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Selective synthesis of organic sulfides or disulfides by solvent exchange from aryl halides and KSCN catalyzed by NiCl2·6H2O
Journal of Organometallic Chemistry 822 (2016) 112e117
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Journal of Organometallic Chemistry journal homepage: www.elsevier.com/locate/jorganchem
Selective synthesis of organic sulfides or disulfides by solvent exchange from aryl halides and KSCN catalyzed by NiCl2$6H2O Mohammad Abbasi*, Najmeh Nowrouzi, Hadis Latifi Department of Chemistry, Faculty of Sciences, Persian Gulf University, Bushehr, 75169, Iran
a r t i c l e i n f o
a b s t r a c t
Article history: Received 23 June 2016 Received in revised form 19 August 2016 Accepted 24 August 2016 Available online 26 August 2016
A method for selective synthesis of symmetric sulfides or disulfides from the reaction of aryl halides with KSCN by solvent exchange is introduced. Aryl halides were selectively converted to the symmetric disulfides or sulfides in high yields when they are treated with KSCN in the presence of NiCl2$6H2O and DMAP at 140 C in DMF or poly ethylene glycol (PEG-200) respectively. © 2016 Elsevier B.V. All rights reserved.
Keywords: Sulfides Disulfides Aryl halides KSCN NiCl2$6H2O
1. Introduction Aryl thioethers are important organosulfur compounds and widely exist in natural products, functional materials and pharmaceuticals [1,2]. In the polymer industry, aryl disulfides are necessary monomers for preparing high-performance engineering plastics [3]. In biological studies, some aryl disulfide molecules have shown herbicidal activity in some resistant types of plants [4]. The CeS bond formation between an aryl carbon and a sulfurtransfer reagent using transition metal catalysts [5e21] specially Cu and Ni is a powerful tool to synthesize aryl-sulfides and disulfides. In this line, aryl thioethers have been synthesized by treatment of aryl halides with thiols/CuI [22e24], thiols/NiCl2 [25,26], thioacetamide/CuI [27e30], thiourea/CuFe2O4 [31], KSCN/CuI [32], Na2S$9H2O/CuI [33,34], thiourea/CuO [35], thiourea/CuI [36], ethanethiolic acid/CuCl2 [37], dithiooxamide/CuI [38], KSCN/CuO [40e43], S/CuI [44,45] and KSCN/CuCl2 [39]. Similarly, symmetric aryl disulfides have been prepared by treatment of the corresponding aryl halides with thioacetamide/CuCl/KF/Al2O3 in DMF [46], Na2S/S/CuI in DMSO [34], S/CuO/in DMSO [47], With sulfur, potassium hydroxide in water [48], S/Mg or Al/CuI in DMF [30], S/ CuCl2/(n-Bu)4NF in H2O [49], potassium 5-methyl-1,3,4-oxadiazole-
* Corresponding author. E-mail addresses: [email protected], [email protected] (M. Abbasi). http://dx.doi.org/10.1016/j.jorganchem.2016.08.026 0022-328X/© 2016 Elsevier B.V. All rights reserved.
2-thiolate/CuCl in DMF [50], Potassium 5-Methyl-1,3,4-oxadiazole2-thiolate/NiCl2 in DMF-H2O [50], morpholin-4-iummorpholine-4carbo-dithioate/CuCl in DMF-H2O [51], and morpholin-4-ium morpholine-4-carbo-dithioate/NiCl2 in DMF [52]. 2. Results and discussion The synthesis of organosulfur derivatives using alkane thiols, in situ generated from the reaction of a sulfur transfer reagent and alkyl halides, has been the subject of our investigations in recent years [53e66]. In continuation, we were interested to develop our studies to synthesize of thiophenol derivatives using aryl halides. In this regard, our attention was focused on the reaction of aryl halides with KSCN and finally we succeeded to develop a method for selective synthesis of symmetric aryl-sulfides or disulfides using NiCl2$5H2O and DMAP by solvent exchange. At first, the model reaction of iodobenzene with KSCN in the presence of NiCl2$6H2O and DMAP was studied under various conditions. The results are presented in Table 1. It was found that, the reaction of iodobenzene with KSCN in DMF in the presence of NiCl2$6H2O and DMAP gives the corresponding symmetric disulfide as the sole product. Considering both reaction time and yield, the best result was obtained by using 30 mol% of NiCl2$6H2O and 40 mol% of DMAP at 140 C which gave the desired disulfide in 89% yield within 12 h (Table 1, entry 3). The similar reactions in the presence of lower amounts of DMAP or
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Table 1 Optimization of the reaction conditions for conversion of iodobenzene into the corresponding symmetric sulfide and disulfide.a
Entry
NiCl2$6H2O (mol%)
DMAP (mol%)
Solvent
T ( C)
t (h)
I (%)
II (%)
1 2 3b 4 5 6 7 8 9b 10 11 12 13 14 15
10 20 30 40 30 30 e 30 30 20 30 30 40 e 30
40 40 40 40 40 30 40 e 40 40 40 30 40 40 e
DMF DMF DMF DMF DMF DMF DMF DMF PEG-200 PEG-200 PEG-200 PEG-200 PEG-200 PEG-200 PEG-200
140 140 140 140 120 140 140 140 140 140 120 140 140 140 140
24 24 12 12 24 24 24 24 24 24 24 24 24 24 24
50 70 89 91 88 77 e trace e e e e e e
e e e e e e e 70 (88)c 55 51 57 73 e 27
a b c
Reaction conditions: Ph-I (2.0 mmol), KSCN (2.2 mmol), solvent (2 mL). The best reaction conditions. The reaction was carried out using 4.0 mmol of KSCN.
NiCl2$6H2O were uncompleted during 24 h and gave the desired product in lower yields (Table 1, entries 1, 2, 6). Also, the similar reaction conducted at 120 C proceeded to completion within 24 h to produce disulfide in 88% yield (Table 1, entry 5). The increasing amount of NiCl2$6H2O to 40 mol% did not result the better reaction time or yield (Table 1, entry 4). The reaction in the absence of NiCl2 (Table 1, entry 7) or DMAP (Table 1, entry 8) did not proceed efficiently. Next, the reaction of iodobenzene (2.0 mmol) with KSCN (2.2 mmol) in the presence of NiCl2 and DMAP in polyethylene glycol (PEG-200) was studied. Under these conditions, diphenyl sulfide was produced solely. As the best result, diphenyl sulfide was produced in 70% yield when a mixture of iodobenzene and KSCN in PEG-200 was treated with 30 mol% of NiCl2$6H2O and 40 mol% of DMAP at 140 C for 24 h (Table 1, entry 9). A little amount of the starting iodobenzene was also recovered unaltered after this period. Increasing the quantity of KSCN to 4.0 mmol led to an improvement in yield from 70% to 88% (Table 1, entry 9). To study the reaction in more detail and specially to understand the effect of solvent on the kind of reaction product, the interaction between NiCl2$6H2O catalyst and two solvents was separately studied by UV spectroscopy (Fig. 1). Two absorbance peaks for an aqueous solution of NiCl2 at around 400 and 700 nm were found at room temperature (I). When a solution of NiCl2$6H2O in DMF was heated at 140 C for 5 min, the starting clear solution became turbid and no absorbance peaks were found in its UV spectrum (II). Addition of KSCN to the mixture, did not cause any change in the UV spectrum (V), clearness and color of mixture. It can be concluded that, DMF plays an important role in reaction by formation of Ni(0) catalyst from Ni2þ solution. It should be noted that, the reduction of metal ions by DMF is wellknown and has been reported earlier [67e73]. However, when a clear solution of NiCl2$6H2O in PEG-200 was heated at 140 C for 5 min or 24 h and then subjected to UV spectroscopy, it showed the absorbance peaks of Ni2þ as shown in curve (III) of Fig 1. Its light green color was changed to dark green by adding KSCN to solution perhaps due to the formation of Ni(SCN)2 (curve IV). Now, it can be concluded that, the reaction output depends on the Ni catalyst oxidation state. It will be symmetric sulfide in the
presence of Ni2þ and symmetric disulfide in the presence of Ni(0) catalyst. In order to evaluate this hypothesis, a reaction between iodobenzene and KSCN in PEG in the presence of NiCl2$6H2O and a ligand which can reduce Ni2þ to Ni(0) could be helpful. In this line, a mixture of NiCl2$6H2O (30 mol%) and PPh3 (2.0 mmol) as a reducing ligand in PEG (2 mL) was prepared and stirred for 5 min at 140 C and subjected to UV spectroscopy. No absorbance peaks for NiCl2$6H2O were found in UV spectrum indicating complete reduction of starting Ni2þ to Ni(0) (curve VI of Fig. 1). Next, other reactants including iodobenzene (2.0 mmol) and KSCN (4 mmol) were added to the mixture and the stirring was resumed at 140 C. The reaction proceeded to completion within 24 h and gave diphenyl disulfide (not diphenyl sulfide) in 82% yield, confirming the dependence of reaction product with oxidation state of the Ni catalyst. Now, with more certainty, it could be claimed that the reaction of iodobenzene with KSCN gives sulfide and disulfide in the presence of Ni(II) and Ni(0), respectively. With these results in hand, the conversion of other aryl halides to the corresponding sulfides and disulfides under best reaction conditions based on the reaction time and yield was studied. The results are presented in Table 2. As the results show, aryl iodides and bromides have been converted to the symmetric sulfides and disulfides successfully. The conversion of p-chlorobenzonitrile as an aryl chloride to the corresponding sulfide or disulfide under reaction conditions was completely failed and unreacted chloride was recovered from the reaction mixture in near quantitative yield after 24 h. Also, o-iodo toluene as a more sterically hindered substrate remained intact under reaction conditions within 24 h. The actual mechanism of the protocol and the precise role of Ni catalyst are not clear at this stage. Nickel is found in one of several oxidation states, ranging from 1 to þ4 [75]. A handful of Ni(IV) complexes were synthesized, isolated or characterized in situ [76]. However, conversion of Ni(II) to Ni(IV) intermediate via oxidative addition and vice versa (a Ni(II)/Ni(IV) catalytic cycle) for many Ni catalyzed cross-coupling reactions has been previously proposed [77e91]. On the basis of those precedents, we hypothesized that a high-valent Ni(IV) intermediate might be involved in these Nicatalyzed protocols (Schemes 1 and 2).
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Fig. 1. UV spectra of NiCl2$6H2O I) in H2O, (II) in DMF; (III) in PEG; (IV) in PEG in the presence of KSCN; (V) in DMF in the presence of KSCN; (VI) and in PEG in the presence of PPh3.
As it is proposed in Scheme 1, Ni(SCN)2 is formed in the reaction mixture from the reaction of NiCl2 with KSCN which subsequently undergoes oxidative addition by insertion to aryl CeX bond to produce Ni(IV) intermediate (1). This step is followed by reductive elimination to give AreSCN and the Ni(II) catalyst as XeNieSCN (cycle A). The starting Ni(SCN)2 catalyst, is regenerated by reacting XeNieSCN with KSCN (cycle A). The in situ generated aryl mercaptane (from the Ni2þ catalyzed hydrolysis of ArSCN) (path B) undergoes arylation by second molecule of AreX to produce symmetric sulfide (cycle C). This process occurs through replacement of halide anion of intermediate (1) by thiolate followed by reductive elimination (cycle C). According to proposed mechanism presented in Scheme 2, Ni(0) inserts itself into CeX bond of aryl halide to produce AreNi(II)eX (cycle D). This intermediate is then converted to AreNi(II)eSCN by replacement of halide by thiocyanate ion. Reductive-elimination step, gives ArSCN along with regeneration of Ni(0) catalyst (cycle D). ArSeNi(II)eCN is then generated by insertion of Ni(0) into SeCN bond of in situ generated aryl thiocyanate (cycle E). The intermediate (3) is subsequently produced via oxidative addition of Ni (II) to the SeCN bond of the second molecule of RSeCN. Finally, the reductive elimination of this intermediate takes place to give the target symmetric disulfide and Ni(II) catalyst which in turn, undergoes reduction with DMF to regenerate Ni(0) catalyst. 3. Conclusion In summary, the first Ni-catalyzed coupling of aryl halides and KSCN was developed. Symmetric diaryl-sulfides or disulfides were synthesized selectively in high yields by treatment of aryl halides with KSCN in the presence of NiCl2$6H2O and DMAP in PEG-200 and DMF, respectively. A variety of aryl bromides and iodides bearing the electron donating and withdrawing groups were screened without difficulty. The method is simple, high yielding which tolerates a variety of functional groups on the aryl rings. 4. Experimental 4.1. General information Chemicals were purchased from Merck, Fluka and Acros
Chemical Companies. 1H NMR and 13C NMR spectra were recorded in CDCl3 using a Bruker Avance DPX instrument (1H NMR 250 MHz, 13 C NMR 62.5 MHz). Chemical shifts are reported in ppm (d) downfield from TMS. Coupling constants (J) are in Hertz. Elemental analyses were run on a Thermo Finnigan Flash EA-1112 series. Thinlayer chromatography was carried out on silica gel 254 analytical sheets obtained from Fluka. Column chromatography was performed on Merck Kiesel gel (230e270 mesh). 4.2. General procedure for synthesis of disulfides KSCN (2.2 mmol) was added to a magnetically stirred mixture of an aryl halide (2 mmol), NiCl2$6H2O (0.6 mmol, 30 mol%, 0.143 g) and DMAP (0.8 mmol, 40 mol%, 0.098 g) in DMF (2 mL) at 140 C. The stirring was continued until the starting halide was completely consumed. Next, the reaction mixture was diluted with water (1 mL) and extracted with 1:1 EtOAc/hexane (4 2 mL). The organic extracts were combined, concentrated and purified by chromatography on silica gel. The desired disulfides were produced in 79e92% yields (Table 2). 4.2.1. 1,2-Diphenyldisulfane (Table 2, entry 1) MP: 57e58 C (Lit. 59e60 C) [51]. 1H NMR (250 MHz, CDCl3): dH ¼ 7.53e7.49 (m, 4H), 7.34e7.23 (m, 6H) ppm. 13C NMR (62.9 MHz, CDCl3): dC ¼ 137.0, 129.4, 127.5, 127.1 ppm. Anal. Calcd for (C12H10S2): C, 66.02; H, 4.62; S, 29.37. Found: C, 66.15; H, 4.52; S, 29.33. 4.2.2. 1,2-Di-p-tolyldisulfane (Table 2, entry 3) MP: 43e45 C (Lit. 41e45 C) [74]. 1H NMR (250 MHz, CDCl3): dH ¼ 7.36 (d, J ¼ 8.6 Hz, 4H), 7.07 (d, J ¼ 8.6 Hz, 4H), 2.28 (s, 6H) ppm. 13 C NMR (62.9 MHz, CDCl3): dC ¼ 137.4, 134.0, 129.8, 128.6, 21.1 ppm. Anal. Calcd for (C14H14S2): C, 68.25; H, 5.73; S, 26.02. Found: C, 68.29; H, 5.83; S, 25.88. 4.2.3. 1,2-Bis(4-methoxyphenyl)disulfane (Table 2, entry 2) MP: 40e43 C (Lit. 41e43 C) [51]. 1H NMR (250 MHz, CDCl3): dH ¼ 7.34 (d, J ¼ 8.8 Hz, 4H), 6.89 (d, J ¼ 8.8 Hz, 4H), 3.83 (s, 6H) ppm. 13C NMR (62.9 MHz, CDCl3): dC ¼ 159.1, 132.8, 127.5, 114.7, 55.5 ppm. Anal. Calcd for (C14H14O2S2): C, 60.40; H, 5.07; S, 23.03. Found: C, 60.23; H, 5.17; S, 23.13.
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Table 2 Conversion of aryl halides into symmetric sulfides or disulfides.
Entry
AreX
Product ArSeSAra
AreSeArb
Time (h)
Yield (%) [Ref]
Time (h)
Yield (%) [Ref]
1
12
89 [30]
24
88 [44]
2
16
92 [30]
24
85 [44]
3
16
85 [30]
24
87 [44]
4
20
90 [30]
24
87 [31]
5
15
85 [47]
24
80 [44]
6
24
e
24
e
7
14
90 [30]
24
86 [44]
8
18
83 [30]
24
84 [44]
9
22
79 [30]
24
86 [31]
10
15
85 [74]
24
81 [44]
11
15
85 [47]
24
79 [44]
12
24
e
24
e
a b
Reaction conditions: ArX (2.0 mmol), KSCN (2.2 mmol), NiCl2$6H2O (30 mol%), DMAP (40 mol%), DMF (2 mL), 140 C. Reaction conditions: ArX (2.0 mmol), KSCN (4.0 mmol), NiCl2$6H2O (30 mol%), DMAP (40 mol%), PEG-200 (2 mL), 140 C.
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NiCl2.6H2O KSCN KCl KX
ArX
II
II
Ni(SCN)2
Ni(SCN)2 KSCN
ArSAr
ArX
II
X Ni
NCS SCN
NCS NCS
Ar
IV
Ni
IV
NCS
Ni
Ar X
NCS
(1)
X
NCS
(1) ArSH
Ni2+ Ni Ar
S
C
2+
N OH2
(2)
Ar SAr
HX
cycle A
ArSCN
IV
Ni
NH2
NH Ar
S
OH
O
S Ar
Ni2+
NH2 Ni2+
O
S Ar
cycle C
OH2 HOCONH2
path B Scheme 1. Proposed reaction pathway for the Ni(II)-catalyzed formation of symmetric sulfides.
4.3.2. Di-p-tolylsulfune (Table 2, entry 8) 1 H NMR (250 MHz, CDCl3): dH ¼ 7.20e7.16 (m, 4H), 6.77e6.71 (m, 4H), 2.33 (s, 6H) ppm. Anal. Calcd for (C14H14S): C, 78.46; H, 6.58; S, 14.96. Found: C, 78.61; H, 6.52; S, 14.87. 4.3.3. Bis(4-methoxyphenyl)sulfane (Table 2, entry 2) 1 H NMR (250 MHz, CDCl3): dH ¼ 7.38e7.30 (m, 4H), 6.78e6.74 (m, 4H), 3.72 (s, 6H) ppm. Anal. Calcd for (C14H14O2S): C, 68.26; H, 5.73; S, 13.02. Found: C, 68.16; H, 5.70; S, 13.15.
Scheme 2. Proposed reaction pathway for the Ni(0)-catalyzed formation of symmetric disulfides.
4.2.4. 1,2-Bis(4-nitrophenyl)disulfane ((Table 2, entry 5) MP: 174e176 C (Lit. 173e175 C) [51]. 1H NMR (250 MHz, CDCl3): dH ¼ 8.16e8.10 (m, 4H), 7.44e7.40 (m, 4H) ppm. Anal. Calcd for (C12H8N2O4S2): C, 46.75; H, 2.62; N, 9.09; S, 20.80. Found: C, 46.89; H, 2.73; N, 8.91; S, 20.65. 4.3. General procedure for synthesis of symmetric sulfides KSCN (4 mmol) was added to a magnetically stirred mixture of an aryl halide (2 mmol), NiCl2$6H2O (0.6 mmol, 30 mol%, 0.143 g) and DMAP (0.8 mmol, 40 mol%, 0.098 g) in PEG-200 (2 mL). the reaction mixture was stirred magnetically at 140 C for 24 h. Next, the reaction mixture was diluted with water (1 mL) and extracted with 1:1 EtOAc/hexane (4 2 mL). The organic extracts were combined, concentrated and purified by chromatography on silica gel. The desired symmetric sulfides were produced in 79e88% yields (Table 2). 4.3.1. Diphenylsulfane (Table 2, entry 7) 1 H NMR (250 MHz, CDCl3): dH ¼ 7.25e7.16 (m, 10H) ppm. Anal. Calcd for (C12H10S): C, 77.38; H, 5.41; S, 17.21. Found: C, 77.30; H, 5.35; S, 17.35.
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Journal of Organometallic Chemistry journal homepage: www.elsevier.com/locate/jorganchem
Selective synthesis of organic sulfides or disulfides by solvent exchange from aryl halides and KSCN catalyzed by NiCl2$6H2O Mohammad Abbasi*, Najmeh Nowrouzi, Hadis Latifi Department of Chemistry, Faculty of Sciences, Persian Gulf University, Bushehr, 75169, Iran
a r t i c l e i n f o
a b s t r a c t
Article history: Received 23 June 2016 Received in revised form 19 August 2016 Accepted 24 August 2016 Available online 26 August 2016
A method for selective synthesis of symmetric sulfides or disulfides from the reaction of aryl halides with KSCN by solvent exchange is introduced. Aryl halides were selectively converted to the symmetric disulfides or sulfides in high yields when they are treated with KSCN in the presence of NiCl2$6H2O and DMAP at 140 C in DMF or poly ethylene glycol (PEG-200) respectively. © 2016 Elsevier B.V. All rights reserved.
Keywords: Sulfides Disulfides Aryl halides KSCN NiCl2$6H2O
1. Introduction Aryl thioethers are important organosulfur compounds and widely exist in natural products, functional materials and pharmaceuticals [1,2]. In the polymer industry, aryl disulfides are necessary monomers for preparing high-performance engineering plastics [3]. In biological studies, some aryl disulfide molecules have shown herbicidal activity in some resistant types of plants [4]. The CeS bond formation between an aryl carbon and a sulfurtransfer reagent using transition metal catalysts [5e21] specially Cu and Ni is a powerful tool to synthesize aryl-sulfides and disulfides. In this line, aryl thioethers have been synthesized by treatment of aryl halides with thiols/CuI [22e24], thiols/NiCl2 [25,26], thioacetamide/CuI [27e30], thiourea/CuFe2O4 [31], KSCN/CuI [32], Na2S$9H2O/CuI [33,34], thiourea/CuO [35], thiourea/CuI [36], ethanethiolic acid/CuCl2 [37], dithiooxamide/CuI [38], KSCN/CuO [40e43], S/CuI [44,45] and KSCN/CuCl2 [39]. Similarly, symmetric aryl disulfides have been prepared by treatment of the corresponding aryl halides with thioacetamide/CuCl/KF/Al2O3 in DMF [46], Na2S/S/CuI in DMSO [34], S/CuO/in DMSO [47], With sulfur, potassium hydroxide in water [48], S/Mg or Al/CuI in DMF [30], S/ CuCl2/(n-Bu)4NF in H2O [49], potassium 5-methyl-1,3,4-oxadiazole-
* Corresponding author. E-mail addresses: [email protected], [email protected] (M. Abbasi). http://dx.doi.org/10.1016/j.jorganchem.2016.08.026 0022-328X/© 2016 Elsevier B.V. All rights reserved.
2-thiolate/CuCl in DMF [50], Potassium 5-Methyl-1,3,4-oxadiazole2-thiolate/NiCl2 in DMF-H2O [50], morpholin-4-iummorpholine-4carbo-dithioate/CuCl in DMF-H2O [51], and morpholin-4-ium morpholine-4-carbo-dithioate/NiCl2 in DMF [52]. 2. Results and discussion The synthesis of organosulfur derivatives using alkane thiols, in situ generated from the reaction of a sulfur transfer reagent and alkyl halides, has been the subject of our investigations in recent years [53e66]. In continuation, we were interested to develop our studies to synthesize of thiophenol derivatives using aryl halides. In this regard, our attention was focused on the reaction of aryl halides with KSCN and finally we succeeded to develop a method for selective synthesis of symmetric aryl-sulfides or disulfides using NiCl2$5H2O and DMAP by solvent exchange. At first, the model reaction of iodobenzene with KSCN in the presence of NiCl2$6H2O and DMAP was studied under various conditions. The results are presented in Table 1. It was found that, the reaction of iodobenzene with KSCN in DMF in the presence of NiCl2$6H2O and DMAP gives the corresponding symmetric disulfide as the sole product. Considering both reaction time and yield, the best result was obtained by using 30 mol% of NiCl2$6H2O and 40 mol% of DMAP at 140 C which gave the desired disulfide in 89% yield within 12 h (Table 1, entry 3). The similar reactions in the presence of lower amounts of DMAP or
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113
Table 1 Optimization of the reaction conditions for conversion of iodobenzene into the corresponding symmetric sulfide and disulfide.a
Entry
NiCl2$6H2O (mol%)
DMAP (mol%)
Solvent
T ( C)
t (h)
I (%)
II (%)
1 2 3b 4 5 6 7 8 9b 10 11 12 13 14 15
10 20 30 40 30 30 e 30 30 20 30 30 40 e 30
40 40 40 40 40 30 40 e 40 40 40 30 40 40 e
DMF DMF DMF DMF DMF DMF DMF DMF PEG-200 PEG-200 PEG-200 PEG-200 PEG-200 PEG-200 PEG-200
140 140 140 140 120 140 140 140 140 140 120 140 140 140 140
24 24 12 12 24 24 24 24 24 24 24 24 24 24 24
50 70 89 91 88 77 e trace e e e e e e
e e e e e e e 70 (88)c 55 51 57 73 e 27
a b c
Reaction conditions: Ph-I (2.0 mmol), KSCN (2.2 mmol), solvent (2 mL). The best reaction conditions. The reaction was carried out using 4.0 mmol of KSCN.
NiCl2$6H2O were uncompleted during 24 h and gave the desired product in lower yields (Table 1, entries 1, 2, 6). Also, the similar reaction conducted at 120 C proceeded to completion within 24 h to produce disulfide in 88% yield (Table 1, entry 5). The increasing amount of NiCl2$6H2O to 40 mol% did not result the better reaction time or yield (Table 1, entry 4). The reaction in the absence of NiCl2 (Table 1, entry 7) or DMAP (Table 1, entry 8) did not proceed efficiently. Next, the reaction of iodobenzene (2.0 mmol) with KSCN (2.2 mmol) in the presence of NiCl2 and DMAP in polyethylene glycol (PEG-200) was studied. Under these conditions, diphenyl sulfide was produced solely. As the best result, diphenyl sulfide was produced in 70% yield when a mixture of iodobenzene and KSCN in PEG-200 was treated with 30 mol% of NiCl2$6H2O and 40 mol% of DMAP at 140 C for 24 h (Table 1, entry 9). A little amount of the starting iodobenzene was also recovered unaltered after this period. Increasing the quantity of KSCN to 4.0 mmol led to an improvement in yield from 70% to 88% (Table 1, entry 9). To study the reaction in more detail and specially to understand the effect of solvent on the kind of reaction product, the interaction between NiCl2$6H2O catalyst and two solvents was separately studied by UV spectroscopy (Fig. 1). Two absorbance peaks for an aqueous solution of NiCl2 at around 400 and 700 nm were found at room temperature (I). When a solution of NiCl2$6H2O in DMF was heated at 140 C for 5 min, the starting clear solution became turbid and no absorbance peaks were found in its UV spectrum (II). Addition of KSCN to the mixture, did not cause any change in the UV spectrum (V), clearness and color of mixture. It can be concluded that, DMF plays an important role in reaction by formation of Ni(0) catalyst from Ni2þ solution. It should be noted that, the reduction of metal ions by DMF is wellknown and has been reported earlier [67e73]. However, when a clear solution of NiCl2$6H2O in PEG-200 was heated at 140 C for 5 min or 24 h and then subjected to UV spectroscopy, it showed the absorbance peaks of Ni2þ as shown in curve (III) of Fig 1. Its light green color was changed to dark green by adding KSCN to solution perhaps due to the formation of Ni(SCN)2 (curve IV). Now, it can be concluded that, the reaction output depends on the Ni catalyst oxidation state. It will be symmetric sulfide in the
presence of Ni2þ and symmetric disulfide in the presence of Ni(0) catalyst. In order to evaluate this hypothesis, a reaction between iodobenzene and KSCN in PEG in the presence of NiCl2$6H2O and a ligand which can reduce Ni2þ to Ni(0) could be helpful. In this line, a mixture of NiCl2$6H2O (30 mol%) and PPh3 (2.0 mmol) as a reducing ligand in PEG (2 mL) was prepared and stirred for 5 min at 140 C and subjected to UV spectroscopy. No absorbance peaks for NiCl2$6H2O were found in UV spectrum indicating complete reduction of starting Ni2þ to Ni(0) (curve VI of Fig. 1). Next, other reactants including iodobenzene (2.0 mmol) and KSCN (4 mmol) were added to the mixture and the stirring was resumed at 140 C. The reaction proceeded to completion within 24 h and gave diphenyl disulfide (not diphenyl sulfide) in 82% yield, confirming the dependence of reaction product with oxidation state of the Ni catalyst. Now, with more certainty, it could be claimed that the reaction of iodobenzene with KSCN gives sulfide and disulfide in the presence of Ni(II) and Ni(0), respectively. With these results in hand, the conversion of other aryl halides to the corresponding sulfides and disulfides under best reaction conditions based on the reaction time and yield was studied. The results are presented in Table 2. As the results show, aryl iodides and bromides have been converted to the symmetric sulfides and disulfides successfully. The conversion of p-chlorobenzonitrile as an aryl chloride to the corresponding sulfide or disulfide under reaction conditions was completely failed and unreacted chloride was recovered from the reaction mixture in near quantitative yield after 24 h. Also, o-iodo toluene as a more sterically hindered substrate remained intact under reaction conditions within 24 h. The actual mechanism of the protocol and the precise role of Ni catalyst are not clear at this stage. Nickel is found in one of several oxidation states, ranging from 1 to þ4 [75]. A handful of Ni(IV) complexes were synthesized, isolated or characterized in situ [76]. However, conversion of Ni(II) to Ni(IV) intermediate via oxidative addition and vice versa (a Ni(II)/Ni(IV) catalytic cycle) for many Ni catalyzed cross-coupling reactions has been previously proposed [77e91]. On the basis of those precedents, we hypothesized that a high-valent Ni(IV) intermediate might be involved in these Nicatalyzed protocols (Schemes 1 and 2).
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Fig. 1. UV spectra of NiCl2$6H2O I) in H2O, (II) in DMF; (III) in PEG; (IV) in PEG in the presence of KSCN; (V) in DMF in the presence of KSCN; (VI) and in PEG in the presence of PPh3.
As it is proposed in Scheme 1, Ni(SCN)2 is formed in the reaction mixture from the reaction of NiCl2 with KSCN which subsequently undergoes oxidative addition by insertion to aryl CeX bond to produce Ni(IV) intermediate (1). This step is followed by reductive elimination to give AreSCN and the Ni(II) catalyst as XeNieSCN (cycle A). The starting Ni(SCN)2 catalyst, is regenerated by reacting XeNieSCN with KSCN (cycle A). The in situ generated aryl mercaptane (from the Ni2þ catalyzed hydrolysis of ArSCN) (path B) undergoes arylation by second molecule of AreX to produce symmetric sulfide (cycle C). This process occurs through replacement of halide anion of intermediate (1) by thiolate followed by reductive elimination (cycle C). According to proposed mechanism presented in Scheme 2, Ni(0) inserts itself into CeX bond of aryl halide to produce AreNi(II)eX (cycle D). This intermediate is then converted to AreNi(II)eSCN by replacement of halide by thiocyanate ion. Reductive-elimination step, gives ArSCN along with regeneration of Ni(0) catalyst (cycle D). ArSeNi(II)eCN is then generated by insertion of Ni(0) into SeCN bond of in situ generated aryl thiocyanate (cycle E). The intermediate (3) is subsequently produced via oxidative addition of Ni (II) to the SeCN bond of the second molecule of RSeCN. Finally, the reductive elimination of this intermediate takes place to give the target symmetric disulfide and Ni(II) catalyst which in turn, undergoes reduction with DMF to regenerate Ni(0) catalyst. 3. Conclusion In summary, the first Ni-catalyzed coupling of aryl halides and KSCN was developed. Symmetric diaryl-sulfides or disulfides were synthesized selectively in high yields by treatment of aryl halides with KSCN in the presence of NiCl2$6H2O and DMAP in PEG-200 and DMF, respectively. A variety of aryl bromides and iodides bearing the electron donating and withdrawing groups were screened without difficulty. The method is simple, high yielding which tolerates a variety of functional groups on the aryl rings. 4. Experimental 4.1. General information Chemicals were purchased from Merck, Fluka and Acros
Chemical Companies. 1H NMR and 13C NMR spectra were recorded in CDCl3 using a Bruker Avance DPX instrument (1H NMR 250 MHz, 13 C NMR 62.5 MHz). Chemical shifts are reported in ppm (d) downfield from TMS. Coupling constants (J) are in Hertz. Elemental analyses were run on a Thermo Finnigan Flash EA-1112 series. Thinlayer chromatography was carried out on silica gel 254 analytical sheets obtained from Fluka. Column chromatography was performed on Merck Kiesel gel (230e270 mesh). 4.2. General procedure for synthesis of disulfides KSCN (2.2 mmol) was added to a magnetically stirred mixture of an aryl halide (2 mmol), NiCl2$6H2O (0.6 mmol, 30 mol%, 0.143 g) and DMAP (0.8 mmol, 40 mol%, 0.098 g) in DMF (2 mL) at 140 C. The stirring was continued until the starting halide was completely consumed. Next, the reaction mixture was diluted with water (1 mL) and extracted with 1:1 EtOAc/hexane (4 2 mL). The organic extracts were combined, concentrated and purified by chromatography on silica gel. The desired disulfides were produced in 79e92% yields (Table 2). 4.2.1. 1,2-Diphenyldisulfane (Table 2, entry 1) MP: 57e58 C (Lit. 59e60 C) [51]. 1H NMR (250 MHz, CDCl3): dH ¼ 7.53e7.49 (m, 4H), 7.34e7.23 (m, 6H) ppm. 13C NMR (62.9 MHz, CDCl3): dC ¼ 137.0, 129.4, 127.5, 127.1 ppm. Anal. Calcd for (C12H10S2): C, 66.02; H, 4.62; S, 29.37. Found: C, 66.15; H, 4.52; S, 29.33. 4.2.2. 1,2-Di-p-tolyldisulfane (Table 2, entry 3) MP: 43e45 C (Lit. 41e45 C) [74]. 1H NMR (250 MHz, CDCl3): dH ¼ 7.36 (d, J ¼ 8.6 Hz, 4H), 7.07 (d, J ¼ 8.6 Hz, 4H), 2.28 (s, 6H) ppm. 13 C NMR (62.9 MHz, CDCl3): dC ¼ 137.4, 134.0, 129.8, 128.6, 21.1 ppm. Anal. Calcd for (C14H14S2): C, 68.25; H, 5.73; S, 26.02. Found: C, 68.29; H, 5.83; S, 25.88. 4.2.3. 1,2-Bis(4-methoxyphenyl)disulfane (Table 2, entry 2) MP: 40e43 C (Lit. 41e43 C) [51]. 1H NMR (250 MHz, CDCl3): dH ¼ 7.34 (d, J ¼ 8.8 Hz, 4H), 6.89 (d, J ¼ 8.8 Hz, 4H), 3.83 (s, 6H) ppm. 13C NMR (62.9 MHz, CDCl3): dC ¼ 159.1, 132.8, 127.5, 114.7, 55.5 ppm. Anal. Calcd for (C14H14O2S2): C, 60.40; H, 5.07; S, 23.03. Found: C, 60.23; H, 5.17; S, 23.13.
M. Abbasi et al. / Journal of Organometallic Chemistry 822 (2016) 112e117
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Table 2 Conversion of aryl halides into symmetric sulfides or disulfides.
Entry
AreX
Product ArSeSAra
AreSeArb
Time (h)
Yield (%) [Ref]
Time (h)
Yield (%) [Ref]
1
12
89 [30]
24
88 [44]
2
16
92 [30]
24
85 [44]
3
16
85 [30]
24
87 [44]
4
20
90 [30]
24
87 [31]
5
15
85 [47]
24
80 [44]
6
24
e
24
e
7
14
90 [30]
24
86 [44]
8
18
83 [30]
24
84 [44]
9
22
79 [30]
24
86 [31]
10
15
85 [74]
24
81 [44]
11
15
85 [47]
24
79 [44]
12
24
e
24
e
a b
Reaction conditions: ArX (2.0 mmol), KSCN (2.2 mmol), NiCl2$6H2O (30 mol%), DMAP (40 mol%), DMF (2 mL), 140 C. Reaction conditions: ArX (2.0 mmol), KSCN (4.0 mmol), NiCl2$6H2O (30 mol%), DMAP (40 mol%), PEG-200 (2 mL), 140 C.
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NiCl2.6H2O KSCN KCl KX
ArX
II
II
Ni(SCN)2
Ni(SCN)2 KSCN
ArSAr
ArX
II
X Ni
NCS SCN
NCS NCS
Ar
IV
Ni
IV
NCS
Ni
Ar X
NCS
(1)
X
NCS
(1) ArSH
Ni2+ Ni Ar
S
C
2+
N OH2
(2)
Ar SAr
HX
cycle A
ArSCN
IV
Ni
NH2
NH Ar
S
OH
O
S Ar
Ni2+
NH2 Ni2+
O
S Ar
cycle C
OH2 HOCONH2
path B Scheme 1. Proposed reaction pathway for the Ni(II)-catalyzed formation of symmetric sulfides.
4.3.2. Di-p-tolylsulfune (Table 2, entry 8) 1 H NMR (250 MHz, CDCl3): dH ¼ 7.20e7.16 (m, 4H), 6.77e6.71 (m, 4H), 2.33 (s, 6H) ppm. Anal. Calcd for (C14H14S): C, 78.46; H, 6.58; S, 14.96. Found: C, 78.61; H, 6.52; S, 14.87. 4.3.3. Bis(4-methoxyphenyl)sulfane (Table 2, entry 2) 1 H NMR (250 MHz, CDCl3): dH ¼ 7.38e7.30 (m, 4H), 6.78e6.74 (m, 4H), 3.72 (s, 6H) ppm. Anal. Calcd for (C14H14O2S): C, 68.26; H, 5.73; S, 13.02. Found: C, 68.16; H, 5.70; S, 13.15.
Scheme 2. Proposed reaction pathway for the Ni(0)-catalyzed formation of symmetric disulfides.
4.2.4. 1,2-Bis(4-nitrophenyl)disulfane ((Table 2, entry 5) MP: 174e176 C (Lit. 173e175 C) [51]. 1H NMR (250 MHz, CDCl3): dH ¼ 8.16e8.10 (m, 4H), 7.44e7.40 (m, 4H) ppm. Anal. Calcd for (C12H8N2O4S2): C, 46.75; H, 2.62; N, 9.09; S, 20.80. Found: C, 46.89; H, 2.73; N, 8.91; S, 20.65. 4.3. General procedure for synthesis of symmetric sulfides KSCN (4 mmol) was added to a magnetically stirred mixture of an aryl halide (2 mmol), NiCl2$6H2O (0.6 mmol, 30 mol%, 0.143 g) and DMAP (0.8 mmol, 40 mol%, 0.098 g) in PEG-200 (2 mL). the reaction mixture was stirred magnetically at 140 C for 24 h. Next, the reaction mixture was diluted with water (1 mL) and extracted with 1:1 EtOAc/hexane (4 2 mL). The organic extracts were combined, concentrated and purified by chromatography on silica gel. The desired symmetric sulfides were produced in 79e88% yields (Table 2). 4.3.1. Diphenylsulfane (Table 2, entry 7) 1 H NMR (250 MHz, CDCl3): dH ¼ 7.25e7.16 (m, 10H) ppm. Anal. Calcd for (C12H10S): C, 77.38; H, 5.41; S, 17.21. Found: C, 77.30; H, 5.35; S, 17.35.
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