JP3127604B2 - Novel bisbiphenylene sulfuran and method for producing the same - Google Patents
Novel bisbiphenylene sulfuran and method for producing the sameInfo
- Publication number
- JP3127604B2 JP3127604B2 JP04253391A JP25339192A JP3127604B2 JP 3127604 B2 JP3127604 B2 JP 3127604B2 JP 04253391 A JP04253391 A JP 04253391A JP 25339192 A JP25339192 A JP 25339192A JP 3127604 B2 JP3127604 B2 JP 3127604B2
- Authority
- JP
- Japan
- Prior art keywords
- sulfuran
- novel
- formula
- producing
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- DZCSELWKKDJVEK-UHFFFAOYSA-N [Li]C1=CC=CC=C1C1=CC=CC=C1[Li] Chemical group [Li]C1=CC=CC=C1C1=CC=CC=C1[Li] DZCSELWKKDJVEK-UHFFFAOYSA-N 0.000 claims description 4
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 claims description 4
- NGDPCAMPVQYGCW-UHFFFAOYSA-N dibenzothiophene 5-oxide Chemical compound C1=CC=C2S(=O)C3=CC=CC=C3C2=C1 NGDPCAMPVQYGCW-UHFFFAOYSA-N 0.000 claims description 3
- -1 bis (2,2'-biphenylene) sulfane Chemical compound 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000021028 berry Nutrition 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000004772 tellurides Chemical class 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】この発明は、機能性試薬として或
は合成反応中間体として有用な新規ビスビフェニレンス
ルフラン及びその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel bisbiphenylene sulfuran useful as a functional reagent or as a synthetic reaction intermediate, and a method for producing the same.
【０００２】[0002]
【従来の技術】硫黄原子に炭素リガンドのみが４個結合
したテトラアリール型σースルフランは、これまでその
存在の可能性については予測されていたが、現実には証
明されていない。即ち、三配位の有機硫黄化合物と有機
リチウム試薬との反応では、中間体として、σースルフ
ランを経由すると考えられていたが、直接的な証明はこ
れまで成功した例はない。2. Description of the Related Art The possibility of the existence of a tetraaryl-type σ-sulfuran in which only four carbon ligands are bonded to a sulfur atom has been predicted so far, but has not been proven in practice. That is, in the reaction of a three-coordinate organosulfur compound and an organolithium reagent, it was thought that the reaction was via σ-sulfuran as an intermediate, but no direct proof has been found so far.
【０００３】[0003]
【発明が解決しようとする課題】この発明は、従来その
存在が証明されていなかった電子状態や構造に特異性を
有する新規テトラアリール型σースルフランを提供する
ことを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a novel tetraaryl-type .sigma.-sulfurane having specificity in an electronic state and a structure whose existence has not been proved conventionally.
【０００５】[0005]
【課題を解決するための手段】即ち本発明は、次式
（Ｉ）： で表される新規ビス（２，２′−ビフエニレン）スルフ
ランである。That is, the present invention provides the following formula (I): Is a novel bis (2,2'-biphenylene) sulfuran represented by
【０００６】また本発明は、次式（ＩＩ）： で表されるジベンゾチオフェン５−オキシドを、トリメ
チルシリルトリフルオロメタンスルホネートと反応さ
せ、ついで、２，２’−ジリチオビフェニルと反応させ
ることを特徴とする次式（Ｉ）： で表されるビス（２，２′−ビフエニレン）スルフラン
の製造方法である。Further, the present invention provides the following formula (II): Reacting dibenzothiophene 5-oxide represented by the following formula with trimethylsilyl trifluoromethanesulfonate and then with 2,2'-dilithiobiphenyl: This is a method for producing bis (2,2'-biphenylene) sulfuran represented by the following formula:
【０００７】本発明の式（Ｉ）で表される化合物は、次
式： で表される反応式によって製造することができる。The compound represented by formula (I) of the present invention has the following formula: Can be produced by the reaction formula represented by
【０００８】式（ＩＩ）で表される化合物を、トリメチ
ルシリル トリフルオロメタンスルホネートと、原料及
び生成物と作用することなく、反応温度に於いて液体で
ある溶剤例えば無水テトラヒドロフラン中、好ましくは
窒素雰囲気下、低温好ましくは−５０〜−１００℃で、
１０分〜３０分間程度反応させ、ついで−１０℃〜１０
℃に昇温し、１０分〜１時間程度反応させ、上記式（Ｉ
ＩＩ）で表される化合物とする。The compound of the formula (II) is reacted with trimethylsilyl trifluoromethanesulfonate and a solvent which is liquid at the reaction temperature, such as anhydrous tetrahydrofuran, preferably without a nitrogen atmosphere, without reacting with the starting materials and products. Low temperature, preferably at -50 to -100C,
Reaction is carried out for about 10 to 30 minutes, then -10 ° C to 10
C., and allowed to react for about 10 minutes to 1 hour.
A compound represented by II).
【０００９】上記式（ＩＩＩ）で表される化合物を含有
する反応混合物を、低温好ましくは−５０〜−１００℃
に冷却し、２，２′−ジリチオビフェニルのエーテル溶
液と、窒素雰囲気中３０分〜２時間程度反応させ、つい
で−１０℃〜１０℃に昇温して、１０分〜１時間程度反
応させる。The reaction mixture containing the compound represented by the above formula (III) is subjected to a low temperature, preferably -50 to -100 ° C.
And reacted with an ether solution of 2,2'-dilithiobiphenyl in a nitrogen atmosphere for about 30 minutes to 2 hours, and then heated to -10 ° C to 10 ° C and reacted for about 10 minutes to 1 hour. .
【００１０】上記反応中、−７８℃の低温状態でのＮＭ
Ｒ測定の結果、本発明の式（Ｉ）で表される化合物が確
認され、更に温度を室温まで上昇させてもＮＭＲスペク
トルに変化はなく、本発明の式（Ｉ）で表される化合物
が安定に存在することが確認された。During the above reaction, NM at a low temperature of -78 ° C.
As a result of R measurement, a compound represented by the formula (I) of the present invention was confirmed. Even when the temperature was further increased to room temperature, there was no change in the NMR spectrum. It was confirmed that it existed stably.
【００１１】上記反応混合物から、減圧下で溶媒を留去
し、残留物に適当な溶媒例えば無水テトラヒドロフラン
を加えて再結晶すると、融点１１４〜１１８℃（分解）
の黄色固体として、式（１）で表される化合物が単離さ
れる。From the above reaction mixture, the solvent is distilled off under reduced pressure, and the residue is recrystallized by adding an appropriate solvent such as anhydrous tetrahydrofuran.
As a yellow solid, the compound represented by the formula (1) is isolated.
【００１２】[0012]
【実施例】次に、実施例を挙げて本発明を説明するが、
本発明はこの実施例に限定されない。ジベンゾチオフェ
ン５−オキシド２００ミリグラム（１ミリモル）の乾燥
テトラヒドロフラン溶液１０ミリリットルに、トリメチ
ルシリル トリフルオロメタンスルホネート０．２５ミ
リリットル（１ミリモル）を、窒素雰囲気下、−７８℃
で滴下し、１５分間攪拌した。ついで、温度を０℃に上
昇させて３０分間攪拌した。再び反応混合物を−７８℃
に冷却し、２，２′−ジリチオビフェニル１モルのエー
テル溶液１ミリモルを加えると黄色の懸濁液になった。
このまま１時間攪拌した後、温度を０℃に上昇させ、３
０分間攪拌した。溶媒をエバポレーターで留去し、残留
物に乾燥エーテル２０ミリリットルを注入した。再び−
７８℃で１時間静置した後、窒素雰囲気下グラスフイル
ターで瀘過した。グラスフイルター上の残渣を乾燥ベン
ゼンで溶出し、黄色となった溶液から減圧下で溶媒を留
去し、減圧乾燥し、黄色の粉末３２２ｍｇ（収率９６
％）を得た。粗製物を乾燥テトラヒドロフランに溶解
し、−２０℃で再結晶を行い融点１１４〜１１８℃（分
解）の塊状の結晶として、次式（１）： で表されるビス（２，２′ービフェニレン）スルフラン
を得た。Next, the present invention will be described with reference to examples.
The present invention is not limited to this embodiment. To 10 ml of a dry tetrahydrofuran solution of 200 mg (1 mmol) of dibenzothiophene 5-oxide was added 0.25 ml (1 mmol) of trimethylsilyl trifluoromethanesulfonate at −78 ° C. under a nitrogen atmosphere.
And stirred for 15 minutes. Then, the temperature was raised to 0 ° C. and the mixture was stirred for 30 minutes. Again bring the reaction mixture to -78 ° C
And 1 mmol of 2,2'-dilithiobiphenyl in ether was added to give a yellow suspension.
After stirring for 1 hour, the temperature was raised to 0 ° C.
Stirred for 0 minutes. The solvent was distilled off with an evaporator, and 20 ml of dry ether was poured into the residue. Again-
After standing at 78 ° C. for 1 hour, the mixture was filtered with a glass filter under a nitrogen atmosphere. The residue on the glass filter was eluted with dry benzene, the solvent was distilled off from the solution that turned yellow under reduced pressure, and dried under reduced pressure to obtain 322 mg of a yellow powder (yield: 96).
%). The crude product was dissolved in dry tetrahydrofuran, and recrystallized at -20 ° C to obtain a mass of crystals having a melting point of 114 to 118 ° C (decomposed) as a mass of the following formula (1): To give bis (2,2'-biphenylene) sulfuran.
【００１３】 [0013]
【００１４】１ＨＮＭＲ（５００ＭＨｚ，ＴＨＦ−ｄ
ｇ）δ７．２３（ｔ，Ｊ＝７．６Ｈｚ，４−ＡｒＨ），
７．４２（ｔ，Ｊ＝７．６Ｈｚ，５−ＡｒＨ），７．７
１（ｄ，Ｊ＝７．６Ｈｚ，３−ＡｒＨ），８．１５
（ｄ，Ｊ＝７．６Ｈｚ，６−ＡｒＨ），１３ＮＭＲ（１
２５ＭＨｚ，ＴＨＦ−ｄｇ）δ１２２．９（６−Ａｒ
Ｃ），１２７．３（４−ＡｒＣ），１２８．２（３−Ａ
ｒＣ），１２８．８（５−ＡｒＣ），１３４．５（１−
ＡｒＣ），１４８．６（２−ＡｒＣ）． 1 H NMR (500 MHz, THF-d
g) δ 7.23 (t, J = 7.6 Hz, 4-ArH),
7.42 (t, J = 7.6 Hz, 5-ArH), 7.7
1 (d, J = 7.6 Hz, 3-ArH), 8.15
(D, J = 7.6 Hz, 6-ArH), 13 NMR (1
25 MHz, THF-dg) [delta] 122.9 (6-Ar
C), 127.3 (4-ArC), 128.2 (3-A
rC), 128.8 (5-ArC), 134.5 (1-
ArC), 148.6 (2-ArC).
【００１５】上記本発明の化合物のテトラヒドロフラン
中での構造は、ＮＭＲスペクトルによって特徴づけられ
る。１Ｈ及び１３ＣのＮＭＲによってビフェニレンの各
々のアリール環は、室温で磁気的に等価であった。更
に、これら信号は、１００℃で変化しなかった。このこ
とは、相当するセレン及びテルル化令物と対照的に、本
発明の化合物は低温でさえ、ベリー擬似回転がＮＭＲ時
間目盛りに於いて急速に起こることを示唆している。The structure of the compound of the present invention in tetrahydrofuran is characterized by an NMR spectrum. By 1 H and 13 C NMR, each aryl ring of biphenylene was magnetically equivalent at room temperature. Furthermore, these signals did not change at 100 ° C. This suggests that, in contrast to the corresponding selenium and telluride derivatives, the compounds of the present invention, even at low temperatures, have a berry pseudo-rotation that occurs rapidly on the NMR time scale.
【００１６】式（１）で表される本発明化合物の結晶構
造は、Ｘ線回折によって確認された。エカトリアルＳ
（１）−Ｃ（８）結合の長さは、平均１．８１３（２）
Åの標準Ｓ−Ｃ値と同じであった。アピカルＳ（１）−
Ｃ（２）結合の長さは、１．９２６（２）Åであり、従
来公知の第１級Ｓ−Ｃ結合の最も長いものと同じであっ
た。エカトリアルーエカトリアルＣ（８）−Ｓ（１）−
Ｃ（８’）の結合角は、１２１．５２（９）゜であり、
ペンタ配位イオウ化合物として従来公知のものの中で最
も大きかった。アピカルーアピカルＣ（２）−Ｓ（１）
−Ｃ（２’）の結合角は、１７５．１９（９）゜であ
り、ほぼ直線状であった。結晶状態の式（１）で表され
る本発明の化合物は、２個のアピカルＳ−Ｃ結合、２個
のエカトリアルＳ−Ｃ結合及び第３のエカトリアルの位
置に孤立電子対を有する僅かにゆがめられた擬似トリゴ
ナルービピラミタル（Ψ−ＴＢＰ）配置を有する。これ
ら結果は、２個の異なる種類のＳ−Ｃ結合からなるテト
ラオルガノ６−スルフランの構造特性を表している。The crystal structure of the compound of the present invention represented by the formula (1) was confirmed by X-ray diffraction. Equatorial S
The average length of (1) -C (8) bonds is 1.813 (2)
標準 was the same as the standard SC value. Apical S (1)-
The length of the C (2) bond was 1.926 (2) Å, which was the same as the longest conventionally known primary SC bond. Ecatria Rue Equatorial C (8) -S (1)-
The bond angle of C (8 ′) is 121.52 (9) ゜,
It was the largest among the conventionally known penta-coordinated sulfur compounds. Apical-Apical C (2) -S (1)
The bond angle of -C (2 ') was 175.19 (9) °, which was almost linear. The compound of the present invention represented by the formula (1) in a crystalline state has a slight distortion having two apical SC bonds, two equatorial SC bonds and a lone electron pair at the third equatorial position. Pseudo-trigonarubipyramital (タ ル -TBP) configuration. These results indicate the structural properties of tetraorgano 6-sulfurane, which consists of two different types of S—C bonds.
【００１７】[0017]
【効果】以上述べたごとく、本発明の化合物は、電子状
態や構造が特異であるため、その電子的特徴を利用した
電子材料や構造的特性を利用して医薬中間体等への応用
が期待されると共に、学術的にも新たな領域を開くもの
として今後の展開が期待される。As described above, since the compound of the present invention has a unique electronic state and structure, it is expected to be applied to a pharmaceutical intermediate or the like utilizing an electronic material utilizing its electronic characteristics or a structural property. In addition to this, it is expected that future development will open up a new area in academic terms.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C07D 495/10 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued on the front page (58) Fields investigated (Int. Cl. 7 , DB name) C07D 495/10 CA (STN) REGISTRY (STN)
Claims (2)
ラン。1. The following formula (I): A novel bis (2,2'-biphenylene) sulfane represented by the formula:
チルシリルトリフルオロメタンスルホネートと反応さ
せ、ついで、２，２’−ジリチオビフェニルと反応させ
ることを特徴とする次式（Ｉ）： で表される新規ビス（２，２′−ビフエニレン）スルフ
ランの製造方法。2. The following formula (II): Reacting dibenzothiophene 5-oxide represented by the following formula with trimethylsilyl trifluoromethanesulfonate and then with 2,2'-dilithiobiphenyl: A method for producing a novel bis (2,2'-biphenylene) sulfane represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04253391A JP3127604B2 (en) | 1992-08-10 | 1992-08-10 | Novel bisbiphenylene sulfuran and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04253391A JP3127604B2 (en) | 1992-08-10 | 1992-08-10 | Novel bisbiphenylene sulfuran and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0665251A JPH0665251A (en) | 1994-03-08 |
| JP3127604B2 true JP3127604B2 (en) | 2001-01-29 |
Family
ID=17250722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04253391A Expired - Fee Related JP3127604B2 (en) | 1992-08-10 | 1992-08-10 | Novel bisbiphenylene sulfuran and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3127604B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06286803A (en) * | 1993-04-07 | 1994-10-11 | Maruzen Kogyosho:Kk | Automobile equipped with refuse collecting and air purifying functions |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5283494B2 (en) * | 2008-12-10 | 2013-09-04 | ダイキン工業株式会社 | Method for producing fluorene derivative |
| KR102642888B1 (en) * | 2016-04-04 | 2024-03-04 | 솔루스첨단소재 주식회사 | Organic compound and organic electroluminescent device using the same |
-
1992
- 1992-08-10 JP JP04253391A patent/JP3127604B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06286803A (en) * | 1993-04-07 | 1994-10-11 | Maruzen Kogyosho:Kk | Automobile equipped with refuse collecting and air purifying functions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0665251A (en) | 1994-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bechgaard et al. | Synthesis of 1, 3-diselenole-2-selones and-2-thiones | |
| JP3127604B2 (en) | Novel bisbiphenylene sulfuran and method for producing the same | |
| JPS623154B2 (en) | ||
| Mitter et al. | Bicyclic silanes from cyclosilane-metal derivatives | |
| JP2000502661A (en) | Method for synthesizing 2-chloro-5-chloromethylthiazole | |
| Keblys et al. | Novel Mercury-Tantalum Carbonyl Derivatives | |
| GB2078725A (en) | N-chlorocarbonyl Lactams | |
| JP2719841B2 (en) | Thiourea derivative and method for producing the same | |
| JP2685120B2 (en) | Method for producing dithiazolium salt | |
| JPH01143878A (en) | Production of silicon azide | |
| US3953437A (en) | Process of preparing cephalosporanic acid ester derivatives | |
| Thaler et al. | Synthesis and structure of free and complexed cyclopentadienyl selanes | |
| JPS61218555A (en) | Manufacture of acids substituted with trifluorodichloroethylgroup and zinc compounds | |
| JPH0372486A (en) | Novel organosilicon compound | |
| JP3135658B2 (en) | New production method of lactone derivative | |
| HU187976B (en) | Process for producing 5,11-dihydro-11-//4-methyl-1-piperazinyl/-acetyl/-6h-pyrido/2,3-b//1,4/benzodiazepin-6-one | |
| Bochkarev et al. | Oxidative-reductive transmetallation reactions of germylmercury compounds with bis (ethylbenzene) vanadium and vanadocene | |
| US5151527A (en) | Synthesis of the carbanion 1,1,2-tricyano-2-(3,4-dicyano-5-imino-2,5-dihydro-1h-pyrrol-2-ylidene) ethanide | |
| JP3303051B2 (en) | Dihalogeno compound and method for producing the same | |
| JPH02308818A (en) | Novel polysilane compound, production and use thereof | |
| JP3506759B2 (en) | Method for producing oxazinone ring-containing compound | |
| CN116396191A (en) | Preparation method of N-tert-butoxycarbonyl-L-glutamic acid dimethyl ester derivative | |
| JPH0369911B2 (en) | ||
| JP2001516741A (en) | Sulfo-N-hydroxysuccinimide and method for producing the same | |
| JPH02247190A (en) | Novel organosilicic compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20001010 |
|
| LAPS | Cancellation because of no payment of annual fees |