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Communication

Modification of 1-Hexene Vinylidene Dimer into Primary and Tertiary Alkanethiols

by
Pavel V. Kovyazin
*,
Almira Kh. Bikmeeva
,
Eldar R. Palatov
and
Lyudmila V. Parfenova
Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, Prospekt Oktyabrya, 141, 450075 Ufa, Russia
*
Author to whom correspondence should be addressed.
Molbank 2022, 2022(2), M1379; https://doi.org/10.3390/M1379
Submission received: 28 April 2022 / Revised: 30 May 2022 / Accepted: 31 May 2022 / Published: 4 June 2022
(This article belongs to the Section Organic Synthesis)
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Abstract

:
Aliphatic thiols are in high demand in materials chemistry. Herein, a synthesis of thio-derivatives of 1-hexene vinylidene dimer is described. The approach, based on a hydroalumination reaction with further replacement of the organoaluminum function with sulfur using thiourea or dimethyl disulfide, provides anti-Markovnikov products, 2-butyloctane-1-thiol or 5-(methylsulfanylmethyl)undecane, in moderate yields. The reaction of a vinylidene dimer with phosphorus pentasulfide in the presence of catalytic amounts of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) selectively gives the Markovnikov product, 5-methylundecane-5-thiol, with a yield of up to 77%.

1. Introduction

The focus on the development of methods for the synthesis of alkyl-substituted thiols Alk-SH is driven by the prospect of using these products as extractants of noble metals [1,2] and components of self-assembled monolayers [3,4,5], including the preparation and stabilization of AuNPs [6,7]. It was noted that the electronic and steric factors of the S-ligand largely determine the properties of the resulting nanoparticles [8].
The literature describes a number of methods for the synthesis of aliphatic thiols from alkenes, alcohols, halogen derivatives, etc. [9,10,11,12,13]. Nevertheless, the high demand for this class of compounds has led to the search for new structures and approaches to their synthesis. Of particular interest is the utilization of terminal alkene dimers with a long branched hydrocarbon chain as an aliphatic component of thiols [14,15], which is viewed as a promising approach in materials chemistry. The present work is aimed at the study of 1-hexene dimer thiolation via hydrometalation and thiolene chemistry using P2S5 as a reagent.

2. Results and Discussion

Previously, the conditions for the chemoselective synthesis of alkene dimers in systems based on zirconocenes, alkylalanes, and Al- or B-containing activators were determined [16,17,18,19,20,21]. It was shown that 1-hexene undergoes dimerization to give vinylidene dimer with a high yield and selectivity in the presence of a catalytic system of Cp2ZrCl2–HAlBui2–MMAO-12 at a ratio of [Zr]:[Al]:[MMAO-12] = 1:3:30 and a temperature 60 °C (Scheme 1) [19].
Further, we searched for efficient methods of vinylidene dimer thiolation. Initially, a variant of the 1-hexene dimer functionalization by thermal hydroalumination and the subsequent conversion of the resulting organoaluminum compound into thio-derivatives was considered (Scheme 2, routes A and B). The heating between 60 and 80 °C of an equimolar mixture of vinylidene dimer 2 and HAlBui2 in toluene for 3 h gave a hydroalumination product 3 with a yield of 90–95% (determined by GC/MS of hydrolysis or deuterolysis products of the reaction mixture). As a result of bubbling the reaction mixture with oxygen for 1 h with additional stirring in an O2 atmosphere for 3 h, alcohol 4 was obtained with a yield of 80–89% (route A). The reaction of 4 with P2S5 in toluene gave product 6 with a very low yield (Table 1, entry 1). Further transformations of 4 were carried out in accordance with the method described in [12]. Thus, the alcohol 4 was converted into tosylate 5. The reaction of 5 with thiourea in ethanol for 8 h provided thiol 6 with a yield of up to 41% (entry 2).
As an alternative method, the replacement of an aluminum atom in the organoaluminum compound with a sulfur atom was considered [22,23]. For this purpose, the reactions of OAC 3, obtained in situ, with dimethyl disulfide (MeS)2, thiourea (H2N)2C=S, and P2S5 were studied (route B). The reactions of 3 with (H2N)2C=S and P2S5, followed by thehydrolysis of the reaction mixture, gave the thiolated product 6 in a yield of no more than 5% (entries 3, 4). OAC 3 was reacted with Me2S2 at room temperature for 16 h to give thioether R-SMe (7) with a yield of up to 63% (entry 5).
The further search for synthetic ways to S-modify alkene dimers led to the development of a method based on the reaction of vinylidene dimer with P2S5 at a ratio of 1:1 in the presence of 0.8 mol% TEMPO (entries 7–16). In this case, the Markovnikov product, tertiary thiol 8, was formed with a yield of up to 77% (entry 7). Reducing the amount of P2S5 to 0.5 eq. or using other solvents decreases the product yield.
In summary, studied various methods for the preparation of alkene dimer thio-derivatives. Dimer hydrometalation followed by reactions of oxidized product or OAC with thiourea or dimethyl disulfide provides anti-Markovnikov products, alkylthiol or methylalkyl sulfide, in moderate yields. The reaction of 1-hexene dimer with P2S5 in the presence of catalytic amounts of TEMPO leads to the selective formation of tertiary thiol, with yields of up to 77%.

3. Materials and Methods

General Procedures

All operations for organometallic compounds were performed under argon, according to Schlenk technique. The solvents (CHCl3 and CH2Cl2) were distilled from P2O5 immediately prior to use. The solvents (toluene, hexane, THF, and Et2O) were distilled from CaH2 immediately prior to use. Commercially available P2S5 (99%, Merck KGaA, Darmstadt, Germany), (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) (98%, Acros, Geel, Belgium), Me2S2 (99%, Acros), HAlBui2 (99%, Merck), (H2N)2C=S (99%, Acros), TsCl (99%, Acros), and Et3N (99%, Merck) were used. CAUTION: pyrophoric nature of aluminum alkyl and hydride compounds means that they require special safety precautions in their handling.
The 1H and 13C NMR spectra were recorded on a Bruker AVANCE-400 spectrometer (400.13 MHz (1H), 100.62 MHz (13C)) (Bruker, Rheinstetten, Germany). CDCl3 was employed as the solvent and the internal standard. 1D and 2D NMR spectra (COSY HH, HSQC, HMBC) were recorded using standard Bruker pulse sequences.
The products were analyzed using a gas chromatograph-mass spectrometer GCMS-QP2010 Ultra (Shimadzu, Tokyo, Japan) equipped with the GC-2010 Plus chromatograph (Shimadzu, Tokyo, Japan), TD-20 thermal desorber (Shimadzu, Tokyo, Japan), and an ultrafast quadrupole mass-selective detector (Shimadzu, Tokyo, Japan).
Synthesis of Compound4. A flask with a magnetic stirrer was filled under argon with 1.0 g (5.6 mmol) of dimer 2, 1.0 mL (5.6 mmol) of HAlBui2, and 2 mL of toluene. The reaction was carried out through stirring at 60 °C. After 3 h, the reaction mixture was cooled to 0 °C and dry oxygen was passed through the mixture for 1 h. The resultant mixture was further stirred in oxygen atmosphere for 3 h, and then treated with 10% HCl and extracted with CH2Cl2. The organic layer was dried over Na2SO4. The products were analyzed by GC/MS. The crude product was air-dried and purified by flash chromatography over silica gel (0.060–0.200 mm 60 A, eluent: petroleum ether/Et2O = 7/1). Yield 0.92 g (89%). δH (400 MHz, CDCl3) 0.79–1.02 (m, 6H, CH3); 1.16–1.44 (m, 16H, CH2); 1.38–1.55 (m, 1H, CH); 3.55 (d, 2H, J = 5.3 Hz, CH2OH) (Figure S1). δC (100.13 MHz, CDCl3) 14.1 (CH3); 22.7, 23.1, 26.9, 29.1, 29.7, 31.9 (CH2); 30.6, 30.9 (CH2CH); 40.5, (CH); 65.7 (CH2OH) (Figure S2). m/z (I, %) [M-H2O] = 168 (2), 154 (2), 140 (3), 139 (1), 126 (5), 125 (7), 124 (1), 113 (4), 112 (8), 111 (22), 110 (4), 99 (10), 98 (12), 97 (20), 96 (5), 85 (36), 84 (21), 83 (22), 71 (46), 70 (29), 65 (36), 57 (100).
Synthesis of Compound 5. A flask with a magnetic stirrer was filled under argon at 0 °C with 0.9 g (4.9 mmol) of 2, 1.7 g (5.4 mmol) of TsCl, 25 mL of dry THF and 1.0 mL (7.4 mmol) of freshly distilled Et3N. The reaction was carried out through stirring at 20 °C for 8 h, and then treated with 10% HCl and extracted with CH2Cl2. The organic layer was dried over Na2SO4, filtered, and concentrated to give 1.51 g (90%) of tosylate 5. δH (400 MHz, CDCl3) 0.76–0.96 (m, 6H, CH3); 0.98–1.68 (m, 16H, CH2); 1.50–1.65 (m, 1H, CH); 3.91 (d, 2H, J = 5.1 Hz, CH2OH), 2.48 (s, 3H, CH3Ph), 7.34 (d, 2H, J = 7.8 Hz, Ph), 7.78 (d, 2H, J = 7.8 Hz, Ph) (Figure S3). δC (100.13 MHz, CDCl3) 14.0, 14.1 (CH3); 22.6, 22.8, 26.4, 28.6, 29.5, 31.7 (CH2); 30.3, 30.6 (CH2CH); 37.6 (CH); 72.8 (CH2OH); 21.6 (CH3Ph); 129.8, 130.3, 133.1, 146.9 (Ph) (Figure S4). m/z (I, %) [M-O2SPhMe] = 187 (3), 173 (31), 172 (10), 169 (7), 168 (46), 155 (31), 140 (11), 126 (22), 125 (21), 112 (28), 111 (71), 110 (14), 98 (45), 97 (42), 92 (26), 91 (100).
Synthesis of Compound 6. Thiourea (0.4 g, 5.4 mmol) was added in portions to a solution of 1.5 g (4.4 mmol) tosylate 5 in ethanol. The reaction was carried out through stirring at room temperature for 8 h, and then treated with water and extracted with CH2Cl2. The organic layer was dried over Na2SO4, filtered, concentrated, and purified by flash chromatography over silica gel (0.060–0.200 mm 60 A, eluent: petroleum ether). Yield 0.37 g (41%). The NMR data corresponded to those reported in the literature [14]. m/z (I, %) [M] = 202 (12), 203 (2), 168 (15), 145 (2), 140 (4), 126 (5), 125 (10), 117 (2), 113 (4), 112 (7), 111 (20), 110 (5), 99 (8), 98 (11), 97 (17), 96 (4), 85 (31), 84 (17), 83 (22), 82 (7), 71 (45), 70 (27), 69 (37), 57 (100).
Synthesis of Compound 7. A flask with a magnetic stirrer was filled under argon with 200 mg (1.2 mmol) of dimer 2, 0.2 mL (1.2 mmol) of HAlBui2, and 2 mL of toluene. The reaction was carried out through stirring at 60 °C. After 3 h, 0.1–0.3 mL (1.2–3.6 mmol) of Me2S2 was added to the reaction mixture at 0 °C and stirred for 16 h at 20 °C. The mixture was then decomposed with 10% HCl and extracted with CH2Cl2. The organic layer was dried over Na2SO4. The products were analyzed by GC/MS. The crude product was air-dried and purified by flash chromatography over silica gel (0.060–0.200 mm 60 A, eluent: petroleum ether) to give 162 mg (63%) of 7. δH (400 MHz, CDCl3) 0.790–0.99 (6H, CH3); 2.10 (s, 3H, CH3S); 2.49 (d, 2H, J = 6.3 Hz, CH3SCH2CH), 1.46–1.53 (1H, CH), 1.04–1.51 (16H, CH2) (Figure S5). δC (100.13 MHz, CDCl3) 14.1 (CH3); 16.3 (CH3S) 22.7, 23.0, 26.6, 28.8, 29.7, 31.9 (CH2); 32.9 (CHCH2(CH2)2CH3); 33.2 (CH3(CH2)4CH2CH); 37.6 (CH); 39.6 (CHCH2SCH3) (Figure S6). m/z (I, %) [M] = 216 (65), 218 (4), 217 (11), 203 (1), 202 (4), 201 (25), 169 (1), 168 (11), 159 (3), 145 (1), 131 (3), 127 (1), 126 (11), 125 (15), 124 (3), 112 (16), 111 (45), 110 (11), 99 (8), 98 (30), 97 (39), 96 (10), 85 (21), 84 (38), 83 (45), 82 (13), 81 (6), 71 (33), 70 (61), 69 (67), 62 (21), 61 (54), 57 (87), 56 (65), 55 (76), 43 (100).
Synthesis of Compound 8. A flask with a magnetic stirrer was filled under argon with 264 mg (1.2 mmol) of P2S5, 200 mg (1.2 mmol) of dimer 2, 1.5 mg (0.0095 mmol) of TEMPO, and 2 mL of solvents (toluene, hexane, CHCl3, CH2Cl2, THF, Et2O, H2O, and EtOH). The reaction was carried out with stirring at temperatures between 20 and 80 °C. After 8–24 h, the reaction mixture were decomposed with 10% HCl at 0 °C. Products were extracted with CH2Cl2, and the organic layer was dried over Na2SO4. The products were analyzed by GC/MS. The crude product was-air dried and purified by flash chromatography over silica gel (0.060–0.200 mm 60 A, eluent: petroleum ether) to give 186 mg (77%) of 8. δH (400 MHz, CDCl3) 0.79–1.01 (6H, CH3); 1.30–1.69 (4H, CH2CCH2); 0.99–1.69 (15H, CH2, CCH3) (Figure S7). δC (100.13 MHz, CDCl3) 14.1 (CH3); 22.7, 23.1, 24.74, 27, 30.3, 31.8 (CH2); 29.7 (CH3C); 44.05, 44.33 (CH2CCH2); 48.3 (CSH) (Figure S8). m/z (I, %) [M] = 202 (3), 170 (4), 145 (9), 127 (5), 126 (2), 118 (1), 117 (17), 116 (2), 114 (1), 113 (13), 112 (2), 111 (13), 110 (1), 99 (20), 98 (4), 97 (4), 87 (2), 86 (3), 85 (44), 84 (6),83 (27), 82 (2), 81 (2), 79 (2), 77 (1), 75 (5), 74 (8), 72 (4), 71 (64), 70 (15), 69 (47), 68 (3), 67 (5), 65 (1), 61 (12), 59 (6), 58 (5), 57 (100).

Supplementary Materials

The following supporting information at: Figures S1–S8: NMR spectra of 4, 5, 7, 8.

Author Contributions

Conceptualization, L.V.P.; methodology, P.V.K. and A.K.B.; validation, L.V.P., P.V.K.; formal analysis, P.V.K., A.K.B., and E.R.P.; investigation, P.V.K., A.K.B., and E.R.P.; resources, P.V.K. and L.V.P.; data curation, P.V.K. and L.V.P.; writing—original draft preparation, P.V.K. and L.V.P.; writing—review and editing, L.V.P.; visualization, P.V.K.; supervision, L.V.P.; project administration, P.V.K.; funding acquisition, P.V.K. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Russian Science Foundation, grant number 19-73-10122.

Data Availability Statement

Data are contained within the article.

Acknowledgments

The authors acknowledge the use of equipment in the Agidel Collective Use Centre at the Institute of Petrochemistry and Catalysis of RAS, FMRS-2022-0081.

Conflicts of Interest

The authors declare no conflict of interest.

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Molbank 2022 m1379 sch001 550
Scheme 1. Dimerization of 1-hexene in the presence of catalytic system of Cp2ZrCl2–HAlBui2–MMAO-12.
Scheme 1. Dimerization of 1-hexene in the presence of catalytic system of Cp2ZrCl2–HAlBui2–MMAO-12.
Molbank 2022 m1379 sch001
Molbank 2022 m1379 sch002 550
Scheme 2. Methods for 1-hexene dimer thiolation.
Scheme 2. Methods for 1-hexene dimer thiolation.
Molbank 2022 m1379 sch002
Table
Table 1. Conditions for the synthesis of S-functionalized derivatives of dimer 2.
Table 1. Conditions for the synthesis of S-functionalized derivatives of dimer 2.
EntrySubstrateOACSolventThiolation ReagentSubstrate:HAlBu i2:Reagentt, °CTime, hProduct, Yield
14 tolueneP2S51:0:160166, <3%
25 EtOH(H2N)2C=S1:0:16086, 41%
32HAlBui2toluene(H2N)2C=S1:1:(1–3)8016
42HAlBui2tolueneP2S51:1:(1–3)60166, <5%
52HAlBui2tolueneMe2S21:1:(1–3)20167, 63%
62 tolueneP2S51:0:18016
72 tolueneP2S5 a1:0:160168, 77%
82 tolueneP2S5 a1:0:0.560168, 40%
92 hexaneP2S5 a1:0:160168, 37%
102 CHCl3P2S5 a1:0:160168, 29%
112 CH2Cl2P2S5 a1:0:120168, 41%
122 Et2OP2S5 a1:0:120168, 33%
132 THF bP2S5 a1:0:160168, 27% b
142 H2OP2S5 a1:0:160168, 30%
152 10% HClP2S5 a1:0:160168, 54%
162 EtOHP2S5 a1:0:160168, 9%
a The reaction was carried out in the presence of 0.8 mol% TEMPO. b The products of oxygen atom substitution in THF molecule by sulfur and thiophane (35%), and the products of the ring opening, 1,4-dithiol (12%), were identified by GC/MS.
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Kovyazin, P.V.; Bikmeeva, A.K.; Palatov, E.R.; Parfenova, L.V. Modification of 1-Hexene Vinylidene Dimer into Primary and Tertiary Alkanethiols. Molbank 2022, 2022, M1379. https://doi.org/10.3390/M1379

AMA Style

Kovyazin PV, Bikmeeva AK, Palatov ER, Parfenova LV. Modification of 1-Hexene Vinylidene Dimer into Primary and Tertiary Alkanethiols. Molbank. 2022; 2022(2):M1379. https://doi.org/10.3390/M1379

Chicago/Turabian Style

Kovyazin, Pavel V., Almira Kh. Bikmeeva, Eldar R. Palatov, and Lyudmila V. Parfenova. 2022. "Modification of 1-Hexene Vinylidene Dimer into Primary and Tertiary Alkanethiols" Molbank 2022, no. 2: M1379. https://doi.org/10.3390/M1379

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