PAPER
1279
Convenient and Convergent Syntheses of Long-Chain a,w-Dibromides and
Diphosphines of the Formula X(CH2)nX (n = 18–32)
Synthesi ofLong-Chain , -DibromidesandDiphosphines
Wolfgang
Mohr, Clemens R. Horn, Jürgen Stahl, J. A. Gladysz*
aw
Abstract: The known tetrahydropyranyl ethers Br(CH2)yOTHP
(y = 6, 9, 11), which are easily prepared from commercial bromoalcohols, are sequentially treated with Mg, Li2CuCl4, and X(CH2)zX
(z/X = 6/Br, 7/Br, 8/Br, 10/Br, 10/I) to give the diethers
THPO(CH2)nOTHP in 68–40% yields (n = 2 y + z = 18, 19, 20, 22,
24, 28, 32). Subsequent reactions with Ph3P and 2,4,4,6-tetrabromocyclohexa-2,5-dienone give the title compounds Br(CH2)nBr in
91–75% yields. Reactions with commercial K+–PPh2 give the
diphosphines Ph2P(CH2)nPPh2 in 95–74% yields.
Key words: THP ethers, Grignard reagents, cross-coupling, bromination, phosphines
Long-chain a,w-difunctional compounds of the formula
X(CH2)nX have played an important historical role in organic chemistry. They served as building blocks for some
of the earliest syntheses of large carbocyclic rings,1 as
well as rotaxanes and catenanes.2 They have also figured
prominently in macromolecular, surfactant, and bolaamphiphile chemistry.3–6 With the emergence of nanochemistry over the last decade, and the frequent need for
‘oversized’ or ‘high axial ratio’ molecular components,6
such species are of renewed relevance.
In connection with several ongoing projects, we required
a range of a,w-diphosphines of the formula
Ar2P(CH2)nPAr2.7 There are of course many such species
known, but with what might be termed ‘medium’ values
of n (e.g. n = 6–12, 16 for Ar = Ph).8,9 In addition to such
compounds, we required diphosphines with much higher
values of n. Alkyl diarylmonophosphines are often prepared from alkyl halides and diarylphosphido anions
–
PAr2. The latter can be conveniently generated by several
procedures. Accordingly, we surveyed the existing literature syntheses of a,w-dibromides Br(CH2)nBr, with n
ranging from 18 to 38.10–20
To our surprise, we found various limitations with regard
to the efficiency of chain-lengthening, the number of steps
and convenience. For example, Hünig’s classic method
for the synthesis of long-chain a,w-dicarboxylic acids21
can be combined with a subsequent reduction to give a,wdiols HO(CH2)nOH as illustrated in Scheme 1. However,
this requires (1) a shorter-chain a,w-dicarboxylic acid
dichloride and the morpholine-derived enamine of cyclohexanone; (2) four separate steps, including two harsh
Synthesis 2003, No. 8, Print: 05 06 2003.
Art Id.1437-210X,E;2003,0,08,1279,1285,ftx,en;Z04103SS.pdf.
© Georg Thieme Verlag Stuttgart · New York
reductions; and (3) is limited to twelve-carbon chain extensions of the diacid dichloride. Also, under some
conditions the complete bromination of a,w-diols
HO(CH2)nOH is complicated by phase separation problems [e.g. diminished aqueous solubility of the less polar
initial product Br(CH2)nOH]. Forcing sealed-tube conditions can be necessary (47% aqueous HBr, 140–
160 °C).19b
In this paper, we describe an efficient and general route to
such dibromides that is based upon commercially available shorter-chain a,w-bromoalcohols Br(CH2)yOH and
a,w-dihalides X(CH2)zX (X = Br, I). The sequence exploits Grignard cross-coupling methodology originally
developed by Kochi22 and extended by others.23 To confirm the overall utility of the method, the dibromides are
subsequently converted to the a,w-diphosphines
Ph2P(CH2)nPPh2. These have been used as bidentate
ligands in various diplatinum complexes, including some
that adopt novel double-helical conformations of the general type I (Figure 1).7,24
Ar2
P
Ar'
Pt
Ar2
P
C C m
P
Ar2
Pt
Ar'
P
Ar2
I
Figure 1
Structure of double helical conformation I
The a,w-bromoalcohols Br(CH2)yOH were first converted
to their known tetrahydropyranyl ethers Br(CH2)yOTHP
(y = 6, 9, 11) under standard conditions (dihydropyran,
POCl3, THF).25 As shown in Scheme 2, the corresponding
Grignard reagents were generated, and treated with a catalytic amount of the copper salt Li2CuCl4.22 Then 0.28–
0.39 equivalents of a commercial a,w-dibromide or diiodide, X(CH2)zX (z = 6, 7, 8, 10) was added. Work-ups
gave the expected cross-coupling products, the a,wbis(tetrahydropyranyl) ethers THPO(CH2)nOTHP (n = 2y
+ z = 18, 19, 20, 22, 24, 28, 32), as white powders in 68–
40% unoptimized yields based upon the limiting dihalide
reactant. Although only one dihalide is specified for each
synthesis in the experimental section, dibromides and diiodides could be used interchangeably.
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Institut für Organische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Henkestraße 42, 91054 Erlangen, Germany
Fax +49(9131)8526865; E-mail: gladysz@organik.uni-erlangen.de
Received 21 March 2003
W. Mohr et al.
PAPER
Scheme 1
Hünig’s synthesis of a,w-difunctional alkanes
Since the products were mixtures of diastereomers and not
of special interest, most were characterized only by 1H
NMR and IR spectroscopy, as summarized in the experimental section. However, the highest representative
(n = 32), which was obtained in analytically pure form in
59% yield, was completely characterized. This sequence
has previously been used by Schill to prepare a,w-diethers
THPO(CH2)nOTHP with n = 34 and 35.23 Although these
were not elaborated further, related unsymmetrical species were. Lower homologs are also known (n = 8, 10, 12,
16),26 but all examples in Scheme 2 are new.
Tetrahydropyranyl ethers are commonly deprotected to
alcohols, but they have been directly converted to the corresponding bromides at room temperature using Ph3P and
2,4,4,6-tetrabromocyclohexa-2,5-dienone.27 As shown in
Scheme 2, reactions of THPO(CH2)nOTHP under these
conditions gave the target a,w-dibromides Br(CH2)nBr in
91–75% yields. All are known compounds, as referenced
in the experimental section, and were characterized by IR
and NMR (1H, 13C) spectroscopy. The highest representative (n = 32) was obtained as an analytically pure wax in
75% yield.
Scheme 2
Syntheses of title compounds
Synthesis 2003, No. 8, 1279–1285
ISSN 1234-567-89
In accord with the original goal of this study, the dibromides were treated with >2.0 equivalents of the potassium
diphenylphosphido salt K+ –PPh2, which is commercially
available as a THF solution. Work-up gave the target a,wdiphosphines Ph2P(CH2)nPPh2 in 95–74% yields. Alternatively, the easily-generated lithium salt Li+–PPh2 could
also be employed. These new compounds were characterized by IR and NMR (1H, 13C, 31P) spectroscopy, and mass
spectrometry, as summarized in the experimental section.
Microanalyses were obtained for representative cases.
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1280
Synthesis of Long-Chain a,w-Dibromides and Diphosphines
Finally, syntheses of five analogous diphosphines with
shorter methylene chains were executed (n = 8, 10, 11, 12,
14). All of these are known compounds, although some
characterization data are lacking and in the last case only
a patent report is available. Unlike the examples in
Scheme 2, these involve dibromides that are either commercially available or can be accessed from inexpensive
commercial diols. However, the data are included here to
avoid literature fragmentation.
We note in passing that there are conflicting claims in the
literature regarding the assignment of 13C NMR signals in
Ar2PCaH2CbH2CgH2R systems.9,28 Pulse sequences described in the experimental section unambiguously show
that the Ca, Cb, and Cg signals fall into the following
chemical shift and coupling constant ranges (n = 8–28):
d = 27.6–28.1 ppm (1JCP = 10.2–11.1 Hz), 25.4–26.0 ppm
(2JCP = 15.7–16.2 Hz), and 31.1–31.2 ppm (3JCP = 12.6–
13.2 Hz). Thus, in accord with observations with other organo-phosphorus compounds, the magnitudes of the JCP
values do not correlate to the distance of the carbon from
phosphorus.
The convenience and convergent nature of the methodology described above for the synthesis of a,w-dibromides
Br(CH2)nBr scarcely needs to be emphasized. Unlike
some older approaches to such compounds or the corresponding diols, generality is not limited by ‘gaps’ in commercially available starting materials. As of this writing,
a,w-bromoalcohols Br(CH2)yOH with y = 3, 6, 7, 8, 9, 10,
11, and 12 can be purchased. The most expensive cost ca.
200/5 g and the least expensive ca. 85 €/50 g. Practical
large-scale syntheses have also been developed.29 Similarly, shorter-chain starting a,w-dibromides Br(CH2)zBr
with z = 8, 9, 10, 11, and 12 can be purchased. The most
expensive cost ca. 62 €/13 g and the least expensive ca.
106 €/500 g.
Accordingly, modular syntheses of virtually any target
a,w-dibromide Br(CH2)nBr can be designed, up to a limit
of n = 36 (2 y + z), based upon the commercial building
blocks in the preceding paragraph. Furthermore, the dibromide products can be subjected to additional cycles of
chain lengthening, substituting for X(CH2)yX in
Scheme 2. In other efforts, we have extended the above
diphosphine syntheses by the use of substituted diarylphosphido anions M+ –P(C6H4R)2.24c However, it should
be emphasized in closing that this work has only packaged
established reactions in new ways. The power of this type
of approach to a,w-difunctional compounds was recognized by Schill earlier,23 but not applied towards these exact ends. Additional uses of the dibromides and
diphosphines described herein will be reported in future
publications.7,24
Instrumentation was identical with that given in recent full
papers7b,30 and additional details can be found elsewhere.24 The alcohols Br(CH2)yOH used to prepare Br(CH2)yOTHP25 were obtained from Aldrich, the Li2CuCl4 solutions were freshly generated
from LiCl (0.1696 g, 4.00 mmol), CuCl2 (0.2689 g, 2.00 mmol), and
THF (10 mL),26 and 2,4,4,6-tetrabromocyclohexa-2,5-dienone was
1281
synthesized by a literature method.31 THF was distilled from Na/
benzophenone, and CH2Cl2 was distilled from CaH2. Other solvents
and the following reagents were used as received: a,w-X(CH2)ZX
(Avocado and Aldrich), PPh3 (ABCR), and K+ –PPh2 (Aldrich, 0.5
M in THF).
THPO(CH2)28OTHP; Typical Procedure
A Schlenk flask was charged with Mg (0.192 g, 7.90 mmol), and a
dropping funnel containing a solution of Br(CH2)9OTHP (1.230 g,
4.003 mmol)25 in THF (50 mL) was attached. The THF solution was
slowly added with stirring. The mixture was stirred for 1 h at 50 °C
and cooled in a –20 °C bath. Then freshly prepared Li2CuCl4 (1.0
mL, 0.2 M in THF) and a solution of I(CH2)10I (0.520 g, 1.32 mmol)
in THF (5 mL) were added with stirring. The cold bath was removed. After 14 h, sat. aq NH4OAc (20 mL) was added. The emulsion was stirred for 0.5 h, and the organic phase was separated. The
aqueous phase was extracted with Et2O (3 × 50 mL). The combined
organic phases were washed with H2O (2 × 10 mL) and dried
(Na2SO4). The solvent was removed by oil pump vacuum, and the
residue crystallized from EtOH to give THPO(CH2)28OTHP as a
white powder (0.393 g, 50%).
IR (powder film): 2918 (s), 2819 (s), 1035 cm–1 (s).
H NMR (CDCl3): d = 4.58 (t, 3JHH = 5.0 Hz, 2 H, OCH), 3.85 (m,
2 H, CH2), 3.70 (m, 2 H), 3.50 (m, 2 H), 3.35 (m, 2 H), 1.80–1.30
(m, 64 H).
1
THPO(CH2)18OTHP
This synthesis was conducted analogously using Br(CH2)6OTHP
(3.161 g, 11.92 mmol),25 Mg (0.385 g, 15.8 mmol), Li2CuCl4 (1.0
mL, 0.2 M in THF), and Br(CH2)6Br (0.994 g, 4.074 mmol); yield:
1.072 g (58%).
IR (powder film): 2919 (s), 2819 (s), 1034 cm–1 (s).
H NMR (CDCl3): d = 4.60 (t, 3JHH = 5.0 Hz, 2 H, OCH), 3.84 (m,
2 H, CH2), 3.74 (m, 2 H), 3.50 (m, 2 H), 3.34 (m, 2 H), 1.80–1.30
(m, 44 H).
1
THPO(CH2)19OTHP
This synthesis was conducted analogously using Br(CH2)6OTHP
(2.782 g, 10.49 mmol),25 Mg (0.389 g, 16.0 mmol), Li2CuCl4 (1.0
mL, 0.2 M in THF), and Br(CH2)7Br (1.032 g, 4.000 mmol); yield:
0.931 g (50%).
IR (powder film): 2918 (s), 2819 (s), 1034 cm–1 (s).
H NMR (CDCl3): d = 4.56 (t, 3JHH = 5.0 Hz, 2 H, OCH), 3.87 (m,
2 H, CH2), 3.71 (m, 2 H), 3.52 (m, 2 H), 3.37 (m, 2 H), 1.80–1.30
(m, 46 H).
1
THPO(CH2)20OTHP
This synthesis was conducted analogously using Br(CH2)6OTHP
(3.004 g, 11.33 mmol),25 Mg (0.440 g, 18.1 mmol), Li2CuCl4 (1.0
mL, 0.2 M in THF), and I(CH2)8I (1.628 g, 4.469 mmol); yield:
1.465 g (68%).
IR (powder film): 2919 (s), 2818 (s), 1034 cm–1 (s).
H NMR (CDCl3): d = 4.58 (t, 3JHH = 5.0 Hz, 2 H, OCH), 3.84 (m,
2 H, CH2), 3.70 (m, 2 H), 3.52 (m, 2 H), 3.35 (m, 2 H), 1.80–1.30
(m, 48 H).
1
THPO(CH2)22OTHP
This synthesis was conducted analogously using Br(CH2)6OTHP
(3.328 g, 12.55 mmol),25 Mg (0.394 g, 16.2 mmol), Li2CuCl4 (1.0
mL, 0.2 M in THF), and Br(CH2)10Br (1.200 g, 4.000 mmol); yield:
0.914 g (45%).
IR (powder film): 2918 (s), 2819 (s), 1035 cm–1 (s).
Synthesis 2003, No. 8, 1279–1285
ISSN 1234-567-89
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PAPER
PAPER
W. Mohr et al.
H NMR (CDCl3): d = 4.58 (t, 3JHH = 5.0 Hz, 2 H, OCH), 3.85 (m,
2 H, CH2), 3.71 (m, 2 H), 3.50 (m, 2 H), 3.34 (m, 2 H), 1.80–1.30
(m, 52 H).
Br(CH2)19Br11
This synthesis was conducted analogously using THPO(CH2)19OTHP (0.469 g, 1.00 mmol); yield: 0.321 g (75%); white
powder.
THPO(CH2)24OTHP
This synthesis was conducted analogously using Br(CH2)9OTHP
(5.085 g, 16.55 mmol),25 Mg (0.443 g, 18.2 mmol), Li2CuCl4 (1.2
mL, 0.2 M in THF), and Br(CH2)6Br (1.113 g, 4.562 mmol); yield:
0.983 g (40%).
IR (powder film): 2918 (s), 2852 (s), 1471 (s), 718 cm–1 (m).
1
IR (powder film): 2918 (s), 2819 (s), 1034 cm–1 (s).
H NMR (CDCl3): d = 4.58 (t, 3JHH = 5.0 Hz, 2 H, OCH), CH2 at
3.85 (m, 2 H), 3.70 (m, 2 H), 3.50 (m, 2 H), 3.35 (m, 2 H), 1.80–1.30
(m, 56 H).
1
THPO(CH2)32OTHP
This synthesis was conducted analogously using Br(CH2)11OTHP
(4.020 g, 12.01 mmol),25 Mg (0.384 g, 15.8 mmol), Li2CuCl4 (1.0
mL, 0.2 M in THF), and I(CH2)10I (1.561 g, 3.965 mmol); yield:
1.512 g (59%); white powder; mp 60–61 °C.
–1
IR (powder film): 2918 (s), 2819 (s), 1034 cm (s).
H NMR (CDCl3): d = 4.57 (t, 3JHH = 5.0 Hz, 2 H, OCH), 3.9–3.3
(m, 8 H, CH2), 1.5–1.6 (m, 12 H), 1.4–1.3 (m, 60 H).
1
13
C{1H} NMR (CDCl3): d = 98.8 (s, OCH), 67.8 (s, OCH2), 62.9 (s,
OC¢H2), 30.1 (s, CH2), 29.7 (s, multiple intensity, CH2), 29.6 (s,
double intensity, CH2), 26.2 (s, CH2), 25.5 (s, CH2), 19.0 (s, CH2).
MS: m/z = 651 (M+, 5), 566 ([M – THP]+, 40) and progressively
more intense fragments corresponding to the loss of CH2.32a
Anal. Calcd for C42H82O4 (651.10): C, 77.48; H, 12.69. Found: C,
77.12; H, 12.30.
H NMR (CDCl3): d = 3.37 (t, 3JHH = 6.9 Hz, 4 H, CH2Br), 1.83 (m,
4 H, CH2CH2Br), 1.40 (m, 4 H, CH2CH2CH2Br), 1.34–1.20 (m, 26
H, CH2).
1
13
C{1H} NMR (CDCl3): d = 34.1 (s, CH2Br), 32.8 (s, CH2CH2Br),
29.7 (s, CH2), 29.6 (s, multiple intensity, CH2), 29.5 (s, CH2), 29.4
(s, CH2), 28.8 (s, CH2), 28.2 (s, CH2).
Br(CH2)20Br10,12,13
This synthesis was conducted analogously using THPO(CH2)20OTHP (0.483 g, 1.00 mmol); yield: 0.364 g (83%); white
powder.
IR (powder film): 2918 (s), 2853 (s), 1472 (s), 719 cm–1 (m).
H NMR (CDCl3): d = 3.38 (t, 3JHH = 6.9 Hz, 4 H, CH2Br), 1.83 (m,
4 H, CH2CH2Br), 1.39 (m, 4 H, CH2CH2CH2Br), 1.34–1.20 (m, 28
H, CH2).
1
13
C{1H} NMR (CDCl3): d = 34.1 (s, CH2Br), 32.8 (s, CH2CH2Br),
29.7 (s, CH2), 29.6 (s, multiple intensity, CH2), 29.5 (s, CH2), 29.4
(s, CH2), 28.8 (s, CH2), 28.2 (s, CH2).
Br(CH2)22Br14
This synthesis was conducted analogously using THPO(CH2)22OTHP (0.511 g, 1.00 mmol); yield: 0.400 g (85%); white
powder.
IR (powder film): 2919 (s), 2853 (s), 1472 (s), 718 cm–1 (m).
H NMR (CDCl3): d = 3.37 (t, 3JHH = 6.9 Hz, 4 H, CH2Br), 1.83 (m,
4 H, CH2CH2Br), 1.40 (m, 4 H, CH2CH2CH2Br), 1.34–1.20 (m, 32
H, CH2).
1
Br(CH2)28Br;17 Typical Procedure
A Schlenk flask was charged with Ph3P (1.182 g, 4.401 mmol) and
CH2Cl2 (10 mL), and was cooled to 0 °C. Then 2,4,4,6-tetrabromocyclohexa-2,5-dienone (1.802 g, 4.404 mmol) was added with
stirring. After the yellow color had disappeared (ca. 0.5 h),
THPO(CH2)28OTHP (0.595 g, 1.00 mmol) was added. The mixture
was stirred for 14 h at r.t. The suspension was filtered through a 1
cm silica gel pad. The solvent was removed from the filtrate by oil
pump vacuum. The residue was extracted with hexane and the extract was passed through a 8 cm silica gel pad. The solvent was removed by rotary evaporation and oil pump vacuum to give
Br(CH2)28Br as a white wax (0.442 g, 80%).
–1
IR (powder film): 2918 (s), 2853 (s), 1471 (s), 719 cm (m).
H NMR (CDCl3): d = 3.37 (t, 3JHH = 6.9 Hz, 4 H, CH2Br), 1.83 (m,
4 H, CH2CH2Br), 1.40 (m, 4 H, CH2CH2CH2Br), 1.34–1.20 (m, 44
H, CH2).
1
C{ H} NMR (CDCl3): d = 34.1 (s, CH2Br), 32.8 (s, CH2CH2Br),
29.7 (s, CH2), 29.6 (s, multiple intensity, CH2), 29.5 (s, CH2), 29.4
(s, CH2), 28.8 (s, CH2), 28.2 (s, CH2).
13
1
10
Br(CH2)18Br
This synthesis was conducted analogously using THPO(CH2)18OTHP (0.455 g, 1.00 mmol); yield: 0.374 g (91%); white
powder.
–1
IR (powder film): 2919 (s), 2853 (s), 1473 (s), 719 cm (m).
H NMR (CDCl3): d = 3.39 (t, JHH = 6.9 Hz, 4 H, CH2Br), 1.83 (m,
4 H, CH2CH2Br), 1.40 (m, 4 H, CH2CH2CH2Br), 1.34–1.20 (m, 24
H, CH2).
1
3
C{ H} NMR (CDCl3): d = 34.1 (s, CH2Br), 32.8 (s, CH2CH2Br),
29.7 (s, CH2), 29.6 (s, multiple intensity, CH2), 29.5 (s, CH2), 29.4
(s, CH2), 28.8 (s, CH2), 28.2 (s, CH2).
13
1
Synthesis 2003, No. 8, 1279–1285
ISSN 1234-567-89
C{1H} NMR (CDCl3): d = 34.1 (s, CH2Br), 32.8 (s, CH2CH2Br),
29.7 (s, CH2), 29.6 (s, multiple intensity, CH2), 29.5 (s, CH2), 29.4
(s, CH2), 28.8 (s, CH2), 28.2 (s, CH2).
13
Br(CH2)24Br10,15
This synthesis was conducted analogously using THPO(CH2)24OTHP (0.539 g, 1.00 mmol); yield: 0.446 g (90%); white
powder.
IR (powder film): 2919 (s), 2853 (s), 1471 (s), 719 cm–1 (m).
H NMR (CDCl3): d = 3.37 (t, 3JHH = 6.9 Hz, 4 H, CH2Br), 1.83 (m,
4 H, CH2CH2Br), 1.40 (m, 4 H, CH2CH2CH2Br), 1.34–1.20 (m, 36
H, CH2).
1
13
C{1H} NMR (CDCl3): d = 34.1 (s, CH2Br), 32.8 (s, CH2CH2Br),
29.7 (s, CH2), 29.6 (s, multiple intensity, CH2), 29.5 (s, CH2), 29.4
(s, CH2), 28.8 (s, CH2), 28.2 (s, CH2).
Br(CH2)32Br19
This synthesis was conducted analogously using THPO(CH2)32OTHP (0.651 g, 1.00 mmol); yield: 0.455 g (75%); white
wax, mp 69–70 °C.
IR (powder film): 2917 (s), 2853 cm–1 (s).
H NMR (CDCl3): d = 3.38 (t, 3JHH = 6.9 Hz, 4 H, CH2Br), 1.83 (m,
4 H, CH2CH2Br), 1.42 (m, 4 H, CH2CH2CH2Br), 1.23 (m, 52 H,
CH2).
1
13
C{1H} NMR (CDCl3): d = 34.0 (s, CH2Br), 32.8 (s, CH2CH2Br),
29.7 (s, multiple intensity, CH2), 29.6 (s, CH2), 29.6 (s, CH2), 29.4
(s, CH2), 28.8 (s, CH2), 28.2 (s, CH2).
MS: m/z = 529 ([M – Br]+, 30) and progressively more intensive
fragments corresponding to the loss of CH2.32a
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1282
Synthesis of Long-Chain a,w-Dibromides and Diphosphines
Anal. Calcd for C32H64Br2 (608.67): C, 63.15; H, 10.60. Found: C,
63.32; H, 10.87.
Ph2P(CH2)18PPh2; Typical Procedure
A Schlenk flask was charged with Br(CH2)18Br (0.825 g, 2.00
mmol) and THF (10 mL). Then K+ –PPh2 (8.0 mL, 0.5 M in THF,
4.0 mmol) was added via syringe with stirring until a light yellow
color remained. After 1 h, the solvent was removed by oil pump
vacuum. The residue was extracted with CH2Cl2 (2 × 10 mL). The
extracts were filtered through a 3 cm silica gel pad, which was
rinsed with CH2Cl2. The solvent was removed by oil pump vacuum
to give Ph2P(CH2)18PPh2 as a white solid (1.101 g, 88%); mp 66–
70 °C.
IR (powder film): 3073 (w), 2926 (m), 2853 (m), 1640 (w), 1482
(w), 1463 (w), 1436 (m), 911 (m), 737 (s), 695 cm–1 (s).
H NMR (CDCl3): d = 7.43–7.38 (m, 8 Harom, o to P), 7.33–7.28 (m,
12 Harom, m/p to P), 2.03 (t, 3JHH = 7.6 Hz, 4 H, PCH2), 1.46–1.34
(m, 8 H, PCH2CH2CH2), 1.29–1.18 (m, 24 H, CH2).
1
C{ H} NMR (CDCl3): d = 139.1 (d, JCP = 13.1 Hz, Carom, i to P),
132.7 (d, 2JCP = 18.4 Hz, CHarom, o to P), 128.4 (s, CHarom, p to P),
128.3 (d, 3JCP = 6.6 Hz, CHarom, m to P), 31.2 (d, 3JCP = 13.2 Hz,
PCH2CH2CH2),33 29.7 (s, CH2), 29.7 (s, CH2), 29.6 (s, CH2), 29.5
(s, CH2), 29.3 (s, CH2), 28.1 (d, 1JCP = 11.0 Hz, PCH2),33 26.0 (d,
2
JCP = 15.9 Hz, PCH2CH2).33
13
31
1
1
MS: m/z = 622 (M+, 43), 545 ([M – Ph]+, 11), 437 ([M – PPh2]+,
100), and fragments corresponding to the loss of CH2, 185 ([PPh2]+,
39), 108 ([PPh]+, 44).32b
Anal. Calcd for C42H56P2 (622.85): C, 80.99; H, 9.06. Found: C,
81.01; H, 8.99.
Ph2P(CH2)19PPh2
This synthesis was conducted analogously using Br(CH2)19Br
(0.853 g, 2.00 mmol); yield: 0.943 g (74%); white solid; mp 61–
63 °C.
IR (powder film): 3073 (w), 2926 (m), 2853 (m), 1640 (w), 1482
(w), 1463 (w), 1436 (m), 911 (m), 737 (s), 695 cm–1 (s).
H NMR (CDCl3): d = 7.43–7.38 (m, 8 Harom, o to P), 7.33–7.28 (m,
12 Harom, m/p to P), 2.04 (t, 3JHH = 7.6 Hz, 4 H, PCH2), 1.46–1.34
(m, 8 H, PCH2CH2CH2), 1.29–1.18 (m, 26 H, CH2).
1
13
C{1H} NMR (CDCl3): d = 138.1 (d, 1JCP = 13.1 Hz, Carom, i to P),
132.7 (d, 2JCP = 18.3 Hz, CHarom, o to P), 128.5 (s, CHarom, p to P),
128.4 (d, 3JCP = 6.5 Hz, CHarom, m to P), 31.2 (d, 3JCP = 13.2 Hz,
PCH2CH2CH2),33 29.6 (s, CH2), 29.6 (s, CH2), 29.6 (s, CH2), 29.5
(s, CH2), 29.5 (s, CH2), 29.3 (s, CH2), 29.2 (s, CH2), 29.0 (s, CH2),
27.8 (d, 1JCP = 11.0 Hz, PCH2),33 25.8 (d, 2JCP = 15.9Hz,
PCH2CH2).33
31
PCH2CH2CH2),33 29.7 (s, CH2), 29.6 (s, CH2), 29.6 (s, CH2), 29.5
(s, CH2), 29.5 (s, CH2), 29.3 (s, CH2), 29.2 (s, CH2), 28.0 (d,
1
JCP = 11.0 Hz, PCH2),33 25.9 (d, 2JCP = 15.9 Hz, PCH2CH2).33
31
P{1H} NMR (CDCl3): d = –15.0 (s).
MS: m/z = 636 ([M + 2 O]+, 100).32b
Ph2P(CH2)20PPh2
This synthesis was conducted analogously using Br(CH2)20Br
(0.881 g, 2.00 mmol); yield: 1.120 g (86%); white solid; mp 65–
67 °C.
IR (powder film): 3073 (w), 3019 (w), 2918 (s), 2849 (s), 1586 (w),
1471 (m), 1432 (m), 737 (s), 695 cm–1 (s).
H NMR (CDCl3): d = 7.42–7.37 (m, 8 Harom, o to P), 7.32–7.27 (m,
12 Harom, m/p to P), 2.03 (t, 3JHH = 7.6 Hz, 4 H, PCH2), 1.45–1.35
(m, 8 H, PCH2CH2CH2), 1.28–1.17 (m, 28 H, CH2).
1
13
C{1H} NMR (CDCl3): d = 138.8 (d, 1JCP = 13.1 Hz, Carom, i to P),
132.6 (d, 2JCP = 18.4 Hz, CHarom, o to P), 128.4 (s, CHarom, p to P),
128.3 (d, 3JCP = 6.6 Hz, CHarom, m to P), 31.2 (d, 3JCP = 13.2 Hz,
P{1H} NMR (CDCl3): d = –15.3 (s).
MS: m/z = 683 ([M + 2 O]+, 100), 667 ([M + O]+, 50), 651 (M+,
80).32b
Ph2P(CH2)22PPh2
This synthesis was conducted analogously using Br(CH2)22Br
(0.937 g, 2.00 mmol); yield: 1.180 g (87%); white solid; mp 60–
62 °C.
IR (powder film): 3073 (w), 3019 (w), 2918 (s), 2849 (s), 1590 (w),
1471 (m), 1436 (m), 737 (s), 695 cm–1 (s).
H NMR (CDCl3): d = 7.43–7.38 (m, 8 Harom, o to P), 7.33–7.28 (m,
12 Harom, m/p to P), 2.03 (t, 3JHH = 7.6 Hz, 4 H, PCH2), 1.46–1.34
(m, 8 H, PCH2CH2CH2), 1.29–1.18 (m, 32 H, CH2).
1
C{1H} NMR (CDCl3): d = 138.8 (d, 1JCP = 13.1 Hz, Carom, i to P),
132.6 (d, 2JCP = 18.4 Hz, CHarom, o to P), 128.4 (s, CHarom, p to P),
128.3 (d, 3JCP = 6.6 Hz, CHarom, m to P), 31.2 (d, 3JCP = 13.2 Hz,
PCH2CH2CH2),33 29.7 (s, CH2), 29.6 (s, CH2), 29.6 (s, CH2), 29.5
(s, CH2), 29.5 (s, CH2), 29.5 (s, CH2), 29.3 (s, CH2), 29.2 (s, CH2),
28.0 (d, 1JCP = 11.0 Hz, PCH2),33 25.9 (d, 2JCP = 15.9 Hz,
PCH2CH2).33
13
31
P{1H} NMR (CDCl3): d = –15.4 (s).
1283
P{1H} NMR (CDCl3): d = –15.4 (s).
MS: m/z = 711 ([M + 2 O]+, 100), 695 ([M + O]+, 50), 679 (M+,
80).32b
Ph2P(CH2)24PPh2
This synthesis was conducted analogously using Br(CH2)24Br
(0.993 g, 2.00 mmol); yield: 1.202 g (85%); white solid; mp 58–
60 °C.
IR (powder film): 3073 (w), 3019 (w), 2918 (s), 2849 (s), 1590 (w),
1471 (m), 1436 (m), 737 (s), 695 cm–1 (s).
H NMR (CDCl3): d = 7.43–7.38 (m, 8 Harom, o to P), 7.33–7.28 (m,
12 Harom, m/p to P), 2.04 (t, 3JHH = 7.6 Hz, 4 H, PCH2), 1.46–1.34
(m, 8 H, PCH2CH2CH2), 1.29–1.18 (m, 36 H, CH2).
1
13
C{1H} NMR (CDCl3): d = 139.1 (d, 1JCP = 13.1 Hz, Carom, i to P),
132.7 (d, 2JCP = 18.4 Hz, CHarom, o to P), 128.4 (s, CHarom, p to P),
128.3 (d, 3JCP = 6.6 Hz, CHarom, m to P), 31.2 (d, 3JCP = 13.2 Hz,
PCH2CH2CH2),33 29.7 (s, CH2), 29.6 (s, CH2), 29.6 (s, CH2), 29.5
(s, CH2), 29.5 (s, CH2), 29.5 (s, CH2), 29.3 (s, CH2), 29.3 (s, CH2),
29.2 (s, CH2), 28.0 (d, 1JCP = 11.0 Hz, PCH2),33 25.9 (d, 2JCP = 15.9
Hz, PCH2CH2).33
31
P{1H} NMR (CDCl3): d = –15.1 (s).
MS: m/z = 740 ([M + 2 O]+, 15), 724 ([M + O]+, 20), 707 (M+,
40).32(b)
Ph2P(CH2)28PPh2
This synthesis was conducted analogously using Br(CH2)28Br
(1.105 g, 2.000 mmol); yield: 1.312 g (86%); white solid; mp 59–
62 °C.
IR (powder film): 3073 (w), 3019 (w), 2918 (s), 2849 (s), 1590 (w),
1471 (m), 1436 (m), 737 (s), 695 cm–1 (s).
H NMR (CDCl3): d = 7.43–7.38 (m, 8 Harom, o to P), 7.33–7.28 (m,
12 Harom, m/p to P), 2.03 (t, 3JHH = 7.6 Hz, 4 H, PCH2), 1.46–1.34
(m, 8 H, PCH2CH2CH2), 1.29–1.18 (m, 44 H, CH2).
1
13
C{1H} NMR (CDCl3): d = 139.1 (d, 1JCP = 13.1 Hz, Carom, i to P),
132.7 (d, 2JCP = 18.4 Hz, CHarom, o to P), 128.4 (s, CHarom, p to P),
128.3 (d, 3JCP = 6.6 Hz, CHarom, m to P), 31.2 (d, 3JCP = 13.2 Hz,
PCH2CH2CH2),33 29.7 (br s, CH2), 29.6 (s, CH2), 29.5 (s, CH2), 29.3
(s, CH2), 28.1 (d, 1JCP = 11.0 Hz, PCH2),33 26.0 (d, 2JCP = 15.9 Hz,
PCH2CH2).33
Synthesis 2003, No. 8, 1279–1285
ISSN 1234-567-89
© Thieme Stuttgart · New York
This document was downloaded for personal use only. Unauthorized distribution is strictly prohibited.
PAPER
1284
31
PAPER
W. Mohr et al.
P{1H} NMR (CDCl3): d = –15.1 (s).
+
+
+
MS: m/z = 795 ([M + 2 O] , 75), 779 ([M + O] , 50), 763 (M ,
100).32(b)
IR (powder film): 3069 (w), 2922 (m), 2849 (m), 1482 (w), 1467
(w), 1432 (m), 1096 (w), 1065 (w), 1027 (w), 1000 (w), 733 (s), 695
cm–1 (vs).
H NMR (CDCl3): d = 7.53–7.42 (m, 8 Harom, o to P), 7.40–7.31 (m,
12 Harom, m/p to P), 2.10 (t, 3JHH = 7.6 Hz, 4 H, PCH2), 1.48 (m, 8
H, PCH2CH2CH2), 1.28 (m, 10 H, CH2).
1
IR (powder film): 2922 (s), 2849 (s), 1436 (s), 737 (s), 695 cm–1 (s).
H NMR (CDCl3): d = 7.74–7.26 (m, 20 H, C6H5), 2.02 (t,
JHH = 7.6 Hz, 4 H, PCH2), 1.38 (m, 8 H, PCH2CH2CH2), 1.3–1.2
(m, 52 H, CH2).
1
3
C{1H} NMR (CDCl3): d = 137.6 (d, 1JCP = 11 Hz, Carom, i to P),
132.7 (d, 2JCP = 17 Hz, CHarom, o to P), 128.7 (s, CHarom, p to P),
128.4 (d, 3JCP = 7 Hz, CHarom, m to P), 31.1 (d, 3JCP = 13 Hz,
PCH2CH2CH2),33 29.7 (s, multiple intensity, CH2), 29.6 (s, multiple
intensity, CH2), 29.6 (s, multiple intensity, CH2), 29.2 (s, multiple
intensity, CH2), 27.6 (d, 1JCP = 7 Hz, PCH2),33 25.7 (d, 2JCP = 14 Hz,
PCH2CH2).33
13
31
P{1H} NMR (CDCl3): d = –15.4 (s).
MS: m/z = 818 (M+, 20), 711 ([M – PPh2]+, 100), and fragments with
lower mass corresponding to the loss of CH2.32b
13
C{1H} NMR (CDCl3): d = 139.0 (d, 1JCP = 13.4 Hz, Carom, i to P),
132.6 (d, 2JCP = 18.0 Hz, CHarom, o to P), 128.3 (s, CHarom, p to P),
128.2 (d, 3JCP = 6.5 Hz, CHarom, m to P), 31.1 (d, 3JCP = 13.0 Hz,
PCH2CH2CH2),33 29.4 (s, CH2), 29.3 (s, CH2), 29.1 (s, CH2), 28.0
(d, 1JCP = 11.1 Hz, PCH2),33 25.9 (d, 2JCP = 16.2 Hz, PCH2CH2).33
31
P{1H} NMR (CDCl3): d = –15.4 (s).
MS: m/z = 524 (M+, 50), 447 ([M – Ph]+, 22), 370 ([M – 2Ph]+, 43),
339 ([M – PPh2]+, 81), and fragments with lower mass corresponding to the loss of CH2, 185 ([PPh2]+, 55), 108 ([PPh]+, 62).32a
Anal. Calcd for C35H42P2 (524.67): C, 80.12; H, 8.07. Found: C,
80.17; H, 7.84.
Ph2P(CH2)12PPh28,9
This synthesis was conducted analogously using Br(CH2)12Br
(0.656 g, 2.00 mmol). Yield: 0.937 g (87%); white solid; mp 66–
69 °C.
Ph2P(CH2)8PPh28,9
This synthesis was conducted analogously using Br(CH2)8Br (1.088
g, 4.000 mmol); yield: 1.624 g (84%); white solid; mp 103–105 °C.
IR (powder film): 3069 (w), 2918 (m), 2849 (m), 1482 (w), 1467
(w), 1432 (m), 1100 (w), 1069 (w), 1023 (w), 1000 (w), 737 (s), 718
(m), 695 cm–1 (vs).
IR (powder film): 3069 (w), 2926 (m), 2849 (w), 1482 (w), 1459
(w), 1432 (m), 1305 (w), 1096 (w), 1069 (w), 1027 (w), 1000 (w),
961 (w), 911 (w), 822 (w), 737 (s), 695 cm–1 (vs).
1
H NMR (CDCl3): d = 7.44–7.36 (m, 8 Harom, o to P), 7.32–7.28 (m,
12 Harom, m/p to P), 2.00 (t, 3JHH = 7.8 Hz, 4 H, PCH2), 1.45–1.32
(m, 8 H, PCH2CH2CH2), 1.21 (m, 4 H, CH2).
13
C{1H} NMR (CDCl3): d = 138.8 (d, 1JCP = 12.0 Hz, Carom, i to P),
132.6 (d, 2JCP = 18.5 Hz, CHarom, o to P), 128.5 (s, CHarom, p to P),
128.3 (d, 3JCP = 6.9 Hz, CHarom, m to P), 31.2 (d, 3JCP = 13.0 Hz,
PCH2CH2CH2),33 29.6 (s, CH2), 29.5 (s, CH2), 29.2 (s, CH2), 28.0
(d, 1JCP = 10.2 Hz, PCH2),33 25.4 (d, 2JCP = 15.7 Hz, PCH2CH2).33
1
13
C{1H} NMR (CDCl3): d = 138.9 (d, 1JCP = 13.2 Hz, Carom, i to P),
132.7 (d, 2JCP = 18.3 Hz, CHarom, o to P), 128.4 (s, CHarom, p to P),
128.3 (d, 3JCP = 6.6 Hz, CHarom, m to P), 31.1 (d, 3JCP = 13.2 Hz,
PCH2CH2CH2),33 29.0 (s, CH2), 28.0 (d, 1JCP = 11.0 Hz, PCH2),33
25.9 (d, 2JCP = 16.1 Hz, PCH2CH2).33
31
P{1H} NMR (CDCl3): d = –15.6 (s).
H NMR (CDCl3): d = 7.43–7.37 (m, 8 Harom, o to P), 7.33–7.29 (m,
12 Harom, m/p to P), 2.02 (t, 3JHH = 7.6 Hz, 4 H, PCH2), 1.44–1.32
(m, 8 H, PCH2CH2CH2), 1.26–1.15 (m, 12 H, CH2).
31
P{1H} NMR (CDCl3): d = –15.3 (s).
MS: m/z = 538 (M+, 66), 461 ([M – Ph]+, 23), 353 ([M – PPh2]+,
100), and fragments with lower mass corresponding to the loss of
CH2, 185 ([PPh2]+, 66), 108 ([PPh]+, 93).32a
Ph2P(CH2)10PPh28,9
This synthesis was conducted analogously using Br(CH2)10Br
(0.600 g, 2.00 mmol); yield: 0.929 g (91%); white solid; mp 91–
93 °C.
Ph2P(CH2)14PPh234
This synthesis was conducted analogously using Br(CH2)14Br
(0.712 g, 2.00 mmol); yield: 0.995 g (88%); white solid; mp 86–
88 °C.
H NMR (CDCl3): d = 7.44–7.36 (m, 8 Harom, o to P), 7.32–7.27 (m,
12 Harom, m/p to P), 2.02 (t, 3JHH = 7.7 Hz, 4 H, PCH2), 1.46–1.32
(m, 8 H, PCH2CH2CH2), 1.27-1.15 (m, 8 H, CH2).
IR (powder film): 3073 (w), 2926 (m), 2853 (m), 1640 (w), 1482
(w), 1463 (w), 1436 (m), 911 (m), 737 (s), 695 cm–1 (s).
1
C{1H} NMR (CDCl3): d = 139.1 (d, 1JCP = 13.2 Hz, Carom, i to P),
132.7 (d, 2JCP = 18.1 Hz, CHarom, o to P), 128.4 (s, CHarom, p to P),
128.3 (d, 3JCP = 6.6 Hz, CHarom, m to P), 31.2 (d, 3JCP = 12.6 Hz,
PCH2CH2CH2),33 29.4 (s, CH2), 29.2 (s, CH2), 28.0 (d, 1JCP = 11.0
Hz, PCH2),33 25.9 (d, 2JCP = 15.9 Hz, PCH2CH2).33
13
31
P{1H} NMR (CDCl3): d = –15.4 (s).
MS: m/z = 510 (M+, 25), 433 ([M – Ph]+, 14), 325 ([M – PPh2]+,
100), and fragments with lower mass corresponding to the loss of
CH2, 185 ([PPh2]+, 70), 108 ([PPh]+, 68).32a
Anal. Calcd for C34H40P2 (510.64): C, 79.97; H, 7.90. Found: C,
78.70; H, 7.91.
Ph2P(CH2)11PPh28,9
This synthesis was conducted analogously using Br(CH2)11Br
(0.628 g, 2.00 mmol); yield: 0.902 g (86%); white solid; mp 49–
52 °C.
Synthesis 2003, No. 8, 1279–1285
ISSN 1234-567-89
H NMR (CDCl3): d = 7.44–7.37 (m, 8 Harom, o to P), 7.33–7.27 (m,
12 Harom, m/p to P), 2.02 (t, 3JHH = 7.6 Hz, 4 H, PCH2), 1.49–1.32
(m, 8 H, PCH2CH2CH2), 1.30–1.13 (m, 16 H, CH2).
1
13
C{1H} NMR (CDCl3): d = 139.1 (d, 1JCP = 13.2 Hz, Carom, i to P),
132.7 (d, 2JCP = 18.1 Hz, CHarom, o to P), 128.4 (s, CHarom, p to P),
128.3 (d, 3JCP = 6.6 Hz, CHarom, m to P), 31.2 (d, 3JCP = 12.6 Hz,
PCH2CH2CH2),33 29.6 (s, CH2), 29.6 (s, CH2), 29.5 (s, CH2), 29.2
(s, CH2), 28.0 (d, 1JCP = 11.0 Hz, PCH2),33 26.0 (d, 2JCP = 15.9 Hz,
PCH2CH2).33
31
P{1H} NMR (CDCl3): d = –15.4 (s).
MS: m/z = 566 (M+, 33), 489 ([M – Ph]+, 14), 381 ([M – PPh2]+,
100), and fragments with lower mass corresponding to the loss of
CH2, 185 ([PPh2]+, 42), 108 ([PPh]+, 40).32a
Anal. Calcd for C38H48P2 (566.75): C, 80.53; H, 8.54. Found: C,
80.44, H, 8.65.
© Thieme Stuttgart · New York
This document was downloaded for personal use only. Unauthorized distribution is strictly prohibited.
PPh2(CH2)32PPh2
This synthesis was conducted analogously using Br(CH2)32Br
(0.290 g, 0.476 mmol); yield: 0.371 g (95%); white solid; mp 66 °C.
Synthesis of Long-Chain a,w-Dibromides and Diphosphines
Acknowledgment
We thank the Deutsche Forschungsgemeinschaft (DFG; SFB 583)
for support.
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(31) Tsubota, M.; Iso, M.; Suzuki, K. Bull. Chem. Soc. Jpn. 1972,
45, 1252.
(32) m/z for most intense peak of isotope envelope (relative
intensity, %): (a) EI (b) (+)-FAB, 3-NBA/CH2Cl2.
(33) The PCH2CH2CH2 linkages of the free phosphines exhibit a
characteristic pattern of 13C signals. A 1H-1H COSY
experiment with Ph2P(CH2)14PPh2 was used to make
definitive assignments of the corresponding 1H signals, and
a 1D-NOE experiment (DPFGSE-NOE) confirmed the
PCH2 signal (close contact to the ortho protons of the phenyl
ring). A 1H-13C COSY experiment in turn gave a definitive
assignment of the PCH2 13C signal. A selective 1D-13CINADEQUATE spectrum verified this conclusion and
enabled assignments of the remaining signals.
(34) Oswald, A. A.; Jermasen, T. G.; Westner, A. A.; Huang, I.
D. (Exxon Research and Engineering Co., USA); US Patent
4687874, 1987; Chem. Abstr. 1988, 108, 40088.
Synthesis 2003, No. 8, 1279–1285
ISSN 1234-567-89
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