JPS63183562A - Pyrrole derivative - Google Patents
Pyrrole derivativeInfo
- Publication number
- JPS63183562A JPS63183562A JP1311287A JP1311287A JPS63183562A JP S63183562 A JPS63183562 A JP S63183562A JP 1311287 A JP1311287 A JP 1311287A JP 1311287 A JP1311287 A JP 1311287A JP S63183562 A JPS63183562 A JP S63183562A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- lower alkyl
- reaction
- mixture
- 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.)
- Pending
Links
- 150000003233 pyrroles Chemical class 0.000 title claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 18
- 241000233866 Fungi Species 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- 238000001228 spectrum Methods 0.000 abstract description 5
- 241000894006 Bacteria Species 0.000 abstract description 4
- 238000010520 demethylation reaction Methods 0.000 abstract description 3
- 238000005618 Fries rearrangement reaction Methods 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 230000000845 anti-microbial effect Effects 0.000 abstract 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 2
- 241000222120 Candida <Saccharomycetales> Species 0.000 abstract 1
- 101100295738 Gallus gallus COR3 gene Proteins 0.000 abstract 1
- 241000223238 Trichophyton Species 0.000 abstract 1
- 230000010933 acylation Effects 0.000 abstract 1
- 238000005917 acylation reaction Methods 0.000 abstract 1
- 230000002421 anti-septic effect Effects 0.000 abstract 1
- 239000004599 antimicrobial Substances 0.000 abstract 1
- 229940064004 antiseptic throat preparations Drugs 0.000 abstract 1
- 230000017858 demethylation Effects 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 230000026045 iodination Effects 0.000 abstract 1
- 238000006192 iodination reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 230000003032 phytopathogenic effect Effects 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 11
- 230000000844 anti-bacterial effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- RNHDAKUGFHSZEV-UHFFFAOYSA-N 1,4-dioxane;hydrate Chemical compound O.C1COCCO1 RNHDAKUGFHSZEV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 244000000003 plant pathogen Species 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 244000000005 bacterial plant pathogen Species 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- NFDFQCUYFHCNBW-SCGPFSFSSA-N dienestrol Chemical compound C=1C=C(O)C=CC=1\C(=C/C)\C(=C\C)\C1=CC=C(O)C=C1 NFDFQCUYFHCNBW-SCGPFSFSSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Pyrrole Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は新規なビロール誘導体、更に詳細には広範な抗
菌スペクトルを有し、医薬品、農薬及び防腐剤等として
有用な一ロール誘導体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel virol derivative, and more particularly to a monorol derivative that has a broad antibacterial spectrum and is useful as a pharmaceutical, an agrochemical, a preservative, and the like.
従来より、人や植物に感染し、悪影響を及ぼす菌類に作
用する抗菌剤を開発すべく、多くの研究がなされている
。そして、その抗菌剤は、強い抗菌力と広い抗菌スペク
トルを有することが望ましい。広い抗菌スペクトルを有
する物質の例としては、ピロロマイクン類があり、これ
は細菌、白癖菌、植物病原菌等に対する抗菌作用を有す
ることが知られている（特開昭５８−１２６８６３号）
。Much research has been conducted to develop antibacterial agents that act on fungi that infect humans and plants and have adverse effects on them. It is desirable that the antibacterial agent has strong antibacterial activity and a broad antibacterial spectrum. Examples of substances with a broad antibacterial spectrum include pyrrolomicrons, which are known to have antibacterial effects against bacteria, white fungi, plant pathogens, etc. (Japanese Patent Application Laid-Open No. 126863/1983).
.
しかしながら、このピロロマイシン類はカンシダ菌に対
して無効であるため更に広い抗菌スペクトルを有する化
合物の開発が要望されていた。However, since these pyrolomycins are ineffective against Cansida, there has been a demand for the development of compounds with a broader antibacterial spectrum.
斯かる実状に鑑み、本発明者らは種々のピロール誘導体
を合成し、その抗菌作用を検討していたところ、下記の
式（Ｉ）で表わされるピロール誘導体が細菌、カンシダ
菌、白癖菌、植物病原菌等に対し優れた抗菌作用を有す
ることを見い出し、本発明を完成した。In view of this situation, the present inventors synthesized various pyrrole derivatives and examined their antibacterial effects, and found that the pyrrole derivative represented by the following formula (I) was found to be effective against bacteria, Cansida fungi, Shirotai fungi, They discovered that it has an excellent antibacterial effect against plant pathogens, etc., and completed the present invention.
すなわち、本発明は次の一般式（Ｉ）
（式中、Ｘｌ及びＸ、は同−又は異なってハロダン原子
を、Ｒ１は水素原子又は基−ＣＯＲ。That is, the present invention is directed to the following general formula (I) (wherein, Xl and X are the same or different and represent a halodane atom, and R1 is a hydrogen atom or a group -COR).
（ここでＲ８は低級アルキル基を示す）を、Ｒ１は水素
原子、ハロゲン原子又は低級アルキル基を示す。ただし
％ Ｒ１が水素原子であって％ Ｒ２が臭素原子の場合
を除く）で表わされるピロール誘導体を提供するもので
ある。(Here, R8 represents a lower alkyl group), and R1 represents a hydrogen atom, a halogen atom, or a lower alkyl group. provided that %R1 is a hydrogen atom and %R2 is a bromine atom).
本発明化合物（Ｉ）は、例えば次の方法のいずれかによ
シ製造することができる。Compound (I) of the present invention can be produced, for example, by any of the following methods.
方法ｌ：
エステル型誘導体（Ｉ）にフリース転位反応を行なうこ
とによシ、化合物（ｆａ ）を製造するＯ
（式中、Ｘｌ、Ｘ、及びＲ１は前述した意味を有する。Method 1: Preparing the compound (fa) by subjecting the ester derivative (I) to a Fries rearrangement reaction.
）
本反応は塩化アルミニウム、塩化亜鉛、四塩化スズ等の
ルイス酸存在下、反応溶媒として二硫化炭素、スルホラ
ン、ニド四ベンゼン等を用い、１００〜２００℃の反応
温度で行なうことが好ましい。) This reaction is preferably carried out in the presence of a Lewis acid such as aluminum chloride, zinc chloride, tin tetrachloride, etc., using carbon disulfide, sulfolane, nidotetrabenzene, etc. as a reaction solvent, and at a reaction temperature of 100 to 200°C.
方法２：
２−（２−メトキシベンゾイル） −４、５−ジハロビ
ロール（Ｉ）をヨウ素化し、次いで脱メチル化反応を行
なうことによ）化合物（Ｉｍ’）を製造する。Method 2: Compound (Im') is produced by iodizing 2-(2-methoxybenzoyl)-4,5-dihalobyrole (I) and then performing a demethylation reaction.
（厘）
（Ｉａ’）（式中、Ｘ
ｌは前述した意味を有する。）本反応は、まずジオキサ
ン−水などの混合溶媒中でヨウ化ナトリウム又はヨウ化
カリウムの存在下にヨウ素を反応させることによシ容易
にヨウ素化される。次の脱メチル化反応は、常法に従い
塩化アルミニウム、三臭化ホウ素等のルイス酸を反応さ
せることによル行なわれる。(Lin)
(Ia') (wherein, X
l has the meaning given above. ) In this reaction, iodine is easily iodinated by first reacting iodine in the presence of sodium iodide or potassium iodide in a mixed solvent such as dioxane-water. The next demethylation reaction is carried out by reacting with a Lewis acid such as aluminum chloride or boron tribromide according to a conventional method.
方法３：
化合物（Ｉｍ ）をアシル化することによシ化合物（Ｉ
ｂ ）を製造する。Method 3: Compound (Im) is acylated to form compound (I)
b) Manufacture.
（ｒｂ ）
（式中、Ｘｌ ＋ Ｘｌ ＋ Ｒ１及びＲ３は前述した
意味を有する。）
本反応は、通常のアフル化反応、例えば低級脂肪酸の無
水物、酸ノ・ライド等を塩基の存在下に反応させること
により行なわれる。(rb) (In the formula, Xl + Xl + R1 and R3 have the above-mentioned meanings.) This reaction is a general affilation reaction, such as lower fatty acid anhydride, acid oride, etc., in the presence of a base. This is done by reacting.
なお、原料であるエステル型誘導体（夏）は、例えば次
式に従い３＋ ４１５− ） ＩＪ ／Ｎロビロールー
２−カルボン酸又はその反応性誘導体とジエノール類を
反応させることによシ製造される。The ester derivative (summer) which is a raw material is produced, for example, by reacting 3+ 415- ) IJ /N robirole-2-carboxylic acid or a reactive derivative thereof with a dienol according to the following formula.
（式中、Ｘｌ、Ｘ、及びＲ，は前述した意味を有する）
反応は常法に従い、例えば、３，４．５−トリハロピロ
Ｎルー２−カルボン酸トフェノール類を無水トリフルオ
ロ酢酸等の縮合剤の存在下に反応させるか、３，４．５
−）ＩＪハロビロール−２−カルボン酸ハライドをフェ
ノール類と反応させることによ）行なわれる。(In the formula, Xl, 3,4.5
-) by reacting IJ halobirol-2-carboxylic acid halide with phenols).
叙上の如くして得られた本発明の代表的化合物について
その抗菌作用を調べた。比較化合物としてピロロマイク
ンｌｉ’、 （特開昭５８−１２６８６３号）を用い、
その結果を第１表に示す。なお、表中の化合物番号は、
後記実施例中に示したものと同一である。The antibacterial activity of representative compounds of the present invention obtained as described above was investigated. Using pyrrolomicun li' (Japanese Unexamined Patent Publication No. 126863/1983) as a comparison compound,
The results are shown in Table 1. In addition, the compound numbers in the table are
This is the same as that shown in Examples below.
以下余白
〔発明の効果〕
斯くして得られた本発明化合物（Ｉ）は、細菌、カンシ
ダ菌、白癖菌、植物病原菌等に対し、優れた抗菌活性を
有するので、医薬、農薬及び防腐剤等として有用なもの
である。The following margins [Effects of the Invention] The compound (I) of the present invention thus obtained has excellent antibacterial activity against bacteria, Cansida fungi, Lepidoptera fungi, plant pathogenic bacteria, etc. It is useful as such.
次に実施例を挙げ、本発明を説明する。 Next, the present invention will be explained with reference to Examples.
実施例１
３．４．５−トリブロモビロール−２−カルデン酸２．
２Ｏｆを含むトルエン２０ｄ溶液に、フェノール１．７
８ Ｆと無水トリフルオロ酢酸Ｚ７ｄを加え、室温で約
１５時間攪拌した。反応液を氷水４Ｑｍに注加し、エー
テルで抽出した。抽出液を２％炭酸水素す） ＩＪウム
水溶液、ＩＮ塩酸、水で順次洗浄し、無水硫酸す） Ｉ
Ｊウムで乾燥後、減圧留去した。残留物を二硫化炭素５
０ｄに溶解し、塩化アルミニウム０．８ Ｏｆを加え、
１時間加熱還流した。次いで二硫化炭素を留去し、反応
温度を約１６０℃に上昇させ、１時間加熱攪拌した。Example 1 3.4.5-Tribromovirol-2-caldenic acid 2.
Phenol 1.7 in a toluene 20d solution containing 2Of
8F and trifluoroacetic anhydride Z7d were added, and the mixture was stirred at room temperature for about 15 hours. The reaction solution was poured into 4Qm of ice water and extracted with ether. Wash the extract with 2% hydrogen carbonate solution, IN hydrochloric acid, and water in sequence, and dilute with anhydrous sulfuric acid.
After drying with Jum, the residue was distilled off under reduced pressure. The residue is carbon disulfide5
0d, add 0.8Of aluminum chloride,
The mixture was heated under reflux for 1 hour. Next, carbon disulfide was distilled off, the reaction temperature was raised to about 160°C, and the mixture was heated and stirred for 1 hour.
今後、反応物にＩＮ塩酸２０ｄを注加し、エーテルで抽
出した。抽出液を水洗し、無水硫酸す） ＩＪウムで乾
燥後、濃縮した。残留物をシリカゲルカラムクロマトグ
ラフィーに付し、クロロホルム流出画分から得られた淡
黄色結晶を四塩化炭素よシ再結晶すると、２−（２−ハ
イトロキシペンゾイル）−３，４，５−トリブロモビロ
ール（化合物１）１．ａ５ｒを淡黄色結晶として得た。Thereafter, 20 d of IN hydrochloric acid was added to the reaction mixture and extracted with ether. The extract was washed with water, dried over anhydrous sulfuric acid, and concentrated. The residue was subjected to silica gel column chromatography, and the pale yellow crystals obtained from the chloroform effluent fraction were recrystallized from carbon tetrachloride to give 2-(2-hydroxypenzoyl)-3,4,5-tribromobi Roll (compound 1)1. a5r was obtained as pale yellow crystals.
実施例２
１１一
実施例１で得られた化合物１０．５０ｆをピリシン３ｄ
に溶解し、無水酢酸３１ｔｌに加え、室温で４時間攪拌
した。反応液を氷水２０１１１７に注加し、エーテルで
抽出した。抽出液をＩＮ塩酸、２％炭酸水素す） ＩＪ
ウム水溶液、水で順次洗浄し、無水硫酸ナトリウムで乾
燥後、濃縮した。析出した結晶をイソゾロビルエーテル
−アセトン混液よシ再結晶すると、２−（２−アセトキ
シベンゾイル）−３，４，５−トリブロモビロール（化
合物２）０．４ｓｒを無色結晶として得た。Example 2 Compound 10.50f obtained in Example 1 was added to pyricin 3d.
The mixture was added to 31 tl of acetic anhydride, and the mixture was stirred at room temperature for 4 hours. The reaction solution was poured into ice water 201117 and extracted with ether. Add the extract to IN hydrochloric acid, 2% hydrogen carbonate) IJ
The mixture was washed successively with an aqueous solution of sodium chloride and water, dried over anhydrous sodium sulfate, and then concentrated. The precipitated crystals were recrystallized from a mixture of isozolobyl ether and acetone to obtain 0.4 sr of 2-(2-acetoxybenzoyl)-3,4,5-tribromovirol (compound 2) as colorless crystals.
実施例３
２−（２−メトキシベンゾイル） −４、５−ゾクロロ
ビ四−ル０．５４ ｆにジオキサン−水混液（Ｉ：１）
８ｍ／とｌ Ｎ ＮａＯＨ水溶液２ｄを加えて溶かし
、ヨウ素０．６ Ｏｆとヨウ化ナトリウム０．７２ Ｆ
を含む水溶液６ｗＬｌを加え、室温で１５時間攪拌した
。反応液にＩＮチオ硫酸ナトリウム水溶液２０ｍを加え
て１時間攪拌した。析出した結晶をｒ取し、水洗後乾燥
するｌ！：％２−（２−メトキシベンゾイル）−３−ヨ
ード−４，５−シクロルビロール０．６２ ｆを無色結
晶として得た。この結晶０．３２ ｆをジクロルメタン
２０−に溶解し、塩化アルミニウム０．６６ｆを加え、
室温で５時間攪拌した。反応液にＩＮ塩酸２０１１Ｅ／
を注加し、ジクロルメタンで抽出した。抽出液を水洗し
、無水硫酸す） ＩＪウムで乾燥後、濃縮した。析出し
た結晶を四塩化炭素よシ再結晶すると、２−（２−ハイ
ドロキシベンゾイル）−３−ヨートー４．５−ジクロロ
ビロール０．２６ ｆを淡黄色結晶として得た。Example 3 Dioxane-water mixture (I:1) to 0.54 f of 2-(2-methoxybenzoyl)-4,5-zochlorobi-4-yl
Add and dissolve 2 d of 8 m/l N NaOH aqueous solution, 0.6 Of iodine and 0.72 F of sodium iodide.
6wLl of an aqueous solution containing was added, and the mixture was stirred at room temperature for 15 hours. 20 ml of IN sodium thiosulfate aqueous solution was added to the reaction solution, and the mixture was stirred for 1 hour. Collect the precipitated crystals, wash them with water, and then dry them! :%2-(2-methoxybenzoyl)-3-iodo-4,5-cycloruvirol 0.62 f was obtained as colorless crystals. Dissolve 0.32 f of this crystal in 20-dichloromethane, add 0.66 f of aluminum chloride,
The mixture was stirred at room temperature for 5 hours. IN hydrochloric acid 2011E/
was added and extracted with dichloromethane. The extract was washed with water, dried over anhydrous sulfuric acid, and concentrated. The precipitated crystals were recrystallized from carbon tetrachloride to obtain 0.26 f of 2-(2-hydroxybenzoyl)-3-ioto-4,5-dichloropyrol as pale yellow crystals.
実施例４〜１０
実施例１又は２のいずれかと同様にして第２表に示す化
合物番号４〜１０の化合物を調製した。なお、同表中に
は化合物１〜３の物性も併せて示した。Examples 4 to 10 Compounds Nos. 4 to 10 shown in Table 2 were prepared in the same manner as in either Example 1 or 2. In addition, the physical properties of Compounds 1 to 3 are also shown in the same table.
以下余白
１１開口ＵＧ３−１８３５６２ （８）１、 事件の
表示
昭和６２年特許願第 １３１１２ 号２、 発明の名
称
ビｑ−ル誘導体
３、補正をする者
事件との関係 出願人
名 称 ニスニス製薬株式会社
６、補正の゛対象
明細書の「発明の詳細な説明」の欄
７、補正の内容
（Ｉ）明細書中、第４頁第３行
ｒ Ｒｓは低級アルキル基」とあるを
「ＲｓはＣ！〜Ｃ４の低級アルキル基」と訂正する。Margin below 11 openings UG3-183562 (8) 1. Indication of the case Patent Application No. 13112 of 1988 2. Name of the invention Beer Q-derivative 3. Person making the amendment Relationship to the case Applicant name Name Nisnis Pharmaceutical Co., Ltd. 6. Column 7 of "Detailed Description of the Invention" of the subject specification of the amendment, contents of the amendment (I) In the specification, page 4, line 3 r.Rs is a lower alkyl group instead of "Rs is a C !~C4 lower alkyl group” is corrected.
（２）同第１５頁第３行 ［実施例４〜ＩＯＪとあるを 「実施例４〜１１」と訂正する。(2) Page 15, line 3 [Example 4 - IOJ Corrected to "Examples 4 to 11."
（３）同第１５頁第５行 ［化合物番号４〜ＩＯＪとあるを 「化合物番号４〜１１」と訂正する。(3) Page 15, line 5 [Compound number 4 ~ IOJ Correct to "Compound Nos. 4-11".
（４）同第１７頁「第２表」の末尾に次の欄を挿入する
。(4) Insert the following column at the end of "Table 2" on page 17.
Claims (1)
原子を、Ｒ＿１は水素原子又は基−ＣＯＲ＿３（ここで
Ｒ＿３は低級アルキル基を示す）を、Ｒ＿２は水素原子
、ハロゲン原子又は低級アルキル基を示す。ただし、Ｒ
＿１が水素原子であつてＲ＿２が臭素原子の場合を除く
） で表わされるピロール誘導体。[Claims] 1. The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X_1 and X_2 are the same or different and represent a halogen atom, and R_1 is a hydrogen atom or a group. -COR_3 (here, R_3 represents a lower alkyl group), and R_2 represents a hydrogen atom, a halogen atom, or a lower alkyl group. However, R
A pyrrole derivative represented by (except when _1 is a hydrogen atom and R_2 is a bromine atom).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1311287A JPS63183562A (en) | 1987-01-22 | 1987-01-22 | Pyrrole derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1311287A JPS63183562A (en) | 1987-01-22 | 1987-01-22 | Pyrrole derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63183562A true JPS63183562A (en) | 1988-07-28 |
Family
ID=11824072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1311287A Pending JPS63183562A (en) | 1987-01-22 | 1987-01-22 | Pyrrole derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63183562A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10414725B2 (en) * | 2015-07-16 | 2019-09-17 | Board Of Regents Of The University Of Nebraska | Pyrrolomycins and methods of using the same |
-
1987
- 1987-01-22 JP JP1311287A patent/JPS63183562A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10414725B2 (en) * | 2015-07-16 | 2019-09-17 | Board Of Regents Of The University Of Nebraska | Pyrrolomycins and methods of using the same |
| US10954192B2 (en) | 2015-07-16 | 2021-03-23 | Board Of Regents Of The University Of Nebraska | Pyrrolomycins and methods of using the same |
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