 5.78 (4, 4, two COZCHZCH~), and 8.70 (t, 6,
The fourth peak gave 5 in 20% yield as a colorless oil: n166~ two COzCHZCHs).
1.5524; ir (neat) 2300 and 737 cm-'; uv max (EtOH) 227 and 238 Further elution gave only unidentified oily minor products.
nm (e 800 and 490); mass spectrum m/e (re1 intensity) 179 (0.3,
+
&I 2), 177 (1, M+), 142 (16, M - Cl), 115 (46, R I HCN), -
Registry No.-1, 121-46-0; 2a, 1070-71-9; 2b,
66 (57, cyclopentadiene), and 51 (100, cyanoacetylene).
Anal. Calcd for CloH8NCl: C, 67.62; H, 4.54; N, 7.88. 22237-84-9; 2c, 2003-31-8; 2d, 536-74-3; 2e, 33064-
Found: C,67.85; H,4.59; r\',7.60. 30-1; 2f, 28112-07-4; 3a, 34627-34-4; 3b, 34627-35-5;
Reaction of 1 with Methy1enebisurethane.-To a refluxing 3c, 34627-36-6; 4, 34627-45-7; 5, 34627-37-7; 9a,
mixture of methylenebisurethane (9.5 g, 0.05 mol) and 4770
boron trifluoride etherate (1.81 g) in dry benzene (50 ml) was 34627-38-8; 9b, 27593-62-0; 9c, 16723-30-1; 10,
added a solution of 1 (4.6 g, 0.05 mol) in dry benzene (20 ml) 34627-41-3; 11,34627-42-4.

Palladium-Catalyzed Vinylic Hydrogen Substitution Reactions with Aryl,

Benzyl, and Styryl Halides
R. F. HECK"AND J. P. NOLLEY,
JR.
University of Delaware, Newark, Delaware 19711
Received January IS, 19Yd

Aryl, benzyl, and styryl halides react with olefinic compounds in the presence of a hindered amine and a cat-
alytic amount of palladium metal to form vinylic derivatives in which the aryl, benzyl, or styryl group has re-
placed a vinylic hydrogen of the original olefin. The reactions occur readily a t 100" and yields are generally
good.

Mizoroki' and coworkers have recently reported a very useful, they suffer from two major difficulties.
palladium-catalyzed arylation reaction of olefinic com- There is often a problem of obtaining the necessary
pounds with aryl iodides and potassium acetate in organomercury, -lead, or -tin compounds and there is
methanol a t 120". We have independently discovered the problem of working with thick slurries of salts,
this reaction and find that it can be carried out under particularly if the reaction is carried out catalytically
much more convenient laboratory conditions than were in palladium. This new method eliminates both diffi-
used by Mizoroki and that the reaction provides an culties.
extremely convenient method for preparing a variety
of olefinic compounds. Results and Discussion
The reaction is undoubtedly closely related to the It is well known that Pd[P(CeH6)3]4 reacts readily
known olefinic arylations and alkylations achieved at with a variety of organic halides to form oxidative addi-
room temperature or below with palladium salts2t3 tion products of the type [P(CBH&]gPd(X)R.4,6I n
using organomercury, -tin, or -lead compounds rather the reaction reported herein, a similar oxidative addition
than organic halides. While the known reactions are apparently occurs between palladium metal (formed
by an in situ reduction of the palladium acetate initially
(1) T. Mizoroki, K. hlori, and A. Ozaki, Bull. Chem. Soc. J a p . , 44, 581
(1971). (4) P. Fitton and E. A. Rick, J. Organometal. Chem., 28, 287 (1971).
(2) R. F. Heck, J . Amer. Chem. Soc., 90,5518 (1968). (5) P. Fitton, IM. P. Johnson, and J. E. McKeon, Chem. Commun., 6
(3) R . F. Heck, ibid., 91, 6707 (1969). (1968).
 VINYLIC
PALLADIUM-CATALYZED HYDROGEN
SUBSTITUTIONS J . Org. Chem., Yol. 37, No. 14, 1972 2321

TABLEI
OLEFINSUBSTITUTION
REACTIONS HALIDES"
WITH ORGANIC
Reaction
Registry Registry time e t Mp of product, OC
Organic halide no. Olefinic compd no. looo, hr Product (yield, %Ib Registry no. (reported)
Iodobenzene 591-50-4 Styrene 100-42-5 2 trans-Stilbene (75) 103-30-0 123-1 24
( 124)c
Iodobenzene 4-Nitrostyrene 100-13-0 2 trans-4-Nitrostilbene (85) 736-31-2 153- 155
(155-156y
Iodobenzene cis-1-Phenyl-1- 766-90-4 2 cis-1,2-Diphenyl- 1-propene 1017-22-7 e
propene (7)
trans-l,2-Diphenyl-l-propene 833-81-8 e
(12)
1,2-Diphenyl-2-propene (4) e
Iodobenzene trans-1-Phenyl- 873-66-5 2 cis-l,%Diphenyl-1-propene e
1-propene (21)
trans-1,2-Diphenyl-l-propene e
(26)
Iodobenzenef Methyl acrylate 96-33-3 1 trans-Methyl cinnamate (81) 1754-62-7 e
4-Iodoanisole 696-62-8 Methyl acrylate 5 trans-Methyl-p-methoxy- 3901-07-3 89-90 (goy
oinnamate (68)
Methyl 4-iOdO- 619-44-3 Styrene 2 trans-4-Carbomethoxy- 34541-73-6 158-160
benzoate stilbene (74) ( 158-159)h
1,4-Diiodo- 624-38-4 Styrene 15 trans,trans-p-Dist yryl- 1608-41-9 266-267
benzene benzene (67) (265)(
l,a-Diiodo- 615-42-9 Styrene 72 trans,trans-o-Dist yryl- 27 164-48-3 117-118
benzene benzene (37) (117-119)i
Benzyl chloride 100-44-7 Methyl acrylate 15 trans-Methyl-4-phenyl-3- 34541-74-7 e
butenoate (67)
traas-Methyl-4-pheny1-2- 34541-75-8 e
butenoate (9)
trans-p-Bromo- 588-72-7 Methyl acrylate 72 trans,trans-Methyl-5-phenyl- 24196-29-2 70-71 (71)k
styrene1 2,4-pentadienoate (47)
a Except as noted, all reactions were carried out with 20 mmol of halide, 25 mmol of olefin, 20 mmol of tri-n-butylamine, and 0.2 mmol
of palladium acetate with magnetic stirring in a steam bath with a water cooler condenser for the time indicated. Yields were based
upon the halide used and were of isolated, recrystallized products except where noted. C. Hell, Ber., 37, 453 (1904). C. Weygand
and R. Gabler, ibid., 71, 2474 (1938). e Yields determined by gas chromatography. Producks were not isolated. f Reaction mixture
consisted of 10 mmol of iodobenzene, 20 mmol of methyl acrylate, 10 mmol of tri-n-propylarnine, 0.1 mmol of palladium acetate, and
9 ml of 1-methyl-2-pyrrolidinone. I. Heilbron, "Dictionary of Organic Compounds," Vol. 4, Oxford University Press, New York,
N. Y., 1965. R. C. Fuson and H. G. Cooke, Jr., J. Amer. Chem. SOC., 62, 1180 (1940). J. Dale, Acta Chem. Scand., 11, 972 (1957).
j D. H. Wadsworth, 0. E. Schupp, 111,E. J. Seus, and J. A. Ford, Jr., J. Org.Chem., 30,680 (1965). k G. Kresze, J. Firl, and H. Braun,
Tetrahedron, 25, 4481 (1969). The use of cis-p-bromostyrene also gave trans,trans-methyl-5-pheny1-2,4-pentadienoate, but only in
27% yield.

added by olefin) and certain organic halides, presumably better ; tri-n-butylamine was generally used. Mizoroki
producing very reactive solvated organopalladium(I1) carried out the reaction in methanol solution at 120")
halides. These are probably the same compounds pro- which required pressurized reaction vessels. We find
duced previously in the exchange reaction between that the reaction t a n be carried out easily at steam
palladium halides and organomercury compounds.'N2 bath temperatures in an open flask with a condenser,
When prepared in the presence of olefinic compounds without use of a solvent. The reaction proceeds well
these organopalladium halides undergo an addition in solvents such as 1-methyl-2-pyrrolidinone at 100"
reaction with the olefin, and then the adduct decom- and atmospheric pressure also, but there seems t o be
poses by eliminating a hydridopalladium halide, form- no advantage to using them. The reactions we have
ing the substituted olefinic compound. carried out are listed in Table I.
Three types of halides were found t o undergo the
RX + Pd * [RPdX] reaction: aryl, benzyl, and styryl. I n the aryl
examples, only the iodides reacted rapidly. Some
product formed with bromobenzene, but the reaction
was very slow even at 150". Benzyl chloride and p-
bromostyrene were less reactive than the aryl iodides
R >C=C, / -t [HPdX] but did give reasonable yields with longer reaction
times. As with the reactions employing organomercury
compounds,1~2these reactions tolerate a variety of
The hydridopalladium halide product finally de- functional groups such as nitro, methoxyl, and carbo-
composes into hydrogen halide and palladium, which methoxyl. Relatively low yields are obtained with
is then available to go through another reaction cycle. olefinic compounds having methylene groups adjacent
The accumulation of hydrogen halide in the reaction to the double bond. The low yields are apparently
mixture has a very detrimental effect and must be the result of the olefinic materials present forming
neutralized by inclusion of a base. Mizoroki used po- inert, a-allylpalladium iodide derivatives with the
tassium acetate, but we find a hindered amine to be catalyst, since, contrary to reactions with other types
2322 J . 01.0.Chem., Vol. 37, No. 14, 1972 HECKAND NOLLEY

of olefins, the palladium metal formed initially dis- Experimental Section

solves, and addition of more palladium acetate in- Materials.-All reagents were commercially available and used
creases thc yields of olefin substitution products sub- without further purification.
stantially. Gas Chromatography.-Samples were analyzed on a 6-ft
We have arbitrarily used 1 mol % palladium acetate silicon rubber on firebrick column a t 175'. Known samples of
as catalyst relative to the halide. Smaller amounts, the products were available from previous
General Procedure for Vinylic Substitution with Organic
no doubt, would be effective with the more reactive Halides.-In a 25-m1 round-bottomed flask containing a mag-
halides. Palladium metal deposited on charcoal may netic stirring bar was placed 0.2 mmol of anhydrous palladium
also be used as the catalyst but the reactions are slower acetate, 20 mmol of the organic halide, 20 mmol of tri-n-butyl-
and yields lower than with the finely divided metal amine, and 25 mmol of the olefinic compound. A water-cooled
obtained from in situ palladium acetate reduction. condenser was placed on the flask and the mixture was stirred
magnetically on a steam bath for the required length of time.
This new vinylic substitution reaction is clearly an On cooling the reaction mixtures often solidify. Several dif-
improvement over the mercurial reaction in many ferent product isolation procedures can be used. If the product
instances, particularly for preparing larger quantities is a high-melting solid, addition of water to the reaction mixture
of material. It does have some limitations, however, generally will give the product as a solid which can be separated
and recrystallized with hot filtration to remove palladium metal
which the mercurial method does not have. The loss present. Alternatively, if the reaction product is soluble in hot
of stereochemistry in the phenylation of cis- and truns- hexane, it may be extracted from the reaction mixture with boiling
1-phenyl-1-propene is one limitation. The isomeriza- hexane several times. The extracts are then concentrated and
tion appears to occur internally, probably through hy- either distilled or cooled to crystallize the product if it is a solid.
dridopalladium halide-olefin a complexes, since neither A more general isolation procedure is to dilute the reaction
mixture with cold dilute hydrochloric acid, extract the product
starting olefin is isomerized to a detectable extent under with ether in the usual way, and distil the extracts. Two ex-
the reaction conditions. In general, at the higher amples of the reaction are given in detail below.
temperatures of the halide reactions, double bond mi- trans-4-Carbomethoxystilbene.-A mixture of 0.045 g (0.2
grations would be expected to be more serious. The mmol) of palladium acetate, 5.24 g (20 mmol) of methyl p-iodo-
benzyl chloride reaction showed this effect in producing benzoate, 2.86 ml (25 mmol) of styrene, and 4.74 ml (20 mmol)
of tri-n-butylamine was stirred with a magnetic stirring bar in a
a rearranged olefinic compound as the major product steam bath under a water-cooled condenser for 2 hr. After
with methyl acrylate. The corresponding reaction cooling the reaction mixture was broken up with a spatula and
Pd
stirred with about 100 ml of water in a beaker. After the lumps
C6HsCHzCl + CH2=CHCOOCHs + n-BusN + were thoroughly mashed, the insoluble product was separated
C6H5CH=CHCH&OOCHa + by filtration. Recrystallization from 225 ml of boiling absolute
ethanol with hot filtration through Celite gave 3.50 g (74%) of
CeH6CH&H=CHCOOCHs + n-BuaNH+Cl- shiny plates, mp 158-160'.
trans,trans-p-Distyry1benzene.-A mixture of 0.045 g (0.2
with benzylmercuric acetate and palladium acetate mmol) of palladium acetate, 3.30 g (10 mmol) of p-diiodobenxene,
at room temperature gave only the expected t~uns- 2.86 ml (25 mmol) of styrene and 4.74 ml (20 m m d ) of tri-n-
methyl-4-phenyl-2-b~tenoate.~ butylamine was stirred magnetically in a steam bath under a
Other limitations include not being able to use base- water-cooled condenser far 15 hr. The mixture solidified during
the heating. The solid reaction mixture was broken up with a
sensitive compounds such as acrolein in the reaction spatula and stirred with water. The solid was filtered, washed
and not being able to methylate by the halide reaction. several times with fresh water, and recrystallized from about
Surprisingly, methyl iodide and methyl iodoacetate do 50 ml of hot dimethylformamide by filtering through Celite
not react with styrene under the usual conditions. hot and adding water until crystals began to appear in the hot
filtrate. After cooling, the pale yellowish product wab isolated
In spite of some limitations, the organic halide- by filtration. After air drying, there was obtained 1.90 g (67%)
olefinic substitution reaction should prove to be a useful of pale yellow crystals, mp 286-267".
synthetic reaction.
(6) R. F. Heck, J . Organometal. Chem., 37, 389 (1972). Registry No. -Palladium, 7440-05-3.