Organocatalytic Chlorination of Alcohols by P(III)/P(V) Redox Cycling

Article abstract of DOI:10.1021/acs.joc.9b00741

A catalytic system for the chlorination of alcohols under Appel conditions was developed. Benzotrichloride is used as a cheap and readily available chlorinating agent in combination with trioctylphosphane as the catalyst and phenylsilane as the terminal reductant. The reaction has several advantages over other variants of the Appel reaction, e.g., no additional solvent is required and the phosphane reagent is used only in catalytic amounts. In total, 27 different primary, secondary, and tertiary alkyl chlorides were synthesized in yields up to 95%. Under optimized conditions, it was also possible to convert epoxides and an oxetane to the dichlorinated products.

Full text of DOI:10.1021/acs.joc.9b00741

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Article
Organocatalytic chlorination of alcohols by P(III)/P(V) redox cycling
Lars Longwitz, Stefan Jopp, and Thomas Werner
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b00741 • Publication Date (Web): 28 May 2019
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The Journal of Organic Chemistry
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Organocatalytic chlorination of alcohols by P(III)/P(V) redox
cycling
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Lars Longwitz, Stefan Jopp, Thomas Werner*
Leibniz Institute for Catalysis at the University of Rostock, Albert-Einstein-Straße 29a, 18059 Rostock, Germany
Supporting Information Placeholder
ABSTRACT: A catalytic system for the chlorination of alcohols under Appel conditions was developed. Benzotrichloride is used as a cheap
and readily available chlorinating agent in combination with trioctylphosphane as the catalyst and phenylsilane as the terminal reductant. The
reaction has several advantages over other variants of the Appel reaction, e.g. no additional solvent is required and the phosphane reagent is
used only in catalytic amounts. In total, 27 different primary, secondary and tertiary alkyl chlorides were synthesized in yields up to 95%.
Under optimized conditions, it was also possible to convert epoxides and an oxetane to the dichlorinated products.
INTRODUCTION
Chlorinated hydrocarbons are amongst the most utilized starting
Scheme 1. Synthesis of alkyl halides from alcohols using phos-
phorus reagents under Appel conditions.
reaction
Stoichiometric
a)
Appel
CCl4
Ph3P
materials in organic synthesis due to the great value of nucleophilic
substitution reactions for the stepwise construction of complex
molecules.1 Their direct synthesis from alcohols can be achieved in
various ways and is performed even on industrial scale.2-7 The Ap-
pel reaction uses phosphanes and organic chlorinating agents like
carbon tetrachloride to convert alcohols stereoselectively to the
corresponding alkyl chlorides (Scheme 1a).8 Although this meth-
odology is excellent for the conversion of complex structures under
mild conditions, a definite drawback is the generation of stoichio-
metric phosphane oxide by-product, which complicates product
purification.9 Recently, there has been a growing interest in the
development of catalytic variants of common organic transfor-
mations like the Wittig10-15 , Cadogan16, Mitsonobu17, 18 or Stauding-
waste
OH
R1 R2
Cl
Stoichiometric Ph3P=O
or as
MeCN CCl4
solvent
R1 R2
Redox neutral catalysis
Denton et al.
b)
by
Cl
(cat.)
(CO
Ph P=O
)
2
monoxide
Release of carbon
OH
R1 R2
Cl
3
added via
Reagent
pump
syringe
R1 R2
as
CHCl3
solvent
van
Catalytic bromination
Delft
et al.
c)
by
Br
Et)2
2SiH2
CH(CO2
Ph
redox catalysis
P(III)/P(V)
Only Bromination
as
R P=O
Br
R1 R2
Catalytic
chlorination
OH
(cat.)
successful
3
MeCN
solvent
R1 R2
20
22
er19, reaction.21, In these reactions, the phosphane oxide is re-
duced in situ back to the phosphane by a suitable terminal reduct-
ant which eliminates problems concerning the separation of the
product from the phosphane oxide waste. The terminal reductant
needs to chemoselectively react with the phosphane oxide and
organosilanes have been found to be especially fitting for this task.23
In recent years, variations of the Appel reaction largely focused on
the use of alternative chlorinating agents like dichloroselenurane
(Ph2SeCl2)24, ammonium salts in combination with DDQ25 or 1,2-
work:
This
d)
PhC
Cl3
PhSiH3
Cheap chlorinating
agent
Solvent-& acid-free conditions
and
P
Oct3
OH
(cat.)
Cl
alcohols,
oxetanes
epoxides
R1 R2
R1 R2
dihaloethanes26, trichloroisocyanuric acid27 or other small com-
pounds bearing a CCl3 group.28 These procedures improved reac-
tion times, stereoselectivity and allowed for the conversion of more
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demanding substrates, but all required the use of stoichiometric Table 1. Screening of potential catalysts, various silanes as
1
2
3
4
5
6
7
8
amounts of phosphane reagent. In 2010 Denton et al. presented a
catalytic chlorination employing a phosphane oxide catalyst under
redox neutral conditions (Scheme 1b).29-32 The active chlorophos-
phonium salt is generated from the oxalylchloride, releasing CO2
and toxic CO in the process. Concerning the development of a
catalytic Appel reaction, van Delft et al. presented dibenzophos-
phole oxides as catalysts for the bromination of alcohols using
reducing agents, chlorine sources and optimization of the
reaction conditions.36
catalyst
OH
silane
Cl
°
source,
Cl
90
18
h
C,
1a
2a
Et
CCl4
Cl3C CO2
34
diphenylsilane as the terminal reductant (Scheme 1c).33, While
Cl
N
CCl3
3a
3c
O
EtO2C
CO2Et
O
O
alkyl bromides could be obtained in moderate to good yields under
catalytic conditions, the protocol could not be transferred to the
chlorination of alcohols. The authors pointed out that the balance
of electrophilicity of the chlorinating agent and nucleophilicity of
the phosphane catalyst would be crucial for a successful catalytic
Appel reaction. Huijbregts et al. reported a life cycle assessment of
the catalytic Appel reaction compared to a classic variant using
stoichiometric amounts of phosphane.35 The highest share of the
cumulative energy demand and greenhouse gas emissions for the
catalytic reaction was attributed the solvent (MeCN) and chlorine
source (diethyl chloromalonate). Thus, a catalytic Appel reaction
would require improvements in these areas to be competitive with
the classic reaction. Herein, we present a protocol using benzotri-
chloride (PhCCl3) as the chlorine source in combination with
trioctylphosphane (Oct3P) as the catalyst to convert alcohols under
solvent-free conditions to the respective chlorides.
9
Cl
Cl3C CN
10
11
12
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Cl3C
CCl3
3e
3f
3g
3b
3d
catalyst
(10 mol %)
silane
(equiv)
Cl
source
yield 2a
/%a
entry
3a
1
2
Ph3P
PhSiH3 (1.00)
PhSiH3 (1.00)
PhSiH3 (1.00)
PhSiH3 (1.00)
Ph2SiH2 (1.50)
9 (14)
39 (46)
2 (13)
3a
3a
3a
3a
3a
3b
3c
3d
3e
3f
Bu3P
3
tBu3P
Oct3P
Oct3P
Oct3P
Oct3P
Oct3P
Oct3P
Oct3P
Oct3P
Oct3P
Oct3P
Oct3P
4
45 (50)
7 (18)
5
6
(MeO)3SiH (3.00)
PhSiH3 (1.00)
PhSiH3 (1.00)
PhSiH3 (1.00)
PhSiH3 (1.00)
PhSiH3 (1.00)
PhSiH3 (1.00)
PhSiH3 (1.00)
PhSiH3 (1.00)
3 (96)
7
34 (84)
27 (52)
51 (94)
6 (68)
8
9
RESULTS AND DISCUSSION
10
11b
12
13c
14d
We started our investigation by staying close to the classic Appel
conditions in the model reaction of 4-phenyl 1-butanol (1a) to the
corresponding chloride 2a.36 When alcohol 1a was converted with
an excess of CCl4 in the presence of 10 mol % triphenylphosphane
and a stoichiometric amount of phenylsilane at 90 °C for 18 h, only
9% of the product was obtained, indicating no successful turnover
under these conditions (Table 1, entry 1). Alkyl phosphanes are
not commonly used in the classic Appel reaction due to their high
nucleophilicity and violent reaction with CCl4.8, 37, 38 However, since
the slow reduction of the phosphane oxide limits the amount of free
phosphane present in the reaction mixture, we envisioned a con-
trolled reaction when using a more nucleophilic trialkyl phosphane
in catalytic amounts. Indeed, a significant higher yield of 39% was
observed using 10 mol % of tributyl phosphane (Bu3P) as the cata-
lyst (entry 2). Increasing the steric demand on the phosphane
generally leads to lower yields and the best catalyst was found to be
trioctylphosphane giving the product in a yield of 45% (entry 3
and 4). Phenylsilane proved to be most suitable terminal reductant
compared to other more substituted organosilanes like diphen-
ylsilane or trimethoxysilane (entry 5 and 6). Subsequently, we
turned our attention to the chlorination reagent 3, which were used
in a large excess (entries 7–12). Enhancing the electrophilic charac-
ter by introduction of cyano or ester groups reduced the yield
slightly to 34% and 27%, respectively, but the selectivity of the
reaction greatly decreased (entry 7 and 8). Triphosgene (3d) could
be used as chlorine source with a moderate yield of 51%, albeit a
poor selectivity was observed (entry 9). Van Delft et al. used diethyl
chloromalonate (3e) in their catalytic Appel reaction, but only with
limited success.34 We also investigated this chlorinating agent with
trioctylphosphane as the catalyst, but only a poor yield of 6% was
observed (entry 10).
8 (84)
3g
3g
3g
55 (65)
82 (96)
93 (>99)
Standard reaction conditions: 1 (1.00 mmol, 1.00 equiv), catalyst
(10 mol %), silane (1.00 equiv), chlorine source 3 (2 mL); 90 °C for
a
18 h. Conversion given in parenthesis. Yield and conversion were
b
determined by GC-FID using hexadecane as internal standard. Sol-
c
d
vent-free, 1.00 equiv of 3f. Solvent-free, 5.00 equiv of 3g. Solvent-
free, 5.00 equiv of 3g, 100 °C, 24 h.
The chloronium source N-chlorosuccinimide (3f) leads to a com-
plex reaction mixture under these conditions, even when only a
stoichiometric amount of 3f was added (entry 11). Additionally,
benzotrichloride (3g) was employed as a halogen source and a
yield of 55% with good selectivity was observed (entry 12). Nota-
bly, benzotrichloride(3g) is readily available in large amounts at
low prices and has to the best of our knowledge not been used
successfully as a chlorination reagent up until now. Subsequently,
the reaction conditions were adjusted by reducing the amount of
the chlorinating agent (entry 13) and changing reaction tempera-
ture and time to give the desired product in a yield of 93%(entry
14).36
With a suitable protocol for the catalytic chlorination of alcohols in
hand, we examined the substrate scope of our catalytic system
under optimized conditions (Scheme 2). The product 2a of the
model reaction was isolated in a yield of 87%. The scalability of the
progress was tested by converting the model substrate 1a in a mul-
tigram scale and a yield of 98% of the corresponding chloride 2a
was obtained. Alkyl chlorides 2b and 2c bearing shorter alkyl
chains were isolated in excellent yields of 85% and 88%, respective-
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The Journal of Organic Chemistry
ly. We were also interested in the possible conversion of mercap-
Scheme 4. Conversion of strained oxocycles under catalytic
Appel conditions.a
1
2
3
4
5
6
7
8
tans, but a yield of only 15% of 1-chloro-2-phenyl ethane (2c) was
obtained starting from the respective thiol. The diphenyl substitut-
ed ethanol 1d gave the respective chloride 2d in a yield of 84%.
Furthermore, different para substituted 2-phenyl 1-ethanol deri-
vates 1e–i were converted with good to excellent yields and func-
tional groups like nitro (2g), cyano (2h) or amino (2i) were com-
patible with the protocol.
Cl
O
Cl
R
R
7a
7b
7c
R=
92%
,
,
,
H,
R= 94%
Cl,
c
6a–
P(III)/P(V)
F,
R=
87%
Cl
O
reaction conditions
Standard
Scheme 2. Scope of primary alcohols in the catalytic Appel
reaction.a
OH
Me
8
Cl
Cl
9
Me
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
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30
31
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37
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45
46
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50
51
52
53
54
55
56
57
58
59
60
9
63%
,
mol
P
Oct3
%)
equiv)
(10
PhSiH
3 (1.00
3g 5.00
,
equiv)
PhC
Cl3
aStandard reaction conditions: 6 or 8 (1.00 mmol, 1.00 equiv),
Oct3P (10 mol %), phenylsilane (1.00 equiv), PhCCl3 (3g,
5.00 equiv), solvent-free; 100 °C for 24 h. Isolated yields are given.
(
R
R
OH
Cl
Cl
solvent-free, 100 °C, 24 h
1
2
Ph
Cl
Cl
Cl
Introduction of a trifluoromethyl group in para, meta or ortho
position gave the corresponding alkyl halides 2j–2l in moderate to
good yields. The thiophene substituted alcohol 1m and naphthyl
derivate 1n were converted in yields of 74% and 81%. The para
substituted benzylchlorides 2o and 2p were obtained in yields of
68% and 69%. Doubling the amount of phosphane, silane and
chlorinating agent enabled the isolation of the dichloride 2q in a
moderate yield of 65%. Four aliphatic alcohols 1r–u were convert-
ed to the respective alkyl chlorides in yields between 75% and 91%
and the alkene groups (2r and 2t) as well as an alkyne group (2s)
were well tolerated.
2a
2a
2b,
85%
87%
98%b,
2c
,
2d
84%
,
,
88%
c
c
:
,
from SH 15%
Cl
Cl
R
Cl
Cl
R
,
2e
2f
R= Br, 75%
R=
79%
S
2m
2j
R= p
-CF3
73%
,
,
OMe,
R= NO 81%
,
2g
2h
2n
81%
,
74%
m
,
2k
,
R=
R=
82%
-CF3
,
,
,
,
2
o
2l
-CF3
66%
,
,
R=
95%
CN,
2i
R= NMe 68%
,
,
2
Cl
Cl
Cl
Cl
Cl
F
3C
7
tBu
68%
69%
65%d
2o
2p
2q
2r
75%
,
,
,
,
With overall good to excellent yields for the primary substrates, we
then applied our reaction conditions onto secondary and tertiary
alcohols 4a–h (Scheme 3). The secondary alkyl chloride 5a was
obtained in a good yield of 64% without changing reaction condi-
tions. Biaryl-substituted alcohol 4b was converted to the respective
chloromethylene dibenzene (5b) in a yield of 61%. The conversion
of cyclohexanol (4c) gave chlorocyclohexane (5c) in an isolated
yield of 57%. The chloride 5d could not be obtained under these
conditions and only the elimination product was isolated. Further-
more, the protected glucose substrate 4e was chlorinated to 5e in a
yield of 31%. Tertiary alcohols bearing an adamantyl or trityl group
gave the corresponding chlorides in rather low yields of 37% and
41%.
O
Cl
Cl
7
EtO
Cl
2s
,
2t
2u
80%
,
85%
91%
,
aStandard reaction conditions: 1 (1.00 mmol, 1.00 equiv), Oct3P
(10 mol %), phenylsilane (1.00 equiv), PhCCl3 (3g, 5.00 equiv),
solvent-free; 100 °C for 24 h. Isolated yields are given. The reac-
tion was performed on a 5.00 g (33.3 mmol) scale. Yield was
determined with GC-FID using hexadecane as internal standard.
b
c
d
1,2-Benzenedimethanol (1q, 1.00 mmol, 1.00 equiv), Oct3P
(20 mol %), phenylsilane (2.00 equiv), PhCCl3 (3g, 10.00 equiv).
Scheme 3. Scope of secondary and tertiary alcohols in the
catalytic Appel reaction.a
mol
P
Oct3
%)
equiv)
(10
PhSiH
3 (1.00
OH
Cl
PhC
3g 5.00
,
equiv)
Cl3
(
It is also possible to synthesize 1,2-dichloro substituted alkanes by
converting epoxides under Appel reaction conditions, which was
among other things utilized for the stereoselective synthesis of
chlorosulfolipids.39-42 In fact, our catalytic methodology converted
styrene oxide derivates 6a–c to the respective dichloroalkanes 7a–c
in excellent yields up to 94% (Scheme 4). When oxetane derivate 8
was converted, three chlorination reactions took place and the
trichloride 9 was isolated.
R1
R1
R2
R3
R3
solvent-free, 100 °C, 24 h
Cl
R2
5
4
Cl
Cl
Cl
:
4a
R
)-
from
(
5a
ee=
5a
5b
5c
,
64%
S
)-
66%,
31%
61%
57%
Cl
,
,
,
(
O
O
A major advantage over other chlorination methods is the stereose-
lectivity of the Appel reaction. Our next goal was to verify the ste-
reoselectivity of the catalytic Appel reaction by converting the
enantiopure alcohol (R)-4a to the respective alkyl halide (S)-5a
(Scheme 3). While the product was isolated in a yield similar to the
racemic substrate 5a, significant racemization was observed and
only an enantiomeric excess of 31% was found in the alkyl halide.
We further investigated the poor stereoselectivity by converting an
enatiopure alkyl chloride (S)-5a under the standard reaction condi-
tions. Interestingly, stereodegradation was observed and the alkyl
Cl
O
Cl
O
Cl
O
b
=
5d
5e
5f
5g
41%
,
de >99%
37%
, 0%
, 31%,
,
(71%)
a
For standard reaction conditions, see Scheme 2. Enantiomeric
excess (ee) was determined by chiral GC-FID. Diastereomeric
excess (de) was determined by GC-FID. Isolated yield of corre-
sponding alkene derivate in parenthesis.
b
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chloride was isolated quantitatively with an enantiomeric excess of
direct conversion of epoxides or oxetanes to the chlorinated deri-
vates via a ring opening reaction.
1
2
3
4
5
6
7
8
only 35%. We also investigated the carbohydrate derivate 5e, which
was isolated as a single diastereomer, indicating no epimerization
occurred during the reaction. We suspect that the carbohydrate 5e
is protected from this epimerization due to the bulky isopropy-
lidene groups.36
EXPERIMENTAL SECTION
General considerations. All reagents and solvents were purchased
from commercial sources and used as received without further
purification. All reactions were performed in 6 mL
12x100 DURAN® culture tubes with GL 14 screw caps and heated
in an aluminum block. It is also possible to perform the reaction in
standard pressure tubes. Thin layer chromatography was per-
formed on Merck TLC-plates with fluorescence indication (silica
type 60, F254), visualization was accomplished using UV-light,
iodine stains or 10% ethanolic sulphuric acid solution. Flash chro-
matography was performed using silica with a grain size of 40–63
µm from Macherey-Nagel. Deuterated chloroform was purchased
from Deutero. NMR spectra were recorded on Bruker AV 300 and
Scheme 5. Proposed mechanism for the catalytic Appel reac-
tion with benzotrichloride and trioctylphosphane.
R
3SiH
R
H
2
3SiO
SN
pathway
9
R2
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
R1
=
Cl
P
Oct3
Ph
CCl3
P
Oct3
O
3g
R2
R1
Cl
or
2
5
Ph
Cl
1
Bruker AV 400 spectrometers. The chemical shifts (δ) for H and
R2
13C in CDCl3 are given in parts per million (ppm) and referenced to
7.27 and 77.0 ppm, respectively. Coupling constants are given in
Hertz (Hz). The following abbreviations are used: s = singlet, d =
doublet, t = triplet, q = quadruplet, p = pentet, sext = sextet, m =
multiplet, dd = doublet of doublets, dt = doublet of triplets, tt =
triplet of triplets. IR spectra were recorded on a Nicolet iS10 MIR
FT-IR-spectrometer from Thermo Fisher Scientific. Gas chromatog-
raphy was performed on Agilent 7890A GC System, mass spectra
were measured on downstream 5975C inert XL MSD mass detec-
tor from Agilent. The reported GC-FID yields are based on a cali-
brated area of hexadecane as internal standard. High resolution
mass spectra were obtained either from a MAT 95 XP from Thermo
(EI) or from an HPLC system 1200 and downstream ESI-TOF-MS
6210 from Agilent (ESI).
P
Oct3 Cl
Cl
R2
R1
P
R2
Oct3
R1
O
Cl
R1
H
O
Cl
1
SN
pathway
or
1
4
PhCHCl2
10
We propose a mechanism very similar to the classic Appel reaction
(Scheme 5).36 The nucleophilic phosphane reacts with the electro-
philic chlorinating agent to a chlorophosphonium salt. This salt can
further react with an alcohol to form an alkoxyphosphonium salt
and dichlorotoluene (10) as a side product. The alkoxyphosphoni-
um salt undergoes a Michaelis-Arbusov-rearrangement under the
reaction conditions to liberate the product. The product may un-
dergo a nucleophilic substitution reaction which leads overall to the
loss of stereoinformation in the case of chiral alcohols. Another
possible pathway is a SN1 type mechanism, in which the phosphane
oxide is eliminated and a carbocation is formed. This leads to the
formation of elimination side products for secondary alcohols like
4d and could also be the reason for the poor stereoselectivity of
substrate (R)-4a. Subsequently, the phosphane oxide is then re-
duced by the organosilane to close the catalytic cycle. It is also
possible to start the reaction with the corresponding oxide without
significant loss of activity, which is especially useful since most
phosphanes are oxygen-sensitive. Furthermore, we investigated the
General procedure (GP1) for catalyst screening and optimiza-
tion: A solution of 4-phenylbutan-1-ol (1a, 150 mg, 1.00 mmol,
1.00 equiv), chlorinating agent
3 (2 mL or 5.00 equiv),
phenylsilane (108 mg, 1.00 mmol, 1.00 equiv) and the catalyst
(0.10 mmol, 0.10 equiv) was stirred in a culture tube at 100 °C for
24 h. The reaction mixture was cooled to room temperature, dilut-
ed with EtOAc (5 mL) and hexadecane (113 mg, 0.50 mmol,
0.50 equiv) was added. The conversion and yield were determined
by GC-FID analysis using hexadecane as internal standard.
General procedure (GP2) for the synthesis of alkyl chlorides:
Alcohol 1 or 4 (1.00 mmol), 3g (977 mg, 5.00 mmol), and tri-n-
octylphosphane (37 mg, 0.01 mmol) were added to a 5 mL culture
tube. The vial is purged with argon and after adding phenylsilane
(108 mg, 1.00 mmol) the vial was capped and stirredfor 24 h at 100
°C. After cooling to room temperature the reaction mixture is
diluted with EtOAc (5 mL) and the product is isolated by column
chromatography (SiO2) or Kugelrohr distillation. All volatiles were
removed carefully in vacuum to afford the desired alkyl chloride 2
or 5.
31
resting state of the catalyst by in situ P NMR spectroscopy and
found a mixture of phosphane oxide and phosphane during the
reaction. Thus it appears that both the reduction and nucleophilic
attack on the benzotrichloride (3g) influence the rate of the reac-
tion.
CONCLUSION
In conclusion, we have developed a highly effective new methodol-
ogy for the chlorination of alcohols. The key to the high activity
and selectivity of the system is the balance of the nucleophilicity of
the alkyl phosphane catalyst and electrophilic character of the
chlorinating agent in the presence of an organosilane as the termi-
nal reductant. In total, 21 primary alcohols were converted into the
alkyl chlorides with good functional group tolerance and good to
excellent yields. Secondary and tertiary alcohols were also compat-
ible with the procedure, although lower yields were obtained. The
conversion of chiral alcohols indicates partial racemization under
the reaction conditions. Moreover, the protocol can be used for the
1-Chloro-4-phenylbutane (2a)43
: According to GP2, 4-
phenylbutan-1-ol (1a, 150 mg, 1.00 mmol), benzotrichloride
(977 mg, 5.00 mmol), phenylsilane (108 mg, 1.00 mmol) and tri-n-
octylphosphane (37 mg, 0.10 mmol) were reacted and after purifi-
cation by column chromatography (SiO2, cyclohexane) 2a
(146 mg, 0.866 mmol, 87%) was obtained as colourless liquid. Rf
1
(SiO2, cyclohexane)= 0.46; H-NMR (300 MHz, CDCl3, 25 °C):
δ= 1.71–1.75 (m, 4H), 2.59 (t, J= 6.9 Hz, 2H), 3.48 (t, J= 6.0 Hz,
13
2H), 7.12–7.16 (m, 3H), 7.21–7.26 (m, 2H) ppm; C{1H}-NMR
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The Journal of Organic Chemistry
(CH2), 55.2 (CH2), 113.9 (CH), 129.8 (CH), 130.2 (C), 158.5
(75 MHz, CDCl3, 25 °C): δ= 28.5 (CH2), 32.0 (CH2), 35.0 (CH2),
44.8 (CH2), 125.8 (CH), 128.3 (CH), 141.8 (C) ppm.
1
2
3
4
5
6
7
8
(C) ppm.
1-Chloro-2-(4-nitrophenyl)ethane (2g)47: According to GP2, 2-
(4-nitrophenyl)ethanol (1g 167 mg, 1.00 mmol), benzotrichloride
(977 mg, 5.00 mmol), phenylsilane (108 mg, 1.00 mmol) and tri-n-
octylphosphane (37 mg, 0.10 mmol) were reacted and after purifi-
cation by column chromatography (SiO2, cyclohexane/EtOAc,
15:1) 2g (151 mg, 0.814 mmol, 81%) was obtained as yellow solid.
1-Chloro-3-phenylpropane (2b)31: According to GP2, 3-
phenylpropan-1-ol (1b, 136 mg, 1.00 mmol), benzotrichloride
(977 mg, 5.00 mmol), phenylsilane (108 mg, 1.00 mmol) and tri-n-
octylphosphane (37 mg, 0.10 mmol) were reacted and after purifi-
cation by column chromatography (SiO2, cyclohexane) 2b
(131 mg, 0.847 mmol, 85%) was obtained as colourless liquid. Rf
1
1
Rf (SiO2, cyclohexane/EtOAc 15:1)= 0.33; H-NMR (300 MHz,
(SiO2, cyclohexane)= 0.54; H-NMR (300 MHz, CDCl3, 25 °C):
9
CDCl3, 27 °C): δ= 3.19 (t, J= 6.9 Hz, 2H), 3.78 (t, J= 6.9 Hz, 2H),
7.41 (d, J= 8.9 Hz, 2H), 8.19 (d, J= 8.7 Hz, 2H) ppm; 13C{1H}-
NMR (75 MHz, CDCl3, 27 °C): δ= 38.48 (CH2), 43.96 (CH2),
123.73 (CH), 129.73 (CH), 145.54 (C), 147.01 (C) ppm.
δ= 2.15 (p, J= 6.9 Hz, 2H), 2.85 (t, J= 7.4 Hz, 2H), 3.59 (t, J= 6.5
Hz, 2H), 7.26–7.30 (m, 3H), 7.35–7.40 (m, 2H) ppm; 13C{1H}-
NMR (75 MHz, CDCl3, 25 °C): δ= 32.7 (CH2), 34.0 (CH2), 44.1
(CH2), 126.0 (CH), 128.4 (CH), 128.5 (CH), 140.6 (C) ppm.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1-Chloro-2-phenylethane (2c)24
: According to GP2, 2-
1-Chloro-2-(4-cyanophenyl)ethane (2h): According to GP2, 2-
(4-cyanophenyl)ethanol (1h, 147 mg, 1.00 mmol), benzotrichlo-
ride (977 mg, 5.00 mmol), phenylsilane (108 mg, 1.00 mmol) and
tri-n-octylphosphane (37 mg, 0.10 mmol) were reacted and after
purification by column chromatography (SiO2, cyclohex-
ane/EtOAc, 15:1) 2h (157 mg, 0.948 mmol, 95%) was obtained as
phenylethanol (1c, 122 mg, 1.00 mmol), benzotrichloride
(977 mg, 5.00 mmol), phenylsilane (108 mg, 1.00 mmol) and tri-n-
octylphosphane (37 mg, 0.10 mmol) were reacted and after purifi-
cation by column chromatography (SiO2, cyclohexane) 2c
(123 mg, 0.875 mmol, 88%) was obtained as colourless liquid. Rf
1
1
colourless liquid. Rf (SiO2, cyclohexane/EtOAc 15:1)= 0.21; H-
(SiO2, cyclohexane)= 0.51; H-NMR (300 MHz, CDCl3, 25 °C):
NMR (300 MHz, CDCl3, 27 °C): δ= 3.13 (t, J= 6.9 Hz, 2H), 3.74
(t, J= 6.9 Hz, 2H), 7.35 (d, J= 8.1 Hz, 2H), 7.61 (d, J= 8.2 Hz, 2H)
ppm; 13C{1H}-NMR (75 MHz, CDCl3, 27 °C): δ= 38.7 (CH2),
44.00 (CH2), 110.7 (C), 118.7 (C), 129.6 (CH), 132.2 (CH),
143.4 (C) ppm; IR (ATR): 2960 (vw), 2228 (m), 1924 (vw), 1608
(w), 1505 (w), 1435 (vw), 1415 (vw), 1299 (vw), 1285 (w), 1250
(vw), 1178 (w), 1107 (vw), 1021 (w), 943 (vw), 906 (w), 851
(vw), 821 (m), 760 (w), 706 (w), 688 (w), 652 (m) cm–1; MS (EI,
70 eV): m/z (%): 165 (20) [M+ (35Cl)], 116 (100), 89 (12);
HRMS (ESI-TOF) m/z: [M (37Cl)]+ calcd for C9H8ClN 167.0310;
Found: 167.0310.
δ= 3.14 (t, J= 7.5 Hz, 2H), 3.79 (t, J= 7.5 Hz, 2H), 7.29–7.44 (m,
5H) ppm; 13C{1H}-NMR (75 MHz, CDCl3, 25 °C): δ= 39.1
(CH2), 44.9 (CH2), 126.8 (CH), 128.4 (CH), 128.7 (CH), 138.0
(C) ppm.
1-Chloro-2,2-diphenylethane (2d)44: According to GP2, 2,2-
diphenylethanol (1d, 198 mg, 1.00 mmol), benzotrichloride
(977 mg, 5.00 mmol), phenylsilane (108 mg, 1.00 mmol) and tri-n-
octylphosphane (37 mg, 0.10 mmol) were reacted and after purifi-
cation by column chromatography (SiO2, cyclohexane) 2d
(182 mg, 0.840 mmol, 84%) was obtained as yellow oil. Rf (SiO2,
1
cyclohexane)= 0.34; H-NMR (300 MHz, CDCl3, 20 °C): δ= 4.00
1-Chloro-2-(4-dimethylaminophenyl)ethane (2i): According to
(d, J= 7.8 Hz, 2H), 4.27 (t, J= 7.8 Hz, 2H), 7.14–7.19 (m, 6H),
7.22–7.28 (m, 4H) ppm; 13C{1H}-NMR (75 MHz, CDCl3, 25 °C):
δ= 41.2 (CH2), 53.6 (CH), 127.0 (CH), 128.0 (CH), 128.7 (CH),
141.2 (C) ppm.
GP2,
2-(4-dimethylaminophenyl)ethanol
(1i,
165 mg,
1.00 mmol), benzotrichloride (977 mg, 5.00 mmol), phenylsilane
(108 mg, 1.00 mmol) and tri-n-octylphosphane (37 mg,
0.10 mmol) were reacted and after purification by column chroma-
tography (SiO2, cyclohexane/EtOAc, 15:1) 2i (125 mg,
0.681 mmol, 68%) was obtained as yellow liquid. Rf (SiO2, cyclo-
1-Chloro-2-(4-bromophenyl)ethane (2e)45: According to GP2,
2-(4-bromophenyl)ethanol (1e, 201 mg, 1.00 mmol), benzotri-
chloride (977 mg, 5.00 mmol), phenylsilane (108 mg, 1.00 mmol)
and tri-n-octylphosphane (37 mg, 0.10 mmol) were reacted and
after purification by column chromatography (SiO2, cyclohexane)
2e (165 mg, 0.752 mmol, 75%) was obtained as colourless liquid.
Rf (SiO2, cyclohexane)= 0.44; 1H-NMR (300 MHz, CDCl3, 25 °C):
δ= 3.02 (t, J= 7.2 Hz, 2H), 3.69 (t, J= 7.2 Hz, 2H), 7.10 (d, J=
8.6 Hz, 2H), 7.45 (d, J= 8.44 Hz, 2H) ppm; 13C{1H}-NMR (75
MHz, CDCl3, 25 °C): δ= 38.40 (CH2), 44.6 (CH2), 120.8 (C),
130.5 (CH), 131.6 (CH), 137.0 (C) ppm.
1
hexane/EtOAc 15:1)= 0.38; H-NMR (300 MHz, CDCl3, 27 °C):
δ= 2.94 (s, 6H), 2.99 (t, J= 7.7 Hz, 2H), 3.67 (t, J= 7.7 Hz, 2H),
6.71 (d, J= 8.7 Hz, 2H), 7.11 (d, J= 8.9 Hz, 2H) ppm; 13C{1H}-
NMR (75 MHz, CDCl3, 27 °C): δ= 38.4 (CH2), 40.7 (CH3), 45.5
(CH2), 112.8 (CH), 129. 5 (CH), 129.6 (C), 149.6 (C) ppm; IR
(ATR): 2954 (vw), 2925 (vw), 2804 (vw), 1676 (w), 1612 (w),
1519 (w), 1430 (vw), 1346 (vw), 1132 (m), 1115 (w), 945 (vw),
810 (vw), 745 (vw), 700 (vw) cm–1; MS (EI, 70 eV): m/z (%): 183
(18) [M+ (35Cl)], 135 (11), 134 (100), 118 (11); HRMS (ESI-
TOF) m/z: [M (35Cl)]+ calcd for C10H14ClN 183.0809; Found:
183.0810.
1-Chloro-2-(4-methoxyphenyl)ethane (2f)46: According to
GP2, 2-(4-methoxyphenyl)ethanol (1f, 152 mg, 1.00 mmol),
benzotrichloride (977 mg, 5.00 mmol), phenylsilane (108 mg,
1.00 mmol) and tri-n-octylphosphane (37 mg, 0.10 mmol) were
reacted and after purification by column chromatography (SiO2,
cyclohexane) 2f (134 mg, 0.785 mmol, 79%) was obtained as
1-Chloro-2-(4-trifluoromethylphenyl)ethane (2j): According
to GP2, 2-(4-trifluoromethylphenyl)ethanol (1j, 190 mg,
1.00 mmol), benzotrichloride (977 mg, 5.00 mmol), phenylsilane
(108 mg, 1.00 mmol) and tri-n-octylphosphane (37 mg,
0.10 mmol) were reacted and after purification by column chroma-
tography (SiO2, cyclohexane) 2j (152 mg, 0.729 mmol, 73%) was
1
yellow liquid. Rf (SiO2, cyclohexane)= 0.14; H-NMR (300 MHz,
CDCl3, 23 °C): δ= 3.03 (t, J= 7.5 Hz, 2H), 3.70 (t, J= 7.5 Hz, 2H),
3.82 (s, 3H), 6.86–6.91 (m, 2H), 7.14–7.19 (m, 2H) ppm;
13C{1H}-NMR (75 MHz, CDCl3, 23 °C): δ= 38.3 (CH3), 45.3
1
obtained as yellow liquid. Rf (SiO2, cyclohexane)= 0.38; H-NMR
(300 MHz, CDCl3, 22 °C): δ= 3.14 (t, J= 7.1 Hz, 2H), 3.75 (t, J=
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7.1 Hz, 2H), 7.36 (d, J= 8.1 Hz, 2H), 7.60 (d, J= 8.1 Hz, 2H) ppm;
13C{1H}-NMR (75 MHz, CDCl3, 22 °C): δ= 38.7 (CH2), 44.4
(CH2), 124.2 (q, J= 271.9 Hz, CF3), 125.5 (q, J= 3.8 Hz, CH),
129.2 (CH), 129.2 (q, J= 32.4 Hz, C), 142.1 (q, J= 1.3 Hz, C) ppm;
19F-NMR (282 MHz, CDCl3, 22 °C): δ= 62.06 ppm; IR (ATR):
1620 (vw), 1438 (vw), 1419 (vw), 1322 (vs), 1249 (vw), 1162
(m), 1118 (s), 1105 (s), 1067 (vs), 1019 (s), 944 (vw), 907 (w),
851 (w), 823 (m), 772 (vw), 738 (w), 715 (w), 660 (w) cm–1; MS
(EI, 70 eV): m/z (%): 208 (19) [M+ (35Cl)], 160 (9), 159 (100),
109 (14); HRMS (ESI-TOF) m/z: [M (35Cl)]+ calcd for C9H8ClF3
208.0261; Found: 208.0263.
Hz, J= 0.9 Hz, 1H), 6.97 (dd, J= 5.1 Hz, J= 3.4 Hz, 1H), 7.20 (dd,
13
J= 5.1 Hz, J= 1.2 Hz, 1H) ppm; C{1H}-NMR (75 MHz, CDCl3,
1
2
3
4
5
6
7
8
27 °C): δ= 33.2 (CH2), 44.7 (CH2), 124.2 (CH), 125.8 (CH),
126.9 (CH), 140.1 (C) ppm.
1-(Chloromethyl)napthalene (2n)48: According to GP2, 1-
naphthalenemethanol (1n, 158 mg, 1.00 mmol), benzotrichloride
(977 mg, 5.00 mmol), phenylsilane (108 mg, 1.00 mmol) and tri-n-
octylphosphane (37 mg, 0.10 mmol) were reacted and after purifi-
cation by column chromatography (SiO2, cyclohexane) 2n
(143 mg, 0.810 mmol, 81%) was obtained as colorless solid. Rf
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
(SiO2, cyclohexane)= 0.40; H-NMR (300 MHz, CDCl3, 20 °C):
δ= 5.08 (s, 2H), 7.43–7.48 (m, 1H), 7.53–7.66 (m, 3H), 7.87–7.93
1-Chloro-2-(3-trifluoromethylphenyl)ethane (2k): According
to GP2, 2-(3-trifluoromethylphenyl)ethanol (1k, 190 mg,
1.00 mmol), benzotrichloride (977 mg, 5.00 mmol), phenylsilane
(108 mg, 1.00 mmol) and tri-n-octylphosphane (37 mg,
0.10 mmol) were reacted and after purification by column chroma-
tography (SiO2, cyclohexane) 2k (170 mg, 0.815 mmol, 82%) was
13
(m, 2H), 8.18 (d, J= 8.2 Hz, 1H) ppm; C{1H}-NMR (75 MHz,
CDCl3, 20 °C): δ= 44.5 (CH2), 123.6 (CH), 125.2 (CH), 126.1
(CH), 126.7 (CH), 127.6 (CH), 128.8 (CH), 129.7 (CH), 131.1
(C), 132.9 (C), 133.9 (C) ppm.
1
4-tert-Butylbenzyl chloride (2o)49: According to GP2, 4-tert-
butylbenzyl alcohol (1o, 164 mg, 1.00 mmol), benzotrichloride
(977 mg, 5.00 mmol), phenylsilane (108 mg, 1.00 mmol) and tri-n-
octylphosphane (37 mg, 0.10 mmol) were reacted and after purifi-
cation by column chromatography (SiO2, cyclohexane) 2o
(124 mg, 0.679 mmol, 68%) was obtained as colourless liquid. Rf
obtained as colourless liquid. Rf (SiO2, cyclohexane)= 0.38; H-
NMR (300 MHz, CDCl3, 23 °C): δ= 3.14 (t, J= 7.1 Hz, 2H), 3.75
(t, J= 7.1 Hz, 2H), 7.14–7.55 (m, 4H) ppm; 13C{1H}-NMR (75
MHz, CDCl3, 23 °C): δ= 38.7 (CH2), 44.4 (CH2), 123.8 (q, J=
3.9 Hz, CH), 124.1 (q, J= 272.3 Hz, CF3), 125.6 (q, J= 3.8 Hz,
CH), 129.0 (CH), 130.9 (q, J= 32.2 Hz, C), 132.3 (CH), 138.9
1
(SiO2, cyclohexane)= 0.46; H-NMR (300 MHz, CDCl3, 23 °C):
19
(C) ppm; F-NMR (282 MHz, CDCl3, 23 °C): δ= 62.23 ppm; IR
13
δ= 1.42 (s, 9H), 4.65 (s, 2H), 7.40–7.50 (m, 4H) ppm; C{1H}-
(ATR): 1492 (vw), 1455 (w), 1324 (s), 1248 (w), 1197 (w), 1162
(m), 1118 (vs), 1071 (s), 1002 (vw), 955 (vw), 913 (w), 878 (w),
838 (vw), 797 (m), 759 (w), 735 (w), 700 (s), 658 (s) cm–1; MS
(EI, 70 eV): m/z (%): 208 (26) [M+ (35Cl)], 189 (9), 160 (12), 159
(100), 109 (14); HRMS (ESI-TOF) m/z: [M (35Cl)]+ calcd for
C9H8ClF3 208.0261; Found: 208.0265.
NMR (75 MHz, CDCl3, 23 °C): δ= 31.2 (CH3), 34.6 (C), 46.1
(CH2), 125.6 (CH), 128.3 (CH) 134.5(C), 151.4 (C) ppm.
4-Trifluoromethylbenzyl chloride (2p)50: According to GP2, 4-
trifluoromethylbenzyl alcohol (1p, 176 mg, 1.00 mmol), benzotri-
chloride (977 mg, 5.00 mmol), phenylsilane (108 mg, 1.00 mmol)
and tri-n-octylphosphane (37 mg, 0.10 mmol) were reacted and
after purification by column chromatography (SiO2, cyclohexane)
2p (134 mg, 0.689 mmol, 69%) was obtained as yellow liquid. Rf
1-Chloro-2-(2-trifluoromethylphenyl)ethane (2l): According
to GP2, 2-(2-trifluoromethylphenyl)ethanol (1l, 190 mg,
1.00 mmol), benzotrichloride (977 mg, 5.00 mmol), phenylsilane
(108 mg, 1.00 mmol) and tri-n-octylphosphane (37 mg,
0.10 mmol) were reacted and after purification by column chroma-
tography (SiO2, cyclohexane) 2l (137 mg, 0.657 mmol, 66%) was
1
(SiO2, cyclohexane)= 0.41; H-NMR (300 MHz, CDCl3, 27 °C):
δ= 4.63 (s, 2H), 7.53 (d, J= 8.2 Hz, 2H), 7.64 (d, J= 8.2 Hz, 2H)
ppm; 13C{1H}-NMR (75 MHz, CDCl3, 27 °C): δ= 45.1 (CH2),
124.0 (q, J= 277.0 Hz, CF3), 125.7 (q, J= 3.7 Hz, CH), 128.8 (CH),
130.6 (q, J= 32.50 Hz, C), 141.3 (q, J= 1.49 Hz, C) ppm; 19F-NMR
(282 MHz, CDCl3, 22 °C): δ= 62.30 ppm.
1
obtained as colourless liquid. Rf (SiO2, cyclohexane)= 0.44; H-
NMR (300 MHz, CDCl3, 27 °C): δ= 3.29 (t, J= 7.5 Hz, 2H), 3.74
(t, J= 7.5 Hz, 2H), 7.36–7.44 (m, 2H), 7.51–7.56 (m, 1H), 7.67–
7.70 (m, 1H) ppm; 13C{1H}-NMR (75 MHz, CDCl3, 27 °C):
δ= 35.9 (q, J= 1.4 Hz, CH2), 44.0 (q, J= 1.5 Hz, CH2), 124.4 (q, J=
273.4 Hz, CF3), 126.1 (CH), 126.2 (q, J= 5.7 Hz, CH), 127.09
(CH), 129.7 (q, J= 32.8 Hz, C), 131.9 (CH), 136.4 (q, J= 1.5 Hz,
1,2-Bis(chloromethyl)benzene (2q)51: According to GP2, 1,2-
phenylenedimethanol (1q, 138 mg, 1.00 mmol), benzotrichloride
(977 mg, 5.00 mmol), phenylsilane (108 mg, 1.00 mmol) and tri-n-
octylphosphane (37 mg, 0.10 mmol) were reacted and after purifi-
cation by column chromatography (SiO2, cyclohexane) 2q
(113 mg, 0.646 mmol, 65%) was obtained as colorless solid. Rf
19
C) ppm; F-NMR (282 MHz, CDCl3, 23 °C): δ= 59.17 ppm; IR
(ATR): 1608 (vw), 1584 (vw), 1493 (vw), 1453 (w), 1311 (s),
1251 (vw), 1174 (m), 1143 (m), 1114 (s), 1101 (s), 1060 (m),
1039 (s), 956 (vw), 908 (vw), 870 (vw), 837 (vw), 765 (s), 745
(w), 715 (m), 652 (m) cm–1; MS (EI, 70 eV): m/z (%): 208 (21)
[M+ (35Cl)], 160 (8), 159 (100), 109 (14); HRMS (ESI-TOF)
m/z: [M(35Cl)]+ calcd for C9H8ClF3 208.0261; Found: 208.0267.
1
(SiO2, cyclohexane)= 0.33; H-NMR (300 MHz, CDCl3, 26 °C):
δ= 4.77 (s, 4H), 7.34–7.43 (m, 4H) ppm; 13C{1H}-NMR (75
MHz, CDCl3, 26 °C): δ= 43.2 (CH2), 129.4 (CH), 130.7 (CH),
136.2 (C) ppm.
1-Chlorodec-9-ene (2r)52: According to GP2, dec-9-en-1-ol (1r,
156 mg, 1.00 mmol), benzotrichloride (977 mg, 5.00 mmol),
phenylsilane (108 mg, 1.00 mmol) and tri-n-octylphosphane
(37 mg, 0.10 mmol) were reacted and after purification by column
chromatography (SiO2, cyclohexane) 2r (131 mg, 0.750 mmol,
75%) was obtained as colourless liquid. Rf (SiO2, cyclohexane)=
0.60; 1H-NMR (300 MHz, CDCl3, 25 °C): δ= 1.30–1.42 (m, 10H),
1.72–1.81 (m, 2H), 2.01–2.07 (m, 2H), 3.53 (t, J= 6.8 Hz, 2H),
2-(2-Chloroethyl)thiophene (2m)25: According to GP2, 2-
thiopheneethanol (1m, 128 mg, 1.00 mmol), benzotrichloride
(977 mg, 5.00 mmol), phenylsilane (108 mg, 1.00 mmol) and tri-n-
octylphosphane (37 mg, 0.10 mmol) were reacted and after purifi-
cation by column chromatography (SiO2, cyclohexane) 2m
(108 mg, 0.737 mmol, 74%) was obtained as colourless liquid. Rf
1
(SiO2, cyclohexane)= 0.47; H-NMR (300 MHz, CDCl3, 27 °C):
δ= 3.30 (t, J= 7.3 Hz, 2H), 3.74 (t, J= 7.3 Hz, 2H), 6.91 (dd, J= 3.4
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The Journal of Organic Chemistry
cation by column chromatography (SiO2, cyclohexane) 5a
4.91–5.03 (m, 2H), 5.74–5.88 (m, 1H) ppm; 13C{1H}-NMR (75
1
2
3
4
5
6
7
8
(108 mg, 0.640 mmol, 64%) was obtained as colourless liquid. Rf
(SiO2, cyclohexane)= 0.41; H-NMR (300 MHz, CDCl3, 27 °C):
MHz, CDCl3, 25 °C): δ= 26.8 (CH2), 28.8 (CH2), 28.8 (CH2),
29.0 (CH2), 29.3 (CH2), 32.6 (CH2), 33.8 (CH2), 45.1 (CH2),
114.2 (CH2), 139.1 (CH), ppm.
1
δ= 1.57 (d, J= 6.5 Hz, 3H), 2.01–2.09 (m, 2H), 2.73–2.94 (m, 2H),
4.03 (sext, J= 6.6 Hz, 1H), 7.21–7.26 (m, 3H), 7.31–7.36 (m, 2H)
ppm; 13C{1H}-NMR (75 MHz, CDCl3, 27 °C): δ= 26.0 (CH3),
32.9 (CH2), 41.9 (CH2), 57.9 (CH), 126.0 (CH), 128.4 (CH),
128.5 (CH), 141.1 (C) ppm.
1-Chloroundec-10-yne (2s)15: According to GP2, undec-10-yn-
1-ol (1s, 168 mg, 1.00 mmol), benzotrichloride (977 mg,
5.00 mmol), phenylsilane (108 mg, 1.00 mmol) and tri-n-
octylphosphane (37 mg, 0.10 mmol) were reacted and after purifi-
cation by column chromatography (SiO2, cyclohexane) 2s
(158 mg, 0.846 mmol, 85%) was obtained as yellow liquid. Rf
Chlorodiphenylmethane (5b)31: According to GP2, diphenyl-
methanol (4b, 184 mg, 1.00 mmol), benzotrichloride (977 mg,
5.00 mmol), phenylsilane (108 mg, 1.00 mmol) and tri-n-
octylphosphane (37 mg, 0.10 mmol) were reacted and after purifi-
cation by Kugelrohr distillation 5b (124 mg, 0.612 mmol, 61%)
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14
15
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17
18
19
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24
25
26
27
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31
32
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35
36
37
38
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45
46
47
48
49
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51
52
53
54
55
56
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1
(SiO2, cyclohexane)= 0.29; H-NMR (300 MHz, CDCl3, 25 °C):
δ= 1.29–1.56 (m, 12H), 1.75 (p, J= 7.1 Hz, 2H), 1.92 (t, J= 2.6 Hz,
1H), 2.16 (dt, J= 6.8 Hz, J= 2.6 Hz, 2H), 3.51 (t, J= 6.7 Hz, 2H)
ppm; 13C{1H}-NMR (75 MHz, CDCl3, 25 °C): δ= 18.3 (CH2),
25.8 (CH2), 28.4 (CH2), 28.6 (CH2), 28.8 (CH2), 28.9 (CH2),
29.2 (CH2), 32.6 (CH2), 45.1 (CH2), 68.0 (CH), 84.6 (C) ppm.
1
was obtained as colourless liquid. H-NMR (300 MHz, CDCl3, 27
°C): δ= 6.15 (s, 1H), 7.29–7.38 (m, 6H), 7.42–7.46 (m, 4H) ppm;
13C{1H}-NMR (75 MHz, CDCl3, 27 °C): δ= 64.2 (CH), 127.7
(CH), 128.0 (CH), 128.5 (CH), 141.0 (C) ppm.
(R)-Citronellyl chloride (2t): According to GP2, (R)-citronellol
(1t, 156 mg, 1.00 mmol), benzotrichloride (977 mg, 5.00 mmol),
phenylsilane (108 mg, 1.00 mmol) and tri-n-octylphosphane
(37 mg, 0.10 mmol) were reacted and after purification by column
chromatography (SiO2, cyclohexane) 2t (159 mg, 0.910 mmol,
91%) was obtained as colourless liquid. Rf (SiO2, cyclohexane)=
Cyclohexyl chloride (5c)31: According to GP2, cyclohexanol (4c,
100 mg, 1.00 mmol), benzotrichloride (977 mg, 5.00 mmol),
phenylsilane (108 mg, 1.00 mmol) and tri-n-octylphosphane
(37 mg, 0.10 mmol) were reacted and after purification by Ku-
gelrohr distillation 5c (68 mg, 0.573 mmol, 57%) was obtained as
1
1
0.58; H-NMR (300 MHz, CDCl3, 26 °C): δ= 0.92 (d, J= 6.4 Hz,
colourless liquid. H-NMR (300 MHz, CDCl3, 27 °C): δ= 1.28–
3H), 1.13–1.41 (m, 2H), 1.83–1.86 (m, 9H), 1.95–2.05 (m, 2H),
3.50–3.64 (m, 2H), 5.10 (tt, J= 7.1 Hz, J= 1.4 Hz, 1H) ppm;
13C{1H}-NMR (75 MHz, CDCl3, 26 °C): δ= 17.6 (CH3), 19.0
(CH3), 25.3 (CH2), 25.7 (CH3), 30.1 (CH), 36.7 (CH2), 39.7
(CH2), 43.3 (CH2), 124.5 (CH), 131.5 (C) ppm; IR (ATR): 2964
(vw), 2915 (w), 2872 (vw), 2854 (vw), 1448 (vw), 1378 (vw),
1286 (vw), 1110 (vw), 984 (vw), 881 (vw), 830 (vw), 805 (vw),
725 (w), 658 (w) cm–1; MS (EI, 70 eV): m/z (%): 174 (26) [M+
(35Cl)], 83 (13), 70 (22), 69 (100), 67 (16), 56 (30), 55 (45), 53
(12), 41 (57), 39 (17); HRMS (ESI-TOF) m/z: [M (35Cl)]+ calcd
for C10H19Cl 174.1170; Found: 174.1172.
1.42 (m, 3H), 1.49–1.56 (m, 1H), 1.60–1.72 (m, 2H), 1.75–1.85
13
(m, 2H), 2.02–2.09 (m, 2H), 3.95–4.04 (m, 1H) ppm; C{1H}-
NMR (75 MHz, CDCl3, 27 °C): δ= 24.8 (CH2), 25.1 (CH2), 35.6
(CH2), 60.1 (CH) ppm.
(3R)-3-Chloro-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-
allofuranose (5e)54: According to GP2, 1,2:5,6-di-O-
isopropylidene-α-D-glucofuranose (4e, 260 mg, 1.00 mmol), ben-
zotrichloride (977 mg, 5.00 mmol), phenylsilane (108 mg,
1.00 mmol) and tri-n-octylphosphane (37 mg, 0.1 mmol) were
reacted and after purification by column chromatography (SiO2,
cyclohexane/EtOAc, 15:1) 5e (87 mg, 0.312 mmol, 31%) was
obtained as a viscous, yellow liquid. Rf (SiO2, cyclohexane/EtOAc,
15:1)= 0.24; 1H-NMR (300 MHz, CDCl3, 27 °C): δ= 1.34 (s, 3H),
1.38 (s, 3H), 1.39 (s, 3H), 1.50 (s, 3H), 3.61 (dd, J= 12.3 Hz, J= 7.7
Hz, 1H), 3.73–3.78 (m, 2H), 4.24 (d, J= 3.9 Hz, 1H), 4.36 (dd, J=
7.0 Hz, J= 3.9 Hz, 1H), 4.59 (d, J= 3.7 Hz, 1H), 6.00 (d, J= 3.7 Hz,
1H) ppm; 13C{1H}-NMR (75 MHz, CDCl3, 27 °C): δ= 23.8
(CH3), 23.9 (CH3), 26.5 (CH3), 27.2 (CH3), 45.0 (CH2), 72.2
(CH), 75.1 (CH), 80.5 (CH), 83.9 (CH), 101.3 (C), 106.4 (CH),
112.3 (C) ppm.
Ethyl 6-chlorohexanoate (2u): According to GP2, ethyl 6-
hydroxyhexanoate (1u, 160 mg, 1.00 mmol), benzotrichloride
(977 mg, 5.00 mmol), phenylsilane (108 mg, 1.00 mmol) and tri-n-
octylphosphane (37 mg, 0.10 mmol) were reacted and after purifi-
cation by column chromatography (SiO2, cyclohexane) 2u
1
(142 mg, 0.795 mmol, 80%) was obtained as yellow liquid. H-
NMR (300 MHz, CDCl3, 23 °C): δ= 1.24 (t, J= 7.1 Hz, 3H), 1.43–
1.51 (m, 2H), 1.59–1.69 (m, 2H), 1.73–1.82 (m, 2H), 2.30 (t, J=
7.4 Hz, 2H), 3.52 (t, J= 6.7 Hz, 2H), 4.11 (q, J= 7.1 Hz, 2H) ppm;
13C{1H}-NMR (75 MHz, CDCl3, 23 °C): δ= 14.2 (CH3), 24.1
(CH2), 26.3 (CH2), 32.2 (CH2), 34.0 (CH2), 44.7 (CH2), 60.2
(CH2), 173.4 (C=O) ppm; IR (ATR): 2982 (vw), 2938 (vw), 2868
(vw), 1731 (s), 1446 (vw), 1372 (w), 1300 (vw), 1260 (w), 1178
(m), 1096 (w), 1096 (vw), 1027 (w), 910 (w), 858 (w), 749 (w)
cm–1; MS (EI, 70 eV): m/z (%): 179 (1) [M++H (35Cl)], 143 (6),
135 (17) , 133 (52), 115 (13), 101 (15), 88 (100), 73 (14), 70
(18), 69 (51), 61 (11), 60 (20), 55 (17), 43 (10), 42 (12), 41 (29),
39 (12). HRMS (ESI-TOF) m/z: [M (35Cl) + Na]+ calcd for
C8H15ClO2Na 201.0653; Found: 201.0652.
1-Chloroadamantane (5f)46: According to GP2, 1-adamantol (4f,
152 mg, 1.00 mmol), benzotrichloride (977 mg, 5.00 mmol),
phenylsilane (108 mg, 1.00 mmol) and tri-n-octylphosphane
(37 mg, 0.10 mmol) were reacted and after purification by column
chromatography (SiO2, cyclohexane) 5f (63 mg, 0.369 mmol,
1
37%) was obtained as colorless crystals. H-NMR (300 MHz,
13
CDCl3, 28 °C): δ= 1.68 (s, 6H), 2.15 (s, 9H) ppm; C{1H}-NMR
(75 MHz, CDCl3, 28 °C): δ= 31.7 (CH), 35.6 (CH2), 47.7 (CH2),
68.9 (C) ppm.
Trityl chloride (5g)55: According to GP2, triphenylmethanol (4g,
260 mg, 1.00 mmol), benzotrichloride (977 mg, 5.00 mmol),
phenylsilane (108 mg, 1.00 mmol) and tri-n-octylphosphane
(37 mg, 0.10 mmol) were reacted and after purification by column
2-Chloro-4-phenylbutane (5a)53
: According to GP2, 4-
phenylbutan-2-ol (4a, 150 mg, 1.00 mmol), benzotrichloride
(977 mg, 5.00 mmol), phenylsilane (108 mg, 1.00 mmol) and tri-n-
octylphosphane (37 mg, 0.10 mmol) were reacted and after purifi-
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 10
chromatography (SiO2, cyclohexane/EtOAc, 15:1) 5g (113 mg,
Corresponding Author
1
2
3
4
0.405 mmol, 41%) was obtained as colorless crystals. Rf (SiO2,
cyclohexane/EtOAc, 15:1)= 0.21; 1H-NMR (300 MHz, CDCl3, 22
°C): δ= 7.28–7.37 (m, 15H) ppm; 13C{1H}-NMR (75 MHz,
CDCl3, 22 °C): δ= 81.3 (C), 127.7 (CH), 127.8 (CH), 129.7
(CH), 145.2 (C) ppm.
thomas.werner@catalysis.de
Author Contributions
The manuscript was written through contributions of all authors. All
authors have given approval to the final version of the manuscript.
5
6
7
8
9
(1,2-Dichloroethyl)benzene (7a)56: According to GP2, styrene
oxide (6a, 120 mg, 1.00 mmol), benzotrichloride (977 mg,
5.00 mmol), phenylsilane (108 mg, 1.00 mmol) and tri-n-
octylphosphane (37 mg, 0.10 mmol) were reacted and after purifi-
cation by column chromatography (SiO2, cyclohexane) 7a
(161 mg, 0.920 mmol, 92%) was obtained as yellow liquid. Rf
ACKNOWLEDGMENT
This research was performed within the scope of the Leibniz-
ScienceCampus Phosphorus Research Rostock.
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1
(SiO2, cyclohexane)= 0.42; H-NMR (300 MHz, CDCl3, 27 °C):
δ= 3.91–4.05 (m, 2H), 5.00–5.05 (m, 1H), 7.38–7.45 (m, 5H)
ppm; 13C{1H}-NMR (75 MHz, CDCl3, 27 °C): δ= 48.3 (CH2),
61.7 (CH), 127.4 (CH), 128.8 (CH), 129.1 (CH), 138.0 (C) ppm.
1-(1,2-Dichloroethyl)-4-fluorobenzene (7b)42: According to
GP2, 4-fluorostyrene oxide (6b, 138 mg, 1.00 mmol), benzotri-
chloride (977 mg, 5.00 mmol), phenylsilane (108 mg, 1.00 mmol)
and tri-n-octylphosphane (37 mg, 0.10 mmol) were reacted and
after purification by column chromatography (SiO2, cyclohexane)
7b (181 mg, 0.938 mmol, 94%) was obtained as colourless liquid.
Rf (SiO2, cyclohexane)= 0.33; 1H-NMR (400 MHz, CDCl3, 27 °C):
δ= 3.87–4.03 (m, 2H), 4.98–5.02 (m, 1H), 7.07–7.12 (m, 2H),
7.39–7.43 (m, 2H) ppm; 13C{1H}-NMR (100 MHz, CDCl3, 27
°C): δ= 48.2 (CH2), 60.8 (CH), 115.8 (d, J= 21.8 Hz, CH), 129.3
(d, J= 8.3 Hz, CH), 133.9 (d, J= 3.7 Hz, C), 162.9 (d, J= 248.5 Hz,
CF) ppm; 19F-NMR (282 MHz, CDCl3, 23 °C): δ= 111.63 ppm.
1-(1,2-Dichloroethyl)-4-chlorobenzene (7c)57: According to
GP2, 4-chlorostyrene oxide (6c, 157 mg, 1.00 mmol), benzotri-
chloride (977 mg, 5.00 mmol), phenylsilane (108 mg, 1.00 mmol)
and tri-n-octylphosphane (37 mg, 0.10 mmol) were reacted and
after purification by Kugelrohr distillation 7c (12 mg, 0.87 mmol,
1
87%) was obtained as colourless liquid. H-NMR (300 MHz,
CDCl3, 27 °C): δ= 3.77–3.94 (m, 2H), 4.86–4.91 (m, 1H), 7.11–
7.32 (m, 4H) ppm; 13C{1H}-NMR (75 MHz, CDCl3, 27 °C):
δ= 48.0 (CH2), 60.7 (CH), 128.8 (CH), 129.0 (CH), 135.1 (C),
136.5 (C) ppm.
1,3-Dichloro-2-(chloromethyl)-2-methylpropane (9)58
: Ac-
cording to GP2, 3-methyl-3-hydroxymethyloxetane (8, 102 mg,
1.00 mmol), benzotrichloride (977 mg, 5.00 mmol), phenylsilane
(108 mg, 1.00 mmol) and tri-n-octylphosphane (37 mg,
0.10 mmol) were reacted and after purification by column chroma-
tography (SiO2, cyclohexane) 9 (110 mg, 0.627 mmol, 63%) was
1
obtained as colourless liquid. H-NMR (300 MHz, CDCl3, 27 °C):
δ= 1.20 (s, 3H), 3.58 (s, 6H) ppm; 13C{1H}-NMR (75 MHz,
CDCl3, 27 °C): δ= 19.3 (CH3), 41.9 (C), 48.3 (CH2) ppm.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information includes spectral data and also addi-
tional information on the optimization experiments and mechanis-
tic investigations. This material is available free of charge via the
Internet at http://pubs.acs.org.
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AUTHOR INFORMATION
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