Benzylic Phosphates in Friedel-Crafts Reactions with Activated and Unactivated Arenes: Access to Polyarylated Alkanes

Article abstract of DOI:10.1021/acs.joc.5b02441

Easily reachable electron-poor/rich primary and secondary benzylic phosphates are suitably used as substrates for Friedel-Crafts benzylation reactions with only 1.2 equiv activated/deactivated arenes (no additional solvent) to access structurally and electronically diverse polyarylated alkanes with excellent yields and selectivities at room temperature. Specifically, diversely substituted di/triarylmethanes are generated within 2-30 min using this approach. A wide number of electron-poor polyarylated alkanes are easily accomplished through this route by just tuning the phosphates.

Full text of DOI:10.1021/acs.joc.5b02441

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Note
Benzylic Phosphates in Friedel-Crafts Reactions with Activated
and Unactivated Arenes: Access to Polyarylated Alkanes
Gangaram Pallikonda, and Manab Chakravarty
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.5b02441 • Publication Date (Web): 02 Feb 2016
Downloaded from http://pubs.acs.org on February 2, 2016
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Benzylic Phosphates in Friedel-Crafts Reactions with Activated and
Unactivated Arenes: Access to Polyarylated Alkanes
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Gangaram Pallikonda and Manab Chakravarty*a
Department of Chemistry, Birla Institute of Technology and Sciences, Pilani Hyderabad Campus,
Jawahar nagar, Shameerpet Mandal, Hyderabad , Telanganaꢀ500078, India
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Email: manabchakravarty@gmail.com
_____________________________________________________________________________
ABSTRACT: Easily reachable electronꢀpoor/rich primary and secondary benzylic phosphates
are suitably used as substrates for FriedelꢀCrafts benzylation reactions with only 1.2 equiv
activated/deactivated arenes (no additional solvent) to access structurally and electronically
diverse polyarylated alkanes with excellent yields and selectivities at room temperature.
Specifically, diversely substituted di/triarylmethanes are generated within 2ꢀ30 min using this
approach. A wide number of electronꢀpoor polyarylated alkanes are easily accomplished through
this route just by tuning the phosphates.
______________________________________________________________________________
The FriedelꢀCrafts (FC) benzylation reaction1 is one of the traditional synthetic protocols for
polyarylated alkanes, a valuable structural motif in the field of pharmaceutical, biological as well
as material sciences.2ꢀ3 The low reactivity, selectivity, limitation for only electron rich substrates
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and the need for harsh reaction conditions including hazardous solvents/reagents are the potential
drawbacks for this route. The beneficial alternative source for functionalized polyarylated
alkanes includes metal catalyzed crossꢀcoupling reactions.4 Although these all are certainly
remarkable processes, the major concerns are the necessity of solvents, expensive transition
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o
metals and their toxicities,5 long duration, elevated temperature (60ꢀ140 C) and special care for
moisture/air sensitive organometallic reagents. Therefore, being much more economical,
improvements of the FC reactions are still of priority.1e In this aspect, the practices of using
different kinds of electrophilic species such as benzyl alcohols,6aꢀb,6h acetates,6c halides,6d
ethers,6e Nꢀsulfonyl aldimines or sulphonamido sulfones6f and silyl ethers6g are attractive.
Recently, significant advances on the FC reaction have been achieved using primary benzylic
hydroxamates at moderate temperature by Bode et al.7 Nevertheless, most of these methods are
limited to the synthesis of mainly diarylalkanes in the presence of excess activated (majorly)
arenes or solvents along with aforesaid drawbacks. Being poor nucleophiles, arenes tend to
undergo reactions only under heating and excess stoichiometry of arenes. Hence, such FC
benzylation reactions only at rt are sporadically reported in the literature.6a,6d,6gꢀh
Therefore, with our current interest,8 we present here both secondary and primary benzylic
phosphates as easily accessible and unique substrates for the FC benzylation reactions to access
electronically and structurally diverse triarylmethanes predominantly, along with diarylꢀethanes
and methanes at rt within short duration using only 1.2 equiv of both activated or deactivated
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arenes. Moreover, in the literature primary benzylic phosphates were known to be used in
transition metal catalyzed crossꢀcoupling route to generate mainly diarylmethanes in the
presence of solvents at 60ꢀ100 0C.9 Notably, efforts to access diphenylethane via SuzukiꢀMiyaura
cross coupling were unsuccessful by starting from secondary benzylic phosphate.9a In the very
recent report, the crossꢀcoupling of benzylic phosphate with bromobenzene was considered
challenging due to the poor electrophilicity of phosphates.9f Indeed, the synthetic approach for
diarylethanes and triarylmethanes using secondary benzylic phosphates is almost undeveloped.9e
It is highly pertinent to note the pioneering work by Johnson et al. with a completely different
target where αꢀarylꢀαꢀketophosphonates10a and αꢀhydroxyꢀβꢀphosphonyloxy esters10b were
successfully used in (excess) acid mediated nucleophilic substitution reactions to access a variety
of α,αꢀdiaryl ketones and αꢀhydroxy esters, respectively. However, only limited arenes in much
excess quantities were explored for these reactions in chlorinated solvent, and the minimum
reaction duration was 1 h. Even though CꢀO and PꢀO bond cleavage for phosphate monoesters
was extensively studied before under both acidicꢀand photochemical conditions,11 surprisingly,
so far, these were not explored to accomplish polyarylated alkanes. More importantly, the route
described herein, can expediently afford electronꢀpoor polyarylated methanes efficiently, which
is not an expected outcome from the traditional FC benzylation reactions. Thus, one of the major
drawbacks on synthesis of electronꢀdeficient polyarylated alkanes via the FC route has been
circumvented using the electronꢀpoor phosphates as a source of electrophiles that are
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comfortably prepared through phosphaꢀBrook rearrangement (highly favorable for electronꢀpoor
systems). A much cleaner, economical and less cumbersome process has been demonstrated by
using catalytic amount of triflic acid (TfOH) as a replacement of traditional metal chlorides.
Our recent protocol via nꢀBuLi triggered phosphaꢀBrook rearrangement has made both
electronꢀpoor/rich primary and secondary benzylic phosphates easily reachable.8d Being mainly
interested in triarylmethanes, we kept our focus on the FC type benzylation reactions of the most
inexpensive secondary benzylic phosphate 1a with toluene (only 1.2 equiv) at rt to obtain the
desired product 2a (entry 1, Table 1) under key reaction parameters such as variety of acid
catalysts in different quantities and reaction times (Table S1, Supporting Information). As the
formation of desired compound was satisfactory at rt, we could avoid the need of excess volatile
arenes. In some cases, the formation of ether Ph2HCꢀOꢀCHPh2 was also observed as expected.6j
Although there were many choices for the selection of Lewis or protic acids, the catalytic amount
of TfOH (20 mol %, entry 9, Table S1, Supporting Information) was selected for all the reactions
to afford desired products efficiently within a few minutes at rt. Moreover, TfOH was reported to
be suitable for the FC reactionsin the literature.1f The phosphate 1a reacted with both anisole as
well as nonꢀactivated, halogenated anisoles to synthesize functionalized triarylmethanes 2b-d in
excellent yields and regioselectivity within 2ꢀ10 min (entries 2 and 3, Table 1).
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Table 1: List of triarylmethanes synthesized using phosphatesa
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a reaction conditions: 1 (1 equiv), ArH (1.2 equiv) [e. g. 1a (1.56 mmol), toluene (1.87 mmol)
and TfOH (0.31 mmol)]; only for 2j, 1,2ꢀdichloroethane (DCE, 3 mL) was used; regioisomeric
(p/o) ratio (determined by 1H NMR) b85:15; c87:13; d83:17; e84:16; f 74:26; g 92:8.
In fact halogenated compounds 2c-d could be utilized for further derivatization through
wellꢀknown metal catalyzed CꢀC or CꢀN coupling reactions.12 The other electronically different
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phosphates 1b-e are used to access a wide range of triarylmethanes. We have experienced the
instability of mainly electronꢀrich secondary benzylic phosphates 1b-c that tend to form diaryl
alcohols or ethers during the purification through column chromatography (SiO2). However,
without purification, both these phosphates are successfully used in the benzylation reactions to
generate 2e-h (entries 4ꢀ7, Table 1) appreciably within 2ꢀ4 min. Notably, both unsymmetrical
and symmetrical crowded triarylmethanes 2f and 2h are completely new and synthesized
comfortably using this approach at rt. Further, we have extended the scope of this route by using
stable phosphates 1d-e where benzylation of 1d afforded the synthetically unexplored
triarylmethanes 2i-j satisfactorily (entries 8ꢀ9, Table 1), and electronically diverse
triarylmethanes 2k-o (entries 10ꢀ12, table 1) were generated conveniently within 6ꢀ22 min from
benzylation reaction of 1e. It is worth noting that being weakly inactive groups, syntheses of
such electronically deactivated triarylmethanes 2i-o are considerably challenging using the
traditional FC route.
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Next, we moved toward the benzylation reactions of much electronꢀpoorer, easily
synthesized, inexpensive and stable phosphate 1f that afforded unsymmetrical triarylmethanes
2p-s within 30 min (Scheme 1) in a similar fashion. These highly functionalized unsymmetrical
triarylmethanes 2p-s are completely new and challenging to achieve within this short reaction
time at rt.13 Thus, these reactions offer a timeꢀsaving path to obtain a large number of
unsymmetrical and electronꢀpoorer triarylmethanes in a simple, economic and convenient
manner.
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Scheme 1. Reactions of phosphate 1f with arenes including chlorobenzene; regioisomeric ratio
(determined by 1H NMR) bp/o 74:26; cp/o/m: 82:14:4; dp/o/m 83:12:5.
To establish the role of phosphate as an electrophile, few of the above mentioned
reactions were repeated by using the corresponding diarylmethanols in place of phosphates as
shown in Scheme 2. Although compound 2a was obtained successfully within 25 min [longer
reaction time in comparison to phosphate], the halogen substituted triarylmethanes such as 2k-l
or 2i were not reachable by starting with these unfunctionalized diarylmethanols. Under similar
conditions, compounds 2p-s were also not formed even after 12 h when (2ꢀchloroꢀ5ꢀ
nitrophenyl)(phenyl)methanol was treated with arenes. Thus, the necessity of phosphate as a
leaving group is very important for this strategy.
a
Scheme 2. Reactions of diarylmethanols with arenes. there was no reaction at rt but upon
heating at 60 oC for 6 h, the respective ether formation was observed.
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As synthesis of diarylethane from Pdꢀcatalyzed cross coupling reaction of 1g with PhB(OH)2
was unfruitful,9a we made an attempt for the synthesis of such alkanes by starting with
conveniently synthesized electronically diverse secondary benzylic phosphates 1g-j. To our
delight, the expected diarylethanes 3a-f (Table 2) were generated appreciably at rt although the
reaction time was somewhat longer (50ꢀ180 min). It reflects that these phosphates are
comparatively less reactive toward the arenes under similar reaction conditions [TfOH (20 mol
%)/rt, 1.2 equiv arenes]. Although only toluene or mesitylene were chosen as arenes, the
phosphates 1h-j are significantly electronꢀpoor systems due to the presence of strongly
deactivating group such as –NO2, ꢀF and ꢀCF3. The required timings for the synthesis of 3b-f
indicate that the reactivities of the phosphates 1h-j are very much comparable to each other. The
electronꢀpoor, structurally diverse diarylethanes 3c-f are unknown in the literature and most
likely difficult to access through the FC route by using other electrophilic species. Therefore,
these phosphates have opened a new door as an electrophile to access such electronꢀpoor
diarylethanes successfully. Highly relevant compounds (diarylalkanes) are synthesized by Lei et
al. by ZnCl2 mediated benzylation of secondary benzyltrifluoroacetate with highly air sensitive
arylzinc reagent using toluene as solvent at 50 oC for 24 h.4c
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Table 2: List of synthesized diarylethanes using phosphatesa
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a reaction conditions: 1 (1 equiv), ArH (1.2 equiv) [e. g. 1g (1.94 mmol), toluene (2.32 mmol and
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b
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TfOH (0.39 mmol)]; regioisomeric ratio (p/o) (determined by H NMR) 83:17; 67:33; 82:18;
e86:14.
Although the synthesis of diarylmethanes are very well established,1e,6 we planned to
examine the approachability of diarylmethanes using a few limited primary benzylic phosphates
1k-n under these reaction conditions. The diarylmethanes bearing weakly activated (4a-c) and
deactivated (4d-e) benzene rings were conveniently synthesized at rt within 8ꢀ18 min (Table 3)
and hence these phosphates are essentially efficient substrates for the synthesis of variety of
diarylmethanes. The 1ꢀnaphthylphosphate 1l was recently used for the Pdꢀcatalyzed cross
coupling reactions to produce the polycylic diarylmethanes9e and inspired by these outcomes,
useful polycyclic di(1ꢀnaphthylmethane) 4b14 was synthesized in pure isomeric form (entry 2,
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Table 3). In addition, we could also conveniently synthesize diarylmethane 4c where ferrocene
was connected with 1ꢀnaphthalene (entry 2, Table 3).
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We could not separate some of these polyarylated alkanes in pure isomeric form from the
regioisomeric mixture due to the minute difference in polarity for these isomers that are highly
nonpolar in nature.
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Table 3: List of synthesized diarylmethanes using phosphatesa
a reaction conditions: 1 (1 equiv), Ar'H (1.2 equiv) [e. g. 1k (1.94 mmol) , toluene (2.32 mmol)
and TfOH (0.39 mmol)] only for 4b-c, DCE (3 mL) was used; regioisomeric ratio (p/o)
(determined by 1H NMR): b62:38; c61:39; d64:36.
By the support of experimental results and related literature reports,10 these reactions
presumably proceed via carbocationic intermediate as shown in Scheme 3. The formation of
products with strongly deactivating substituents can apparently be justified by the formation of
relatively stable species of type B through A. There is no considerable solvent effect to stabilize
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intermediate B. However, a strong ionꢀdipole interaction between the cation and phosphate
(leaving group) may lead to an improvement in the optimum stability of B to facilitate the FC
type benzylation reactions of such electrophiles with deactivating group (s) as well as
unactivated arenes within a short time.
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Scheme 3. Plausible reaction mechanism for the FC reactions of benzylic phosphates.
In conclusion, an easy access of electronꢀpoor/rich primary and secondary benzylic phosphates
via favorable phosphaꢀBrook rearrangement has opened a new entry to access structurally and
electronically diverse polyarylated alkanes at room temperature in excellent yields and
selectivities via the FriedelꢀCrafts benzylation reactions. This reaction was operated in the
presence of triflic acid as catalyst using only 1.2 equiv activated or deactivated arenes (including
haloarenes) at room temperature. No additional solvents were entertained. Moreover, the reaction
was complete within 2ꢀ30 min to access diꢀ and triarylmethanes and thus this method offers a
timeꢀsaving approach toward these alkanes.
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Experimental Section
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General Comments: Organic extracts were dried over anhydrous sodium sulfate. Solvents were
removed in a rotary evaporator under reduced pressure. Silica gel (100ꢀ200 mesh size) was used
for the column chromatography. Reactions were monitored by TLC on silica gel 60 F254 (0.25
mm). 1H, 13C, and 31P NMR spectra (1H, 400 or 500 MHz; 13C, 101 or 126 MHz; 31P, 162 or 201
MHz) were recorded using a 400 or 500 MHz spectrometer in CDCl3 with shifts referenced to
SiMe4 (δ = 0) or 85% H3PO4 (δ = 0). IR spectra were recorded on FTꢀIR spectrophotometer.
Melting points were determined by using a local hotꢀstage melting point apparatus and are
uncorrected. Phosphates are prepared using our developed procedures.8d Phosphates 1b-c and 1f
were freshly prepared and used without further purification and isolation.
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General procedure for synthesis of polyarylated methanes from phosphates:
Trifluoromethanesulfonic acid (0.027 mL, 0.31 mmol) was added dropwise to a solution of
phosphate 1a (0.500 g, 1.56 mmol) and toluene (0.198 mL, 1.87 mmol) at room temperature and
the mixture was stirred until the phosphate disappeared (by tlc). The reaction was quenched with
water and the required compounds were extracted with EtOAc (3x25 mL). The combined
organic layer was washed with brine, was dried with Na2SO4, and then was evaporated under
reduced pressure. The residue was purified with a flash column chromatography (EtOAc/hexane
~1:99) to give triarylmethane 2a. Unless otherwise stated, all other triaryl/diaryl methanes and
diarylethanes are synthesized using similar molar quantities (quantities are mentioned with
respect to 0.500 g phosphate) of the respective phosphates in a manner similar to the synthesis of
2a. In case of solid arenes such as naphthalene and ferrocene, 1,2ꢀdichloroethane (DCE, 3 mL)
was used and dichloromethane was used for the extraction followed by the purification through
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column chromatography. [Warning note: DCE is currently considered as a potential cancer
inducing agent]
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Spectroscopic data for triarylmethanes
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(p-Tolylmethylene)dibenzene (2a)6h The reaction mixture was stirred for 2 min. viscous liquid;
yield 94% (0.38 g); The other regioisomer (ortho) was also present in 15% along with this
1
sample. H NMR (400 MHz, CDCl3) δ 2.50 (s, 3H), 5.71 (s, 1H), 7.26ꢀ7.30 (m, 2H), 7.32ꢀ 7.35
(m, 6H), 7.39ꢀ7.43 (m, 2H), 7.44ꢀ7.46 (m, 4H); 13C NMR (101 MHz, CDCl3) δ 21.2, 56.5, 126.3,
128.4, 129.1, 129.4, 129.5, 135.9, 141.0, 144.2.
((4-Methoxyphenyl)methylene)dibenzene (2b)6h The reaction mixture was stirred for 2 min
using anisole (0.203 mL, 1.87 mmol). viscous liquid; yield 93% (0.39 g); The other regioisomer
1
(ortho) was also present in 13% along with this sample. H NMR (400 MHz, CDCl3) δ 3.83 (s,
3H ), 5.56 (s, 1H), 6.87ꢀ6.89 (m, 2H), 7.07ꢀ7.09 (m, 2H), 7.16ꢀ 7.18 (m, 4H), 7.26ꢀ7.28 (m, 2H),
7.32ꢀ7.35 (m, 4H); 13C NMR (101 MHz, CDCl3) δ 55.2, 56.1, 113.7, 126.3, 128.3, 129.4, 130.4,
136.2, 144.3, 158.1.
((4-Chloro-2-methoxyphenyl)methylene)dibenzene (2c)15 The reaction mixture was stirred for
10 min using 4ꢀchloroanisole (0.229 mL, 1.87 mmol). white solid; mp 118ꢀ120 oC; (lit 120 oC)3;
yield 90% (0.43 g); 1H NMR (400 MHz, CDCl3) δ 3.73 (s, 3H), 5.94 (s, 1H), 6.84 (d, J = 8.7 Hz,
1H), 6.89 (d, J = 2.1 Hz, 1H), 7.13ꢀ7.15 (m, 4H), 7.21ꢀ 7.23 (m, 1H), 7.27ꢀ7.28 (m, 2H), 7.31ꢀ
7.35 (m, 4H); 13C NMR (101 MHz, CDCl3) δ 49.6, 55.9, 111.9, 125.4, 126.4, 127.4, 128.4,
129.4, 130.2, 134.7, 143.1, 155.8.
((4-Bromo-2-methoxyphenyl)methylene)dibenzene (2d)16 The reaction mixture was stirred for
10 min using 4ꢀbromoanisole (0.234 mL, 1.87 mmol). white solid; mp 128ꢀ130 oC (lit 133 oC)4b;
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yield 90% (0.49 g); H NMR (400 MHz, CDCl3) δ 3.73 (s, 3H ), 5.94 (s, 1H), 6.79 (d, J = 8.8
Hz, 1H), 7.02ꢀ7.03 (m, 1H), 7.13ꢀ7.15 (m, 4H), 7.25ꢀ 7.31 (m, 2H), 7.34ꢀ7.38 (m, 5H); 13C NMR
(101 MHz, CDCl3) δ 49.6, 55.8, 112.5, 112.9, 126.4, 128.3, 129.4, 130.4, 133.0, 135.1, 143.1,
156.3.
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4,4'-(Phenylmethylene)bis(methylbenzene) (2e)13a Trifluoromethanesulfonic acid (0.026 mL,
0.29 mmol), phosphate 1b (0.500 g, 1.49 mmol), and toluene (0.19 mL, 1.79 mmol) were used.
The reaction mixture was stirred for 3 min. viscous liquid; yield 85% (0.34 g); The other
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regioisomer (ortho) was also present in 17% along with this sample. H NMR (400 MHz,
CDCl3) δ 2.42 (s, 6H), 5.58 (s, 1H), 7.06ꢀ7.12 (m, 4H), 7.29ꢀ7.38 (m, 7H), 7.35ꢀ7.38 (m, 2H);
13C NMR (101 MHz, CDCl3) δ 21.1, 56.1, 126.2, 128.3, 129.1, 129.3, 129.4, 135.7, 141.1, 144.3.
1,3,5-Trimethyl-2-(phenyl(p-tolyl)methyl)benzene (2f) Trifluoromethanesulfonic acid (0.026
mL, 0.29 mmol), phosphate 1b (0.500 g, 1.49 mmol) and mesitylene (0.25 mL, 1.79 mmol) were
used. The reaction mixture was stirred for 4 min. viscous liquid; yield 87% (0.39g);1H NMR
(400 MHz, CDCl3) δ 2.20 (s, 6H), 2.47 (s, 3H), 2.51 (s, 3H), 6.16 (s, 1H), 7.04 (s, 2H), 7.19ꢀ7.20
(m, 2H), 7.26ꢀ7.36 (m, 4H), 7.37ꢀ7.41 (m, 1H), 7.43ꢀ7.44 (m, 2H); 13C NMR (101 MHz, CDCl3)
δ 21.0, 21.2, 22.2, 50.8, 125.9, 128.3, 129.1, 129.4 (merged with other signal), 130.3, 135.5,
136.1, 137.4, 137.7, 139.4, 143.1; LC/MS m/z 300 [M]+; Anal. Calcd. for C23H24: C, 91.95; H,
8.05, Found: C, 91.76; H, 8.15.
Tri-p-tolylmethane (2g)17 Trifluoromethanesulfonic acid (0.025 mL, 0.28 mmol), phosphate 1c
(0.500 g, 1.43 mmol), toluene (0.18 mL, 1.72 mmol) were used. The reaction mixture was stirred
for 2 min. viscous liquid; yield 84% (0.34 g); The other regioisomer (ortho) was also present in
17% along with this sample. 1H NMR (400 MHz, CDCl3) δ 2.48 (s, 9H), 5.62 (s, 1H), 7.18 (d, J
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= 8.0 Hz, 6H), 7.25 (d, J = 8.0 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 21.2, 55.9, 129.1, 129.4,
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4,4'-(Mesitylmethylene)bis(methylbenzene) (2h) Trifluoromethanesulfonic acid (0.025 mL,
0.28 mmol), phosphate 1c (0.500 g, 1.43 mmol) and mesitylene (0.24 mL, 1.72 mmol) were
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used. The reaction mixture was stirred for 4 min. white solid; mp 88ꢀ90 C. yield 87% (0.39 g);
1H NMR (400 MHz, CDCl3) δ 2.16, (s, 6H), 2.43 (s, 3H), 2.47 (s, 6H), 6.09 (s, 1H), 6.99 (s, 2H),
7.13ꢀ7.15 ( m, 4H), 7.20ꢀ7.22( m, 4H); 13C NMR (101 MHz, CDCl3) δ 20.9, 21.1, 22.1, 50.4,
128.9, 129.3, 130.2, 135.4, 135.9, 137.5, 137.7, 139.8; Anal. Calcd. for C24H26: C, 91.67; H,
8.33, Found: C, 91.29; H, 8.58.
1-Bromo-4-(phenyl(p-tolyl)methyl)benzene (2i) Trifluoromethanesulfonic acid (0.022 mL,
0.25 mmol), phosphate 1d (0.500 g, 1.25 mmol) and toluene (0.159 mL, 1.51 mmol) were used
for this reaction. The reaction mixture was stirred for 7 min. viscous liquid; yield 90% (0.38 g);
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The other regioisomer (ortho) was also present in 16% along with this sample; H NMR (400
MHz, CDCl3) δ 2.40 (s, 3H), 5.54 (s, 1H), 7.05ꢀ7.07 (m, 4H), 7.16ꢀ7.18 (m, 4H), 7.29ꢀ7.31 (m,
1H), 7.34ꢀ7.38 (m, 2H), 7.46 (d, J = 8.0 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ 21.1, 55.9,
120.3, 126.5, 128.4, 129.2, 129.3, 129.4, 131.2, 131.4, 136.1, 140.4, 143.3, 143.6; LC/MS m/z
336 [M]+, 338 [M+2]+; Anal. Calcd. for C20H17Br: C, 71.23; H, 5.08, Found: C, 71.15; H, 5.14.
2-((4-Bromophenyl)(phenyl)methyl)thiophene (2j) Trifluoromethanesulfonic acid (0.022 mL,
0.25 mmol), phosphate 1d (0.500 g, 1.25 mmol) and thiophene (0.12 mL, 1.51 mmol) were used.
The reaction mixture was stirred for 6 min. viscous liquid; yield 78% (0.32 g); The other
regioisomer was also present in 13% along with this sample; 1H NMR (400 MHz, CDCl3) δ 5.68
(s, 1H), 6.72ꢀ6.73 (m, 1H), 6.97ꢀ6.99 (m, 1H), 7.12ꢀ7.14 (m, 2H), 7.22ꢀ7.25 (m, 3H), 7.29ꢀ7.31
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(m, 1H), 7.33ꢀ7.37 (m, 2H), 7.45ꢀ7.48 (m, 2H); 13C NMR (101 MHz, CDCl3) δ 51.6, 120.7,
124.8, 126.5, 126.7, 126.9, 128.6, 128.8, 130.6, 131.5, 142.9, 143.2, 147.2. LC/MS m/z 328
[M]+; Anal. Calcd. for C17H13BrS: C, 62.01; H, 3.98; Found: C, 62.15; H, 3.92.
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4,4'-(p-Tolylmethylene)bis(chlorobenzene) (2k) Trifluoromethanesulfonic acid (0.022 mL,
0.25 mmol), phosphate 1e (0.500 g, 1.28 mmol) and toluene (0.163 mL, 1.54 mmol) were used.
The reaction mixture was stirred for 10 min. viscous liquid; yield 88% (0.37 g); The other
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regioisomer (ortho) was also present in 15% along with this sample; H NMR (400 MHz,
CDCl3) δ 2.38 (s, 3H), 5.49 (s, 1H), 6.99ꢀ7.02 (m, 2H), 7.06ꢀ7.08 (m, 4H), 7.15ꢀ7.17 (m, 2H),
7.29ꢀ7.32 (m, 4H); 13C NMR (101 MHz, CDCl3) δ 21.1, 55.1, 128.6, 129.2, 129.3, 130.7, 132.4,
136.4, 139.9, 142.2; LC/MS: m/z 325 [M+ꢀ1]; Anal. Calcd. for C20H16Cl2: C, 73.40; H, 4.93;
Found: C, 73.31; H, 4.87.
4,4'-(Mesitylmethylene)bis(chlorobenzene) (2l)18 Trifluoromethanesulfonic acid (0.022 mL,
0.25 mmol), phosphate 1e (0.500 g, 1.28 mmol) and mesitylene (0.216 mL, 1.54 mmol) were
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used. The reaction mixture was stirred for 4 min. Gummy solid; yield 87% (0.39g); H NMR
(400 MHz, CDCl3) δ 2.03 (s, 6H), 2.33 (s, 3H), 5.94 (s, 1H), 6.91 (s, 2H), 7.05 (d, J = 8.4 Hz,
4H), 7.28ꢀ7.29 (d, J = 8.4 Hz, 4H); 13C NMR (101 MHz, CDCl3) δ 20.8, 21.9, 49.9, 128.4,
130.4, 130.6, 131.9, 136.1, 136.6, 137.4, 140.6.
Tris(4-chlorophenyl)methane (2m)19 Trifluoromethanesulfonic acid (0.022 mL, 0.25 mmol),
phosphate 1e (0.500 g, 1.28 mmol) and chlorobenzene (0.156 mL, 1.54 mmol) were used.
Gummy liquid; The reaction mixture was stirred for 18 min. yield 82% (0.36 g); The other
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isomer (ortho) was also present (26%) with this sample; H NMR (400 MHz, CDCl3) δ 5.50 (s,
1H), 7.04ꢀ7.06 (m, 6H), 7.30ꢀ7.33 (m, 6H); Other peaks appeared at δ 5.95 (s), 6.90ꢀ6.95 (m),
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7.12ꢀ7.14 (m), 7.23ꢀ7.25 (m), 7.38ꢀ7.45 (m) for the minor isomer; 13C NMR (101 MHz, CDCl3)
δ 54.9, 128.7, 130.6, 132.7, 141.5. Other peaks appeared at δ 52.2, 126.9, 128.3, 128.4, 128.8,
129.9, 130.1, 130.2, 130.8, 132.6, 140.6 for the minor isomer.
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4,4'-((4-bromophenyl)methylene)bis(chlorobenzene) (2n) Trifluoromethanesulfonic acid
(0.023 mL, 0.26 mmol), phosphate 1e (0.500 g, 1.28 mmol) and bromobenzene (0.162 mL, 1.54
mmol) were used. The reaction mixture was stirred for 22 min. Gummy liquid; yield 73% (0.36
g);1H NMR (400 MHz, CDCl3) δ 5.54 (s, 1H), 7.05 (d, J = 8.4 Hz, 2H), 7.10 (d, J = 8.5 Hz, 4H),
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7.34ꢀ7.37 (m, 4H), 7.49ꢀ7.52 (m, 2H); C NMR (101 MHz, CDCl3) δ 55.1, 120.9, 128.8, 130.7,
131.1, 131.8, 132.8, 141.4, 142.0; Anal. Calcd. for C19H13BrCl2: C, 58.20; H, 3.34. Found: C,
58.36; H, 3.41.
2-(Bis(4-chlorophenyl)methyl)thiophene (2o) Trifluoromethanesulfonic acid (0.028 mL, 0.25
mmol), phosphate 1e (0.500 g, 1.28 mmol) and thiophene (0.123 mL, 1.55 mmol) were used.
The reaction mixture was stirred for 12 min. viscous liquid; yield 80% (0.32 g); The other
regioisomer was also present in 8% along with this sample. 1H NMR (400 MHz, CDCl3) δ 5.7 (s,
1H), 6.74ꢀ6.75 (m, 1H), 7.00 (m, 1H), 7.01ꢀ7.02 (m, 4H), 7.18ꢀ7.19 (m, 1H), 7.33ꢀ7.36 (m, 4H),
13C NMR (101 MHz, CDCl3) δ 50.9, 125.1, 126.7, 126.8, 128.7, 130.2, 132.9, 141.9, 146.7;
LC/MS m/z 318 [M]+, 320 [M+2]+, 322 [M+4]+; Anal. Calcd. for C17H12Cl2S: C, 63.96; H, 3.79;
S, 10.04. Found: C, 64.36; H, 4.10; S, 10.03.
1-Chloro-2-((4-chlorophenyl)(phenyl)methyl)-4-nitrobenzene (2p) Trifluoromethanesulfonic
acid (0.022 mL, 0.25 mmol), phosphate 1f (0.500 g, 1.25 mmol), and chlorobenzene (0.152 mL,
1.50 mmol) were used. The reaction mixture was stirred for 30 min. light yellow solid, mp 108ꢀ
0
110 C, yield 86% (0.38g); The other regioisomer was also present in 26% along with this
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sample; IR (KBr, cmꢀ1) 1519, 1342; HꢀNMR (400 MHz, CDCl3) δ 5.98 (s, 1H), 7.03ꢀ7.10 (m,
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4H), 7.33ꢀ7.39 (m, 5H), 7.61 (d, J = 8.8 Hz, 1H), 7.85 (d, J = 2.8 Hz, 1H), 8.10 (dd, J = 8.0 Hz,
2.8 Hz, 1H); Peaks appeared at δ 6.31 (s), 6.87ꢀ6.89 (m), 7.23ꢀ7.28 (m), 7.44ꢀ7.47 (m), 7.62 (d, J
= 8.7 Hz), 7.76 (d, J = 2.8 Hz), 8.09ꢀ8.13 (m) for other isomers. 13CꢀNMR (101 MHz, CDCl3) δ
52.9, 123.0, 125.7, 127.5, 128.9, 129.6, 130.1, 130.6, 130.7, 134.6, 140.5, 141.4, 141.8, 146.6,
146.7; peaks at δ 50.9, 125.3, 127.1, 128.8, 128.9, 129.3, 129.5, 130.7, 130.8, 133.1, 139.1,
139.2, 139.5, 142.7, 143.3 were observed for other isomers; Anal. Calcd. for C19H13Cl2NO2: C,
63.71; H, 3.66; N, 3.91. Found: C, 63.85; H, 3.61; N, 3.86.
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1-Chloro-4-nitro-2-(phenyl(p-tolyl)methyl)benzene (2q) Trifluoromethanesulfonic acid (0.022
mL, 0.25 mmol), phosphate 1f (0.500 g, 1.25 mmol), toluene (0.159 mL, 1.50 mmol) were used.
The reaction mixture was stirred for 14 min. white solid, mp 90ꢀ92 oC, yield 91% (0.38g); Other
regioisomers were observed with the ratio (p/o/m 82:14:4) in this sample; IR (KBr, cmꢀ1) 1516,
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1343, 1046; HꢀNMR (400 MHz, CDCl3) δ 2.25 (s, 3H), 5.85 (s, 1H), 6.87 (d, J = 8.1Hz, 2H),
6.97 (d, J = 12Hz,2H), 7.04 (d, J =8.1 Hz, 2H), 7.19ꢀ7.25 (m, 3H), 7.45 (d, J =5.0Hz, 1H), 7.76
(d, J = 2.8 Hz, 1H), 7.94ꢀ7.96 (m, 1H); 13CꢀNMR (101 MHz, CDCl3) δ 21.1, 53.5, 122.7, 125.7,
126.2, 129.3, 129.5, 129.6, 130.6, 130.9, 137.9, 139.5, 141.4, 141.5, 144.1, 146.6; the other
peaks appeared at δ 19.7, 50.6, 122.8, 125.8, 127.1, 127.3, 127.5, 128.7, 128.8, 128.9, 129.2,
136.6, 136.9, 141.2, 143.7 due to other isomers; Anal. Calcd. for C20H16ClNO2: C, 71.11; H,
4.77; N, 4.15. Found: C, 71.22; H, 4.71; N, 4.23.
2-((2-Chloro-5-nitrophenyl)(phenyl)methyl)-1,3,5-trimethylbenzene
(2r)
Trifluoromethanesulfonic acid (0.022 mL, 0.25 mmol), phosphate 1f (0.500 g, 1.25 mmol), and
mesitylene (0.21 mL, 1.50 mmol) were used. The reaction mixture was stirred for 17 min. light
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(400 MHz, CDCl3) δ 2.03 (s, 6H), 2.33 (s, 3H), 6.17 (s, 1H), 6.92 (s, 2H), 7.02 (d, J = 8.8 Hz,
2H), 7.28ꢀ7.36 (m, 3H), 7.61 (d, J = 8.8 Hz, 1H), 7.91 (d, J = 2.4Hz, 1H), 8.12 (dd, J = 8.0 Hz,
2.8 Hz, 1H); 13CꢀNMR (101MHz, CDCl3) δ 20.9, 22.0, 49.8, 122.7, 126.5, 126.8, 128.7 (merged
with other carbon), 130.4, 130.6, 134.4, 136.9, 137.3, 140.2, 142.1, 142.9, 146.7; Anal. Calcd.
for C22H20ClNO2: C, 72.22; H, 5.51; N, 3.83. Found: C, 72.15; H, 5.58; N, 3.79.
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2-((4-Bromophenyl)(phenyl)methyl)-1-chloro-4-nitrobenzene (2s) The reaction mixture was
stirred for 26 min. light yellow gummy solid, yield 84% (0.42g); Other regioisomers with the
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ratio (p/o/m 83:12:5) were observed in this sample; IR (KBr, cmꢀ1) 1523, 1345, 1046; HꢀNMR
(400MHz, CDCl3) δ 5.94 (s, 1H), 6.96 (d, J = 8.4 Hz, 2H), 7.06 (d, J = 8.0 Hz, 2H), 7.32ꢀ7.39
(m, 3H), 7.47 (d, J = 8.0 Hz, 2H), 7.60 (d, J = 8.8 Hz, 1H), 7.82 (d, J = 2.8 Hz, 1H), 8.11 (dd, J
= 8.0, 2.8 Hz, 1H); other isomers appeared at δ 5.78 (s, 0.06H), 6.25 (s. 0.15H), 6.85ꢀ6.87 (m,
0.16H), 7.17ꢀ7.21 (m, 0.16H), 7.30ꢀ7.432 (m), 7.60 (d, J = 8.8 Hz), 7.63ꢀ7.65 (m, 0.16H), 7.72
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(d, J = 2.8 Hz, 0.16H), 8.07ꢀ8.12 (m, 0.16H): CꢀNMR (101MHz, CDCl3) δ 52.9, 121.2, 122.9,
125.6, 127.4, 128.9, 129.2, 130.8, 131.0, 131.9, 140.0, 140.3, 141.4, 143.2, 146.6; the other
minor peaks at δ 123.3, 125.3, 127.6, 128.6, 128.9, 129.6, 133.6, 139.3, 140.7 were appeared due
to other isomers; Anal. Calcd. for C19H13BrClNO2: C, 56.67; H, 3.25; N, 3.48, Found: C, 56.73;
H, 3.21; N, 3.52.
Spectroscopic data for diarylethanes
1-Methyl-4-(1-phenylethyl)benzene (3a)6k Trifluoromethanesulfonic acid (0.034 mL, 0.39
mmol), phosphate 1g (0.500 g, 1.94 mmol) and toluene (0.246 mL, 2.32 mmol) were used. The
reaction mixture was stirred for 50 min. viscous liquid; yield 91% (0.34 g); The other
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regioisomer (ortho) was also present in 17% along with this sample; H NMR (400 MHz,
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CDCl3) δ 1.69 (d, J = 7.2 Hz, 3H), 2.38 (s, 3H), 4.20 (q, J ~ 7.0 Hz, 1H), 7.17ꢀ7.18 (m, 3H),
7.19ꢀ7.20 (m, 1H), 7.23ꢀ7.24 (m, 1H), 7.29ꢀ7.30 (m, 2H), 7.33ꢀ7.37 (m, 2H); other peaks at δ
1.67ꢀ1.69 (m), 2.31 (s), 4.40 (q, J = 7.0 Hz), 7.16 (br), 7.24 (br), 7.37 (br) were due to minor
isomer. 13C NMR (101 MHz, CDCl3) δ 21.0, 21.9, 44.4, 125.9, 127.5, 127.6, 128.4, 129.1, 135.5,
143.5, 146.7; other isomer peaks appeared at δ 19.8, 22.2, 41.0, 125.8, 126.1, 126.14, 126.7,
127.7, 128.3, 130.4, 136.1, 143.9, 146.3.
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1-Methyl-4-(1-(4-nitrophenyl)ethyl)benzene (3b)20 Trifluoromethanesulfonic acid (0.029 mL,
0.33 mmol), phosphate 1h (0.500 g, 1.65 mmol) and toluene (0.209 mL, 1.98 mmol) were used.
The reaction mixture was stirred for 170 min. viscous liquid; yield 93% (0.37 g); Isolated as a
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mixture of regioisomer 67:33 (p/o); The peaks due to other isomer were not separable in H
NMR. 1H NMR (400 MHz, CDCl3) δ 1.69 (d, J = 7.2 Hz, 3H), 1.66 (d, J = 7.2 Hz, 1.5H), 2.23
(s, 1.5 H), 2.35 (s, 3H), and 4.24 (q, J = 7.2 Hz, 1H), 4.44 (q, J = 7.2 Hz, 0.5H), 7.10ꢀ7.27 (m,
5H), 7.27ꢀ7.28 (m, 1H), 7.32 ꢀ7.34 (m, 1H), 7.38ꢀ7.40 (m, 2H), 8.14ꢀ8.17 (m, 3H); 13C NMR
(101 MHz, CDCl3) δ 21.0, 21.6, 44.4, 123.7, 127.4, 128.4, 129.4, 130.7, 136.3, 141.6, 154.4. The
other regioisomer peaks are observed at δ 19.8, 21.8, 41.1, 124.6, 126.4, 126.6, 126.8, 127.5,
128.4, 128.8, 136.0, 142.2, 154.1.
1,3,5-Trimethyl-2-(1-(4-nitrophenyl)ethyl)benzene (3c) Trifluoromethanesulfonic acid (0.029
mL, 0.33 mmol), phosphate 1h (0.500 g, 1.65 mmol) and mesitylene (0.276 mL, 1.98 mmol)
o
were used. The reaction mixture was stirred for 180 min. yellow solid; mp 172ꢀ174 C; yield
1
94% (0.41 g); IR (KBr, cmꢀ1) 1523, 1448, 1344; H NMR (400 MHz, CDCl3) δ 1.75 (d, J = 7.2
Hz, 3H), 2.15 (s, br, 6H), 2.32 (s, 3H), 4.72 (q, J ~ 7.2 Hz, 1H), 6.9 (s, 2H), 7.38 (d, J = 9.0 Hz,
2H), 8.16 (d, J = 8.8 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ 16.9, 20.8, 21.1, 38.3, 123.4,
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127.7, 130.3, 136.2, 136.3, 138.7, 145.9, 153.8; Anal. Calcd. for C17H19NO2: C, 75.81; H, 7.11;
N, 5.20. Found: C, 75.86; H, 7.06; N, 5.28.
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1-(1-(p-Tolyl)ethyl)-2-(trifluoromethyl)benzene (3d) Trifluoromethanesulfonic acid (0.027
mL, 0.31 mmol), phosphate 1i (0.500 g, 1.53 mmol) and toluene (0.19 mL, 1.84 mmol) were
used. The reaction mixture was stirred for 120 min. viscous liquid; yield 93% (0.37 g); The other
regioisomer (ortho) was also present in 18% along with this sample. Other isomer signals were
not separable. 1H NMR (400 MHz, CDCl3) δ 1.71 (d, J ~ 7.1 Hz, 3H), 2.40 (s, 3H), 4.80 (q, J ~
7.0 Hz, 1H), 7.18ꢀ7.21 (m, 2H), 7.25ꢀ7.27 (m, 2H), 7.32ꢀ7.35 (m, 2H), 7.47ꢀ7.50 (m, 1H), 7.72
(d, J =8.5 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 21.0, 22.2, 39.1 (q, J = 1.8 Hz), 125.6 (q, J =
5.9 Hz), 125.9, 126.5 (q, J = 35.0 Hz), 127.6, 127.1 (q, J = 259.1 Hz), 129.1, 129.8, 132.1,
135.8, 142.1, 146.5 (d, J = 1.3 Hz). Anal. Calcd. for C16H15F3: C, 72.71; H, 5.72. Found: C,
72.81; H, 5.65.
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2-(1-(2-Fluorophenyl)ethyl)-1,3,5-trimethylbenzene (3e) Trifluoromethanesulfonic acid (0.032
mL, 0.36 mmol), phosphate 1j (0.500 g, 1.81 mmol) and mesitylene (0.303 mL, 2.17 mmol)
were used. The reaction mixture was stirred for 170 min. white solid; yield 93% (0.40 g); mp 98ꢀ
o
100 C; 1H NMR (400 MHz, CDCl3) δ 1.98 (d, J = 7.4 Hz, 3H), 2.53 (s, 6H), 2.58 (s, 3H), 5.08
13
(q, J = 7.3 Hz, 1H), 7.14 (s, 2H), 7.21ꢀ7.26 (m, 1H), 7.39ꢀ7.49 (m, 2H), 7.72ꢀ7.74 (m, 1H); C
NMR (101 MHz, CDCl3) δ 17.3, 21.0, 21.3, 34.3 (d, J = 1.5 Hz), 115.5 (d, J = 1.5 Hz), 123.7 (d,
J = 3.5 Hz), 127.7 (d, J = 8.2 Hz), 129.2 (d, J = 4.8 Hz), 130.5, 132.4 (d, J = 13.7 Hz), 135.6,
136.3 138.9, 161.8 (d, J = 245.2 Hz). Anal. Calcd. for C17H19F: C, 84.26; H, 7.90, Found: C,
84.38; H, 8.04.
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1-Fluoro-2-(1-(p-tolyl)ethyl)benzene (3f) Trifluoromethanesulfonic acid (0.032 mL, 0.36
mmol), phosphate 1j (0.500 g, 1.81 mmol) and toluene (0.23 mL, 2.17 mmol) were used.The
reaction mixture was stirred for 150 min. viscous liquid; yield 91% (0.35 g); The other
regioisomer (ortho) was also present in 14% along with this sample. The signals in 1H NMR for
minor isomer were merged with the major isomer. 1H NMR (400 MHz, CDCl3) δ1.98 (d, J = 7.0
Hz, 0.48 H minor isomer), 2.00 (d, J = 7.2 Hz, 3H), 2.62 (s, 0.48H minor isomer), 2.68 (s, 3H),
4.87 (q, J ~ 7.2 Hz, 1H), 5.06 (q, J = 7.2 Hz, 0.16H), 7.32ꢀ7.42 (m, 2.5H), 7.46ꢀ7.50 (m, 3H),
7.54ꢀ7.59 (m, 3.6H), 7.69ꢀ7.70 (m, 0.2H); 13C NMR (101 MHz, CDCl3) δ 21.1, 21.3, 37.6 (d, J =
2.6 Hz), 115.7 (d, J = 22.5 Hz), 124.4 (d, J = 3.6 Hz), 127.8, 127.9 (d, J = 8.2 Hz), 128.8 (d, J =
4.5 Hz), 129.5, 133.9 (d, J = 14.4 Hz), 135.9, 142.4, 160.9 (d, J = 245.4 Hz). Peaks at δ 19.7,
21.0, 34.1 (d, J = 2.6 Hz), 115.4 (d, J = 22.3 Hz), 124.4 (d, J = 3.6 Hz), 126.5 (d, J = 28.8 Hz),
126.8, 127.8 (d, J = 3.8 Hz), 128.8 (d, J = 245.4 Hz), 129.4, 130.83, 130.84, 133.9 (d, J = 14.4
Hz), 136.4, 143.1 were appeared for other isomer: Anal. Calcd. for C15H15F: C, 84.08; H, 7.06,
Found: C, 84.23; H, 7.12.
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Spectroscopic data for diarylmethanes
1-Methyl-3-(4-methylbenzyl)benzene (4a)9e. Trifluoromethanesulfonic acid (0.034 mL, 0.39
mmol), phosphate 1k (0.500 g, 1.94 mmol) and toluene (0.246 mL, 2.32 mmol) were used. The
reaction mixture was stirred for 8 min. viscous liquid; yield 88% (0.33 g); The other regioisomer
(ortho) was also present in 38% along with this sample. Some signals for both the isomers were
1
not clearly distinguished; H NMR (400 MHz, CDCl3) δ 2.53, 2.58, 2.586, 2.59 (4s, 9.6H), 4.18
13
(s, 2H), 4.22 (s, 1.2H minor), 7.20ꢀ7.29 (m, 4.8H), 7.34ꢀ7.39 (m, 4H), 7.395ꢀ7.47 (m, 4H); C
NMR (101 MHz, CDCl3) δ 19.9 (minor), 21.3, 21.69, 21.7 (minor), 41.8, 126.1, 126.2, 126.3,
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126.7, 126.9, 127.0, 128.5, 128.6, 129.0, 129.4, 129.8, 129.9, 130.2, 130.5, 135.7, 136.8, 138.1,
138.2, 138.5, 139.3, 140.6, 141.6.
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Di(naphthalen-1-yl)methane (4b)21 Trifluoromethanesulfonic acid (0.03 mL, 0.34 mmol),
phosphate 1l (0.500 g, 1.70 mmol) and naphthalene (0.26 g, 2.04 mmol) were used. The reaction
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mixture was stirred for 19 min. yield 85% (0.38 g); H NMR (400 MHz, CDCl3) δ 4.9 (s, 2H),
7.13 (d, J = 7.1 Hz, 2H), 7.37ꢀ7.40 (m, 2H), 7.51ꢀ7.54 (m, 4H), 7.81 (d, J = 8.2 Hz, 2H), 7.94ꢀ
7.96 (m, 2H), 8.07ꢀ 8.09 (m, 2H); 13C NMR (101 MHz, CDCl3) δ 35.7, 123.9, 125.6, 125.7,
126.1, 127.1, 127.14, 128.8, 132.2, 133.8, 136.2.
(Naphthalen-1-ylmethyl)ferrocene (4c)22. Trifluoromethanesulfonic acid (0.03 mL, 0.34
mmol), phosphate 1l (0.500 g, 1.70 mmol) and ferrocene (0.379 g, 2.04 mmol) were used. The
o
1
reaction mixture was stirred for 15 min. orange solid; mp: 98ꢀ100 C; yield 80% (0.44 g); H
NMR (400 MHz, CDCl3) δ 4.12 (m, 2H), 4.17 (m, 2H), 4.19 (s, 5H),4.21 (s, 2H), 7.29ꢀ7.3 (m,
1H), 7.4ꢀ7.43 (m,1H), 7.51ꢀ7.55(m, 2H), 7.74ꢀ7.76 (m, 1H), 7.87ꢀ7.89(m, 1H), 8.12ꢀ8.14 (m,
1H).13C NMR (101 MHz, CDCl3) δ 33.2, 67.1, 67.4, 68.8, 69.1, 123.9, 125.5, 125.54, 125.8,
126.1, 126.8, 128.7, 131.9, 133.7, 137.8. This compound was isolated with 90% purity.
1-Bromo-4-(4-methylbenzyl)benzene (4d)9c Trifluoromethanesulfonic acid (0.027 mL, 0.31
mmol), phosphate 1m (0.500 g, 1.55 mmol) and toluene (0.197 mL, 1.86 mmol) were used. The
reaction mixture was stirred for 12 min. viscous liquid; yield 93% (0.37 g); The other
regioisomer (ortho) was also present in 39% along with this sample. Some signals for both the
1
isomers were not separable. H NMR (400 MHz, CDCl3) δ 2.36 (s, 2.1H minor), 2.46 (s, 3H),
4.01 (s, 2H), 4.05 (s, 1.4H minor), 7.10ꢀ7.13 (m, 1.6H), 7.16ꢀ7.19 (m, 4H), 7.23ꢀ7.25 (m, 2H),
13
7.29ꢀ7.31 (m, 2H), 7.50ꢀ7.53 (m, 4H); C NMR (101 MHz, CDCl3) δ 19.8 (minor), 21.2, 39.0
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(minor), 41.0, 119.9, 120.0, 126.3, 126.8, 128.9, 129.4, 130.0, 130.58, 130.6, 130.8, 131.59,
131.6, 135.9, 136.7, 137.5, 138.4, 139.5, 140.6.
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Bis(4-chlorophenyl)methane (4e)7 Trifluoromethanesulfonic acid (0.027 mL, 0.31 mmol),
phosphate 1n (0.500 g, 1.79 mmol) and chlorobenzene (0.217 mL, 2.16 mmol) were used. The
reaction mixture was stirred for 18 min. viscous liquid; yield 93% (0.39 g); The other
regioisomer (ortho) was also present in 36% along with this sample. Some signals for both the
isomers were not separable; 1H NMR (400 MHz, CDCl3) δ 3.94 (s, 2H), 4.11 (s, 1.12 H minor),
7.12 (d, J = 8.4 Hz, 4H), 7.29 (d, J = 8.4H, 4H), 7.14ꢀ7.24 (m, 2.8H), 7.28ꢀ7.31 (m, 0.9H), 7.33ꢀ
7.43 (m, 1.36H); 13C NMR (101 MHz, CDCl3) δ 40.6, 128.7, 130.2, 132.2, 139.0; peaks at δ
38.6, 126.5, 126.9, 127.9, 128.6, 129.7, 130.3, 130.9, 132.18, 138.0, 138.2 were observed for
other isomer.
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ASSOCIATED CONTENT
Supporting Information Spectral data for all compounds. This material is available free of charge via the
Internet at http://pubs.acs.org/.
AUTHOR INFORMATION
Corresponding Author * Eꢀmail: manabchakravarty@gmail.com
Notes The authors declare no competing financial interest.
ACKNOWLEGEMENTS
We thank DSTꢀSERB (SB/S1/ICꢀ07A/2013) for financial support. DSTꢀFIST grant partly
supported this work. GP thanks BITS Pilani Hyderabad campus for his fellowship. Special
thanks to Mr. Prasad, Dr. Swamy and Dr. Sathish for their help. The NMR facility of BITSꢀ
Pilani is greatly acknowledged.
REFERENCES
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