Practical synthesis of aromatic dithiocarbamates

Article abstract of DOI:10.1080/00397911.2014.894527

Oxidation-sensitive N,N-diaryl dithiocarbamates (DTCs) are synthesized in good yields by the generation of metal amide salts from N-benzoyl precursors, followed by addition of CS₂. para-Substituted diphenylamines are prepared by electrophilic aromatic substitution of diphenylbenzamide and saponification. Deacylation of electron-rich species such as bis(p-dimethylaminophenyl)benzamide is challenging because of the oxidative sensitivity of the anionic intermediate but could be achieved in good yield by using n-BuLi to generate a hemiaminal adduct, prior to acidification. The N,N-diaryl DTCs are stable as alkali salts and can be used to produce densely packed monolayers on gold surfaces. Copyright

Full text of DOI:10.1080/00397911.2014.894527

This article was downloaded by: [Aston University]
On: 02 September 2014, At: 07:45
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Synthetic Communications: An
International Journal for Rapid
Communication of Synthetic Organic
Chemistry
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/lsyc20
Practical Synthesis of Aromatic
Dithiocarbamates
Panuwat Padungros a & Alexander Wei b
a Department of Chemistry, Faculty of Science , Chulalongkorn
University , Bangkok , Thailand
b Department of Chemistry , Purdue University , West Lafayette ,
Indiana , USA
Accepted author version posted online: 22 Apr 2014.Published
online: 13 Jun 2014.
To cite this article: Panuwat Padungros & Alexander Wei (2014) Practical Synthesis of Aromatic
Dithiocarbamates, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 44:16, 2336-2343, DOI: 10.1080/00397911.2014.894527
To link to this article: http://dx.doi.org/10.1080/00397911.2014.894527
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &

Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Synthetic Communications1, 44: 2336–2343, 2014
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2014.894527
PRACTICAL SYNTHESIS OF AROMATIC
DITHIOCARBAMATES
Panuwat Padungros1 and Alexander Wei2
1Department of Chemistry, Faculty of Science, Chulalongkorn University,
Bangkok, Thailand
2Department of Chemistry, Purdue University, West Lafayette,
Indiana, USA
GRAPHICAL ABSTRACT
Abstract Oxidation-sensitive N,N-diaryl dithiocarbamates (DTCs) are synthesized in good
yields by the generation of metal amide salts from N-benzoyl precursors, followed by
addition of CS2. para-Substituted diphenylamines are prepared by electrophilic aromatic
substitution of diphenylbenzamide and saponification. Deacylation of electron-rich species
such as bis(p-dimethylaminophenyl)benzamide is challenging because of the oxidative sen-
sitivity of the anionic intermediate but could be achieved in good yield by using n-BuLi to
generate a hemiaminal adduct, prior to acidification. The N,N-diaryl DTCs are stable as
alkali salts and can be used to produce densely packed monolayers on gold surfaces.
Keywords Benzamide; deprotection; dithiocarbamate; oxidation sensitive
INTRODUCTION
Dithiocarbamates (DTCs) are important precursors for a wide range of chemi-
cal applications,[1] such as intermediates in the chemical synthesis of biologically
active compounds and natural products,[2,3] as ligands in coordination chemistry
to stabilize various transition metals,[4] and as initiators in the vulcanization of rub-
ber and in the synthesis of polymers by reversible addition-fragmentation (RAFT)
processes.[5] Dithiocarbamates can also serve as ligands for novel applications in sur-
face chemistry. It has been argued that DTCs can form more robust monolayers
Received January 15, 2014.
Address correspondence to Panuwat Padungros, Department of Chemistry, Faculty of Science,
Chulalongkorn University, 254 Phayathai Road, Pathumwan, Bangkok 10330, Thailand. E-mail:
panuwat.p@chula.ac.th
2336

SYNTHESIS OF AROMATIC DITHIOCARBAMATES
2337
than alkylthiols on gold, aided by the favorable epitaxy between the bidentate car-
bodithioate unit and the Au(111) surface.[6] DTCs have been used to anchor a variety
of functional molecules and polymers[7,8] onto metal surfaces, such as peptides,[6] car-
bohydrates,[9] DNA,[10] and cancer-targeting ligands.[11]
DTCs have particularly intriguing potential as interconnects for molecular
electronics, because of their extended conjugation. Wessels et al. first demonstrated
this possibility using bisDTC ligands as molecular junctions between Au nanoparti-
cles, with large increases in overall conductivity relative to dithiol spacers.[12] Surface
spectroscopy studies on DTC monolayers further established a high charge transport
across aromatic DTCs assembled on Au.[13] Advances in this research area may be
supported by developing a practical synthesis of DTCs attached to p-conjugated sys-
tems with tunable electronic structures.
Many DTCs can be conveniently prepared simply by combining the corre-
sponding amine and CS2 in polar solvents.[6,14,15] However, this is not the case
for diaryl DTCs; at present only a few syntheses have been reported, mostly for
simple N,N-diphenyl DTCs.[16,17,18] Diaryl DTCs, particularly those with electron-
donating substituents, are of strong interest for studies in molecular electronics,
but to our knowledge a general synthetic procedure is lacking. This may be due
partly to the oxidative sensitivity of electron-rich diarylamines, which are challenging
to isolate in neutral form. We note that while para-substituted N,N-diphenylamines
have been prepared by Buchwald–Hartwig coupling,[19] this approach involves the
coupling of substituted anilines and phenyl halides and does not address the air
sensitivity of the products.
In this article we show that para-substituted N,N-diphenyl DTCs can be
synthesized by addition of CS2 to the corresponding metal amide, generated in situ
from N-benzamide derivatives. This practical approach allows us to use standard
electrophilic aromatic substitution to generate the desired N,N-diphenylamine
derivatives and permits the isolation of the desired DTCs as air-stable alkali salts.
RESULTS AND DISCUSSION
para-Substituted N,N-diphenylamines were synthesized from the diphenylben-
zamide 1 (Scheme 1). Bromination of benzamide 1 followed by saponification with
Claisen’s base (KOH in H2O=MeOH) provided N,N-bis(p-bromophenyl)amine 3
Scheme 1. Synthesis of para-substituted N,N-diphenylamines.

2338
P. PADUNGROS AND A. WEI
in 84% yield. The double nitration of benzamide 1 was less straightforward; using
70% HNO3 as the nitrating agent produced the mononitrated benzamide (N-Bz-4)
as the major product.[20] N,N-Bis(p-dinitrophenyl)benzamide 5 could be obtained
by treatment with a stronger Brønsted acid, namely a mixture of 70% HNO3 and
TFA, accompanied by small amounts of N-Bz-4. The N-Bz-4 and benzamide 5 were
saponified with Claisen’s base to yield N-(p-nitrophenyl)-N-phenylamine 4 and N,N-
bis(p-nitrophenyl)amine 6 in 48% and 67% yield, respectively. Compound 5 could
also be reduced by SnCl2 to bis(p-amino)phenylbenzamide,[21] followed by reductive
amination to provide N,N-bis(p-dimethylaminophenyl)benzamide 7 in 94% yield.
To obtain N,N-bis(p-dimethylaminophenyl)amine 8, benzamide 7 was sub-
jected to a variety of deacylation conditions (Table 1). Claisen’s base did not react
with 7 at 25 ꢀC and caused decomposition at 100 ꢀC (Table 1, entry 1); saponifica-
tions with phenylthiolate salts were likewise unsuccessful (entries 2 and 3). We sus-
pected that the electron-rich diarylamine was susceptible to oxidation under basic
conditions[22] and attempted to remove the benzoyl group under acidic conditions
at 100 ꢀC, but this resulted in only partial conversion (entry 4). We then investigated
acyl addition and cleavage under anhydrous conditions using stronger nucleophiles
and were pleased to find that n-BuLi added readily to the benzamide carbonyl at
0 ꢀC. Acidic workup (6 M HCl) produced the hydrochloride salt of 8 in good yields
(entry 5). Isolation of 8 as its HCl salt was necessary to prevent product oxidation
during storage and handling. We note that 1-phenylpentanone was obtained as a
reaction by-product only after acidic workup, not during the course of the reaction,
indicating that deacylation proceeds through a stable hemiaminal intermediate,[23,24]
one that is presumably less susceptible to oxidation than the free amine (Scheme 2).
With diarylamines in hand, we surveyed several basic conditions for generating
aromatic DTCs (Table 2). In principle, DTCs can be prepared from their corre-
sponding amines under mildly basic conditions, if the latter is sufficiently nucleophi-
lic.[3,6,15] However, diphenylamine (pKa ꢁ 25)[25] and related aromatic amines are
insufficiently reactive toward CS2, and thus require generation of their conjugate
base. In the cases of diphenylamine and bis(p-bromophenyl)amine 3, deprotonation
with n-BuLi or n-BuLi=DMSO (dimsyl-Li) followed by addition of CS2 was
Table 1. Synthesis of N,N-bis(p-dimethylaminophenyl)amine hydrochloride
Entry
Reaction conditions
Claisen’s base, 100 ꢀC
Yield
1
2
3
4
5
Complex mixture
Complex mixture
No reaction
40%a
PhSK, Claisen’s base, 100 ꢀC
PhSLi, THF, 70 ꢀC
Aq. HCl, 100 ꢀC (mwave)
(i) n-BuLi, THF, 0 ꢀC; (ii) 6 M HCl
94%b
aConversion determined by 1H NMR.
bIsolated yield.

SYNTHESIS OF AROMATIC DITHIOCARBAMATES
2339
Scheme 2. Formation of 8 via hemiaminal intermediate.
sufficient to produce lithium salts of N,N-diphenyl DTC (9) and N,N-bis
(p-bromophenyl) DTC (10) respectively, which were isolated in good yields by pre-
cipitation with Et2O (Table 2, entries 1–4). The 13C NMR spectra of these diaryl
DTCs revealed thiocarbonyl signals at d 219–224 ppm, more downfield than those
produced by dialkyl DTCs (d 200–210 ppm).[26] However, DTC formation from
deprotonated N-(p-nitrophenyl)-N-phenylamine 4 or N,N-bis(p-nitrophenyl)amine
6 was sluggish and did not reach completion regardless of reaction temperature or
the amount of CS2 added, with only trace amounts of DTC formed based on 13C
NMR analysis (entries 5 and 6). The poor reactivity was attributed to the reduced
nucleophilicity of the amide anion by one or both nitro groups.
Electron-rich diarylamine 8 was converted straightforwardly into N,N-bis
(p-dimethylaminophenyl) DTC (11) by deprotonation of the HCl salt using 2 equiva-
lents of n-BuLi or dimsyl-Li, followed by dropwise addition of CS2 and precipitation
Table 2. Synthesis of substituted diphenylamine DTCs
Entry
Amine
Basea
Diaryl DTC (yield)b
1
2
3
4
5
6
7
8
9
Ph2NH
Ph2NH
=
3 (X Br)
=
3 (X Br)
=
4 (X H,NO2)
n-BuLi
dimsyl-Li
n-BuLi
9 (64%)
9 (98%)
10 (96%)
10 (93%)
Trace
dimsyl-Li
dimsyl-Li
dimsyl-Li
n-BuLi
=
6 (X NO2)
Trace
c
c
=
8 (X NMe2)
=
11 (94%)
11 (72%)
12 (55%)e
8 (X NMe2)
Carbazoled
dimsyl-Li
NaH
a1.0–2.5 equiv.
bIsolated yields unless stated otherwise.
cHydrochloride salt, neutralized with one equivalent of n-BuLi or dimsyl-Li.
dReaction conditions: (i) 50 ꢀC for 5 h, then ꢂ78 ꢀC; (ii) CS2 (5–10 equiv), warmed to rt.
eYield after a single precipitation.

2340
P. PADUNGROS AND A. WEI
in Et2O to produce the lithium salt of DTC 11 in good isolated yield (Table 2, entries
7 and 8). The lithium salt of N-carbazolyl DTC (12) could also be obtained by depro-
tonating carbazole with n-BuLi or dimsyl-Li followed by CS2 addition; however,
attempts to precipitate this product were not successful. Deprotonation with NaH
instead produced sodium N-carbazolyl DTC, which could be isolated in satisfactory
yields (entry 9). It should be mentioned that the yield of sodium N-carbazolyl DTC
(12) was moderate because the instability of the product prevented us from perform-
ing a second precipitation. Converting the sodium salt in N-carbazolyl DTC (12) into
a triethylammonium (Et3HNþ) salt prolonged its stability and allowed collection of
all spectroscopic data. We note that N-carbazolyl DTC can also be synthesized using
potassium metal as a base,[27] but the potassium salt of 12 is highly air sensitive and
decomposes within seconds upon contact with air.
CONCLUSION
A practical method of converting N-benzoyl diarylamines into dithiocarba-
mates is presented. In some cases, diarylamines can be obtained straightforwardly,
then deprotonated with a strong base, treated with CS2, and precipitated from the
reaction mixture to yield the desired DTCs as lithium salts. Electron-rich diaryla-
mines can be prepared by adding n-BuLi to the benzamide to form a hemiaminal
intermediate and isolated as their ammonium salts by acidic workup. These aromatic
DTCs can be used to prepare self-assembled monolayers on Au(111) for surface
spectroscopy studies, which will be reported in due course.
EXPERIMENTAL
All chemicals and reagents were obtained from commercial sources and used
as received unless stated otherwise. Solvents were freshly distilled prior to use. A
0.2 M solution of dimsyl lithium (the conjugate base of dimethyl sulfoxide) was
prepared by treating DMSO (1.42 mL, 20 mmol) in anhydrous THF (43.5 mL) with
n-BuLi (5 mL, 10 mmol) at 0 ꢀC, then stirred for 30 min and maintained at 0 ꢀC
1
prior to use. H and 13C NMR spectra were recorded on a Varian Inova 300, a
Bruker ARX400, or a Bruker DRX500 and referenced to the solvent used (CDCl3:
7.27 and 77 ppm; CD3OD: 3.31 and 49.2 ppm; DMSO-d6: 2.50 and 39.5 ppm).
DTC salts 9–12 decompose rapidly upon atmospheric exposure and are best
handled under anaerobic conditions and stored as powders in vacuum-sealed
ampoules.
General Procedure for Synthesis of Aromatic Dithiocarbamates
A solution of aromatic amine (2.96 mmol) was dissolved in degassed THF
(6 mL), then cooled to 0 ꢀC, and treated with dimsyl lithium solution (5.92 mmol,
2 equiv) or n-BuLi (5.92 mmol, 2 equiv). After stirring for 30 min at 0 ꢀC, CS2
(29.6 mmol, 10 equiv) was added. The ice bath was removed and the mixture was
stirred for 12 h room temperature. The crude mixture was precipitated from THF
in Et2O to afford diaryl DTC product.

SYNTHESIS OF AROMATIC DITHIOCARBAMATES
2341
Lithium N,N-Diphenyl Dithiocarbamate (9)
Off-white solid. 1H NMR (300 MHz, CD3OD): d 7.37–7.20 (m, 8 H), 7.17–7.06
(m, 2 H). 13C NMR (75 MHz, CD3OD): d 219.0, 150.4, 129.7, 129.3, 127.2. IR (thin
film): n 3354, 1592, 1491, 1452, 1343, 1313, 1223, 1110, 1048, 1012, 884, 834 cmꢂ1
ESI-MS: m=z for C26H20LiN2S4 [2M–Li]ꢂ 495.[16]
.
Lithium N,N-Bis(p-bromophenyl)dithiocarbamate (10)
Pale-yellow solid. 1H NMR (500 MHz, DMSO-d6): d 7.35 (d, 4 H, J ¼ 8.7 Hz),
7.13 (d, 4 H, J ¼ 8.7 Hz). 13C NMR (125 MHz, DMSO-d6): d 218.8, 148.6, 131.3,
131.0, 117.5. IR (thin film): n 3426, 1512, 1484, 1432, 1282, 1296, 1010, 956, 887,
867, 790 cmꢂ1. ESI-MS: m=z for C12H8Br2N [M–Li–CS2]ꢂ 326.
Lithium N,N-Bis(p-dimethylaminophenyl)dithiocarbamate (11)
Off-white solid. 1H NMR (300 MHz, CD3OD): d 7.60 (d, 4 H, J ¼ 8.8 Hz), 7.12
(d, 4 H, J ¼ 8.8 Hz), 3.31 (s, 12 H). 13C NMR (75 MHz, CD3OD): d 218.2, 150.3,
141.2, 129.5, 129.2, 114.1, 113.8, 41.0. IR (thin film): n 3401, 1634, 1607, 1516,
1445, 1331, 1281, 1221, 1183, 1153, 1127, 1050, 884, 707, 693 cmꢂ1. ESI-MS: m=z
for C17H20N3S2 [M–Li]ꢂ 330.
Sodium N-Carbazolyl Dithiocarbamate (12)
1
Yellow solid. H NMR (300 MHz, CD3OD): d 8.67 (d, 2 H, J ¼ 8.3 Hz), 7.79
(d, 2 H, J ¼ 7.6 Hz), 7.24 (t, 2 H, J ¼ 7.7 Hz), 7.05 (t, 2 H, J ¼ 7.3 Hz). 13C NMR
(75 MHz, CD3OD): d 224.4, 141.0, 126.2, 125.2, 121.9, 119.9, 116.3. Sodium
N-carbazolyl dithiocarbamate 12 was converted to more stable triethylammonium
salt for the characterization purpose. Triethylammonium N-carbazolyl dithiocarba-
1
mate was an orange-yellow solid. H NMR (300 MHz, CDCl3): d 8.92 (d, 2 H,
J ¼ 8.4 Hz), 8.05 (d, 2 H, J ¼ 7.6 Hz), 7.48 (t, 2 H, J ¼ 7.0 Hz), 7.33 (m, 2 H), 3.26
(q, 6 H, J ¼ 7.5 Hz), 1.42 (t, 9 H, J ¼ 7.2 Hz). IR (thin film): n 3369, 1631, 1490,
1450, 1351, 1328, 1306, 1274, 1046, 884, 707, 693 cmꢂ1. ESI-MS: m=z for C12H8N
[M–Et3NH–CS2]ꢂ 166.
FUNDING
We gratefully acknowledge financial support from the National Science
Foundation (CHE-0957738) and Grants for Development of New Faculty Staff,
Ratchadaphiseksomphot Endowment Fund, Chulalongkorn University. P. P. is
thankful for a start-up grant for laboratory equipment from the Department of
Chemistry, Chulalongkorn University. NMR and MS analyses were also supported
by the Purdue Interdepartmental NMR facility and the Purdue University Center for
Cancer Research.
SUPPLEMENTAL MATERIAL
Supplemental data for this article can be accessed on the publisher’s website.

2342
P. PADUNGROS AND A. WEI
REFERENCES
1. (a) Aly, A. A.; Brown, A. B.; Bedair, T. M. I.; Ishak, E. A. J. Sulfur Chem. 2012, 33,
605–617; (b) Hassan, E. A.; Zayed, S. E. Phosphorus, Sulfur Silicon Relat. Elem. 2013,
189, 300–323.
2. (a) Buac, D.; Schmitt, S.; Ventro, G.; Kona, F. R.; Dou, Q. P. Mini-Rev. Med. Chem.
2012, 12, 1193–1201; (b) Nagy, E. M.; Ronconi, L.; Nardon, C.; Fregona, D. Mini-Rev.
Med. Chem. 2012, 12, 1216–1229.
3. (a) Padungros, P.; Alberch, L.; Wei, A. Org. Lett. 2012, 14, 3380–3383; (b) Padungros, P.;
Alberch, L.; Wei, A. J. Org. Chem. 2014, 79, 2611–2624.
4. (a) Hogarth, G. Prog. Inorg. Chem. 2005, 53, 71–561; (b) Victoriano, L. I. Coord. Chem.
Rev. 2000, 196, 383–398.
5. (a) Moad, G.; Rizzardo, E.; Thang, S. H. Polymer 2008, 49, 1079–1131; (b) Keddie, D. J.;
Moad, G.; Rizzardo, E.; Thang, S. H. Macromolecules 2012, 45, 5321–5342.
´
6. (a) Zhao, Y.; Perez-Segarra, W.; Shi, Q.; Wei, A. J. Am. Chem. Soc. 2005, 127, 7328–7329;
(b) Zhu, H.; Coleman, D. M.; Dehen, C. J.; Geisler, I. M.; Zemlyanov, D.; Chmielewski, J.;
Simpson, G. J.; Wei, A. Langmuir 2008, 24, 8660–8666.
7. Huff, T. B.; Hansen, M. N.; Zhao, Y.; Cheng, J.-X.; Wei, A. Langmuir 2007, 23,
1596–1599.
8. (a) Park, M.-H.; Duan, X.; Ofir, Y.; Creran, B.; Patra, D.; Ling, X. Y.; Huskens, J.;
Rotello, V. M. ACS Appl. Mater. Interfaces 2010, 2, 795–799; (b) Leonov, A. P.; Wei, A.
J. Mater. Chem. 2011, 21, 4371–4376.
9. Adak, A. K.; Leonov, A. P.; Ding, N.; Thundimadathil, J.; Kularatne, S.; Low, P. S.; Wei, A.
Bioconjugate Chem. 2010, 21, 2065–2075.
10. Sharma, J.; Chhabra, R.; Yan, H.; Liu, Y. Chem. Commun. 2008, 2140–2142.
11. (a) Huff, T. B.; Tong, L.; Zhao, Y.; Hansen, M. N.; Cheng, J.-X.; Wei, A. Nanomedicine
2007, 2, 125–132; (b) Tong, L.; Zhao, Y.; Huff, T. B.; Hansen, M. N.; Wei, A.; Cheng, J.-X.
Adv. Mater. 2007, 19, 3136–3141.
12. Wessels, J. M.; Nothofer, H.-G.; Ford, W. E.; von Wrochem, F.; Scholz, F.; Vossmeyer, T.;
Schroedter, A.; Weller, H.; Yasuda, A. J. Am. Chem. Soc. 2004, 126, 3349–3356.
13. von Wrochem, F.; Gao, D. Q.; Scholz, F.; Nothofer, H. G.; Nelles, G.; Wessels, J. M. Nat.
Nanotechnol. 2010, 5, 618–624.
14. Selected examples: (a) Li, R.-T.; Ding, P.-Y.; Han, M.; Cai, M.-S. Synth. Commun. 1998,
28, 295–300; (b) Cui, J.-L.; Ge, Z.-M.; Cheng, T.-M.; Li, R. Synth. Commun. 2003, 33,
1969–1976; (c) Chaturvedi, D.; Ray, S. Tetrahedron Lett. 2006, 47, 1307–1309; (d) Azizi, N.;
Aryanasab, F.; Torkiyan, L.; Ziyaei, A.; Saidi, M. R. J. Org. Chem. 2006, 71, 3634–3635;
(e) Azizi, N.; Aryanasab, F.; Saidi, M. R. Org. Lett. 2006, 8, 5275–5277; (f) Azizi, N.;
Aryanasab, F.; Tourkian, L.; Saidi, M. R. Synth. Commun. 2010, 41, 94–99.
15. Selected examples: (a) Tan, Y.; Jin, S.; Hamers, R. J. ACS Appl. Mater. Interfaces 2013, 5,
12975–12983; (b) Frederick, M. T.; Weiss, E. A. ACS Nano 2010, 4, 3195–3200; (c) Morf, P.;
Raimondi, F.; Nothofer, H.-G.; Schnyder, B.; Yasuda, A.; Wessels, J. M.; Jung, T. A.
Langmuir 2005, 22, 658–663; (d) Morf, P.; Ballav, N.; Putero, M.; von Wrochem, F.;
Wessels, J. M.; Jung, T. A. J. Phys. Chem. Lett. 2010, 1, 813–816.
16. (a) Moloy, K. G. Inorg. Chem. 1988, 27, 677–681; (b) Ma, H.; Wang, G.; Yee, G. T.;
Petersen, J. L.; Jensen, M. P. Inorg. Chim. Acta 2009, 362, 4563–4569.
17. Kumar, S.; Roy, N. N. Indian J. Eng. Mater. Sci. 1994, 1, 292–294.
18. (a) Krugmann, T.; Krugmann, M. GB Patent 877358, August 14, 1959; (b) Shaw, J. T. U.S.
Patent 3198829, August 3, 1965; (c) Van Duijn, S.; Durville, P. F. M.; Van Rosmalen, G. M.
EP Patent 116988, August 29, 1984.
19. Pratt, D. A.; DiLabio, G. A.; Valgimigli, L.; Pedulli, G. F.; Ingold, K. U. J. Am. Chem.
Soc. 2002, 124, 11085–11092; (b) Hanthorn, J. J.; Valgimigli, L.; Pratt, D. A. J. Am. Chem.

SYNTHESIS OF AROMATIC DITHIOCARBAMATES
2343
Soc. 2012, 134, 8306–8309; (c) Hanthorn, J. J.; Valgimigli, L.; Pratt, D. A. J. Org. Chem.
2012, 77, 6908–6916.
20. See Table S1 in the supporting information for details.
21. (a) Bellamy, F. D.; Ou, K. Tetrahedron Lett. 1984, 25, 839–842; (b) Bellamy, F. D.; Ou, K.
Tetrahedron Lett. 1985, 26, 1362.
22. (a) Shashin, S. S.; Emanuel, O. N.; Skibida, I. P. Russ. Chem. Bull. 1994, 43, 1646–1650;
(b) Shashin, S. S.; Emanuel, O. N.; Skibida, I. P. Russ. Chem. Bull. 1994, 43, 1651–1656.
´
23. Szostak, M.; Yao, L.; Aube, J. J. Am. Chem. Soc. 2010, 132, 2078–2084.
24. The hemiaminal intermediate may also exist as a dimer. See Adler, M.; Marsch, M.;
Nudelman, N. S.; Boche, G. Angew. Chem. Int. Ed. 1999, 38, 1261–1263.
25. Bordwell, F. G.; Branca, J. C.; Hughes, D. L.; Olmstead, W. N. J. Org. Chem. 1980, 45,
3305–3313.
26. Van Gaal, H. L. M.; Diesveld, J. W.; Pijpers, F. W.; Van der Linden, J. G. M. Inorg.
Chem. 1979, 18, 3251–3260.
27. Bereman, R. D.; Nalewajek, D. Inorg. Chem. 1978, 17, 1085–1087.