JP2000336089A - Bisthioacetal compound - Google Patents
Bisthioacetal compoundInfo
- Publication number
- JP2000336089A JP2000336089A JP11149043A JP14904399A JP2000336089A JP 2000336089 A JP2000336089 A JP 2000336089A JP 11149043 A JP11149043 A JP 11149043A JP 14904399 A JP14904399 A JP 14904399A JP 2000336089 A JP2000336089 A JP 2000336089A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- group
- bisthioacetal
- raw material
- 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.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 41
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- NZARHKBYDXFVPP-UHFFFAOYSA-N tetrathiolane Chemical compound C1SSSS1 NZARHKBYDXFVPP-UHFFFAOYSA-N 0.000 abstract description 9
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 abstract description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 4
- 229910015900 BF3 Inorganic materials 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 229920001021 polysulfide Polymers 0.000 abstract description 2
- 239000005077 polysulfide Substances 0.000 abstract description 2
- 150000008117 polysulfides Polymers 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 15
- 125000001624 naphthyl group Chemical group 0.000 description 5
- -1 thioacetal compound Chemical class 0.000 description 5
- 238000006719 thioacetalization reaction Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 0 *C1(SCC(CC=CC2CSC(*)(SC3)I)C4=C2C3=CC[C@]4CS1)I Chemical compound *C1(SCC(CC=CC2CSC(*)(SC3)I)C4=C2C3=CC[C@]4CS1)I 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 101150018759 CG10 gene Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- UXTMROKLAAOEQO-UHFFFAOYSA-N chloroform;ethanol Chemical compound CCO.ClC(Cl)Cl UXTMROKLAAOEQO-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003555 thioacetals Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規化合物であるビス
チオアセタール化合物（I）、ならぴにその製造方法に
関する。The present invention relates to a novel compound, a bisthioacetal compound (I), and a method for producing the same.
【０００２】[0002]
【従来の技術】従来、ナフタレンのペリ位（1、8位）
に、ジチアペンタメテレン鎖（−CH２SCH２SCH２−）が
環化した、ナフタレンのペリ環式チオアセタール化合物
（A）は、すでに知られている（T．Kamada他，Bull．Ch
em．Soc．Jpn．，Vol．62，3024（1989））．2. Description of the Related Art Conventionally, the peri position of naphthalene (1,8 position)
In addition, a naphthalene pericyclic thioacetal compound (A) in which a dithiapentametherene chain (—CH 2 SCH 2 SCH 2 —) is cyclized is already known (T. Kamada et al., Bull. Ch.).
em. Soc. Jpn. , Vol. 62, 3024 (1989)).
【化４】 しかしながら、ナフタレン環の、更に、もう一方のペリ
位（4、5位）にもジチアペンタメチレン鎖が環化した、
ナフタレンのビスペリ環式構造を有するビスチオアセタ
ール化合物（I）は、応用面での幅広い用途が期待され
ているにもかかわらず、合成化学上の困難さから、現在
に至るまで未知化合物である。Embedded image However, the dithiapentamethylene chain was cyclized to the other peri-position (positions 4 and 5) of the naphthalene ring.
The bisthioacetal compound (I) having a bispericyclic structure of naphthalene is an unknown compound to date up to the present due to its difficulty in synthetic chemistry, despite its wide application prospects.
【０００３】[0003]
【発明が解決しようとする課題】したがって、本発明の
目的は、新規化合物であるビスチオアセタール化合物
（I）、ならびにその製造方法を提供することにある。Accordingly, an object of the present invention is to provide a novel compound, a bisthioacetal compound (I), and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明者らは上記課題を
解決すべく、メルカブト基によるチオアセタール化反応
について鋭意研究を重ねた結果、ナフタレンのビスペリ
置換体であるテトラチオール（II）を三沸化ホウ素エー
テル錯体の存在下にカルボニル化合物（III）と反応さ
せれば、チオアセタール化・環化反応が進行してナフタ
レンのビスペリ環式骨格が生成することを見出し、この
知見に基づき本発明をなすに至った。Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on the thioacetalization reaction with a mercapto group and found that tetrathiol (II) which is a bisperi-substituted product of naphthalene was obtained. It has been found that, when the carbonyl compound (III) is reacted in the presence of a boron fluoride ether complex, a thioacetalization / cyclization reaction proceeds to form a bispericyclic skeleton of naphthalene. Was reached.
【０００５】[0005]
【発明の実施の形態】本発明の、新規化合物の式（I）
で表されるビスチオアセタール化合物は、ナフタレン環
のペリ位に2個のジチアペンタメテレン鎖（−CH２SCH２
SCH２−）が環化した（すなわち、ナフタレン環の1、8
位に1個のジチアペンタメチレン鎖が環化し、そして4、
5位にも1個のジチアペンタメテレン鎖が環化した）ナフ
タレンのビスペリ環状構造を有する二環式チオアセター
ル化合物である。（I）式中、置換基Rｌ及びR２は、水
素原子、アルキル基、またはアリール基をとることがで
きる。そして化合物（I）は、ナフタレンのビスペリ置
換体であるテトラチオール（II）（鎌田、和佐田、日本
国特許第1771811号（平成5年）；CA．1990、114：16378
4）に、一般式（III）で示されるカルボニル化合物と三
沸化ホウ素エーテル錯体を作用させることにより製造さ
れる。まず、原料のテトラチオールく（II）と化合物
（III）を、クロロホルムなどのハロゲン化炭化水素ま
たはTHFなどのエーテル類の有機溶媒に溶かし、次に、
この溶液を三沸化ホウ素エーテル錯体で処理する。する
と、三沸化ホウ素エーテル錯体の作用により、（II）の
ペリ位の2個のメルカブトメチル置換基（−CH２SH）の2
個のチオール基（一SH）とカルボニル化合物（III）の
カルボニル基（−C＝0）との間でチオアセタール化・環
化反応が起こり、硫黄原子2個を環内に含むペリー8一環
式環が生成する。本発明によれば、このチオアセタール
化・環化反応は、テトラチオール（II）の1、8位および
4、5位の2つのペリ位で進行し、したがって、化合物（I
I）の分子1モルに対してカルポニル化合物（III）の分
子2モルが反応する。すなわち、化合物（II）の1、8位
の2個のメルカブトメチル基の2個のSH基と1個のC＝0基
が反応してチオアセタール化・環化し、1個のペリ−8−
環式環が生成する。一方、4、5位の2個のメルカブトメ
チル基の2個のSH基もまた同様にして1個のC＝0基と反応
してチオアセタール化・環化し、1個のペリ−8−環式環
が生成する。その結果、ナフタレン分子の1、8位及び
4、5位の各ペリ位にジチアペンタメチレン鎖が環化した
ビスペリ−8−環式系のビスチオアセタール化合物（I）
が生成する。本発明のビスチオアセタール化合物（I）
の製造方法によれば、反応温度は、三沸化ホウ素エーテ
ル錯体の添加前と、添加後1ないし6時間は、−10〜5℃
の温度範囲であり、その後は室温で反応させる。反応収
率を上げるためには、たえず効果的に反応液を撹拌する
ことが好ましい。このようにして反応を行うと、反応液
は始めの無色から黄またはピンク、または褐色へと、反
応の進行にともない変化する。反応終了後に有機溶媒を
加えて生成物を抽出し、抽出物をアルカリ洗浄すると一
般式（I）で示されるビスチオアセタール化合物を得る
ことができる。この場合、生成されるビスチオアセター
ル化合物（I）としては、上記反応において、テトラチ
オール（II）と反応させるカルボニル化合物（III）の
種類によって、ペリリング上に置換基をもたないもの、
すなわちR１、R２が共に水素原子である化合物、モノ置
換体、すなわちRｌまたはR２の一方がアルキル基または
アリール基である化合物、またはジ置換体、すなわちR
ｌ、R２が共にアルキル基、アリール基または一方がア
ルキル基、他方がアリール基である化合物の3種類が得
られる。また本発明の反応に用いられる式（II）で表さ
れるテトラチオールのナフタレン環上には、チオアセタ
ール化反応に影響しない不活性な任意の基を導入してお
いてもよい。そのょうな基としては、アルキル基、アリ
ール基、へテロ環基、アルケニル基、アラルキル基、ヒ
ドロキシル基、アルコキシ基、アリーロキシ基、ニトロ
基、アルキルチオ基、アリールチオ基、エステル基、カ
ルポキシル基、スルホニル基、ハロゲン原子などが挙げ
られる。本発明で得られたビスチオアセタール化合物
（I）は、いずれも新規化合物である。BEST MODE FOR CARRYING OUT THE INVENTION The novel compound of the formula (I)
The bisthioacetal compound represented by the formula has two dithiapentameterene chains (—CH 2 SCH 2 ) at the peri position of the naphthalene ring.
SCH 2- ) is cyclized (that is, 1,8 of the naphthalene ring)
One dithiapentamethylene chain in position cyclizes, and 4,
This is a bicyclic thioacetal compound having a bispericyclic structure of naphthalene (in which one dithiapentameterene chain is also cyclized at the 5-position). (I) In the formula, the substituents R 1 and R 2 can take a hydrogen atom, an alkyl group, or an aryl group. Compound (I) is tetrathiol (II) which is a bisperi-substituted product of naphthalene (Kamata, Wasada, Japanese Patent No. 1771811 (1993); CA. 1990, 114: 16378).
The compound is produced by reacting a carbonyl compound represented by the general formula (III) with a boron triboride ether complex on 4). First, the starting materials tetrathiol (II) and compound (III) are dissolved in an organic solvent such as a halogenated hydrocarbon such as chloroform or an ether such as THF.
This solution is treated with a boron triboride ether complex. Then, by the action of the boron triboride ether complex, two mercaptomethyl substituents (—CH 2 SH) at the peri-position of (II) are substituted.
Thioacetalization and cyclization reaction between the thiol group (1SH) and the carbonyl group (-C = 0) of the carbonyl compound (III) occurs, and Perry 8 has two sulfur atoms in the ring. A ring forms. According to the present invention, this thioacetalization / cyclization reaction is carried out at the 1,8-position of tetrathiol (II) and
Proceeding in the two peri positions at positions 4 and 5, and therefore the compound (I
One mole of the molecule (I) reacts with 2 moles of the carbonyl compound (III). That is, two SH groups of two mercaptomethyl groups at the 1- and 8-positions of the compound (II) react with one C = 0 group to form a thioacetal and cyclize, thereby forming one per-8 −
A cyclic ring forms. On the other hand, two SH groups of two mercaptomethyl groups at the 4 and 5 positions also react with one C = 0 group in the same manner to thioacetalize and cyclize, thereby forming one per-8- A cyclic ring forms. As a result, the 1,8-position of the naphthalene molecule and
Bisperyl-8-cyclic bisthioacetal compounds in which a dithiapentamethylene chain is cyclized at each of the 4 and 5 peri positions (I)
Is generated. Bisthioacetal compound (I) of the present invention
According to the production method, the reaction temperature is between -10 to 5 ° C. before the addition of the boron triboride ether complex and for 1 to 6 hours after the addition.
The reaction is then performed at room temperature. In order to increase the reaction yield, it is preferable to constantly stir the reaction solution effectively. When the reaction is performed in this manner, the reaction solution changes from the initial colorless state to yellow or pink or brown as the reaction progresses. After completion of the reaction, an organic solvent is added to extract the product, and the extract is washed with an alkali to obtain a bisthioacetal compound represented by the general formula (I). In this case, as the bisthioacetal compound (I) to be produced, one having no substituent on the perilling depending on the type of the carbonyl compound (III) to be reacted with tetrathiol (II) in the above reaction,
That compound R 1, R 2 are both hydrogen atom, mono-substituted product, i.e. compound one of R l or R 2 is an alkyl group or an aryl group, or a di-substituted compound, i.e. R
There are obtained three types of compounds in which l and R 2 are both an alkyl group, an aryl group or one is an alkyl group and the other is an aryl group. Further, on the naphthalene ring of the tetrathiol represented by the formula (II) used in the reaction of the present invention, any inert group which does not affect the thioacetalization reaction may be introduced. Examples of such groups include an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, an aralkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a nitro group, an alkylthio group, an arylthio group, an ester group, a carboxyl group, and a sulfonyl group. And a halogen atom. The bisthioacetal compounds (I) obtained in the present invention are all novel compounds.
【実施例】次に本発明を実施例により、さらに詳細に説
明する。 実施例1 テトラチオール（II）100mg、アセトン150mg（カルボニ
ル化合物（III）、Rｌ＝ R２＝ CH３）、三沸化ホウ
素エーテル錯体400mg、クロロホルム10mlの混合物を、0
℃で5時間、次いで室温で13時間撹拌した。反応後、生
じた濃紫色溶液を、常法に従い処理して得られた粗結晶
を、エタノール−クロロホルムの混合溶媒から再結晶
し、無色微結晶として94mg（収率75％）のビスチオアセ
タール化合物（（I）、R１＝R２＝CH３）を得た。 Mp：251℃（分解） Rf（SiO２／ベンゼン）：0．29 M＋（m／z）： 392 IR（Nujol）：3050,1595,1530,1420,1365,730cm−１ 上記と同様にして、表1に示す各種R１およぴR２を有し
た化合物（III）とテトラチオール（II）との反応を行
い、上記ビスチオアセタール化合物とR１および／また
はR２が異なる種々のビスチオアセタール化合物（I）を
合成した。結果を表1に示す。Next, the present invention will be described in more detail by way of examples. Example 1 A mixture of 100 mg of tetrathiol (II), 150 mg of acetone (carbonyl compound (III), R 1 = R 2 = CH 3 ), 400 mg of boron trifluoride ether complex, and 10 ml of chloroform was added to
Stirred at C for 5 h then at room temperature for 13 h. After the reaction, the resulting dark purple solution was treated in a conventional manner, and the crude crystals obtained were recrystallized from a mixed solvent of ethanol-chloroform to give 94 mg (75% yield) of bisthioacetal compound as colorless fine crystals. ((I), R 1 = R 2 = CH 3 ) was obtained. Mp: 251 ° C. (decomposition) Rf (SiO 2 / benzene): 0.29 M + (m / z): 392 IR (Nujol): 3050, 1595, 1530, 1420, 1365, 730 cm −1 In the same manner as above, the compound (III) having various R 1 and R 2 shown in Table 1 is reacted with tetrathiol (II), and the bisthioacetal compound is reacted with R 1 and / or R 2. And various bisthioacetal compounds (I) were synthesized. Table 1 shows the results.
【表1】
・ 【table 1】
・
【発明の効果】以上述べたように本発明によれば、種々
の置換基をもつビスチオアセタール化合物（I）が得ら
れる。この化合物は、本発明の製造方法により、市販の
既知物質から容易に製造することができると共に、文献
未載の新系列の化合物であり、新しい骨格の化合物の製
造原料として使用されるほか、ポリスルフイドやポリチ
オエステルのモノマー用原料として、さらに、界面活性
剤や重金属捕集剤の原料としても使用され、産業上有用
である。As described above, according to the present invention, bisthioacetal compounds (I) having various substituents can be obtained. This compound can be easily produced from commercially available known substances by the production method of the present invention, and is a new series of compounds not described in the literature. In addition to being used as a raw material for producing a compound having a new skeleton, polysulfide is also used. It is used as a raw material for monomers of polythioesters and polythioesters, and also as a raw material for surfactants and heavy metal collectors, and is industrially useful.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4C071 AA02 AA08 BB01 BB06 CC24 DD31 EE16 FF26 GG01 KK01 LL07 4H039 CA42 CG10 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C071 AA02 AA08 BB01 BB06 CC24 DD31 EE16 FF26 GG01 KK01 LL07 4H039 CA42 CG10
Claims (2)
ル基）で示されるビスチオアセタール化合物。[Claim 1] The following formula (I) (Wherein R 1 and R 2 are a hydrogen atom, an alkyl group, or an aryl group).
基である）で示されるテトラチオールを、三沸化ホウ素
エーテル錯体の存在下で、一般式（III） 【化３】 で示されるカルボニル化合物と反応させることを特徴と
する、請求項1記載の式（I）で表されるビススチオアセ
タール化合物の製造方法。2. The following formula (II): (Wherein, R1 and R2 are hydrogen atoms, alkyl groups, and aryl groups) in the presence of a boron triboride ether complex with a general formula (III) 2. The method for producing a bissuthioacetal compound represented by the formula (I) according to claim 1, wherein the compound is reacted with a carbonyl compound represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11149043A JP3096736B1 (en) | 1999-05-28 | 1999-05-28 | Bisthioacetal compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11149043A JP3096736B1 (en) | 1999-05-28 | 1999-05-28 | Bisthioacetal compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP3096736B1 JP3096736B1 (en) | 2000-10-10 |
| JP2000336089A true JP2000336089A (en) | 2000-12-05 |
Family
ID=15466411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11149043A Expired - Lifetime JP3096736B1 (en) | 1999-05-28 | 1999-05-28 | Bisthioacetal compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3096736B1 (en) |
-
1999
- 1999-05-28 JP JP11149043A patent/JP3096736B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP3096736B1 (en) | 2000-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20130105840A (en) | Method for producing a methylene disulfonate compound | |
| EP3845521A2 (en) | Synthesis methods for upadacitinib and intermediate thereof | |
| JPH11512407A (en) | Method for preparing 2-chloro-5-chloromethyl-thiazole compounds | |
| EP3808750A1 (en) | Triazolinedione adduct, method for producing triazolinedione adduct, method for producing ene compound, and method for analyzing ene compound | |
| KR0178542B1 (en) | Salts of dithiocarbamic acid, a method for producing the same, and a method for producing isothiocyanates using the salts of the dithiocarbamic acid | |
| JP3096736B1 (en) | Bisthioacetal compounds | |
| Koster et al. | Chlorination of the cephem dihydrothiazine ring. Factors influencing C-2 substitution vs. degradation to isothiazoles1 | |
| CN102276556B (en) | Preparation method of 4-benzyl piperazi ethyliminumacyl (formimidoyl benzol) hydrazine compounds | |
| Yonemoto et al. | Reaction of 1, 4, 2-dithiazolium and 1, 3-dithiolium salts with malononitrile. | |
| JP3171400B2 (en) | Hydroxycarbonyl derivative and method for producing the same | |
| NZ200857A (en) | Preparation of 5,6,7,7a-tetrahydro-4h-thienol(3,2-e)pyridin-2-ones | |
| Fujihara et al. | A new double bond bridged dibenzodithiocin: Preparation, characterization, and its transannular pπ-(> S+ S+) interaction | |
| JP2685120B2 (en) | Method for producing dithiazolium salt | |
| JP3012933B1 (en) | Dithianaphthalenophane compound and method for producing the same | |
| JPS63104955A (en) | Manufacture of sulfonylisothiourea | |
| JP3165823B2 (en) | Bislactone compound and method for producing the same | |
| Mihara et al. | Silica gel-promoted synthesis of 3, 4, 5-triaryltetrahydro-1, 4-thiazine derivatives from β, β′-dichloro sulfides and aromatic amines | |
| JPH01261362A (en) | Production of thiuram polysulfide | |
| Hansen et al. | Preparation of N-Alkyl-N′-4-Pyridylthioureas via Isolable 4-Pyridylisothiocyanate or via Aerial Oxidation of 4-Pyridyldithiocarbamic Acid | |
| JPH03178959A (en) | Production of bisalkylsulfonomethyl ethers or bisarylsulfonoxymethyl ethers | |
| KR910003636B1 (en) | Process for the preparation of benzophenon oxime compounds | |
| JPH0383988A (en) | Production method of diester compound | |
| JPH0571593B2 (en) | ||
| D'amico et al. | DERIVATIVES OF 4-CHLORO-3, 5-DINITROBENZO-TRIFLUORIDE. IV. SYNTHESIS OF BIS [6-(ETHYLTHIO)-5-NITRO-α, α, α-TRIFLUORO-m-TOLYL] DISULFIDE (1) AND ETHYL 2, 6-DINITRO-α, α, α-TRIFLUORO-p-TOLYL SULFIDE (2) | |
| KR860001087B1 (en) | Process for preparing cephalosporanic acid derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |