Full text of DOI:10.1007/BF02659546

R E A C T I O N
O F S E C O N D A R Y A M I N E S W I T H C Y C L I C
C A T A L Y Z E D B Y N I C K E L C O M P L E X E S
1 , 3 - D I E N E S ,
U . M . D z h e m i l e v , A . Z . Y a k u p o v a ,
and G. A . T o l s t i k o v
UDC 542.97:547.822.3:547.592.3
We were the f i r s t to study the reaction of secondary amines with cyclic 1,3-dienes in the presence of
nickel complexes and activating additives. 1-Morpholyl-2-cyclopentene (I) is formed in 60% yield when cyclo-
peutadiene (CRD) is reacted with morpholine in the presence of Ni(acac)~--Al(C~Hs)s-- P(C4H~s--CF~COzH,
1 : 2 : 3 : 1 0 (80°C, 5 h). The reaction is complicated by the formation of dicyclopentadiene (DCP), which lowers
the yield of (I) substantially. Compound (I) is not formed i n t h e absence of CFsCOOH.
Under the optimum conditions (80*, 5 h), piperidine when reacted with CH) i n t h e same catalytic system
is converted to 1-piperidyl-2-cyclopentene (II) in 50% yield. After reaction the catalyzate contains, together
with (II), um'eacted piperldine, DCP, and 5% of CPD. The yield of ([) and (H) could not be increased by in-
creasing the temperature and reaction time due to the competing dimerization of CPD to DCP. At the decom-
position temperature of DCP (180-190°) the yield of ([) and (II) is low, probably because of the decomposition
of the catalytically active complex.
....
N~C / - ~
~
N.._/
v
X
--O11), CHilli)
W h e n C P D is replaced by 1,3-cyclohexadiene the yields of amines (HI) and (IV) are, respectively, 90
and 80~. In contrast to CPD, 1,3-cyclohexadiene also reacts with piperidine and morpholine inthe absence of
CF~CO~H, but here the yield of the amines does not exceed 10%.
X
N H + ~ _ /
.
~ . / N - - ~ _ _ /
X=-CHs(lll). O(lV)
I _ _ + © _ x _
In our experiments we were unable to make 1,3-cyclooctadiene r e a c t with amines.
E X P E R I M E N T A
L
The employed dienss were at least 99.5~ pure. The amines were analyzed on a Chrom-31 chromato-
graph, using a 2 - m long column, packed with Silicons Eiastomer E-301 depoeited on Celite, and nitrogen as
the c a r r i e r gas. The UR spectra were taken on a UR-20 spectrophotometer (as a film). The NMR spectra
were recorded on a Tesia BS-480B inatrume-~ using CC14 solutions add HMDS as the internal standard. The
mass spectra were taken on an MKh-1306 inatrumert using ionizing electrons with an energy of 50 eV and an
ionization chamber temperature of 200%
To a solution of 0~5 mmole of Nl(acac)2, 1.5 mmoles of P(C4HI) 3, and 1.0 ml of butadiens in 3 ml of dry
benzene at 0", in an argon stream, was added 1.0 mmo[e of AI(C2Hs)3 and the mixture was stirred for 0.5 h.
The catalyst solutionwas transferred to a 17-ml steel autoclave, which had previously been Loaded with 50
mmoles of the amine, 50 mrnoles of the 1,3-cyclodiene, and 5 mmoles of CFsCO2H, and the mixture was
heated at 80* for 5 h. After cooling, the catalyzate was washed with water, filtered through 10 g of Al~O~ (HI
activity), and washed with benzene. The benzene eluates were combined with the main filtrate, the solvent
was evaporated, and the residue was vacuum-distilled.
Institute of Chemistry, Bashkir Branch of the Academy of Sciences of the USSR, Ufa. Translated from
Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2346-2348, October, 1976. Criginal
article submitted ~anuary 6, 1976.
2190

l-Morpholyl-2-cyclopentene
(1).
Bp 86° (7 mm); nD 2° 1.4934. Infrared spectrum (#, cm-t): 720,
(2H, CH2); 2.1 (2H, CH2C=); 2.29 (4H, CH2N);
3060 (cis-CH=CH).
N M R spectrum (5, ppm): 1.7
m
m
m
I
3.2
CgI-IisNO.
m
(1H, --CHN--); 3.45
m
(4H, CH20); 5.67
70.59; 9.8; N 9.15%.
7.32; CI 18.659[. CSHlsNOCI. Calculated: C 56.99; H 86.44; N7.39; CI 18.739[.
m
(2H, C H = C H ) ; m/e 153. Found: C 70.6; H 9.7; 9.2~.
N
Calculated:
C
H
Hydrochlorlde, m p 199-201°. Found: 56.71; H 8.58;
C
N
1-1>Ipsrldyl-2-cyclopentene (If).
Bp 76° (7 mm); nD2° 1.4903. Infrared spectrum (#, cm-i): 720, 3060
I
(cis-CH=CH).
N M R spectrum (5, ppm): 1.54
m
(8H, CH2); 2.2
9.30%. Ci0Hi7N. Calculated:
Hydrochloride, m p 218-220°. Found: C 63.52; H 9.63; N 7.34; CI 19.5%. CIoHisNCI. Calculated:
m
(6H, CH2N, CH2C=); 3.32
m
(1H, --CHN--);
5.53 (2H, CH=CI-I); m / e 151. Found: C 79.50; H 11.20;
N
C 79.47; H 11.26;
N
C
9.27%.
64.00; H 9.60; N 7.47; CI 18.93%.
1-1>Ipsridyl-2-cyclohexene (HI).
Bp 55° (1 ram); nD~-° 1.5008. Infrared spectrum (#, cm-i): 730,
(10H, CH2); 1.85 br. s (2H, CH2C=); 2.4 (4H,
3030 (cls-CH=CH).
CH2N--); 3.03 (1H, --~HN--); 5.54 s (2H, C H = C H ) ; m/e 165. Found: C 80.1; H 11.5; N 8.3%. CiIHigN.
Calculated: C 65.44; H 10.01; N6.82; CI
N M R spectrum (5, ppm): 1.41 br.
s
m
m
C
80.00; H 11.51; N8.489[.
Hydrochloride, m p 229-231°. Found:
17.7,~.
CIIH20NCI. Calculated:
C 65.50; H 9.93; N 6.95; CI 17.62%.
1-Morpholyl-2-cyclohexene
(IV).
Bp61 ° (1 mm); nD2° 1.5015. Infrared spectrum (#, cm-i): 730,
(2H, CH2); 1.87 br. (2H, CH2C=); 2,42 (4H, CH2N);
3025 (cis-CH=CH).
3.01 (1H, --~HN--); 3.48
Ct0HITNO.
N M R spectrum (5, ppm): 1.56
m
s
m
m
m
(4H, CH20); 5.57 s (2H, C H = C H ) ; m/e 167. Found: C 72.3; H 10,2; N 8.4%.
Calculated: C 71.86; H 10.18; N 8.38%. Hydrochloride, m p 194-195°. Found: 59.04; H 8.84;
6.83; Cl 17.49[. CIoHI8NOCI. Calculated: 58.97; H 8.85; N 6.88; Cl 17.44%.
C
N
C
C O N C L U S I O N S
The reaction of piperidine and morpholine with cyclopsntadiene and 1,3-cyclohexadiene in a system that
cor£alas nickel acetylacstonate, trl-n-butylphosphine, trlsthylalumim~m, and trifluorcacetic acid (1 :3 :2 :10)
leads to cycloalkenylpiperidlnes and morpholines.
R E A C T I O N
O F
A L L Y L M E R C U R Y
H A L I D E S W I T H
P L A T I N U M C O M P O U N D S
UDC 542.91:547.354.9:546.92
A .
Z. R u b e z h o v , A . S. I v a n o v ,
and S. P. G u b i n
Allyl compounds of mercury are universal allylating age-is for metal hatides of the 1~ group (Bu, Os,
It, Rh, Pd) [1-5]. We studied the reaction of allylmercury halides with I~(IV), Pt(II), and Pt(0) compounds.
Depending on the character of their reaction with CH2 =CHCH2HgC1, and Pt (IV) and Pt(II) compounds can
be subdivided trto two groups. The f i r s tgroup includes saltlike compounds of the M2PtCIs and M2PtCI4 type
(M = K, Na), Zelse salt, and its d i m e r (C2H4PtC12) 2. These Pt0I) and Pt(IV) derivatives react with allytmer-
cury chlorides (AMC) to give Pt, HgGI) salts, and the liberation of biallyt (BA).
MeOH
ZtPtCl, (C41"I~] + 2CuHsI-IgCl "*' xh ( ' - ~ -b Pt -t- 2HgCI, -~ KCI + ClI~
~)
The second group of compounds includes complexes of type L 2 P t X4 and L~PtX2, where L ffi P h C N or PPh 3.
Institute of Heteroorganic Compounds, Academy ofSciences of the USSR, Moscow. TransLated from
Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2348-2350, October, 1976. Original
article submitted January 9, 1976.
I TMa matcrisl It protected by copyright registeredIn the name of Plenum Publishing Corporation. 227 West 17th Street, New York, 3/. E 10011. No ~.rt
of th~ l~bU~fion may be reproduced, stored In a retrieval system, or mmmgne@, tn any form or by any. m~ns, electronic, mechanicM, photocopying,
microfilming, recordMgor otherwise, without written pcwmkcsion of the publl~gr. A copy of thisarticleis available from the publisher for $7.50.
2191

These Pt(lI) and Pt(IV) derivatives react with AMCto give BA and Hg(I) salts. The starting Pt compounds
r e m a i n unchanged during reaction, for example,
~ H , ~ I (sPPl~U)~.~, , .. ~ + ~,cl,
(~.)
I~CI,
It is possible that reaction (2) proceeds under the influence of the free llgand L that is present in the benzene
solution [64 which is capable of functioning as a symmetrizlng agent. The dlatlylmercury that is formed dur-
Ing symmetrization decomposes under the reaction conditions to give BA and Fig, and the latter reacts with
HgCI 2 to give calomel. Actually, we were able to isolate Hg in a number of cases.
2C~-I~I-IgCl ~ CsH~--Hg--CsH~ ~- HgCls
C,I-I,HgC,H, --~ C,H,--C,I-I, -t- He
(3)
HgC~ -I- Hg --~ Hg,CI,
L4R (L = PPhs) reacts instantly with allylmercury halides in benzene at ~20". Evaporation of the r e a c -
tion mixture gave r-allyl cation complexes. When reacted with (PPh3)41~t under analogous conditions the alkyl
and aryl derivatives of HgaI) form the ~-complexes (PPhs)2~R(X) ~ = alk-yl, aryl) [7].
11,
I
(PPh,)4 Pt + R
r
C
Benzene
~CH
,
/
\CHr--CHsHgCI
PPha-.1
L
B / " PPhJ
11~11'-~H; 1 1 u H , 11°=-Me; 11==H, 11'mPh; 11=,Me,
11'==H; 11mPh, 11'=-H; II==A©, 1 1 ' s M e
The obtained r-aUyl complexes are stable colorless compounds that are difficultly soluble In organic
solvents and are soluble only in chloroform to glve the (1:1) adducts with the solvent. Despite the fact that
the method proposed by us for the synthesis of the ~-allylbis (triphenylphosphine) complexes of platinum [at
least for ~-allyibis (trlphenylphosphine)platfnum chloride] is less convenient than the reaction of L4Pt with
allyl halides [8], the latter cannot be used to obtain a wide selection of substituted ,r-allyl complexes (for
example, for the synthesis of the 2-phenyl- or 1-acetyl-2-methyl derivatives), since the corresponding s u b -
stituted allyl halides are not available.
E X P E R I M E NTA L
The starting allylmercury halides were obtained as described in [9]; the synthesis of the Pt compounds
was described in [10]. The IR spectra were measured on a UB-10 instrument as KBr pellets, while the NIVIR
spectra were taken on an NR-2305 instrument (60 lVlHz).
Preparation of r-AUyibis(triphenylphosphine)platinum Chlorides (General Method). To the orange-yellow
solution of 0.0004 mole of (PPh3)4Pt in 50 ml of benzene was added in drops, at ~20°C, in an argon atmosphere,
a colorless solution of 0.0004 mole of the allylmercury halide in 20 ml ofbenzene. The mixture decolortzed
within 5 rain and a gray precipitate of Hg deposited. The mixture was stirred for another hour, filtered, and
the filtrate was diluted with ether until all of the reaction product had precipitated, which was filtered, washed
well onthe filter with ether to remove the PPhs, and dried In vacuo. The obtained white compound was r e -
crystallized.
*
Blli~riphenylphosphine)-~-allylplatlnum Chloride [(PPh3)2Pt(C2Hs)]CI. Yield 70~, mp 194-198° (de-
compr~.), mp 195" (decompn.)[8]. Found: C 58.51: H4. 36; C14.90~. C301-1ssPtP2Cl. Calculated: C 58.83;
H 4.43; CI 4.45%. Infrared spectrum (~, c m - t ) : 3080, 3050, 3020, 2995, 1590, 1480, 1435, 1400, 1315,
1280, 1190, 1170, 1125, 1100, 1080, 1030, 1005, 945, 930, 870, 850, 760, 730, 700, 545, 510. NMB spec-
trum (CHCt3, 5, ppm): 3.56 (unresolved signal, 4H); 6.10 m (1 H).
BIS (trtphenytphosphine)-,r-2-phenylattytplatinum Chloride [(PPh3)zPt (CeHg)]CI" CHCI3. Yield 70~, mp
287-293" (decon~pn.). Found: C 55.39; H 3.92; CI 14.00; P 6.80~. C43H40PtP2CI4. Calculated: C 55.71; H
4.06; CI 14.30; P 6.25%.
* I ~ ease of AMC the obtained complex was recrystallized from benzene. In all of the other cases the com-
plexes are insoluble in hot benzene and were recrystaUized from chloroform.
2192

Bis (triphenylphosphine)-~-l-acetyl-2-methylallylplatinum Chloride [(PPh3)2Pt(CsHsO)]Cl • CHCIs. Yield
54%, m p 295-300° (decompn.). Found: C 53.14; H 3.92; Cl 14.02; 6.20~. C4~H40PtP2C[40. Calculated.
53.15; H 4.15; Cl 14.58; P 6.38~. Infrared spectrum (v, cm-t): 3080, 3060, 3030, 3010, 2990, 1680-
1650, 1590, 1580, 1485, 1435, 1315, 1195, 1165, 1100, 1035, 1005, 760, 700, 620, 555, 535, 520, 505.
P
C
Bis(triphenylphosphine)-,r-l-methyla[lylpl~tinum
258-274° (decompn.). Found: C 52.85| H 3.79; Cl 14.98;
Chloride [(PPh3)2Pt(C4HT)]CI - C H C I3, Yield 7(~, m p
6.33~. C4tH~aPtP2CI4. Calculated: 52.97; H
P
C
4.12; CI 15.25;
Bis (triphenylphosphine)-~-2-methylallylplatinum
290-295" (decompn.) Found: C 52.81; H3.94; C1 15.10; P 6 . 2 8 ~ . C41H38PtC14P2. Calculated: C 52.97; H 4.12;
P 6.66%.
Chloride [(PPh3)2Pt (C4H7)]C1" CRCI~. Yield 65%, mp
C1 15.25; 6.66%.
P
Reaction o f Pt(II) and Pt(IV) Compounds with AMC (Genera[ Method). To a solution of 0.003 mole o f the
Pt compound in 100 ml o f CH3OH a t ~20°, in an argon atmosphere, was added a solution o f 0.003 mole o f AMC
in 50 ml of M e O H , after which the mixture was stirred for 3-4 h and then filtered. The filtrate was diluted
with water and extracted with chloroform.
The aqueous layer was evaporated and the residue was analyzed
for the presence of Rg2+ or Hg + by the addition of N a O H . The organic layer w a s evaporated, collecting the
condensate In a cooled (--78°) receiver. After distilling off the solvent the residue was recrystallized and
analyzed in the usual manner. The condensate was analyzed by G L C for the presence of bfally[.
C
O N C L U S I O N S
1.
A study was made of the reaction of allylmercury halides with Pt(0), Pt(II), and pt(rv) compounds.
2. The ~-allylbls{triphenylphosphine) complexes of Pt were synthesized by the allylation of tetrakls-
(triphenylphosphine)platinum with substituted allylmercury halldes.
L I T E R A T U R E C I T E D
1.
A . N . Nesmeyanov, A. Z. Rubezhov, S. P. Gubin, A. S. Ivanov, and A. I. Voronchlkhina, Izv. Akad.
Nauk SSSR, Ser. Khlm., 2359 (1971).
2.
3.
4.
5.
6.
7.
A . Z . Rubezhov, A. S. Ivanov, and S. P. Gubin, Izv. Akad. Nauk SSSR, Ser. Khtm., 951 (1973).
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A . Z . Rubezhov, A. S. Ivanov, and S. P. Gubin, Izv. Akad. Nauk SSSR, Ser. Khim., 1902 (1974).
A . Z . Rubezhov, A. S. Ivanov, and S. P. Gubin, Izv. Akad. l~tuk SSSR, Ser. Khim., 2651 (1974).
R. Ugo, Coord. C h e m . Revs., 3, 319 (1968).
V.I. Sokolov, V. V. Bashilov, L. M. Anishchenko, and O. A. Reutov, J. Organometall. Chem., 71,
C 41 (1974).
8.
9.
H. C. Volger and K. Vrieze, J. Organometall. Chem., 13, 495 (1968).
A . N . Nesmeyanov, A . Z. Rubezhov, L. A . Leites, and S. P. Gubin, J. Organometall. Chem., 12,
187 (1968).
I0.
R . F . Hartley, Organometall. C h e m .
Revs., 6, 119 (1970).
2193