JPH0454664B2 - - Google Patents
Info
- Publication number
- JPH0454664B2 JPH0454664B2 JP11436383A JP11436383A JPH0454664B2 JP H0454664 B2 JPH0454664 B2 JP H0454664B2 JP 11436383 A JP11436383 A JP 11436383A JP 11436383 A JP11436383 A JP 11436383A JP H0454664 B2 JPH0454664 B2 JP H0454664B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- oxo
- phenylthio
- group
- 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
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- -1 aldehyde compound Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- HEHZAJWAFZVYHV-UHFFFAOYSA-N 4-phenylsulfanyl-2h-thiophen-5-one Chemical compound O=C1SCC=C1SC1=CC=CC=C1 HEHZAJWAFZVYHV-UHFFFAOYSA-N 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NMSLUAZZTFUUFZ-UHFFFAOYSA-N 2h-thiophen-5-one Chemical class O=C1SCC=C1 NMSLUAZZTFUUFZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- NKBIPYJKQVXNAV-UHFFFAOYSA-N 4-phenyl-2H-thiophen-5-one Chemical compound O=C1SCC=C1C1=CC=CC=C1 NKBIPYJKQVXNAV-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- ANUZKYYBDVLEEI-UHFFFAOYSA-N butane;hexane;lithium Chemical compound [Li]CCCC.CCCCCC ANUZKYYBDVLEEI-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- QBZXOWQOWPHHRA-UHFFFAOYSA-N lithium;ethane Chemical compound [Li+].[CH2-]C QBZXOWQOWPHHRA-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- UYYCVBASZNFFRX-UHFFFAOYSA-N n-propan-2-ylcyclohexanamine Chemical compound CC(C)NC1CCCCC1 UYYCVBASZNFFRX-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RZWQDAUIUBVCDD-UHFFFAOYSA-M sodium;benzenethiolate Chemical compound [Na+].[S-]C1=CC=CC=C1 RZWQDAUIUBVCDD-UHFFFAOYSA-M 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
Landscapes
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は、例えば医薬分野、農園芸分野などに
おいて抗菌、殺菌、殺虫剤などとして有用な生理
活性化合物、同様な分野における合成中間体とし
て有用な（Ｚ）−５−置換イリデン−３−フエニ
ルチオ−２−オキソ−３−チオレン類及びその製
法に関する。
更に詳しくは、本発明は、下記式（）
但し式中、ＲはC1〜C10のアルキル基、ハロゲ
ン及び低級アルキル基よりなる群からえらばれた
置換基を有していてもよいフエニル基、又はベン
ジル基を示す、
で表わされる（Ｚ）−５−置換イリデン−３−フ
エニルチオ−２−オキソ−３−チオレン類及びそ
の製法に関する。
上記式（）化合物は、例えば、下記式（）
で表わされる３−フエニルチオ−２−オキソ−３
−チオレンのリチウム塩を、下記式（）
Ｒ−CHO ……（）
但し式中、ＲはC1〜C10のアルキル基、ハロゲ
ン及び低級アルキル基よりなる群からえらばれた
置換基を有していてもよいフエニル基、又はベン
ジル基を示す、
で表わされるアルデヒド化合物と反応させること
により製造することができ、本発明は該製法にも
関する。
本発明者等は、たとえば医薬分野、農園芸分野
などにおいて抗菌、殺菌、殺虫剤などとして、更
には合成中間体として有用な３−フエニルチオ−
２−オキソ−３−チオレン系化合物の合成研究を
行つてきたが、今回、前記式（）で表わされる
従来文献未記載の（Ｚ）−５−置換イリデン−３
−フエニルチオ−２−オキソ−３−チオレン類が
存在できること及び該化合物が容易な手段で合成
できることを発見した。
本発明者らの研究によれば、例えば、後に詳し
く述べる方法によつて容易に合成できる上記式
（）化合物のリチウム塩を、上記式（）のア
ルデヒド化合物と反応させることによつて、式
（）化合物の５位に式（）化合物を縮合させ
た前記式（）化合物が容易に且つ好収率で製造
できることが発見された。
従つて、本発明の目的は、前記式（）新規化
合物を提供することにある。
本発明の他の目的は、該式（）新規化合物の
製法を提供するにある。
本発明の上記目的及び更に多くの他の目的なら
びに利点は、以下の記載から一層明らかとなるで
あろう。
前記式（）化合物に於て、式中Ｒのアルキル
基の例としては、メチル、エチル、プロピル（ｎ
−，iso−）、ブチル（ｎ−，iso−，sec−，tert
−）、ペンチル（ｎ−，iso−）、ヘキシル（ｎ−，
iso−）、ヘプチル（ｎ−，iso−）、オクチル（ｎ
−，iso−）、ノニル、デシルなどの如きC1〜C10
のアルキル基を例示することができる。又、式中
Ｒのフエニル基が有していてもよい置換基の例と
しては、塩素、臭素、フツ素などの如きハロゲン
原子及び上記例示のアルキル基中C1〜C4のアル
キル基の如き低級アルキル基を例示することがで
きる。
本発明の式（）化合物は、前述のように、た
とえば、式（）３−フエニルチオ−２−オキソ
−３−チオレンのリチウム塩と前記式（）アル
デヒド化合物の縮合反応によつて容易に好収率で
製造することができる。該式（）化合物は、例
えば、ｒ−ブチロラクトンからそれ自体公知の手
法を利用して容易に合成することができる。該式
（）Ｒ−CHOのアルデヒド化合物におけるＲは
式（）におけると同義であり、該Ｒの具体例と
しては式（）化合物のＲについてすでに例示し
たと同義な基Ｒを例示することができる。
上記ｒ−ブチロラクトンからの式（）化合物
の製造例を含めて、本発明式（）化合物の製造
態様を例にして、本発明（）化合物の製造工程
を例示すると、下記式のように示すことができ
る。
上記式で示した製造例に於て、入手容易な式
（）ｒ−ブチロラクトンから、例えば文献：N.
Kharasch、R.B.Lanford、J.Org.Chem.、28、
190（1963）の方法によつて上記式（）化合物を
経て、上記式（）化合物を合成することができ
る。該式（）化合物は、例えば特開昭50−
70354号に記載の方法によつて、容易に式（）
化合物に転化せしめることができる。このように
して得ることのできる式（）化合物は、たとえ
ばチオフエノール・ナトリウム塩と例えばエタノ
ール溶媒の如き適当な溶媒中、たとえば室温で約
２時間の如き条件で、反応せしめることにより、
式（）の３−フエニルチオ−２−オキソ−チオ
ラクトンに転化できる。得られた式（）化合物
は従来文献末記載の化合物であつて、例えば四塩
化炭素の如き適当なハロゲン化炭化水素溶媒中、
例えば塩化スルフリルの如き適当なハロゲン化剤
とたとえば室温で約８時間の如き条件で反応せし
めて、たとえばそのクロル化合物を形成し、更に
たとえばジメチルホルムアミドの如き適当な溶媒
中、たとえば100℃で塩化リチウムと反応させる
ことにより、従来文献未記載の式（）の３−フ
エニルチオ−２−オキソ−３−チオレンに高収率
で転化することができる。
本発明方法によれば、たとえば上述のようにし
て得ることのできる式（）化合物のリチウム塩
と式（）アルデヒド化合物を反応させて、（Ｚ）
体である式（）の（Ｚ）−５−置換イリデン−
３−フエニルチオ−２−オキソ−３−チオレン類
を選択的に形成することができる。
式（）化合物と式（）Ｒ−CHOアルデヒ
ド化合物との反応は、例えば、適当な不活性有機
溶媒中、適当なリチウムアミド類の存在下で式
（）化合物と式（）化合物とを反応させて行
うことができる。
上記リチウムアミド類の例としては、たとえば
ジエチルアミン、イソプロピルシクロヘキシルア
ミン、ジイソプロピルアミンなどの如き第二アミ
ン類のたとえばTHF溶液と、例えばメチルリチ
ウム、エチルリチウム、プロピルリチウム、ブチ
ルリチウムなどの如きアルキルリチウムのたとえ
ばヘキサン溶液のたとえば当モルを混合して形成
できるリチウムジアルキルアミド例えばリチウム
ジ低級アルキルアミドを例示することができる。
更に、反応に利用する不活性有機溶媒の例として
はテトラヒドロフラン（THF）、ジメトキシエタ
ン、エチルエーテル、それらの適当な混合物など
の如きエーテル系不活性有機溶媒を例示すること
ができる。
反応は、比較的低温条件下で行うのが好まし
く、例えば約−20℃〜約−70℃の如き低温条件を
例示することができる。反応に利用するリチウム
アミド類の使用量は適宜に選択できるが、例えば
式（）３−フエニルチオ−２−オキソ−３−チ
オレンに基いて約１〜約1.2モルの如き使用量を
例示することができる。又、式（）アルデヒド
化合物の使用量も適宜に選択でき、例えば、式
（）化合物に基いて約１〜約1.5モルの如き使用
量を例示することができる。更に、溶媒の使用量
も適宜に選択することができ、例えば、式（）
化合物に基いて約20〜約80倍の如き使用量を例示
することができる。
上記式（）化合物と式（）アルデヒド化合
物とから式（）化合物を製造する一態様につい
て更に詳しく例示すると、例えば、式（）３−
フエニルチオ−２−オキソ−３−チオレンの
THF溶液にジイソプロピルアミンを加え、これ
にｎ−ブチルリチウムのヘキサン溶液を加えて、
たとえば−30℃で約５分間撹拌した後、３−フエ
ニル−２−オキソ−３−チオレンのTHF溶液を
徐々に滴下し、たとえば−30℃で15分間撹拌しな
がら反応を行う。次に上記式（）のＲがフエニ
ル基の化合物を得ようとする場合はＲがフエニル
である式（）のベンズアルデヒド−THF溶液
を徐々に滴下し、−30℃で３時間反応を行う。そ
の後徐々に温度を上昇し、たとえば０℃まで昇温
した後、飽和塩化アンモニウム水溶液を加える。
次にエーテルにて抽出を行い、エーテル溶液を無
水硫酸マグネシウムで脱水した後、シリカゲルカ
ラムにより分離精製を行うと（分離溶媒：石油エ
ーテル：エーテル（10：１）混合溶媒）目的物質
上記式（）の（Ｚ）−５−ベンジリデン−３−
フエニルチオ−２−オキソ−３−チオレンを、例
えば62％の如き収率で得ることができる。Ｒが他
の基である化合物についても上記式（）ベンズ
アルデヒドの代りに、Ｒが他の基である式（）
Ｒ−CHO化合物を用いて同様に行うことができ
る。
以下実施例により本発明方法実施例の数例につ
いて更に詳しく例示できる。
実施例 １
（Ｚ）−５−ベンジリデン−３−フエニルチ
オ−２−オキソ−３−チオレンの合成
ジイソプロピルアミン0.222ｇ（2.2ミリモル）
をTHF5mlに溶解し、これに15％ｎ−ブチル−リ
チウム−ヘキサン溶液1.3ml（２ミリモル）を加
え、−30℃で５分間撹拌を行う。次に３−フエニ
ルチオ−２−オキソ−３−チオレン0.416ｇ（２
ミリモル）をTHF5mlに溶解した溶液を２分間で
滴下し、−30℃で15分間撹拌する。次にベンズア
ルデヒド0.318ｇ（３ミリモル）をTHF5mlに溶
解した溶液を５分間で滴下し、−30℃で３時間反
応を行つた後、徐々に０℃まで昇温した後、飽和
塩化アンモニウム水溶液20mlを加える。次にエー
テルにて抽出し、エーテル溶液を無水硫酸マグネ
シウムで脱水した後、エーテルを除去する。シリ
カゲルカラムを用い展開溶媒石油エーテル・エー
テル（10：１）の混合溶媒で分離精製する。目的
物質：（Ｚ）−５−ベンジリデン−３−フエニル−
チオ−２−オキソ−３−チオレンを0.368ｇ（62
％）得た。
その物理データを表１に示した。
実施例 ２〜７
式（）化合物３−フエニルチオ−２−オキソ
−３−チオレンに反応させるベンズアルデヒド
（Ｒ：フエニル）の代りに後掲表１に示したＲで
ある式（）化合物を用いるほかは実施例１の手
法に準じて行い下掲表１に示した化合物が得られ
た。物理的データも一緒に示してある。
The present invention relates to physiologically active compounds useful as antibacterial, bactericidal, and insecticides in the pharmaceutical field, agricultural and horticultural fields, etc., and (Z)-5-substituted ylidene-3-phenylthio- useful as synthetic intermediates in the same fields. This invention relates to 2-oxo-3-thiolenes and their production method. More specifically, the present invention is based on the following formula () However, in the formula, R represents a phenyl group or a benzyl group which may have a substituent selected from the group consisting of a C1 to C10 alkyl group, halogen, and lower alkyl group. )-5-Substituted ylidene-3-phenylthio-2-oxo-3-thiolenes and their production method. The above formula () compound is, for example, the following formula () 3-phenylthio-2-oxo-3 represented by
-The lithium salt of thiolene is expressed by the following formula () R-CHO... () where R has a substituent selected from the group consisting of a C1 to C10 alkyl group, halogen, and lower alkyl group. The present invention also relates to this production method. The present inventors have discovered that 3-phenylthio-
We have been conducting research on the synthesis of 2-oxo-3-thiolene compounds, and this time we have investigated the synthesis of (Z)-5-substituted ylidene-3, which has not been described in the literature and is represented by the above formula ().
It has been discovered that -phenylthio-2-oxo-3-thiolenes can exist and that the compounds can be synthesized by easy means. According to the research of the present inventors, for example, by reacting a lithium salt of the above formula () compound, which can be easily synthesized by a method described in detail later, with an aldehyde compound of the above formula (), the formula ( ) It has been discovered that the compound of formula () can be easily produced in a good yield by condensing the compound of formula () at the 5-position of the compound. Therefore, it is an object of the present invention to provide novel compounds of the formula (). Another object of the present invention is to provide a method for producing the novel compound of formula (). The above objects and many other objects and advantages of the present invention will become more apparent from the following description. In the above formula () compound, examples of the alkyl group R in the formula include methyl, ethyl, propyl (n
-, iso-), butyl (n-, iso-, sec-, tert
-), pentyl (n-, iso-), hexyl (n-,
iso-), heptyl (n-, iso-), octyl (n
−, iso−), nonyl, decyl, etc. C 1 to C 10
The alkyl group can be exemplified. Examples of substituents that the phenyl group R in the formula may have include halogen atoms such as chlorine, bromine, and fluorine, and C 1 to C 4 alkyl groups among the alkyl groups exemplified above. Examples include lower alkyl groups. As mentioned above, the compound of the formula () of the present invention can be easily obtained by, for example, the condensation reaction of the lithium salt of the formula () 3-phenylthio-2-oxo-3-thiolene and the aldehyde compound of the formula (). can be manufactured at a high rate. The compound of formula () can be easily synthesized, for example, from r-butyrolactone using a method known per se. R in the aldehyde compound of formula ()R-CHO has the same meaning as in formula (), and specific examples of R include the same groups R as already exemplified for R in the formula () compound. . The manufacturing process of the compound of formula () of the present invention is exemplified by the manufacturing method of the compound of formula () of the present invention, including the manufacturing example of the compound of formula () from the above r-butyrolactone, as shown in the following formula. I can do it. In the production example shown by the above formula, from easily available formula ()r-butyrolactone, for example, in the literature: N.
Kharasch, RBLanford, J.Org.Chem., 28 ,
190 (1963), the above formula () compound can be synthesized via the above formula () compound. The compound of the formula () is disclosed in, for example, Japanese Patent Application Laid-open No.
By the method described in No. 70354, the formula () can be easily
It can be converted into a compound. The compound of formula () that can be obtained in this way can be obtained by reacting it with thiophenol sodium salt in a suitable solvent such as ethanol solvent, for example, at room temperature for about 2 hours.
It can be converted to 3-phenylthio-2-oxo-thiolactone of formula (). The obtained compound of formula () is a compound previously described at the end of the literature, and is prepared in a suitable halogenated hydrocarbon solvent such as carbon tetrachloride.
Lithium chloride is reacted with a suitable halogenating agent, such as sulfuryl chloride, for example, at room temperature for about 8 hours, to form, for example, the chloro compound, and then in a suitable solvent, such as dimethylformamide, for example, at 100°C. By reacting with, it is possible to convert in high yield to 3-phenylthio-2-oxo-3-thiolene of formula (), which has not been described in any literature. According to the method of the present invention, for example, by reacting the lithium salt of the compound of formula () which can be obtained as described above with the aldehyde compound of formula (),
(Z)-5-substituted ylidene- of formula () which is
3-phenylthio-2-oxo-3-thiolenes can be selectively formed. The reaction between the formula () compound and the formula ()R-CHO aldehyde compound can be carried out, for example, by reacting the formula () compound and the formula () compound in the presence of a suitable lithium amide in a suitable inert organic solvent. It can be done by Examples of the lithium amides include THF solutions of secondary amines such as diethylamine, isopropylcyclohexylamine, diisopropylamine, etc., and alkyllithiums such as methyllithium, ethyllithium, propyllithium, butyllithium, etc. Examples include lithium dialkylamides, such as lithium di-lower alkylamides, which can be formed by mixing, for example, equimolar amounts of hexane solutions.
Furthermore, examples of the inert organic solvent used in the reaction include ether type inert organic solvents such as tetrahydrofuran (THF), dimethoxyethane, ethyl ether, and appropriate mixtures thereof. The reaction is preferably carried out under relatively low temperature conditions, such as from about -20°C to about -70°C. The amount of lithium amide to be used in the reaction can be selected as appropriate; for example, the amount used is about 1 to about 1.2 mol based on the formula () 3-phenylthio-2-oxo-3-thiolene. can. Further, the amount of the aldehyde compound of formula () to be used can be appropriately selected, and for example, the amount to be used can be about 1 to about 1.5 mol based on the compound of formula (). Furthermore, the amount of solvent to be used can be selected appropriately, for example, the formula ()
Examples of usage amounts include about 20 to about 80 times, based on the compound. To illustrate in more detail one embodiment of producing the formula () compound from the above formula () compound and the formula () aldehyde compound, for example, the formula ()3-
Phenylthio-2-oxo-3-thiolene
Add diisopropylamine to the THF solution, add a hexane solution of n-butyllithium to this,
For example, after stirring at -30°C for about 5 minutes, a THF solution of 3-phenyl-2-oxo-3-thiolene is gradually added dropwise, and the reaction is carried out while stirring at -30°C for 15 minutes, for example. Next, when a compound of the above formula () in which R is a phenyl group is to be obtained, a benzaldehyde-THF solution of the formula () in which R is phenyl is gradually added dropwise, and the reaction is carried out at -30°C for 3 hours. Thereafter, the temperature is gradually increased, for example to 0° C., and then a saturated aqueous ammonium chloride solution is added.
Next, extraction is performed with ether, the ether solution is dehydrated with anhydrous magnesium sulfate, and then separated and purified using a silica gel column (separation solvent: petroleum ether: ether (10:1) mixed solvent). (Z)-5-benzylidene-3-
Phenylthio-2-oxo-3-thiolene can be obtained in yields such as 62%. For compounds where R is another group, the above formula () benzaldehyde can be replaced by the formula () where R is another group.
A similar procedure can be performed using the R-CHO compound. Hereinafter, several examples of the method of the present invention can be illustrated in more detail with reference to Examples. Example 1 Synthesis of (Z)-5-benzylidene-3-phenylthio-2-oxo-3-thiolene Diisopropylamine 0.222 g (2.2 mmol)
was dissolved in 5 ml of THF, 1.3 ml (2 mmol) of a 15% n-butyl-lithium hexane solution was added thereto, and the mixture was stirred at -30°C for 5 minutes. Next, 0.416 g of 3-phenylthio-2-oxo-3-thiolene (2
A solution of 5 ml of THF (mmol) dissolved in 5 ml of THF was added dropwise over 2 minutes, and the mixture was stirred at -30°C for 15 minutes. Next, a solution of 0.318 g (3 mmol) of benzaldehyde dissolved in 5 ml of THF was added dropwise over 5 minutes, the reaction was carried out at -30°C for 3 hours, the temperature was gradually raised to 0°C, and 20 ml of a saturated ammonium chloride aqueous solution was added. Add. Next, the mixture is extracted with ether, the ether solution is dehydrated with anhydrous magnesium sulfate, and then the ether is removed. Separate and purify using a silica gel column with a mixed solvent of petroleum ether and ether (10:1) as a developing solvent. Target substance: (Z)-5-benzylidene-3-phenyl-
0.368 g (62
%)Obtained. The physical data are shown in Table 1. Examples 2 to 7 Compound of formula () The procedure was carried out except that a compound of formula () with R shown in Table 1 below was used instead of benzaldehyde (R: phenyl) reacted with compound 3-phenylthio-2-oxo-3-thiolene. The procedure of Example 1 was followed to obtain the compounds shown in Table 1 below. Physical data are also shown.
【表】【table】
Claims (1)
ン及び低級アルキル基よりなる群からえらばれた
置換基を有していてもよいフエニル基、又はベン
ジル基を示す、 で表わされる（Ｚ）−５−置換イリデン−３−フ
エニルチオ−２−オキソ−３−チオレン類。 ２ 下記式（） で表わされる３−フエニルチオ−２−オキソ−３
−チオレンのリチウム塩を、下記式（） Ｒ−CHO ……（） 但し式中、ＲはC1〜C10のアルキル基、ハロゲ
ン及び低級アルキル基よりなる群からえらばれた
置換基を有していてもよいフエニル基、又はベン
ジル基を示す、 で表わされるアルデヒド化合物と反応させること
を特徴とする下記式（） 但し式中、Ｒは上記したと同義である、 で表わされる（Ｚ）−５−置換イリデン−３−フ
エニルチオ−２−オキソ−３−チオレン類の製
法。[Claims] 1 The following formula () However, in the formula, R represents a phenyl group or a benzyl group which may have a substituent selected from the group consisting of a C1 to C10 alkyl group, halogen, and lower alkyl group. )-5-substituted ylidene-3-phenylthio-2-oxo-3-thiolenes. 2 The following formula () 3-phenylthio-2-oxo-3 represented by
-The lithium salt of thiolene is expressed by the following formula () R-CHO... () where R has a substituent selected from the group consisting of a C1 to C10 alkyl group, halogen, and lower alkyl group. The following formula () is characterized in that it is reacted with an aldehyde compound represented by, which optionally represents a phenyl group or a benzyl group. However, in the formula, R has the same meaning as described above. A method for producing (Z)-5-substituted ylidene-3-phenylthio-2-oxo-3-thiolenes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11436383A JPS606681A (en) | 1983-06-27 | 1983-06-27 | (z)-5-substituted indene-3-phenylthio-2-oxo-3-thiolene and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11436383A JPS606681A (en) | 1983-06-27 | 1983-06-27 | (z)-5-substituted indene-3-phenylthio-2-oxo-3-thiolene and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS606681A JPS606681A (en) | 1985-01-14 |
| JPH0454664B2 true JPH0454664B2 (en) | 1992-08-31 |
Family
ID=14635843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11436383A Granted JPS606681A (en) | 1983-06-27 | 1983-06-27 | (z)-5-substituted indene-3-phenylthio-2-oxo-3-thiolene and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS606681A (en) |
-
1983
- 1983-06-27 JP JP11436383A patent/JPS606681A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS606681A (en) | 1985-01-14 |
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