JP3917826B2 - Tetramercaptobiphenyl and synthesis method thereof - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel tetramercaptobiphenyl represented by the general formula (1) and a method for producing the same.
[0002]
[Prior art]
Compounds having two or more mercapto groups [R- (SH) n, where R is an n-valent organic group, and even if it has a branched group, an alkylene group, an arylene group, etc.] such as polyisocyanate It is known that a resin having a high refractive index (ND20 ° C. ≧ 1.60) is produced by reacting with a narate (JP 60-199016 A, JP 62-267316 A). As a technique related to this, JP-A-8-269161 (Patent No. 2849065) includes 2,2′-dimercaptobiphenyl and 4,4′-dimercaptobiphenyl as biphenyl derivatives of dimercapto compounds. It has been. Further, it is described that an aryl group, halogen, and the like in the reaction component contribute to an improvement in refractive index.
[0003]
Compounds having a thiol group are coordinated by self-organization on the surface of noble metals such as Au, Pt, Ag, and Pd, the surface of metal such as transition metals and the surface of metal fine particles by electrons of S atoms. A film is formed, and the monomolecular film is bonded to the metal surface by a group other than a thiol, by a thiol group other than a coordinated thiol group, or by further binding a compound that exhibits functionality. It is known that a film exhibiting functional characteristics is formed. For example, by forming a self-assembled membrane with a structure-specific (specifically antigen-antibody-like) reactive site and combining it with Quartz-Crystal Microbalance (correlation with a decrease in high-frequency frequency) For example, it has also been proposed to use it in a method for quantitatively detecting DNA (Kenichi Niikura et al. Chem. Lett. 1996, 863-864).
[0004]
Functional group (for example, mercapto group, polyamine group) that can be supported on the surface of metal, metal oxide or semiconductor ultrafine particles is introduced at one end (for example, α-terminal) of PEG, and an antibody at the other end (ω-terminal) A PEG derivative having a functional group capable of reacting with a functional compound such as protein or dye is synthesized, and the PEG derivative having the functional group introduced is supported on a metal, metal oxide or semiconductor ultrafine particle. In addition to improving dispersion stability, a new dispersion-stable complex having a functional group reactive to a functional compound (modified) at the other end of the PEG chain extended from the surface of the ultrafine particles (extended) (The 48th (1999) polymer discussion meeting October 6-8, Niigata University Igarashi canvas "Proceedings of the Society of Polymer Science" Vol. 48, No. 14, 4113-4114, Heisei Issued on September 20, 2011 See).
[0005]
The reactivity, function, etc. of the mercapto group show one aspect of the importance of the mercapto compound. The diverse functionality of the mercapto group is even more important since it increases the functional diversity of the polymercapto compound.
[0006]
For example, as a compound similar to tetramercaptobiphenyl, 3,3 ′, 4,4′-tetrahydroxybiphenyl, 2,2 ′, 4′-tetrahydroxybiphenyl and the like are known, and the four functionalities of these compounds are known. Each group is involved in a variety of reactions, such as polymer formation, crosslinking, and reaction with other reactive groups (compounds or groups present on the surface). With the increase, the functionality of the compound is enhanced.
[0007]
[Problems to be solved by the invention]
The present invention is to provide a novel mercapto compound which has the function of the mercapto group and at the same time has the possibility of enhancing the diversity of functions like the tetrahydroxybiphenyl. Therefore, it is important to find a means for producing such a compound, and the present inventor has intensively studied and (1) reacting ClSO ₃ H with biphenyl as a means for introducing sulfur into the aromatic ring of biphenyl. 4,4′-biphenyldisulfonyl chloride was synthesized, (2) dimethylamine (HNMe ₂ ) was reacted with this to synthesize 4,4′-bis (N, N′-dimethylaminosulfonyl) -biphenyl, 3) This is reacted with normal butyllithium (n-BuLi), and further with a single sulfur S8 to react with 4,4'-bis (N, N'-dimethylaminosulfonyl) -3,3'-dimercaptobiphenyl. synthesized, and (4) this bis by reacting the like LiAlH ₄ / NaBH ₄ (2,2-dimethyl [3,4-d] -1,3,2- Jichiasutanoro) biphenyl Form, finally (5) It thio reacted hydrogen chloride - Le group biphenyl aromatic ring 3,3 ', 4,4' found a method of placing and introduced into. As a result, it became possible to synthesize a novel organic sulfur compound 3,3 ′, 4,4′-tetramercaptobiphenyl. Thereby, the said subject was able to be solved.
[0008]
[Means for Solving the Problems]
The first of the present invention, the general formula (1) relates represented ruthenate tiger mercapto biphenyl according to claim 1. In the second aspect of the present invention, (1) ClSO ₃ H is reacted from biphenyl or a biphenyl derivative to synthesize 4,4′-biphenyldisulfonyl chloride or a derivative thereof, and (2) dimethylamine (HNMe ₂ ) is added thereto. 4,4′-bis (N, N′-dimethylaminosulfonyl) -biphenyl or a derivative thereof is synthesized by reacting, and (3) normal butyllithium (n-BuLi) is reacted therewith, and a single sulfur S8 is further added. Reaction is performed to synthesize 4,4′-bis (N, N′-dimethylaminosulfonyl) -3,3′-dimercaptobiphenyl or a derivative thereof, and (4) dimethyl ([3,4-d] -1,3 , 2-ditistanolo) biphenyl or a derivative thereof, and then (5) reacting this with hydrogen chloride in the general formula (1) including the steps (1) to (5) To methods of synthesizing the compounds.
[0009]
[Embodiments of the present invention]
The present invention will be described in more detail. A. In the compound of the general formula (1) of the present invention, M ₁ and M ₂ can be various derivatives in relation to the intended use of the mercapto compound of the present invention. As the derivative, various functions such as improvement of adhesion to metal and introduction of other functional compounds can be imparted as in the case of the mercapto compound. B. Also in the compound of the general formula (1) of the present invention, various derivatives can be used for carbon in which no thiol group is introduced in relation to the purpose of using the mercapto compound having the basic chemical structure of the present invention. For example, the halogen group can improve the refractive index and flame retardancy when producing polycarbonate. C. The reaction process is illustrated in FIG.
[0010]
【Example】
Example 1
Synthesis of 4,4′-biphenyldisulfonyl chloride (Step 1: Chlorosulfonylation) Under nitrogen atmosphere, chlorosulfuric acid (21.184 mmol) was added to methylene chloride (40 ml) to dilute chlorosulfuric acid. At 0 ° C., biphenyl (6.168 g, 40.00 mmol) was gradually added in several portions, and then stirred at room temperature for 6 hours. The obtained reaction mixture was poured into a saline solution, and a white insoluble matter was precipitated. The insoluble matter was removed by suction filtration. At this time, since the product may be contained in the residue, the residue was thoroughly washed with methylene chloride. Thereafter, the filtrate was extracted with methylene chloride (150 ml × 3), and the separated organic layer was dried with magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was separated by column chromatography (φ = 50 mm, h = 100 mm × 2; CH ₂ Cl ₂ ) and further recrystallized (CHCl ₃ ). Purification gave 4,4′-biphenyldisulfonyl chloride as colorless crystals (8.201 g, 23.349 mmol, 58%). Melting point 206-207 ° C. (literature value, 205-208 ° C.). ¹ N NMR (400 MHz, CDCl ₃ ) δ 7.86 (d, j = 8.5 Hz, 4H, ArH), 8.19 (d, j = 8.5 Hz, 4H, ArH).
[0011]
Synthesis of 4,4′-bis (N, N-dimethylaminosulfonyl) biphenyl (step 2: amidation) 4,4′-biphenyldisulfonyl chloride (7.788 g, 22.17 mmol in tetrahydrofuran (THF) solution (200 ml) ) Was added with 50% dimethylamine solution (10.567 ml, 106.416 mmol), stirred at room temperature for 3 hours, added with water, and further stirred for 30 minutes. The filtrate was dried under reduced pressure, and the filtrate was extracted once with ether (50 ml) to incorporate THF into the organic layer, followed by extraction with methylene chloride (50 ml × 2), and the separated organic layer was dried over magnesium sulfate. the solvent was distilled off under reduced pressure, the resulting crude product is purified by recrystallization (CH 2 _{Cl 2)} And the 4,4'-bis (N, N-dimethylamino sulfonyl) biphenyl colorless crystals (. 8.026g, 21.78mmol, quant) as obtained was mp ^{244 ℃;. 1 H NMR (} 400MHz, CDCl ₃ ) δ 2.77 (s, 12H, CH ₃ ), 7.78 (d, j = 8.3 Hz, 4H, ArH), 7.90 (d, j = 8.3 Hz, 4H, ArH); ¹³ CNMR (101 MHz, CDCl ₃ ) δ 37.9, 127.9, 128.5, 135.5, 143.6; IR (KBr) 134.1, 1163 (SO ₂ ) cm ⁻¹
[0012]
Synthesis of 4,4′-bis (N, N-dimethylaminosulfonyl) -3,3′-dimercaptobiphenyl (step 3: orthotrithioation-sulfuration) 4,4′-bis (N, N -Dimethylaminosulfonyl) -biphenyl (5.527 g, 15.00 mmol) in anhydrous THF suspension (150 ml) was added 2.47 M n-butyllithium (14.6 ml, 36.00 mmol), and at room temperature for 2 hours. After the deceased, elemental sulfur (S8) was added and stirred for another 3 hours, and then lithium aluminum hydride was added to the reaction solution and stirred for 1 hour. The resulting reaction mixture was poured into ice water and acidified with concentrated hydrochloric acid until pH <1. The solution was extracted once with ether (50 ml) to incorporate THF into the organic layer, followed by extraction with methylene chloride (50 ml × 3), and the separated organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was separated by column chromatography (φ = 50 mm, h = 100 mm × 2; CHCl ₃ : AcOEt = 5: 1), and further recrystallized (CHCl ₃ ) To obtain 4,4′-bis (N, N-dimethylaminosulfonyl) -3,3′-dimercaptobiphenyl as yellow crystals (5.00 lg, 56 mmol, 77%). Melting point, 171-172 ° C .; 1H NMR (400 MHz, CDCl ₃ ) δ 2.88 (s, 12H, CH ₃ ), 4.85 (s, 2H, SH), 7.42 (dd, j = 1.8, 8.3 Hz, 2H, ArH), 7.58 (d, j = 1.8 Hz, 2H, ArH), 7.98 (d, j = 8.3 Hz, 2H, ArH), ¹³ CNMR (101 MHz, CDCl) ₃ ) δ 37.6, 124.0, 130.5, 131.9, 133.6, 135.1, 142.9; IR (KBr) 2548 (SH), 1342, 1164 (SO ₂ ) cm ⁻¹ ; MS (70 eV) m / z 432 (M ^<+> ); Anal. _{Calculated, C 16 H 20 N 2 O} 4 S 4: C, 44.42; H, 4.66; N, 6.48%. Found: C, 44.05; H, 4.36; N, 6.38%.
[0013]
Synthesis of bis (2,2-dimethyl [3,4-d] -1,3,2-dithiastanolo) biphenyl (step 4: stannylation) 4,4′-bis (N, N-dimethylaminosulfonyl) -3 Lithium aluminum hydride (1.366 g, 36.00 mmol) was added to a pre-dried THF (75 ml) solution of 3,3′-dimethylcaptobiphenyl (1.298 g, 3.000 mmol) at 0 ° C., and the reaction solution was added. Refluxed for 24 hours. The resulting reaction mixture was poured into ice water and acidified with concentrated hydrochloric acid until pH <1. The solution was extracted with methylene chloride (50 ml × 3), and the separated organic layer was dried with magnesium sulfate. The solvent was distilled off to some extent under reduced pressure, and the resulting insoluble product was dried under reduced pressure to completely remove the solvent. To this pre-dried THF (60 ml) / pre-dried EtOH (12 ml) solution of this insoluble matter, sodium borohydride was added at 0 ° C. and stirred at room temperature for 30 minutes, then water was added and neutralized by adding concentrated hydrochloric acid. (PH 4-7), dimethyltin dichloride was immediately added, and the mixture was stirred at room temperature for 30 minutes. This reaction solution is extracted using methylene chloride (50 ml × 3), and the separated organic layer is dried using magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was separated by column chromatography (φ = 35 mm, h = 80 mm; CHCl ₃ ) and further purified by recrystallization (THF-CHCl ₃ ). Bis (2,2-dimethyl [3,4] -1,3,2-dithianastolo) biphenyl was obtained as pale yellow crystals (0.787 g, 1.37 mmol, 46%). Melting point, 239-240 ° C .; ¹ H NMR (400 MHz, CDCl ₃ ) δ 1.02 (s, 12H, CH ₃ ), 7.08 (dd, j = 2.0, 8.2 Hz, 2H, ArH,), 7.47 (d, j = 8.2 Hz, 2H, ArH), 7.64 (d, j = 2.0 Hz, 2H, ArH), ¹³ CNMR (101 MHz, CDCl ₃ ), δ 2.6, 122.9 , 127.7, 130.0, 136.4, 137.0, 138.7; 119 Sn NMR (149 MHz, CDCl ₃ ), δ 188.7; IR (KBr) 1444, 1258, 1110, 1027, 877, 800, 760 MS (70 eV) m / z 576 (M ⁺ ); analytical calculated, C ₁₆ H ₁₈ S ₄ Sn ₂ : C, 33.36; H, 3.15%. Found: C, 33.44; H, 3.33%.
[0014]
Synthesis of 3,3 ′, 4,4′-tetramercaptobiphenyl (Step 5: Deprotection Reaction) Bis (2,2-dimethyl [3,4-d] -1,3,2dithianastolo) biphenyl under nitrogen atmosphere Hydrogen chloride gas generated from concentrated sulfuric acid and sodium chloride was continuously blown into a pre-dried THF (35 ml) solution of (2.061 g, 3.50 mmol) while monitoring for about 6 hours. After confirming the absence of the substrate, it was cooled to 0 ° C. and water was added. The crystals thus precipitated were suction filtered, and the obtained crystals were dried under heating (50 ° C.) under reduced pressure to obtain 3,3 ′, 4,4′-tetramercaptobiphenyl as yellow crystals (2.365 g, 2.24 mmol, 64%). Melting point, 97-100 ° C .; ¹ H NMR (400 Mz, CDCl ₃ ) δ 3.76 (s, 2 H, SH), 7.22 (dd, j = 2.0, 8.1 Hz, 2 H, ArH,), 7 .40 (d, j = 8.1 Hz, 2H, ArH), 7.52 (d, j = 2.0 Hz, 2H, ArH), ¹³ CNMR (101 MHz, CDCl ₃ ), δ125.2, 129.2 139.7, 131.4, 131.7, 138.3; IR (KBr) 2555 (SH) cm ⁻¹ .
[0015]
Example of Use of Compound of the Present Invention The present compound can be used as a gold particle and gold ion or copper particle or copper ion recovery material. This is based on the utilization of the reactivity of the sulfur-containing groups described above. Application Example An aqueous solution of gold (5 ppm) is heated to 30-50 ° C., and a solution of the compound synthesized in the above Example dissolved in THF is added to this solution. After stirring for a while, the deposited precipitate was separated. When the gold concentration in the solution after separation was measured with an atomic absorption altimeter, no gold was measured. That is, gold reacted with the compound of the present invention, indicating that it was completely removed as a precipitate.
[0016]
【The invention's effect】
Biphenyl with two benzene rings bonded directly forms a rigid structure and is expected to be applied to a robust material. However, by introducing a reactive thiol group into the aromatic ring, the functionality is further enhanced. In addition to the use examples described above, expression of interface functionality, for example, new functionality in the field of bonding and electronic materials is expected.
[Brief description of the drawings]
FIG. 1 Compound synthesis process

Claims (2)

The following general formula (1)

(Wherein M ₁ and M ₂ are independently selected from the group consisting of H, Na, Li, K).
Tetramercaptobiphenyl represented by Biphenyl or al, (1) ClSO ₃ is reacted with H to synthesize 4,4'-biphenyl Soo Gandolfo sulfonyl chloride Lai de, (2) which is reacted with dimethylamine 4,4'-bis (N, N ' - dimethylamino sulfonyl) - were synthesized biphenyl, (3) which is reacted with n-butyl lithium, reacted further elemental sulfur S8 4,4'-bis (N, N '' - dimethylamino sulfonyl) - synthesizing a 3,3'-dimercapto biphenyl, (4) bis (2,2-dimethyl [3,4-d] 1,3,2 Jichiasutanoro) were synthesized biphenyl, then (5) which A method for synthesizing a compound represented by the formula (1) according to claim 1, which comprises the steps of (1) to (5), wherein hydrogen chloride is reacted with the compound.

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