Substrate- and temperature-controlled divergence in reactions of alcohols with TosMIC catalyzed by BF3 · Et2O: Facile access to sulfinates and sulfones

Article abstract of DOI:10.1080/00397911.2017.1321128

An efficient BF₃ · Et₂O-catalyzed divergent synthesis of sulfinate esters and sulfones through C–O and C–S bond formation has been achieved from alcohols and p-toluenesulfonylmethyl isocyanide (TosMIC). Various alcohols reacted smoothly with TosMIC under the present conditions at room temperature providing sulfinate esters exclusively. By tuning the reaction temperature, the alcohols that provide highly stabilized carbocation in the reaction medium afforded sulfones as sole products. This study was aimed at understanding the regioselectivity of ambidentate sulfinate ion and to elucidate the interpretation of sulfinate/sulfone scaffolds.

Full text of DOI:10.1080/00397911.2017.1321128

Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic
Chemistry
ISSN: 0039-7911 (Print) 1532-2432 (Online) Journal homepage: http://www.tandfonline.com/loi/lsyc20
Substrate and temperature controlled divergence
in reactions of alcohols with TosMIC catalyzed by
BF3·Et2O: Facile access to sulfinates and sulfones
Naresh Pogaku, Palakodety Radha Krishna & Y. Lakshmi Prapurna
To cite this article: Naresh Pogaku, Palakodety Radha Krishna & Y. Lakshmi Prapurna
(2017): Substrate and temperature controlled divergence in reactions of alcohols with TosMIC
catalyzed by BF3·Et2O: Facile access to sulfinates and sulfones, Synthetic Communications, DOI:
10.1080/00397911.2017.1321128
To link to this article: http://dx.doi.org/10.1080/00397911.2017.1321128
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Date: 02 May 2017, At: 07:03

Substrate and temperature controlled divergence in reactions of alcohols with
TosMIC catalyzed by BF3.Et2O: facile access to sulfinates and sulfones
Naresh Pogaku1, Palakodety Radha Krishna1, Y. Lakshmi Prapurna1
1Discovery Laboratory, Organic and Biomolecular Chemistry Division, CSIR-Indian
Institute of Chemical Technology, Hyderabad
Corresponding Author: Y. Lakshmi Prapurna, D-207, Discovery Laboratory, Organic and
Biomolecular Chemistry Division, CSIR-Indian Institute of Chemical Technology,
Hyderabad 500 007, Email: ylprapurna.iict@gov.in, prapurnay@gmail.com
Abstract
An efficient BF3.Et2O catalyzed divergent synthesis of sulfinate esters and sulfones via
C-O and C-S bond formation has been achieved from alcohols and TosMIC. Various
alcohols reacted smoothly with TosMIC under the present conditions at room
temperature providing sulfinate esters exclusively. By tuning the reaction temperature,
the alcohols that provides highly stabilized carbocation in the reaction medium afforded
sulfones as sole products. This study was aimed at understanding the regioselectivity of
ambidentate sulfinate ion and to elucidate the interpretation of sulfinate/sulfone scaffolds.
Graphical Abstract:
1

KEYWORDS: Alcohols, TosMIC, BF3.Et2O, Sulfinate ester, Sulfone, C-O and C-S
bond formation
1. INTRODUCTION
The organosulfone compounds are versatile intermediates in organic synthesis and are
important building blocks in the construction of various biologically active molecules,
pharmaceuticals and polymers.[1] They have been proven to exhibit remarkable biological
properties such as anticancer, anti-HIV and antibacterial activities.[2] The sulfonyl group,
which is embedded in these molecules, is a structural motif with numerous uses and can
be employed as a temporary modulator of chemical reactivity. The sulfinate esters are
highly valuable precursors in organic synthesis and can act as either electrophilic or
nucleophilic agents depending on the reaction conditions.[3] The combination of
significant biological activity and compelling synthetic utility has resulted in the
development of efficient methods for the synthesis of these compounds.[4] Among which,
the substitution of alcohol by sulfonyl moiety is one of the attractive and straightforward
method. Nevertheless, due to lower leaving ability of hydroxyl group in alcohols, the
direct nucleophilic substitution is generally difficult and thus its substitution typically
requires harsh conditions[5] or preactivation of the hydroxyl group to afford good leaving
group.[6] Various methods have been developed for the direct nucleophilic substitution of
alcohol by sulfonyl moiety over the past few years.[7] The common sulfonyl sources
employed were sulfonyl chloride, sodium sulfinate, sulfinic acid. The sulfinate ion
mainly involved in synthesis of organosulfone compounds is the ambidentate ion, and
affords either the ester or sulfone functionality depending on O- vs S-attack. Despite the
2

plethora of methods described to access sulfone compounds, the exact underlying reason
for the selectivity of sulfinate/sulfone was not explained by most of the reports. The
present method was performed to study the ambidentate reactivity of sulfinate ion and to
explain the spectral interpretation of sulfinate/sulfonyl molecules. Owing to the
significance, the studies revealing new methods to prepare these compounds that are
efficient, practical and divergent are always in high demand.
Consistent with our continuing interest in TosMIC chemistry,[8] recently we realized
sulfination of alcohols with TosMIC (p-toluenesulfonylmethyl isocyanide) under
Mitsunobu conditions.[8f] In continuation, herein we describe development of a catalytic
reaction indicating substantial improvement of the reaction. The current protocol
represents an interesting substrate and temperature controlled divergent synthesis of
sulfinates/sulfones from alcohols catalyzed by BF3.Et2O, employing TosMIC as a
sulfonyl source (Scheme 1). The relevant literature data shows the sulfonylation of
Baylis-Hillman alcohols and diarylmethanols with TosMIC in ionic liquid by Garima et
al.,[9a] and reports by Wu and coworkers of sulfination of alcohols with TosMIC
employing Bismuth catalysts.[9b,c] However, the former work is limited to diarylmethanols
and Baylis-Hillman alcohols and suffers from use of protic ILs which are not suitable for
large scale applications, potentially toxicological and purity issues. The major limitations
of the latter method are metal and acidic conditions, long reaction times and nitromethane
an undesired medium as solvent. The present reaction is in comparison a simple, more
convenient and preferable alternative for the synthesis of sulfinates/sulfones.
3

2. RESULTS AND DISCUSSIONS
At the outset, we expected that substitution of alcohols with sulfonyl group using
TosMIC as a sulfonyl source, might be achieved in presence of Lewis acid under suitable
conditions. To test this proposal, benzyl alcohol and TosMIC was subjected to the
reaction under different Lewis acids like InCl3, BF3.Et2O, Cu(OTf)2, Zn(OTf)2, FeCl3,
CuI, TMSOTf, Yb(OTf)3, Sc(OTf)3. Among the various Lewis acids tested, only
BF3.Et2O and TMSOTf afforded the sulfinate ester of benzyl alcohol as product.
However, BF3.Et2O was found to be best to furnish the 1a with a yield of 75%. To further
optimize the reaction, various solvents like THF, DCE, CHCl3 and EtOAc were screened
(Table 1, entries 10-14). Among those CH3CN was found to be an optimum solvent. As
the starting material was not consumed completely, the amount of TosMIC was increased
from 1.0 to 1.2 equiv, improvement in the yield was realized (Table 1, entry 14).
However, further increase in amount of TosMIC does not have any significant effect on
the yield. Furthermore, the stoichiometry of BF3.Et2O was lowered (from 1.0 to 0.3
equiv) without affecting the yield (Table 1, entry 15). A further reduction in the amount
of catalyst resulted in an incomplete reaction even after 2 h, producing 1a in 65% yield
(Table 1, entry 16).
With the optimized reaction conditions in hand, we next explored the generality of this
transformation under the established reaction conditions and the results are summarized
in Table 2. Various benzyl alcohols bearing electronically different groups like p-CH3, p-
F, p-Cl, p-NO2, 2,4-dichloro (2-6) gave the corresponding sulfinate esters 2a-6a in high
yields. However, the reaction of p-methoxy benzyl alcohol under the present conditions
4

did not furnish the desired sulfinate, but provided the regioisomeric sulfone in 25% yield
along with a mixture of unidentified products. Next, we examined the reactions between
benzylic secondary alcohols such as benzhydrol 7 and 1-phenylethanol 8. Pleasingly, the
reactions proceeded smoothly providing the corresponding sulfinates in 7a and 8a in 84%
and 80% yields respectively. The compound 8a was found to be 1:1 diastereomeric
mixture and the ratio was determined from the isolated yields. The reaction of 1-
phenylethanol with substituents like -NO2 and –F on the aromatic ring in para position
gave the corresponding sulfinates 9a and 10a in 74 and 76% yields as diastereomeric
mixtures. From the 1H NMR data the diastereomeric ratio of 9a and 10a was found to be
46:54 and 40:60 respectively. The reaction of t-BuOH 11 with TosMIC under the same
reaction conditions afforded the desired product 11a in 70% yield. When phenethyl
alcohol 12, an aliphatic alcohol possessing a phenyl group was used as the substrate, the
desired sulfinate 12a was obtained in 83% yield. We were pleased to observe the
sulfination of aliphatic alcohols methanol 13 and heptanol 14 under the standard
conditions provided the corresponding sulfinate esters 13a and 14a in good yields. The
sulfination of allyl alcohol 15 and propargyl alcohol 16 was efficiently achieved, thus
affording the corresponding sulfinates 15a and 16a respectively in 82% and 79% yields.
Reactions of cinnamyl alcohol 17 and α-allylbenzyl alcohol 18 under standard conditions
afforded the desired sulfinates 17a and 18a in 70 and 78% yields. The sulfination of
cyclohexanol 19 with TosMIC afforded the corresponding product 19a effectively. We
were pleased to find the reaction of mono-TBS protected pentanediol 20 proceeded
smoothly to give 20a in 77% yield, thus manifesting the functional group compatibility of
the current system.
5

Nonetheless, it has remained unclear to us how sulfinates have been formed differing
from generally favored sulfones. The previous reports show that different sulfonyl
sources like sulfonyl chloride, sulfinic acid, sodium sulfinate etc. under different
chemical environments produce either the sulfinate ester or sulfone. Thus, we were
intrigued to test the effect of temperature on reaction under otherwise identical
conditions. Treatment of benzhydrol 7 with TosMIC in presence of BF3.Et2O (0.3 equiv)
in acetonitrile under reflux conditions afforded the product within ten minutes. However,
we found formation of unexpected product i.e sulfone instead of the sulfinate ester by
TLC analysis (more Rf value). Notably, the formation of sulfone was observed in 83%
yield. The 1H NMR of 7aa shows the characteristic -CH proton resonating at 5.26 ppm,
unlike O-CH proton in 7a that resonates at 6.33 ppm. Likewise, in the 13C NMR
spectrum, the same proton resonates at 80.2 ppm instead of 76.5 ppm. The formation
of sulfone is further supported by IR studies, which revealed characteristic S=O
stretching frequency at 1310 cm-1, whereas that of 7a shows the S-O and C-O stretching
frequencies at 1140 and 900 cm-1 respectively. Subsequently, we proceeded to examine
the reaction at elevated temperatures (from 40 oC to 80 oC). The decreasing yield of
sulfinate from 18 to 0% was observed, coinciding with enhanced yield of sulfone to 83%
from 59%. Next, we set out to check the feasibility of the reaction of 1-phenylethanol 8
with TosMIC under present conditions, and the product obtained was sulfone 8aa in 81%
yield. Next, the sulfonylation of 1-(p-tolyl)ethanol 21 gave the corresponding sulfone
21aa in 78% yield. However, the reaction of 1-phenylethanol with substituents like -F
and -NO2, the electron withdrawing groups on the aromatic ring in para position, did not
provide the desired sulfone. We initially assumed the present reaction is temperature
6

controlled and heating the reaction afforded thermodynamically favorable sulfones as
final products.
However, when benzyl alcohol 1 and other substituted benzyl alcohols and cyclohexanol
were employed as substrates under heating conditions, sulfinates are the only products
detected, except the reaction employing p-methoxybenzylalcohol 22 as substrate.
However, the desired sulfone 22aa was observed in 30% yield only. This finding
suggests that the sulfone formation might be favored by the alcohol whose carbocation is
more stable. Next, we set out to screen different substituted benzhydrol derivatives as
shown in Table 3. Pleasingly, the benzhydrols with substituents like -Cl, -CH3, -Ph, -CN
on one of the aromatic ring in the para position (23-26) reacted smoothly with TosMIC
under the standard conditions to generate sulfones (23aa-26aa) in good yields.
Naphthalen-1-yl(phenyl)methanol 27 reacted smoothly with TosMIC under optimized
conditions to give 27aa in 80% yield. The reaction of tetralol 28 with TosMIC provided
the desired sulfone 28aa in 60% yield only. When the phenyl(thiophen-2-yl)methanol 29
derived from 2-thiophenecarboxaldehyde, was subjected to the present conditions 29aa
was obtained in 79% yield. In order to address the sulfinate/sulfone formation, we turned
our attention to study the ambidentate reactivity of p-toluenesulfinate ion. The earlier
reports, suggested that the alkylation of ambidentate anion with hard alkylating agents
gives predominantly the sulfinate ester, whereas with a soft alkylating agent affords
sulfone as the product principle of hard and soft acids and bases (HSAB)[10] or, more
quantitatively, by the Klopman-Salem concept of charge and orbital controlled
reactions.[11] However, later the examples have been reported that do not follow these
7

concepts.[12] These deviations led to the investigation by Mayr and coworkers[13] to
-
understand the regioselectivity of phenylsulfinate ion (PhSO2 ) and revealed that the
highly stabilized carbocations results in the exclusive formation of sulfones due to
thermodynamic product control, mixture of sulfones and sulfinates are formed under
conditions of kinetic control.
In the 1H NMR spectrum, the O-CH proton resonates downfield compared to that of S-
CH proton, which is characteristic to sulfinate ester and sulfone functionality.
Furthermore, O-CH2 protons results in two doublets with different chemical shift values,
indicating different chemical environments due to chiral sulfur atom, wherein S-CH2
protons appears as a singlet integrating for two hydrogen atoms (Figure 1). Moreover, it
is not surprising to note the incorrect functional group assignment i.e the sulfinate/sulfone
due to competitive O- vs S- attack of the sulfinate ion. For instance, in the recent report
by Xiong et al,[7f] the 1H NMR spectra of the products derived from 1-phenyl ethanol and
benzhydrol, the chemical shift of O-CH proton was reported at δ 4.22 and at 5.26 ppm,
and this is inconsistent with that of literature data (δ 5.46 and 6.33)[8f,9b] and contrarily a
downfield shift of 1 ppm might be expected. In the same way, the O-CH2 protons of the
product derived from cinnamyl alcohol was reported at δ 3.94 as a singlet, instead of two
doublets at different chemical shifts.[8f,14] Interestingly, the data of the examples
presented above is in good agreement with that of isomeric sulfones.[9a,15] Likewise,
Sreedhar and coworkers[7e] reported that S-CH2 protons of the sulfone derivatives of
benzylic alcohol and its derivatives bearing different groups (p-CH3, p-F and p-NO2),
shows two doublets in different chemical shifts instead of the singlet integrating for two
8

hydrogens in upfield, the only exception is the sulfone derivative of p-methoxy benzyl
alcohol, which was reported as a singlet. The BF3.Et2O plays a dual role i.e
decomposition of TosMIC to produce sulfinic acid and generation of carbocation by
activating the alcohol through coordination, thereby generating a carbocation to facilitate
nucleophilic attack of sulfonyl moiety. To investigate a better plausible mechanistic
pathway, we conducted the reaction of benzyl alcohol with p-Toluenesulfinic acid
catalyzed by BF3.Et2O under optimized conditions. Interestingly, 1a was isolated in 42%
yield, suggesting that p-Toluenesulfinic acid might be the intermediate in the present
reaction. This leads us to believe that under BF3 conditions TosMIC generates p-
Toluenesulfinic acid in situ, following which O- vs S- attack on alcohols provides either
the sulfinates or sulfones as final products. In order to rationalize the sulfinate/sulfone
formation the reaction of 7 under reflux conditions was monitored continuously by TLC
until complete consumption of the starting material. During the initial stage of the
reaction, both the products were observed in almost equal ratio. As the reaction
progresses, the sulfinate disappeared completely to provide the sulfone as the sole
product. This result indicated that the sulfone formation is not only due to S-attack, but
also through an ionizaton recombination sequence of that of isomeric sulfinate ester.
Based on the above results, a plausible mechanism is depicted in Scheme 2.
3. CONCLUSION
In conclusion, we report a new method for direct substitution of alcohol by a sulfonyl
moiety, using TosMIC as a sulfonyl source. This reaction has raised an intriguing result
i.e. the substrate and temperature controlled C-O and C-S bond formation, allowing
9

access to both sulfinate ester and sulfones from alcohol and TosMIC. The easy
availability of starting materials, operational simplicity and lesser reaction times makes
this protocol efficient and practical. The present studies enriched the content of
ambidentate reactivity of sulfinate ion i.e O- vs S- attack and explicit the formation and
interpretation of sulfones and sulfinates, which in general is ambiguous. Considering the
practicality and novelty of this method and the extreme importance of sulfonyl scaffolds
in synthetic and medicinal chemistry, the protocol described here undoubtedly will find
wide applications in future synthetic endeavors.
EXPERIMENTAL
The chemicals used were obtained from Sigma-Aldrich and used without further
purification. All solvents were used as obtained from the commercial suppliers. 1H NMR
spectra were recorded at 400, and 500 MHz (using TMS as a reference), and 13C NMR
were recorded at 75 and 125 MHz (using the CDCl3 triplet centered at δ 77.0 Hz as
reference) in CDCl3 as solvent at ambient temperature. Chemical shifts (δ) were recorded
in ppm, coupling constants J were given in hertz (Hz), and multiplicity is reported as s
(singlet), d (doublet), dd (doublet of doublet), td (triplet of doublet), t (triplet), m
(multiplet), br. s, (broad singlet). IR spectra were recorded on at Perkin-Elmer IR-683
spectrophotometer with NaCl optics and are reported in wavenumbers (cm-1). Mass
spectra were recorded on Finnigan Mat 1210 double focusing mass spectrometers
operating at a direct inlet system. High Resolution Mass Spectra (HRMS) were
performed on a high resolution magnetic sector mass spectrometer. For low (MS) and
high (HRMS) resolution, m/z ratios are reported as values in atomic mass units. All the
10

reactions monitored by analytical thin layer chromatography (TLC) using E-Merck
silicagel plates (60G-254). All evaporations were carried out under reduced pressure on
Büchi rotary evaporator at below 40 °C. All crude reaction products were purified by
column chromatography silica gel (60-120 mesh) by using ethyl acetate and petroleum
ether solvent system. Melting points were recorded on Büchi 535 melting point apparatus
and are uncorrected.
General Experimental Procedure For Synthesis Of Sulfinate Esters:
To a solution of alcohol (1 mmol), TosMIC 2 (1.2 mmol) in acetonitrile (2 mL),
BF3.Et2O (0.3 mmoL) was added at room temperature and the reaction mixture was
stirred at room temperature and monitored by TLC. After completion of the reaction,
ethyl acetate was added washed with water, brine and then dried over Na2SO4. The
organic layer was dried under reduced pressure. The crude product was purified by
column chromatography to obtain the corresponding sulfinate as the product.
Benzyl 4-Methylbenzenesulfinate (1a)
Obtained as yellow liquid (200 mg, 83% yield) from benzyl alcohol (108 mg, 1 mmol)
and TosMIC (234 mg, 1.2 mmol). 1H NMR (500 MHz, CDCl3): δ 7.63 (d, J = 8.2 Hz,
2H), 7.40-7.25 (m, 7H), 5.02 (d, J = 11.3 Hz, 1H), 4.55 (d, J = 11.3 Hz, 1H), 2.43 (s,
3H); 13C NMR (125 MHz, CDCl3): δ = 142.9, 141.6, 135.6, 129.8, 128.6, 125.4, 65.6,
21.6; ESI-MS: 269 [M+Na]+; HRMS: m/z calcd for C14H15O2S [M+H]+: 247.0787;
found: 247.0780.
11

General Experimental Procedure For Synthesis Of Sulfones:
To a solution of alcohol (1 mmol), TosMIC (1.2 mmol) in acetonitrile (2 mL), BF3.Et2O
(0.03 mL, 0.3 mmoL) was added. The reaction mixture was stirred at 80 oC and
monitored by TLC. After completion of the reaction, the mixture was cooled down to
room temperature, ethyl acetate was added, washed with water, brine and then dried over
Na2SO4. The organic layer was dried under reduced pressure. The crude product was
purified by column chromatography to obtain the corresponding sulfone as the product.
1-(Benzylsulfonyl)-4-Methylbenzene (7aa)
Obtained as white solid (267 mg, 83% yield) from benzhydrol 7 (184mg, 1 mmol) and
TosMIC (234 mg, 1.2 mmol). mp: 190-193 oC. 1H NMR (500 MHz, CDCl3): δ 7.57-7.47
(m, 6H), 7.33-7.29 (m, 6H), 7.16 (d, J = 7.9, 2H), 5.26 (s, 1H), 2.37 (s, 3H); 13C NMR
(125 MHz, CDCl3): δ = 144.4, 135.4, 133.1, 129.9, 129.2, 129.0, 128.7, 128.6, 76.5, 21.6;
ESI-MS: 345 [M+Na]+. HRMS: m/z calcd for C20H22O2SN [M+NH4]+: 340.1126; found:
340.1098.
SUPPORTING INFORMATION
Full experimental detail, 1H and 13C NMR spectra can be found via the “Supplementary
Content” section of this article’s webpage.
ACKNOWLEDGEMENTS
Dr. Y. Lakshmi Prapurna thanks Department of Science and Technology (DST) for
financial grant under Women Scientists Scheme-A (WOS-A), Grant No. SR/WOS-A/CS-
1034/2014 (G). The author N.P. acknowledges UGC, New Delhi for fellowship support.
12

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2016, 4077.
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Pearson, R. G. Chemical Hardness; Wiley: New York, 1997.
15

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16

Table 1. Optimization of reaction conditionsa
Entry
1
Catalyst (mol%)
InCl3 (100)
Solvent Time (h) Yield [%]b
CH3CN 24
CH3CN 0.25
CH3CN 24
CH3CN 24
CH3CN 24
CH3CN 24
CH3CN 12
CH3CN 24
CH3CN 24
0
2
BF3.Et2O (100)
Cu(OTf)2 (100)
Zn(OTf)2 (100)
FeCl3 (100)
75
0
3
4
0
5
0
6
CuI (100)
0
7
TMSOTf (100)
Yb(OTf)3 (100)
Sc(OTf)3 (100)
BF3.Et2O (100)
BF3.Et2O (100)
BF3.Et2O (100)
BF3.Et2O (100)
BF3.Et2O (100)
BF3.Et2O (30)
BF3.Et2O (10)
40
0
8
9
0
10
11
12
13
14
15
16
THF
1
69
71
65
72
83c
83c
65c
DCE
0.25
0.25
0.25
CHCl3
EtOAc
CH3CN 0.25
CH3CN 0.30
CH3CN
2
aReaction conditions: alcohol (1.0 equiv), TosMIC (1.0 equiv), Lewis acid and solvent.
bThe yields refer to isolated products purified by column chromatography.
c1.2 equiv of TosMIC was used.
17

Table 2. Synthesis of sulfinate esters via C-O bond formationa,b
1a, 83% yield
4a, 83% yield
2a, 83% yield
5a, 80% yield
3a, 81% yield
6a, 78% yield
7a, 84% yield
8a, 80% yield
9a, 74% yield
10a, 76% yield
13a, 81% yield
16a, 79% yield
11a, 70% yield
14a, 78% yield
17a, 70% yield
12a, 83% yield
15a, 82% yield
18a, 78% yield
19a, 79% yield
20a, 77% yield
18

aReaction conditions: Alcohol (1.0 equiv), TosMIC (1.2 equiv), BF3.Et2O (0.3 equiv) in
CH3CN.
bAll the products were characterized from spectral data and yields were calculated after
purification by column chromatography.
19

Table 3. Synthesis of sulfones via C-S bond formationa,b
7aa, 83% yield
8aa, 81% yield
21aa, 78% yield
24aa, 82% yield
27aa, 80% yield
22aa, 30% yield
23aa, 80% yield
25aa, 84% yield
28aa, 60% yield
26aa, 75% yield
29aa, 79% yield
aReaction conditions: Alcohol (1.0 equiv), TosMIC (1.2 equiv), BF3.Et2O (0.3 equiv) in
CH3CN.
bAll the products were characterized from spectral data and yields were calculated after
purification by column chromatography.
20

Figure 1. Differentiation between sulfinate ester and sulfone
21

Scheme 1. BF3.Et2O catalyzed divergent synthesis of sulfinates and sulfones from
alcohols and TosMIC
22

Scheme 2. A plausible mechanism
23