One-pot synthesis of tertiary α,ω-diamines via carbonylative bis[hydroaminomethylation] of α,ω-diolefins using di(μ-chlodo)bis(η4-1,5-cyclooctadiene)dirhodium as a catalyst precursor di(μ-chloro)bis(η4-1,5-cyclooctadiene)dirhodium as

Article abstract of DOI:10.1055/s-1998-4481

Tertiary α,ω-diamines are selectively prepared in high yields by the reaction of α,ω-diolefins with secondary amines, carbon monoxide and hydrogen in the presence of [Rh(cod)Cl]₂ as a catalyst precursor. This one pot synthesis proceeds via a hy

Full text of DOI:10.1055/s-1998-4481

January 1998
SYNTHESIS
71
a w
One-Pot Synthesis of Tertiary , -Diamines via Carbonylative Bis[hydroamino-
a w
m
h4
methylation] of , -Diolefins Using Di( -chloro)bis( -1,5-cyclooctadiene)dirhodium
as a Catalyst Precursor
Christian L. Kranemann, Peter Eilbracht*
Organische Chemie I (FB 3), Universität Dortmund, Otto-Hahn-Str. 6, D-44221 Dortmund, Germany
Fax +49 (231)7555363; E-mail: eilbrach@citrin.chemie.uni-dortmund.de
Received 24 March 1997; revised 29 July 1997
or as a two-step procedure from preformed aldehydes.7 We
Tertiary a,w-diamines are selectively prepared in high yields by the
reaction of a,w-diolefins with secondary amines, carbon monoxide
and hydrogen in the presence of [Rh(cod)Cl]2 as a catalyst precursor.
This one-pot synthesis proceeds via a hydroformylation–amine con-
densation–reduction sequence and leads to a mixture of n,n-, n,iso-,
and iso,iso-products.
report here on the one-step conversion of dienes 1a–d,
12, 15 and 19 to saturated tertiary diamines 4–11, 13,
14, 16–18 and 20, respectively, in high yields by reacting
the dienes with secondary amines 2 and 3 in the presence
of synthesis gas and [Rh(cod)Cl]2 as a catalyst precursor.
a,w-Diamines with long aliphatic chains separating the
two amino functions are of importance as synthetical and
biological surfactants, membrane components and bioac-
tive compounds. Usually alkylation methods are used in
their synthesis. We have recently reported on the one-pot
hydroaminomethylation of monoolefins, an addition pro-
cedure employing [Rh(cod)Cl]2 as a readily available cat-
alyst precursor.1 This procedure was originally discovered
by Reppe et al.,2 however, although synthetically attrac-
tive only few investigations are known, mostly using stan-
dard alkenes and amines leading to simple amine
products.3–15 If a,w-diolefins 1 are reacted with secondary
amines 2 or 3 by this method, diamines 4, 5 and 6 or 7, 8
and 9, respectively, are expected as a mixture of the
iso,iso-, the n,iso- and the n,n-regioisomers (see Scheme
1). In addition, the unsaturated species 10 and 11 may be
generated depending on concentration and reaction condi-
tions. Upon further hydroaminomethylation with a differ-
ent amine, these products should lead to unsymmetrical
diamines.
The results for the bis(hydroaminomethylation) of hexa-
1,5-diene (1a), octa-1,7-diene (1b) and deca-1,9-diene
(1c) and 3,3-dimethylpenta-l,4-diene (1d) with morpho-
line and diethylamine (for 1b) are listed in Table 1. Under
modified conditions unsaturated monoamines are ob-
tained from diolefins. Thus, upon lowering the tempera-
ture from 120°C to 80°C the conversion of 1b leads to a
mixture of 10b and 11b (44%, 1:1.3) and 4b, 5b, and 6b
(40 %, 1:2.6:1.6). Gas chromatography of the crude prod-
uct mixture excludes significant formation of any byprod-
ucts such as aldehydes, enamines or amides. In the present
investigation all products were purified by column chro-
matography. For large scale preparations distillation
should be sufficient for product isolation.
Under the conditions applied for bis(hydroaminomethyla-
tion)theregioselectivityoftheinitialhydroformylationstep
is moderate with a 3:1 to 3:2 preference for the n-product.
The chain length of the a,w-diolefin obviously has no sig-
nificant influence on the regioselectivity. Thus hydroami-
nomethylation of each double bond of the diolefin appears
to occur independently one from another. The regioselectiv-
ity of hydroaminomethylation should be controllable via
catalyst modification similar to hydroformylation.15 Prelim-
inary investigations concerning the effect of phosphane ad-
dition on product selectivity reveal significant shifts towards
the n,n-products, especially if Biphephos16 is added.
Hitherto conversions of dienes to diamines have been car-
ried out only in few cases in a one-pot version using pri-
mary amines and various ruthenium or rhodium catalysts9
The regioselectivity is also controlled by bulky groups in
the vicinity of the double bond. Thus the two methyl
groups of the 3,3-dimethylpenta-1,4-diene (1d) effect a
selective formation of the n,n-product 6d, Interestingly,
under similar conditions and in the absence of an amine,
Table 1. Product Ratio in Bis(hydroaminomethylation) of 1a–da
Diene Amine Total yield
of 4–9 (%)
Product ratio (%)b
iso,iso
n,iso
n,n
1a
1b
1b
1c
1d
2
2
3
2
2
98
95
98
90
64
4a 16
4b 10
7b 14
4c 16
5a 49
5b 44
8b 46
5c 53
6a 35
6b 46
9b 40
6c
3l
4d
0
5d
0
6d 100
a Reaction Conditions: temp. 120°C; time: 20 h; PCO = 40 bar, PH
40 bar; catalyst: [Rh(cod)Cl]2 (0.5 mol%).
=
2
b Yields of isolated products (see experimental).

72
Papers
SYNTHESIS
diene 1d with high selectivity leads to 2,3,3-trimethylcy- plants.20 The earlier described two-step synthesis of 13
clopentanone and not to dialdehydes.17 Apparently the and 14 via hydroformylation and reductive amination af-
amine controls the chemoselectivity of the primary car- fords an overall yield of 34%.19,20 This clearly demon-
bonylation step.
strates the advantage of the one-pot procedure.
3,3-Diphenylpenta-1,4-diene (1e) is expected to react Conjugated diolefins undergo hydroformylation with low
like 1d and indeed the n,n-product 6e is generated in 63 % selectivities.21 Usually hydrogenation of at least one dou-
yield. However, as a side product in 30% yield the cyclo- ble bond occurs. 2,3-Dimethylbuta-1,3-diene (15) in the
propane system 5e is obtained. The formation of 5e occurs presence of morpholine gives a mixture of diamine 16
diastereoselectively and according to a NOESY-experi- (21%), the saturated amine 17 (44 %) and the unsaturated
ment, the methyl group and the 2-(4-morpholino)ethyl amine 18 (17 %). Again methyl groups prevent carbonyla-
group are arranged in trans-configuration at the cyclopro- tion of the inner double bond carbons.
pane ring. It is known that methylenecyclopropane deriv-
atives in the presence of a transition metal can undergo
ring opening and thus lead to 1,4-dienes, if e. g. 2-methyl-
1-methylenecyclopropane is employed.18 On the other
hand, 1,4-dienes undergo carbon skeleton rearrangements
via cyclopropane intermedates under the conditions of
rhodium-catalyzed hydrocarbonylation.17 In our case a
process of this type must have taken place. In the case of
1e, this leads after further conversions to the observed
product 5e with the two phenyl groups obviously stabiliz-
ing the cyclopropane ring. For 1d, lacking the phenyl
groups. formation of cyclopropane derivatives is not ob-
served.
Scheme 4
In the case of the diamine product 16 both the double
bonds of the diene precursor are hydroaminomethylated.
The unsaturated monoamine 18 appears to be the final
product of a reaction sequence starting with a 1,4-addition
of the hydrido rhodium species to the diene.22 Further hy-
drogenation or hydroformylation of the tetrasubstituted
double bond generated in this step is hindered for steric
reasons. Therefore, the saturated monoamine 17 obvious-
ly is not formed via hydrogenation of 18, but by hydroge-
nation of the remaining double bond of an unsaturated
monoamine generated via 1,2-addition of the hydrido
rhodium complex to the diene and further conversions of
the resulting metal alkyl intermediate.
The low tendency of highly substituted double bonds to-
wards hydrogenation or hydroformylation is also effec-
tive in the conversion of 2,4-dimethylpenta-1,3-diene
(19) in the presence of morpholine. Here only the less
substituted double bond undergoes hydroaminomethyla-
tion, the other one remains unaffected. Under the condi-
tions applied, 45% of the unsaturated amine 20 is
obtained.
Scheme 2
The unsymmetrical nonconjugated diene (R)-(+)-li-
monene (12) is hydroformylated at the side chain double
bond only in moderate yields.19 Subjected to the condi-
tions of hydroaminomethylation, however, 12 is selec-
tively converted in good yields to the tertiary amines 13
(with morpholine, 93%) or 14 (with diethylamine, 81 %).
As observed in normal hydroformylation, the trisubstitut-
ed ring double bond of 12 remains unaffected. The methyl
substituent at the exocyclic double bond causes selective
formation of the n-product. Formation of an iso-product
would require generation of a quaternary carbon centre,
which is not favourable for steric and/or thermodynamic
reasons. Products 13 and 14 obtained from limonene (12)
are reported to act as growth regulators for tobacco
Scheme 5
In conclusion bis(hydroaminomethylation) of nonconju-
gated a,w-diolefins with secondary amines leads to tertia-
ry a,w-diamines in good yields. Similar results are
expected with primary amines and ammonia. Here how-
ever ring closure or oligomerization can occur and lead to
complex product mixtures. Further investigations in this
direction are in progress.
Scheme 3

January 1998
SYNTHESIS
73
Table 2. Carbonylative Bis(hydroaminomethylation) of a, w-Olefins 1, 12, 15 and 19a
Entry Diene
mb
Amine
Temp. Conv. Eluent
Productsc
n
m
(g)
n
(°C) (%) PE/
MTBE
m
n
Yield
m
Yield
m
n
Yield
(mg)
(mmol)
(mg) (mmol) (%)
(mg) (mmol) (%)
(mg) (mmol) (%)
1
2
3
1a 575
1b 771
1b 771
2
3
2
1.307 15
1.097 15
1.307 15
120 90
120 98
80 84
1:1 4a 279 1.0
2:1 7b 273 1.0
15:1 4b 166 0.5
10b 286 1.4
14
14
8
19
15
5a 876 3.1
44
45
20
25
54
6a 631 2.2
9b 778 4.7
6b 271 0.9
32
39
12
8b 900 3.2
5b 437 1.4
11b 365 1.7
5c 1286 3.8
4
5
6
7
8
9
10
11
1c 978
1d 673 .
1e 600d
1b 771
12 954
12 954
15 575
19e 673
2
2
2
2
2
3
2
2
1.307 15
1.307 15
0.488 5.6
1.307 15
0.653 7.5
0.549 7.5
1.307 15
1.307 15
120 99
120 64
120 93
120 95
80 93
120 81
120 82
120 45
2:1 4c
367 1.1
6c 731 2.1
6d 1330 4.5
6e 716 1.7
6b 1006 3.2
30
64
63
46
1:1
5e 264 0.8
5b 962 3.1
30
44
10:1 4b 219 0.7
13 1545 6.5
14 1271 5.7
10:1 16 418 1.5
20 618 3.1
10
93
81
21
45
17 571 3.1
44
18 218 1.2
17
a Solvent: anhyd MeCN (10 mL); Catalyst: [Rh(cod)Cl]2 (17 mg, 0.5%); Ptota1 = 80 bar (CO/H2 = 1:1); Time: 20 h.
b 7 mmol.
c Isolated yields.
d 2.7 mmol.
e t = 67 h.
NMR spectra were recorded at 20°C on a Bruker spectrometer DRX C16H32N2O2 (284.4): calc. C, 67.6; H, 11.3; N, 9.9. Found C, 67.6; H,
400 using TMS as internal standard (multiplicities marked with an as- 11.4; N, 9.8.
terisk* are not in line with first order spectra). IR spectra were obtained
with a Shimadzu 470, mass spectra on a Finnigan CH 5 and elemental
analysis with a Leco CHNS-932. Column chromatography was carried
out with aluminium oxide N (Act I, ICN Biomedicals, Eschwege) by
using MTBE (methyl tert-butyl ether)/PE (petroleum ether, bp 30 –
60°C) mixtures as eluent. Gas chromatography was carried out on a
Fisons GC-9130 with a 15 m CP19 (CB) capillary. GC-MS spectra and
GC-FTIR spectra were obtained by using a comparable capillary and a
Finnigan MAT 8320 for the CG-MS and a Bruker IFS 48 in case of the
GC-FTIR. The [Rh(cod)Cl]2 catalyst was prepared according to litera-
ture procedures.23 Pressure reactions were carried out in autoclaves
(250 mL, PTFE-insert) from Berghof, Eningen.
2-Methyl-1, 7-di(4-morpholino)heptane (5a): 0.876 g(44%).
1H NMR (400 MHz, CDCl3): d = 0.87 (d, 3J = 6.5 Hz, 3H, CH3), 1.26
(m, 8H, CH2), 1.62 (m, 1H, CH), 2.04 (dd, 3J = 8.0 Hz, 2J = 12.0 Hz,
1H, NCH2CHMe), 2.14 (dd, 3J = 6.7 Hz, 2J = 12.0 Hz, 1H,
NCH2CHMe), 2.35 [m, 10H, N(CH2CH2)2O and NCH2CH2], 3.60
[m, 8H, N(CH2CH2)2O].
13C NMR (100 MHz, CDCl3): d = 17.9 (CH3), 26.2 (CH2), 26.5
(CH2), 27.5 (CH2), 29.5 (CH), 34.7 (CH2), 53.5 [N(CH2CH2)2O],
53.8 [N(CH2CH2)2O], 58.8 (NCH2CH2), 65.8 (NCH2CHMe), 66.6
[N(CH2CH2)2O], 66.7 [N(CH2CH2)2O].
GC-MS (EI, 70 eV): m/z (%) = 284 (17, M+), 254 (8), 211 (5), 168
(6), 152 (5), 126 (7), 100 (100), 86 (8), 70 (19), 56 (18).
IR (NaCl): n = 2954 (vs), 2930 (vs), 2853 (vs), 2806 (vs), 2766 (s),
2685 (m), 1456 (s), 1446 (s), 1398 (m), 1373 (m), 1357 (m), 1297 (s),
1273 (s), 1119 (vs), 1070 (m), 1035 (m), 1012 (s), 866 (s), 797 cm–1
(m).
Bis(hydroaminomethylation) ofa,w-Diolefins; General Procedure:
A mixture of diolefin (7.0 mmol), amine (1 mmol) and [Rh(cod)Cl]2
(0.5 mol%, 17 mg) in anhyd. MeCN (10 mL) was heated for 20 h at
120 °C (see Table 2 for further details) in an autoclave under 40 bar
CO and 40 bar H2 (ptota1 = 80 bar). After filtration through neutral alu-
mina with MTBE, the solvent was removed by rotary evaporation.
The residue was worked up by column chromatography on neutral
alumina (Table 2). All crude mixtures and isolated products were
analysed by GC and GC-MS or GC-FTIR, respectively.
C16H32N2O2 (284.4): calc. C, 67.6; H, 11.3; N, 9.9. Found C, 67.8; H,
11.3; N, 9.9.
1,8-Di(4-morpholino)octane (6a): 0.631 mg (32 %).
1H NMR (400 MHz, CDCl3): d = 1.30 (m, 8H, CH2), 1.47 (m, 4H,
CH2), 2.31 (t*, 3J = 7.5 Hz, 4H, NCH2CH2), 2.43 [m, 8H,
N(CH2CH2)2O], 3.71 [t*, 3J = 4.8 Hz, 8H, N(CH2CH2)2O].
13C NMR (100 MHz, CDCl3): d = 26.4 (CH2), 27.3 (CH2), 29,3 (CH2),
53.7 [N(CH2CH2)2O], 59.1 (NCH2CH2), 66.8 [N(CH2CH2)2O].
GC-MS (EI, 70 eV): m/z (%) = 284 (16, M+), 253 (10), 168 (7), 154
(12), 124 (13), 100 (100), 86 (9), 70 (29), 56 (23).
Entry 1, Table 2
The reaction of 1a (0.575 g, 7 mmol) with morpholine (1.307 g,
15 mmol) yielded 90 % of a mixture containing three regioisomers 4a,
5a and 6a. The products were isolated by column chromatography on
neutral alumina using a 1:1 mixture of PE and MTBE as eluent.
2,5-Dimethyl-1,6-di(4-morpholino)hexane (4a) (1:1 mixture of two
diastereoisomers): 0.279 g (14 %).
IR (KBr): n = 2969 (s), 2947 (vs), 2929 (vs), 2902 (s), 2857 (vs), 2808
(vs), 2781 (vs), 2761 (vs), 2740 (s), 2684 (m), 1473 (s), 1461 (s), 1450
(m), 1373 (m), 1358 (m), 1315 (m), 1303 (m), 1278 (s), 1266 (s), 1252
(s), 1152 (vs), 1131 (vs), 1120 (vs), 1069 (s), 1035 (m), 1016 (s), 87l
(vs), 796 cm–1 (m).
1H NMR (400 MHz, CDCl3): d = 0.87 and 0.89 (d, 3J = 4.8 Hz, 6H,
CH3), 1.08 (m, 2H, MeCHCH2), 1.40 (m, 2H, MeCHCH2), 1.60 (m,
2H, CH), 2.05 (m, 2H, NCH2CHMe), 2.15 (m, 2H, NCH2CHMe),
2.37 [m, 8H, N(CH2CH2)2O], 3.67 [t*, 3J
N(CH2CH2)2O].
= 4.6 Hz, 8H,
C16H32N2O2 (284.4): calc. C, 67.6; H, 11.3; N, 9.9. Found C, 67.5; H,
11.1; N, 9.8.
13C NMR (100 MHz, CDCl3): d = 17.9 and 18.2 (CH3); 29.8 and 30.0
(CH); 32.0 and 32.1 (MeCHCH2); 53.9 (N(CH2CH2)2O); 65.7 and
66.0 (NCH2CHMe); 66.8 (N(CH2CH2)2O).
Entry 7, Table 2
GC-MS (EI, 70 eV): m/z (%) = 284 (14, M+), 269 (4), 254 (8), 154
(10), 140 (8), 100 (100), 81 (4), 70 (22), 56 (21).
The reaction of 1b (0.771 g, 7 mmol) with morpholine (1.307 g,
15 mmol) yielded 95 % of a mixture containing three regioisomers
4b, 5b and 6b. Column chromatography on neutral alumina with a
10:1 mixture of PE and MTBE allowed the isolation of the prod-
ucts.
IR (NaCl): n = 2956 (vs), 2929 (vs), 2852 (vs), 2805 (vs), 2685 (m), 1457
(vs), 1445 (vs), 1397 (m), 1374 (s), 1358 (m), 1296 (s), 1273 (s), 1263 (s),
l 119 (vs), 1070 (m), 1035 (m), 1012 (s), 865 (s), 799 cm–1 (m).

74
Papers
SYNTHESIS
MS (EI, 70 eV): m/z (%) = 211 (14, M+), 196 (35), 100 (100), 56 (26),
41 (17).
IR (NaCl): n = 3076 (w), 2956 (s), 2928 (vs), 2853 (s), 2805 (s), 2784
(m), 2767 (m), 1641 (m), 1456 (s), 1120 (vs), 1012 (m), 909 (m),
865 cm–1 (m).
2,7-Dimethyl-1,8-di(4-morpholino)octane (4b) (1:1 mixture of two
diastereoisomers): 0.219 g (10%).
1H NMR (400 MHz, CDCl3): d = 0.88 (d, 3J = 6.8 Hz, 6H, CH3), 1.04
(m, 2H, MeCHCH2), 1.28 (m, 6H, MeCHCH2 and CH2), 1.63 (m, 2H,
CH), 2.05 (dd, 3J = 8.0 Hz, 2J = 12.0 Hz, 2H, NCH2CHMe), 2.14 (dd,
3J = 6.8 Hz, 2J = 12.0 Hz, 2H, NCH2CHMe), 2.37 [t*, 3J = 4.6 Hz, 8H,
N(CH2CH2)2O], 3.69 [t*, 3J = 4.6 Hz, 8H, N(CH2CH2)2O].
13C NMR (100 MHz, CDCl3): d = 18.2 and 18.2 (CH3); 27.2 and
27.3 (CH2); 29.8 and 29.8 (CH); 35.1 and 35.1 (MeCHCH2);
54.1 [N(CH2CH2)2O]; 66.1 and 66.1 (NCH2CHMe); 67.0
[N(CH2CH2)2O].
HRMS (C13H25NO): calc. 211.19362, found 211.1935.
4-(Non-8-enyl)morpholine (11b): 0.365 g (25 %).
1H NMR (400 MHz, CDCl3): d = 1.30 (m, 8H, CH2), 1.47 (m, 2H,
CH2), 2.03 (q, 3J = 6.8 Hz, 2H, CH2CH=CH2), 2.31 (t*, 3J = 7.8 Hz,
2H, NCH2CH2), 2.42 [m, 4H, N(CH2CH2)2O], 3.72 [t*, 3J = 4.7 Hz,
4H, N(CH2CH2)2O], 4.94 [dd, 3J(Z) = 10.3 Hz, 2J = 1.0 Hz, 1H,
CH=CH2], 4.98 [dd, 3J(E) = 17.2 Hz, 2J = 1.0 Hz, 1H, CH=CH2], 5.80
[ddt, 3J(E) = 17.2 Hz, 3J(Z) = 10.3 Hz, 3J = 6.8 Hz, 1H, CH=CH2].
13C NMR (100 MHz, CDCl3): d = 26.5 (CH2), 27.4 (CH2), 28.8
(CH2), 28.9 (CH2), 29.3 (CH2), 33.7 (CH2), 53.7 [N(CH2CH2)2O],
59.1 (NCH2CH2), 66.9 [N(CH2CH2)2O], 114.1 (CH=CH2), 139.0
(CH=CH2).
MS (EI, 70 eV): m/z (%) = 312 (67, M+), 282 (27), 126 (12), 100
(100), 86 (10), 56 (25), 42 (12).
IR (NaCl): n = 2956 (vs), 2928 (vs), 2853 (vs), 2805 (vs), 2767 (s),
2685 (m), 2656 (m), 1456 (s), 1445 (m), 1296 (m), 1273 (m), 1119
(vs), 1071 (m), 1035 (m), 1013 (s), 865 (s), 798 cm–1 (m).
C18H36N2O2 (312.5): calc. C, 69.2; H, 11.6; N, 9.0. Found C, 69. l; H,
l 1.8; N, 9.1.
MS (EI, 70 eV): m/z (%) = 211 (53, M+), 170 (8), 126 (6), 100 (100),
87 (32), 56 (55), 41 (48).
IR (NaCl): n = 3076 (w), 2928 (vs), 2854 (vs), 2806 (s), 2766 (m),
1641 (m), 1457 (m), 1446 (m), 1274 (m), 1137 (m), 1120 (vs), 910
(m), 867 cm–1 (m).
2-Methyl-1,9-di(4-morpholino)nonane (5b): 0.962 g (44%).
1H NMR (400 MHz, CDCl3): d = 0.87 (d, 3J = 6.5 Hz, 3H, CH3), 1.04
(m, 1H, MeCHCH2), 1.34 (m, 11H, CH2 and MeCHCH2), 1.62 (m,
1H, CH), 2.05 (dd, 3J = 8.0 Hz, 2J = 12.0 Hz, 1H, NCH2CHMe), 2.14
(dd, 3J = 6.8 Hz, 2J = 12.0 Hz, 1H, NCH2CHMe), 2.36 [m, 10H,
N(CH2CH2)2O and NCH2CHMe], 3.70 [m, 8H, N(CH2CH2)2O].
13C NMR (100 MHz, CDCl3): d = 18.1 (CH3), 26.4 (CH2), 26.8
(CH2), 27.4 (CH2), 29.4 (CH2), 29.7 (CH2), 29.7 (CH), 35.0 (CH2),
53.7 [N(CH2CH2)2O], 54.0 [N(CH2CH2)2O], 59.1 (NCH2CH2), 66.0
(NCH2CHMe), 66.8 [N(CH2CH2)2O].
C13H25NO (211.3): calc. C, 73.9; H, 11.9; N, 6.6. Found C, 73.6 %; H,
12.0; N, 6.7.
Entry 4, Table 2
The reaction of 1c (0.978 g, 7 mmol) with morpholine (1.307 g,
15 mmol) yielded 99 % of a mixture containing 3 regioisomers 4c, 5c
and 6c. Column chromatography on neutral alumina with a 2:1 mix-
ture of PE and MTBE led to the isolation of products.
MS (EI, 70 eV): m/z (%) = 312 (67, M+), 282 (35), 252 (12), 100
(100), 56 (30).
IR (NaCl): n = 2954 (s), 2928 (vs), 2853 (vs), 2805 (s), 2766 (m),
2685 (w), 2656 (w), 1456 (m), 1445 (m), 1297 (m), 1273 (m), 1119
(vs), 1071 (m), 1035 (m), 1013 (m), 865 (s), 798 cm–1.
C18H36N2O2 (312.5): calc. C, 69.2; H, 11.6; N, 9.0. Found C, 69.0; H,
11.9; N, 8.9.
2,5-Dimethyl-1,6-di(4-morpholino)decane (4c) (1:1 mixture of two
diastereoisomers): 0.367 g (15 %).
1H NMR (400 MHz. CDCl3): d = 0.88 (d, 3J = 6.5 Hz, 6H, CH3), 1.05
(m, 2H, MeCHCH2), 1.29 (m, 10H, MeCHCH2 and CH2), 1.62 (m,
2H, CH), 2.04 (dd, 3J = 7.8 Hz, 2J = 12.0 Hz, 2H, NCH2CHMe), 2.16
(dd, 3J = 6.8 Hz, 2J = 12.0 Hz, 2H, NCH2CHMe), 2.37 (t*, 3J = 4.6 Hz,
8H, N[CH2CH2)2O], 3.69 [t*, 3J = 4.6 Hz, 8H, N(CH2CH2)2O].
13C NMR (100 MHz, CDCl3): d = 18.1 (CH3), 26.8 (CH2), 29.7 (CH),
29.8 (CH2), 35.0 (CH2), 54.0 [N(CH2CH2)2O], 66.0 (2´
NCH2CHMe), 66.9 [N(CH2CH2)2O].
1,10-Di(4-morpholino)decane (6b): 1.006 g (46 %).
1H NMR (400 MHz, CDCl3): d = 1.28 (m, 12H, CH2), 1.48 (m, 4H,
CH2), 2.31 (dd, 3J = 7.5 Hz, 3J = 6.0 Hz, 4H, NCH2CH2), 2.43 [m, 8H,
N(CH2CH2)2O], 3.72 [t*, 3J = 7.5 Hz, 8H, N(CH2CH2)2O].
13C NMR (100 MHz, CDCl3): d = 26.5 (CH2), 27.5 (CH2), 29.5
(CH2), 29.5 (CH2), 53.8 [N(CH2CH2)2O], 59.2 (NCH2CH2), 67.0
[N(CH2CH2)2O].
MS (EI, 70 eV): m/z (%) = 340 (66, M+), 310 (51), 280 (27), 224 (6),
196 (7), 140 (8), 126 (13), 100 (100), 86 (21), 72 (44), 56 (64), 41 (43).
IR (NaCl): n = 2954 (s), 2926 (vs), 2852 (vs), 2805 (vs), 2766 (m),
2685 (m), 1456 (s), 1273 (m), 1120 (vs), 865 cm–1 (m).
C20H40N2O2 (340.5): calc. C, 70.5; H, 11.8; N, 8,2. Found C, 70.5; H,
11.9; N, 8.1.
MS (EI, 70 eV): m/z (%) = 312 (75, M+), 282 (40), 252 (12), 100
(100), 72 (10), 56 (8).
IR (KBr): n = 2971 (m), 2952 (m), 2925 (vs), 2910 (s), 2867 (m),
2847 (s), 2811 (m), 2766 (m), 1465 (m), 1452 (m), 1277 (m), 1133
(m), 1114 (vs), 1015 (m), 868 cm–1(s).
2-Methyl-1,7-di(4-morpholino)undecane (5c): 1.286 g (54%).
1H NMR (400 MHz, CDCl3): d = 0.87 (d, 3J = 6.5 Hz, 3H, CH3), 1.05
(m, 1H, MeCHCH2), 1.35 (m, 15H, MeCHCH2 and CH2), 1.63 (m,
1H, CH), 2.04 (dd, 3J = 8.0 Hz, 2J = 12.0 Hz, 1H, NCH2CHMe), 2.14
(dd, 3J = 6.8 Hz, 2J = 12.0 Hz, 1H, NCH2CHMe), 2.32 [m, 10H,
C18H36N2O2 (312.5): calc. C, 69.2; H, 11.6; N, 9.0. Found C, 68.8; H,
11.9; N, 8.9.
Entry 3, Table 2
The reaction of 1b (0.771 g, 7 mmol) with morpholine (1.307 g,
l5 mmol) at a temperature of 80 °C instead of 120 °C yielded 84 % of
a mixture containing the 3 regioisomers 4b, 5b and 6b and in addition
10b and 11b. Column chromatography on neutral alumina with a
l5:1 mixture of PE and MTBE led to the isolation of products.
N(CH2CH2)2O, NCH2CH2], 3.67 [t*, 3J
=
4.0 Hz, 4H,
N(CH2CH2)2O], 3.69 [t*, 3J = 4.8 Hz, 4H, N(CH2CH2)2O].
13C NMR (100 MHz, CDCl3): d = 18.0 (CH3), 26.3 (CH2), 26.6
(CH2), 26.7 (CH2), 27.2 (CH2), 29.3 (CH2), 29.3 (CH2), 29.5 (CH),
29.6 (CH2), 34.8 (CH2), 53.5 [N(CH2CH2)2O], 53.8 [N(CH2CH2)2O],
58.9 (NCH2CH2), 65.9 (NCH2CHMe), 66.6 [N(CH2CH2)2O], 66.7
[N(CH2CH2)2O].
4-(2-Methyloct-7-enyl)morpholine (10b): 0.286 g (19 %).
1H NMR (400 MHz, CDCl3): d = 0.88 (d, 3J = 6.7 Hz, 3H, CH3), 1.07
(m, 1H, MeCHCH2), 1.34 (m, 5H, MeCHCH2 and CH2), 1.63 (m, 1H,
CH), 2.05 (m, 3H, H2C=CHCH2, NCH2CHMe), 2.14 (dd, 3J = 6.7 Hz,
2J = 12.0 Hz, 1H, NCH2CHMe), 2.37 (m, 4H, N(CH2CH2)2O), 3.70
(t*, 3J = 4.7 Hz, 4H, N(CH2CH2)2O), 4.94 [dd, 3J(Z) = 10.2 Hz, 2J =
MS (EI, 70 eV): m/z (%) = 340 (41, M+), 310 (24), 280 (8), 100 (100),
72 (5), 56 (6).
IR (KBr): n = 2995 (m), 2916 (vs), 2849 (vs), 2766 (m), 2735 (m),
1456 (s), 1273 (s), 1118 (vs), 1015 (vs), 865 cm–1 (vs).
C20H40N2O2 (340.5): calc. C, 70.5; H, 11.8; N, 8.2. Found C, 70.8; H,
11.8; N, 8.1.
3
2
1.2 Hz, 1H, CH=CH2], 4.98 [dd, J(E) = 17.2 Hz, J = 1.2 Hz, 1H,
CH=CH2], 5.82 [ddt, 3J(E) = 17.2 Hz, 3J(Z) = 10.2 Hz, 3J = 6.6 Hz,
1H, CH=CH2].
13C NMR (100 MHz, CDCl3): d = 18.2 (CH3), 26.4 (CH2), 29.2
(CH2), 29.8 (CH), 33.8 (CH2), 34.9 (CH2), 54.1 [N(CH2CH2)2O],
66.1 (NCH2CHMe), 67.0 [N(CH2CH2)2O], 114.2 (CH=CH2), 139.0
(CH=CH2).
1,8-Di(4-morpholino)dodecane (6c): 0.731 g (30 %).
1H NMR (400 MHz, CDCl3): d = 1.26 (m, 16H, CH2), 1.48 (m, 4H,
CH2), 2.31 (t*, 3J = 7.8 Hz, 4H, NCH2CH2), 2.43 [m, 8H,
N(CH2CH2)2O], 3.72 [t*, 3J = 4.5 Hz, 8H, N(CH2CH2)2O].

January 1998
SYNTHESIS
75
13C NMR (100 MHz, CDCl3): d = 26.4 (CH2), 27.4 (CH2), 29.4
(CH2), 29.5 (CH2), 53.7 [N(CH2CH2)2O], 59.1 (NCH2CH2), 66.9
[N(CH2CH2)2O].
C27H38N2O2 (422.6): calc. C, 76.7; H, 9.1; N, 6.6. Found C, 76.8; H,
9.0; N, 6.5.
MS (EI, 70 eV): m/z (%) = 340 (84, M+), 310 (42), 280 (15), 100
(100), 72 (13), 56 (7).
Entry 2, Table 2
The reaction of 1b (0.771 g, 7 mmol) with diethylamine (1.097 g, 15
mmol) gave 98% of a mixture containing three regioisomers 7b, 8b
and 9b. Column chromatography on neutral alumina with a 2:1 mix-
ture of PE and MTBE led to the isolation of products.
IR (KBr): n = 2948 (s), 2923 (vs), 2849 (s), 2766 (s), 1466 (m), 1276
(m), 1115 (vs), 868 cm–1 (m).
C20H40N2O2 (340.5): calc. C, 70.5; H, 11.8; N, 8.2. Found C, 70.2; H,
l1.8; N, 8.1.
N,N,N¢,N¢-Tetraethyl-2,7-dimethyloctane-1,8-diamine (7b) (1:1 mix-
ture of two diastereoisomers): 0.273 g (14 %).
1H NMR (400 MHz, CDCl3): d = 0.86 (d, 3J = 6.5 Hz, 6H, CHCH3),
0.99 (t, 3J = 7.0 Hz, 12H, NCH2CH3), 1.31 (m, 8H, CH2), 1.55 (m, 2H,
CH), 2.07 (dd, 3J = 7.8 Hz, 2J = 12.6 Hz, 2H, NCH2CHMe), 2.19 and
2.19 (dd, 3J = 6.5 Hz, 2J = 12.6 Hz, 2H, NCH2CHMe), 2.47 and 2.48
(q, 3J = 7.0 Hz, 8H, NCH2CH3).
Entry 5, Table 2
The reaction of 1d (0.673 g, 7 mmol) with morpholine (1.307 g, 15
mmol) yielded 64 % of 6d, which was purified by Kugelrohr distilla-
tion.
3,3-Dimethyl-1,7-di(morpholino)heptane (6d): 1.330 g (64 %).
1H NMR (400 MHz, CDCl3): d = 0.85 (s, 6H, CH3), 1.16 [m, 4H,
(CH3)2CCH2], 1.43 [m, 4H, (CH3)2CCH2CH2], 2.28 (t*, 3J = 7.5 Hz,
4H, NCH2CH2), 2.43 [m, 8H, N(CH2CH2)2O], 3.72 [t*, 3J = 4.5 Hz,
8H, N(CH2CH2)2O].
13C NMR (100 MHz, CDCl3): d = 11.7 (NCH2CH3); 18.5 and 18.5
(CHCH3); 27.4 and 27.5 (CH2); 31.5 and 31.5 (CH); 35.3 and 35.4
(CH2); 47.5 (NCH2CH3); 60.4 and 60.5 (NCH2CHMe).
GC-MS (EI, 70 eV): m/z (%) = 285 (15, M++1), 269 (5), 254 (8), 198
(6), 182 (3), 86 (100), 72 (6), 58 (10).
13C NMR (100 MHz, CDCl3): d = 21.1 (NCH2CH2), 27.0 (CH3), 32.3
[C(CH3)2], 39.3 [(CH3)2CCH2], 53.7 [N(CH2CH2)2O], 59.8
(NCH2CH2), 66.8 [N(CH2CH2)2O].
IR (NaCl): n = 2968 (vs), 2929 (vs), 2797 (vs), 1464 (s), 1383 (s),
1204 (s), 1066 cm–1(s).
GC-MS (EI, 70 eV): m/z (%) = 298 (16, M+), 268 (8), 126 (11), 100
(100), 70 (24), 56 (21).
C18H40N2 (284.5): calc. C, 76.0; H, 14.2; N, 9.9. Found C, 76.2; H,
13.8; N, 10.0.
IR (NaCl): n = 2954 (vs), 2892 (s), 2852 (vs), 2805 (vs), 2706 (s),
1468 (m), 1455 (m), 1275 (m), 1137 (s), 1119 (vs), 1008 (m), 867 cm–1
(m).
N,N,N¢N¢-Tetraethyl-2-methyloctane-1,9-diamine (8b): 0.900 g (45%).
1H NMR (400 MHz, CDCl3): d = 0.86 (d, 3J = 6.8 Hz, 3H, CHCH3),
0.98 (t, 3J = 7.1 Hz, 6H, NCH2CH3), 1.02 (t, 3J = 7.0 Hz, 6H,
NCH2CH3), 1.35 (m, 13H, CH2 and CH), 2.06 (dd, 3J = 7.5 Hz, 2J =
12.6 Hz, 1H, NCH2CHMe), 2.18 (dd, 3J = 6.5 Hz, 2J = 12.6 Hz, 1H,
HRMS (C17H34N2O2): calc. 298.2620, found 298.2710.
3
Entry 6, Table 2
NCH2CHMe), 2.41 (m, 2H, NCH2CH2), 2.46 (q, J = 7.1 Hz, 4H,
NCH2CH3), 2.51 (q, 3J = 7.0 Hz, 4H, NCH2CH3).
The reaction of 1e (0.600 g, 2.7 mmol) with morpholine (0.488 g, 5.6
mmol) afforded 93% of a mixture containing 5e and 6e. Column
chromatography on neutral alumina with a 1:1 mixture of PE and
MTBE allowed the separation of the products.
13C NMR (100 MHz, CDCl3): d = 11.4 (NCH2CH3), 11.5
(NCH2CH3), 18.2 (CHCH3), 26.7 (CH2), 26.8 (CH2), 27.5 (CH2),
29.4 (CH2), 29.7 (CH2), 31.3 (CH), 35.0 (CH2), 46.6 (NCH2CH3),
47.3 (NCH2CH3), 52.7 (NCH2CH2), 60.3 (NCH2CHMe).
GC-MS (EI, 70 eV): m/z (%) = 285 (21, M++1), 269 (6), 255 (5), 211
(3), 182 (6), 126 (5), 86 (100), 72 (5), 58 (7).
4-[2-(3-Methyl-2,2-diphenylcyclopropyl)ethyl]morpholine
(5e):
0.264 g (30%).
1H NMR (400 MHz, CDCl3): d = 0.89 (d, 3J = 6.2 Hz, 3H, CH3), 1.07
(m, 1H, NCH2CH2), 1.27 (dt, 3J = 8.7 Hz, 3J = 6.0 Hz, 1H,
CHCHCH3), 1.46 (m, 2H, CHCH3 and NCH2CH2), 2.37 [m, 6H,
N(CH2CH2)2O and NCH2CH2], 3.65 [t*, 3J = 4.5 Hz, 8H,
N(CH2CH2)2O], 7.20 (m, 10H, phenyl).
IR (NaCl): n = 2968 (vs), 2928 (vs), 2854 (vs), 2797 (vs), 1466 (s),
1382 (s), 1260 (m), 1203 (s), 1091 (s), 1069 (s), 799 cm–1 (m).
C18H40N2 (284.5): calc. C, 76.0; H, 14.2; N, 9.9. Found C, 76.4; H,
14.4; N, 9.9.
13C NMR (100 MHz, CDCl3): d = 15.6 (CH3), 22.6 (CHCH3), 27.2
(NCH2CH2), 28.7 (CHCHCH3), 40.4 (CPh2), 53.7 [N(CH2CH2)2O],
58.7 (NCH2CH2), 66.9 [N(CH2CH2)2O], 125.8 (CH, phenyl), 125.8
(CH, phenyl), 128.0 (CH, phenyl), 128.0 (CH, phenyl) 129.9
(CH, phenyl), 130.0 (CH, phenyl), 143.4 (Cq, phenyl), 143.4 (Cq,
phenyl).
N,N,N¢,N¢-Tetraethyloctane-1,10-diamine (9b): 0.778 g (39 %).
1H NMR (400 MHz, CDCl3): d = 1.30 (t, 3J = 7.0 Hz, 12H,
NCH2CH3), 1.28 (m, 12H, CH2), 1.44 (m, 4H, CH2), 2.40 (m, 4H,
NCH2CH2), 2.51 (q, 3J = 7.0 Hz, 8H, NCH2CH3).
13C NMR (100 MHz, CDCl3): d = 11.6 (NCH2CH3), 26.9 (CH2), 27.7
(CH2), 29.5 (CH2), 29.6 (CH2), 46.8 (NCH2CH3), 52.9 (NCH2CH2).
GC-MS (EI, 70 eV): m/z (%) = 285 (28, M++1), 269 (5), 255 (14), 195
(5), 154 (4), 112 (6), 86 (100), 72 (5), 58 (7).
MS (EI, 70 eV): m/z (%) = 321 (82, M+), 250 (33), 201 (11), 193 (29),
l65 (19), 114 (49), 106 (73), 100 (100), 91 (85), 56 (89), 41 (73).
IR (NaCl): n = 3080 (vw), 3056 (w), 3022 (w), 2995 (w), 2956 (s),
2924 (s), 2853 (m), 2805 (m), 2764 (m), 2732 (w), 1600 (w), 1494 (s),
1456 (m), 1445 (s), 1357 (w), 1308 (w), 1273 (w), 1261 (m), 1143 (s),
11 19 (vs), 1082 (s), 1070 (s), 1032 (s), 864 (m), 748 (s), 701 cm–1 (s).
HRMS (C22H27NO): calc. 321.2093, found 321.2092.
IR (NaCl): n = 2968 (s), 2927 (vs), 2854 (s), 2797 (s), 1467 (m), 1382
(m), 1204 (m), 1086 (m), 1070 cm–1 (m).
C18H40N2 (284.5): calc. C, 76.0; H, 14.2; N, 9.9. Found C, 75.8; H,
14.6; N, 10.0.
Entries 8 and 9, Table 2
1, 7-Di(4-morpholino)-3,3-diphenylheptane (6e): 0.716 g (63 %).
1H NMR (400 MHz, CDCl3): d = 1.18 [m, 4H, (CH3)2CCH2], 2.09 [m,
4H, (CH3)2CCH2CH2], 2.27 [m, 12H, N(CH2CH2)2O and NCH2CH2],
3.63 [t*, 3J = 4.5 Hz, 8H, N(CH2CH2)2O], 7.17 (m, 10H, phenyl).
13C NMR (100 MHz, CDCl3): d = 21.0 (NCH2CH2), 35.1 (Ph2CCH2),
49.0 (CPh2), 53.6 [N(CH2CH2)2O], 59.3 (NCH2CH2), 66.8
[N(CH2CH2)2O], 125.5 (CH, phenyl), 127.7 (CH, phenyl), 127.8
(CH, phenyl), 148.4 (Cq, phenyl).
The reaction of 12 (0.954 g, 7 mmol) with morpholine (0.653 g,
7.5 mmol) or diethylamine (0.549 g, 7.5 mmol) gave after purification
by Kugelrohr distillation the compounds 13 (1.545 g, 93%, 53 : 47
mixture of two diastereoisomers) and 14 (1.271 g, 81%, 53 : 47 mix-
ture of two diastereoisomers). Both products have already been pre-
pared in a stepwise procedure, however, with insufficient spec-
troscopic characterization.20
MS (EI, 70 eV): m/z (%) = 422 (73, M+), 392 (54), 349 (8), 294 (8),
178 (8), 167 (9), 126 (81), 113 (24), 105 (10), 100 (100), 91 (64), 84
(54), 72 (56), 56 (81), 41 (74).
(1R)-4[4-Methylcyclohex-3-en-1-yl)butyl]morpholine (13) (53 : 47
mixture of two diastereoisomers):
1H NMR (400 MHz, CDCl3): d = 0.86 and 0.87 (d, 3J = 5.2 Hz, 3H,
CHCH3), 1.32 (m, 4H, NCH2CH2 and CHCH2CH2MeC=CH and
CHCH3 and CHCHCH3), 1.63 (s, 3H, HC=CCH3), 1.67 (m, 3H,
NCH2CH2 and MeC=CHCH2 and CHCH2CH2MeC=CH), 1.94 (m,
3H, MeC=CHCH2 and CH2MeC=CH), 2.33 (m, 2H, NCH2CH2), 2.43
IR (KBr): n = 3086 (w), 3055 (w), 3022 (w), 2952 (s), 2927 (s), 2868
(m), 2851 (m), 2806 (m), 2764 (m), 1599 (w), 1494 (m), 1445 (m),
1397 (m), 1356 (m), 1.271 (m), 1138 (s), 1119 (vs), 1034 (m), 865 (m),
755 (m), 700 cm 1(s).

76
Papers
SYNTHESIS
3
[m, 4H, N(CH2CH2)2O], 3.71 [t*, J = 4.8 Hz, 4H, N(CH2CH2)2O],
5.36 (s, 1H, MeC=CH).
4-(3,4-Dimethylpent-3-enyl)morpholine (18): 0.218 g (17%).
1H NMR (400 MHz, CDCl3): d = 1.64 [s, 3H, (CH3)2C=CCH3], 1.66
[s, 6H, (CH3)2C=CCH3], 2.24 (m, 2H, NCH2CH2), 2.32 (m, 2H,
NCH2CH2), 2.48 [m, 4H, N(CH2CH2)2O], 3.73 [t*, 3J = 4.7 Hz, 4H,
N(CH2CH2)2O].
13C NMR (100 MHz, CDCl3): d = 15.9 and 16.3 (CHCH3), 23.3
(HC=CCH3), 25.3 and 26.8 (CH2), 27.4 and 29.1 (CH2), 30.4 and 30.7
(CH2), 30.7 and 30.8 (CH2), 35.4 and 35.5 (CH), 38.3 and 38.5 (CH),
53.6 [N(CH2CH2)2O], 57.4 (NCH2CH2), 66.8 [N(CH2CH2)2O], 120.7
and 120.8 (MeC=CH), 133.7 (MeC=CH).
13C NMR (100 MHz, CDCl3): d = 18.7 (CH3), 20.1 (CH3), 20.5
(CH3), 31.7 (NCH2CH2), 53.7 [N(CH2CH2)2O], 57.4 (NCH2CH2),
66.9 [N(CH2CH2)2O], 125.1 (C=C), 125.3 (C=C).
GC-MS (EI, 70 eV): m/z (%) = 184 (16, M++1), 100 (100), 70 (14), 56
(8).
IR (NaCl): n = 2958 (vs), 2918 (vs), 2855 (vs), 2805 (vs), 2763 (s),
1455 (s), 1447 (s), 1142 (s), 1119 (vs), 1003 (s), 868 cm–1 (s).
C11H21NO (183.3): calc. C, 72.08; H, 11.55; N, 7.64. Found C, 71.99;
H, 11.48; N, 7.70.
MS (70 eV, EI): m/z (%) = 237 (24) [M+], 222 (4), 140 (81), 100
(100), 87 (10), 56 (7), 41 (4).
IR (NaCl, Film): n = 3007 (w), 2959 (vs), 2918 (vs), 2853 (vs), 2833
(vs), 2808 (vs), 2767 (s), 2685 (m), 1675 (vw), 1447 (vs), 1377 (s),
1357 (s), 1309 (s), 1274 (s), 1134 (vs), 1119 (vs), 1071 (m), 1004 (s),
914 (s), 867 cm–1 (s).
(1R)-Diethyl-[(4-methylcyclohex-3-en-1-yl)butyl]amine (14) (53 : 47
mixture of two diastereoisomers):
Entry 11, Table 2
1H NMR (400 MHz, CDCl3): d = 0.85 and 0.87 (d, 3J = 5.3 Hz, 3H,
CHCH3), 1.02 (t, 3J = 7.1 Hz, 6H, NCH2CH3), 1.28 (m, 2H,
NCH2CH2 and CHCH2CH2MeC=CH), 1.41 (m, 2H, CHCH3 and
CHCHCH3), 1.64 (s, 3H, HC=CCH3), 1.65 (m, 3H, NCH2CH2
and MeC=CHCH2 and CHCH2CH2MeC=CH), 1.94 (m, 3H,
MeC=CHCH2 and CH2MeC=CH), 2.41 (m, 2H, NCH2CH2), 2.52 and
2.53 (q, 3J = 7.1 Hz, 4H, NCH2CH3), 5.36 (s, 1H, MeC=CH).
13C NMR (100 MHz, CDCl3): d = 11.6 (NCH2CH3), 16.0 and 16.4
(CHCH3), 23.4 (HC=CCH3), 25.5 and 27.0 (CH2), 27.5 and 29.3
(CH2), 30.8 (CH2), 30.9 and 31.1 (CH2), 35.7 and 35.8 (CH), 38.4 and
38.7 (CH), 46.8 (NCH2CH3), 51.2 (NCH2CH2), 121.1 and 120.9
(MeC=CH), 133.9 (MeC=CH).
The reaction of 19 (0.673 g, 7 mmol) with morpholine (1.307 g,
15 mmol) yielded 45 % of 20. The product was purified by Kugelrohr
distillation.
4-(3,5-Dimethylhex-4-enyl)morpholine (20): 0.618 g (45%).
1H NMR (400 MHz, CDCl3): d = 0.93 (d, 3J = 6.8 Hz, 3H, CHCH3),
1.34 (m, 1H, MeCHCH2), 1.50 (m, 1H, MeCHCH2), 1.60 [s, 3H,
HC=C(CH3)2], 1.67 [s, 3H, HC=C(CH3)2], 2.27 (m, 2H, NCH2CH2),
2.42 [m, 5H, N(CH2CH2)2O, CHCH3), 3.71 [t*, 3J = 4.4 Hz, 4H,
N(CH2CH2)2O], 4.87 [d, 3J = 9.3 Hz, 1H, HC=C(CH3)2].
13C NMR (100 MHz, CDCl3): d = 17.8 (CH3), 21.4 (CH3), 25.7
(CH3), 30.7 (CHCH3), 34.4 (NCH2CH2), 53.7 [N(CH2CH2)2O], 57.2
(NCH2CH2), 66.9 [N(CH2CH2)2O], 130.1 [HC=C(CH3)2), 130.8
[HC=C(CH3)2].
GC-MS (70 eV, El): m/z (%) = 224 (14) [M++1], 208 (8), 126 (39),
86 (100).
GC-MS (EI, 70 eV): m/z (%) = 198 (21, M++1), 140 (32), 100 (100),
70 (15), 56 (11).
IR (NaCl): n = 2958 (vs), 2925 (s), 2854 (m), 2806 (m), 1456 (m),
1449 (m), 1376 (w), 1273 (w), 1137 (m), 1120 (vs), 867 cm–1 (m).
HRMS (C12H23NO): calc. 197.1779, found 197.1780.
IR (NaCl, Film): n = 3008 (m), 2966 (vs), 2925 (vs), 2873 (s), 2856
(s), 2832 (s), 2799 (s), 2725 (m), 1675 (vw), 1450 (m), 1378 (m),
1202 (m), 1069 (m), 912 (w), 798 cm–1 (m).
Entry 10, Table 2
The reaction of 15 (0.575 g, 7 mmol) with morpholine (1.307 g,
15 mmol) yielded 82 % of a mixture containing 16, 17 and 18. The
products were separated by column chromatography on neutral alu-
mina with a 10:1 mixture of PE and MTBE as eluent.
This work was supported by the Fonds der Chemischen Industrie. We also
thank the Degussa AG, Hanau and the Hüls AG, Marl for generous donation
of chemicals.
3,4-Dimethyl-1,6-di(4-morpholino)hexane (16) (1 : 1 mixture of two
diastereomers): 0.418 g (21 %).
(1) Eilbracht, P.; Rische, T. Synthesis 1997, 1331.
(2) Reppe, W.; Vetter, H. Liebigs Ann. Chem. 1953, 582, 133.
(3) Iqbal, A. F. M. Helv. Chim. Acta 1971, 45, 1440.
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121.
1H NMR (400 MHz, CDCl3): d = 0.80 and 0.85 (d, 3J = 6.4 Hz, 6H,
CH3), 1.29 (m, 2H, CHCH3), 1.54 (m, 4H, MeCHCH2), 2.34 (m, 4H,
NCH2CH2), 2.44 [m, 8H, N(CH2CH2)2O], 3.72 [t*, 3J = 4.6 Hz, 8H,
N(CH2CH2)2O].
13C NMR (100 MHz, CDCl3): d = 15.1 and 16.3 (CH3); 29.6 and 31.2
(MeCHCH2); 35.2 and 36.0 (CH), 53.8 and 53.8 [N(CH2CH2)2O],
57.6 and 57.7 (NCH2CH2), 66.6 and 66.8 [N(CH2CH2)2O].
GC-MS (EI, 70 eV): m/z (%) = 284 (18, M+), 254 (5), 198 (8), 140
(11), 112 (13), 100 (100), 70 (23), 56 (21).
IR (NaCl): n = 2956 (vs), 2851 (s), 2854 (vs), 2806 (s), 2767 (s), 1457
(s), 1448 (s), 1274 (m), 1119 (vs), 1003 (m), 868 cm–1 (s).
C16H32N2O2 (284.4): calc. C, 67.6; H, 11.3; N, 9.8. Found C, 67.6; H,
11.1; N, 9.8.
(6) (a) Jachimowicz, F. (Grace, W. R., and Co.) Belg. Pat. 887630,
1980; Chem. Abstr. 1981, 95, 152491.
(b) Jachimowicz, F.; Manson, P. (Grace, W. R., and Co.) Can.
Pat. CA 123119, 1984, Chem. Abstr. 1988, 109, 38485.
(c) Jachimowicz, F.; Raksis, J. W. J. Org. Chem. 1982, 47,
445.
(7) McEntire, E. E.; Knifton, J. F. (Texaco Development Corp.), EP
240193, 1987, Chem. Abstr. 1989, 110, 134785.
(8) Brunet, J. J.; Neibecker, D.; Agbossou, F.; Srivastava, R. S.
J. Mol. Cat. 1994, 87, 223.
(9) Drent, E.; Breed, A. J. M. (Shell Int. Res. M.), EP 457386, 1992,
Chem. Abstr. 1992, 116, 83212.
(10) Törös. S.; Gémes-Pésci, I.; Heil, B.; Mahó, S. Tuber, Z.
J. Chem. Soc., Chem. Commun. 1992, 858.
(11) (a) Baig, T.; Kalck, P. J. Chem. Soc., Chem. Commun. 1992,
1373,
(b) Baig, T.; Molinier, J.; Kalck, P. J. Organomet. Chem. 1993,
455, 219.
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(13) Imai, T. (Uop Inc.) U.S. 4220764, 1978, Chem. Abstr. 1980, 93,
239429.
(14) Diekhaus, G.; Kampmann, D.; Kniep, C.; Müller, T.; Walter, J.;
Wber, J. (Hoechst AG) DE 43344809, 1993, Chem. Abstr. 1995,
122, 314160.
4-(3,4-Dimethylpentyl)morpholine (17): 0.571 g (44 %).
1H NMR (400 MHz, CDCl3): d = 0.81 [d, 3J = 6.3 Hz, 6H, CH(CH3)2],
0.86 (d, 3J = 6.8 Hz, 3H, CHCH3), 1.29 [m, 2H, CHCH3 and
CH(CH3)2], 1.56 (m, 2H, CHCH2), 2.32 (m, 2H, NCH2CH2), 2.45 [m,
4H, N(CH2CH2)2O], 3.72 [t*, 3J = 4.4 Hz, 4H, N(CH2CH2)2O].
13C NMR (100 MHz, CDCl3): d = 15.5 (CH3), 18.0 (CH3), 19.9
(CH3), 30.6 (CHCH2), 32.2 (CH), 36.9 (CH), 53.9 [N(CH2CH2)2O],
57.8 (NCH2CH2), 66.9 [N(CH2CH2)2O].
GC-MS (EI, 70 eV): m/z (%) = 186 (14, M+), 170 (8), 154 (8), 100
(100), 70 (21), 56 (16).
IR (NaCl): n = 2958 (vs), 2892 (s), 2871 (vs), 2855 (vs), 2807 (s),
2767 (s), 2686 (m), 1459 (s), 1449 (s), 1385 (m), 1274 (s), 1120 (vs),
1003 (m), 868 cm–1 (s).
C11H23NO (185.3): calc. C, 71.30; H, 12.51; N, 7.56. Found C, 71.10;
H, 12.58; N, 7.49.

January 1998
SYNTHESIS
77
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