JPH02237964A - Tropolone derivative - Google Patents
Tropolone derivativeInfo
- Publication number
- JPH02237964A JPH02237964A JP5777689A JP5777689A JPH02237964A JP H02237964 A JPH02237964 A JP H02237964A JP 5777689 A JP5777689 A JP 5777689A JP 5777689 A JP5777689 A JP 5777689A JP H02237964 A JPH02237964 A JP H02237964A
- Authority
- JP
- Japan
- Prior art keywords
- nmr
- formula
- tropolone
- compound
- cdc
- 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
- 150000004788 tropolones Chemical class 0.000 title claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 15
- MDYOLVRUBBJPFM-UHFFFAOYSA-N tropolone Chemical compound OC1=CC=CC=CC1=O MDYOLVRUBBJPFM-UHFFFAOYSA-N 0.000 abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 abstract description 6
- LOVOYRLAEIBBPN-UHFFFAOYSA-N dodecyl 2,3,4,5,6-pentafluorobenzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=C(F)C(F)=C(F)C(F)=C1F LOVOYRLAEIBBPN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 abstract description 4
- RHKLONPUIWSHCD-UHFFFAOYSA-N 4,5-dihydroxycyclohepta-2,4,6-trien-1-one Chemical compound OC=1C=CC(=O)C=CC=1O RHKLONPUIWSHCD-UHFFFAOYSA-N 0.000 abstract description 3
- MEXUTNIFSHFQRG-UHFFFAOYSA-N 6,7,12,13-tetrahydro-5h-indolo[2,3-a]pyrrolo[3,4-c]carbazol-5-one Chemical compound C12=C3C=CC=C[C]3NC2=C2NC3=CC=C[CH]C3=C2C2=C1C(=O)NC2 MEXUTNIFSHFQRG-UHFFFAOYSA-N 0.000 abstract description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000104 sodium hydride Inorganic materials 0.000 abstract description 3
- 239000012312 sodium hydride Substances 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000000417 fungicide Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 3
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 230000000855 fungicidal effect Effects 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- FBBRKYLXMNQFQU-UHFFFAOYSA-N 4-pentylbenzoyl chloride Chemical compound CCCCCC1=CC=C(C(Cl)=O)C=C1 FBBRKYLXMNQFQU-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000003340 mental effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- -1 n-dodecyl Chemical group 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- 101150041968 CDC13 gene Proteins 0.000 description 1
- 241001275944 Misgurnus anguillicaudatus Species 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- UXJRQNXHCZKHRJ-UHFFFAOYSA-N methyl 2,3,4,5,6-pentafluorobenzoate Chemical compound COC(=O)C1=C(F)C(F)=C(F)C(F)=C1F UXJRQNXHCZKHRJ-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- QVWDCTQRORVHHT-UHFFFAOYSA-N tropone Chemical compound O=C1C=CC=CC=C1 QVWDCTQRORVHHT-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
く産業上の利用分野〉
本発明は、殺菌剤等の農薬の原料あるいは医薬中間体と
して有用なトロポロン誘導体に関するものである．
〈従来の技術〉
本発明における新規なトロポロン誘導体は、今まで全く
報告されていない。またこれらの製造法についても今ま
で全く報告されていない。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to tropolone derivatives useful as raw materials for agricultural chemicals such as fungicides or as pharmaceutical intermediates. <Prior Art> The novel tropolone derivative of the present invention has not been reported at all so far. Furthermore, there have been no reports on these manufacturing methods.
く発明の構成〉
本発明は、下記一般式（Ｉ）で示されるトロポロン誘導
体を提供するものである。Structure of the Invention The present invention provides a tropolone derivative represented by the following general formula (I).
Ｆ
Ｆ
〔ただし、式中、Ｒ１は炭素数１〜２０のアルキル基を
表わし、Ｒ２は■，−ＯＣＲ．またはルキル基、炭素数
１〜２０のアルコキシ基、−ＣＮ基を表わす）を表わす
．〕
具体的には例えば、（ａ）〜（ホ）等の構造式の化合物
が挙げられる．
Ｆ
Ｆ
本発明の化合物はいずれも文献未載の新規化合物であり
、たとえば、上記化合物（ａ）〜（ハ）等については、
下記の経路で合成することができる（ただし、Ｒ，およ
びＲオは前記と同じものを意味する）．この経路に関し
て、前記化合物（ｄ）を合成する方法で説明する。精製
したインゼンにペンタフルオロ安息香酸、ドデシルアル
コール、および硫酸を加えモレキュラーシーブで水を除
去しながら、窒素気流下で加熱還流し、反応後、溶媒を
留去し、残渣をシリカゲルカラムクロマトグラフィーで
分離精製し、ペンタフルオロ安息香酸ドデシルエステル
を得る．次に精製したヘキサメチルホスホリックトリア
ミド（以後ＨＭＰＡと略す．）に５ーヒドロキシトロポ
ロンと水素化ナトリウム（Ｎａｐ）を加え、窒素気流下
、０”Ｃで約１時間撹拌したものに、得られるペンタフ
ルオロ安息香酸ドデシルエステルを加え、反応させる．
次いで得られる反応溶液を塩酸水溶液中に加え、その後
酢酸エチルで抽出する．有機層を水で洗浄し、硫酸マグ
ネシウムで乾燥後、減圧下で溶媒を留去し、化合物（ｄ
）を得る．
また、化合物（ｉ）〜（ホ）については、下記の経路で
合成することができる（だだし、Ｒ１およびＲ，は前記
と同じものを示す）．
って得られるものでないことは言うまでもない。F F [In the formula, R1 represents an alkyl group having 1 to 20 carbon atoms, and R2 represents ■, -OCR. or alkyl group, alkoxy group having 1 to 20 carbon atoms, -CN group). ] Specific examples include compounds having the structural formulas (a) to (e). F F All of the compounds of the present invention are new compounds that have not been published in any literature. For example, for the above compounds (a) to (c), etc.,
It can be synthesized by the following route (where R and R have the same meanings as above). This route will be explained in terms of the method for synthesizing the compound (d). Pentafluorobenzoic acid, dodecyl alcohol, and sulfuric acid are added to purified inzene, and while water is removed using a molecular sieve, the mixture is heated to reflux under a nitrogen stream. After the reaction, the solvent is distilled off and the residue is separated using silica gel column chromatography. Purification yields pentafluorobenzoic acid dodecyl ester. Next, 5-hydroxytropolone and sodium hydride (Nap) were added to the purified hexamethylphosphoric triamide (hereinafter abbreviated as HMPA), and the mixture was stirred at 0"C for about 1 hour under a nitrogen stream. Add pentafluorobenzoic acid dodecyl ester and allow to react.
Next, the resulting reaction solution is added to an aqueous hydrochloric acid solution, and then extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the compound (d
) is obtained. Compounds (i) to (e) can be synthesized by the following route (R1 and R are the same as above). Needless to say, this is not something you can get.
く実施例〉
次に、実施例によって本発明をさらに詳細に説明する．
実施例１
この経路に関して前記化合物（ｊ）を合成する方法で説
明する．
精製したピリジンに、化合物（ｄ）、４−ペンチルベン
ゾイルクロライドを加え、４−ジメチルアミノピリジン
（以後ＤＭＡＰと略す）を触媒として窒素気流下、室温
で反応させ、得られた反応溶液を塩酸水溶液中に加え、
反応を停止し、酢酸エチルで抽出する．有機層を水で洗
浄し、硫酸マグネシウムで乾燥後、減圧下溶媒を留去し
、残渣を酢酸エチルを溶離液としたシリカゲルカラムク
ロマトグラフィーで分離精製し、化合物（Ｊ）を得る．
なお本発明の化合物が上記の合成経路のみによ精製した
ベンゼン１０ｍｆにペンタフルオ口安息香酸５００■（
２．３ ６ｓｍｏｌ） 、ｎ−ドデシルアルコール２．
１ｇ （１１．０ｓｍｏｌ）および硫酸（触媒量）を加
え、モレキュラーシープ３Ａで水を除去しながら、窒素
気流下、１１時間加熱還流した。Examples Next, the present invention will be explained in more detail with reference to Examples. Example 1 This route will be explained by the method of synthesizing the compound (j). Compound (d) and 4-pentylbenzoyl chloride were added to purified pyridine, and the mixture was reacted with 4-dimethylaminopyridine (hereinafter abbreviated as DMAP) at room temperature under a nitrogen atmosphere, and the resulting reaction solution was added to an aqueous hydrochloric acid solution. In addition to
Stop the reaction and extract with ethyl acetate. The organic layer is washed with water, dried over magnesium sulfate, the solvent is distilled off under reduced pressure, and the residue is purified by silica gel column chromatography using ethyl acetate as the eluent to obtain compound (J).
The compound of the present invention was prepared by adding 500 μm of pentafluorobenzoic acid (
2.3 6smol), n-dodecyl alcohol2.
1 g (11.0 smol) and sulfuric acid (catalytic amount) were added, and the mixture was heated under reflux for 11 hours under a nitrogen stream while removing water using a molecular sheep 3A.
反応後溶媒を除去し、酢酸エチル２０ｍｆを加え、水洗
後硫酸マグネシウムで乾燥し、減圧下溶媒を留去した．
残渣をシリカゲルカラムクロマトグラフィー（酢酸エチ
ルで流出）で分離精製し、ペンタフルオロ安息香酸ドデ
シルエステルを得た．次いで得られたペンタフルオロ安
息香酸ドデシルエステル１０００■（２．３６＋＊ｉｔ
ｏｌ）を精製したＨＭＰＡ５ｍｊ！に５−ヒドロキシト
ロポロン３８６■（２．８１１１１０１）および５０％
濃度の水素化ナトリウム１５４■（３． １ ｍｍｏｌ
）を加え、窒素気流下Ｏ℃で約１時間溶液の色が濃紫色
になるまで撹拌したものに加え、窒素気流下１２時間撹
拌した。反応後、反応液を冷２Ｎ−塩酸水溶液にあけ、
酢酸エチルで抽出、水洗、硫酸マグネシウムで乾燥後減
圧下溶媒を留去し、５−（４−ドデシルオキシカルボニ
ルテトラフルオロフエノキシ）トロポロンを得た．
このものの物性を下記に示す．
融点 １０４℃
’Ｈ−ＮＭＲ （ＣＤＣ Ｉｔ ３）δ０．８８（３
Ｈ，ｔ．Ｊ＝７．３Ｈｚ）． １．２−１．５（１８Ｈ
．ｍ）．１．７７（２｝１．ｑｕｉｎｔ．Ｊ＝７．３１
｛ｚＬ ４．４０（２Ｈ．ｔ，Ｊ−６．６Ｈｚ）．７．
１３（２Ｈ．ｄｓ，Ｊ＝１２．５Ｈｚ）． ７．２９（
２Ｈ，ｄａ，Ｊ−１２．５Ｈｚ）” Ｃ−ＮＭＲ （Ｃ
ＤＣ ｌ ｓ）
δ１４．１． ２２．７． ２５．８． ２８．５，
２９．２． ２９．３． ２９．５．２９．５６． ２
９．６３． ３１．９， ６７．１， １１０．０，
１２３．３．１２５．５， １３５．３， １４１
．２（ＪＣＦ寓２４５．５Ｈｚ），１４５．５（Ｊｃｙ
■２５６．３Ｈｚ）． １５５．７， １５９．２，
１７０．０１９Ｆ−ＮＭＲ （ＣＤＣ ｌ ｓ）δ
９．０． ２３．６ （１：１）ＭＳ ｍＨｚ ４
９７（Ｍ”−１），４９８（Ｍ”）．４９９（Ｍ”＋１
），ＩＲ （ＫＢｒ，ｄｉｓｃ）
ν ３５００−３０００． ２９００． ２８３０
． １？３０． １６３０， １６１０，１５７
０． １４９０． １４２０， １３３０．
１２３０． ９９０ ｃｍ−’Ｅｌｅｓｅｎｔａｌ
ａｎａｌｙｓｉｓ ｆｏｒ ＣｚＪ３ａＯｓＦ４
Ｃａｌｃｄ （％） Ｃ ６２．６４ Ｈ
６．０７Ｆｏｕｎｄ （％） Ｃ ６２．６
９ Ｈ ６．３３実施例２〜６
実Ｍｉ例１においてｎ−ドデシルアルコールの代りに、
下記表１のアルコールを用いた以外実施例１と同様に操
作してそれぞれのトロポロン誘導体を得た．
これらの物性を下記に示す。After the reaction, the solvent was removed, 20 mf of ethyl acetate was added, and the mixture was washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.
The residue was separated and purified by silica gel column chromatography (elution with ethyl acetate) to obtain pentafluorobenzoic acid dodecyl ester. Then, the obtained pentafluorobenzoic acid dodecyl ester 1000μ (2.36+*it
HMPA5mj! 5-hydroxytropolone 386 (2.8111101) and 50%
Concentration of sodium hydride 154■ (3.1 mmol
) and stirred at 0° C. under a nitrogen stream for about 1 hour until the color of the solution turned deep purple, and the mixture was stirred for 12 hours under a nitrogen stream. After the reaction, the reaction solution was poured into a cold 2N aqueous hydrochloric acid solution,
After extraction with ethyl acetate, washing with water, and drying over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 5-(4-dodecyloxycarbonyltetrafluorophenoxy)tropolone. The physical properties of this material are shown below. Melting point 104℃ 'H-NMR (CDC It 3) δ0.88 (3
H,t. J=7.3Hz). 1.2-1.5 (18H
．． m). 1.77 (2}1.quint.J=7.31
{zL 4.40 (2H.t, J-6.6Hz). 7.
13 (2H.ds, J=12.5Hz). 7.29 (
2H, da, J-12.5Hz)” C-NMR (C
DC l s) δ14.1. 22.7. 25.8. 28.5,
29.2. 29.3. 29.5.29.56. 2
9.63. 31.9, 67.1, 110.0,
123.3.125.5, 135.3, 141
．． 2 (JCF 245.5Hz), 145.5 (Jcy
■256.3Hz). 155.7, 159.2,
170.019F-NMR (CDCl s)δ
9.0. 23.6 (1:1) MS mHz 4
97 (M"-1), 498 (M"). 499(M”+1
), IR (KBr, disc) ν 3500-3000. 2900. 2830
．． 1?30. 1630, 1610, 157
0. 1490. 1420, 1330.
1230. 990 cm-'Elesental
analysis for CzJ3aOsF4
Calcd (%) C 62.64 H
6.07 Found (%) C 62.6
9 H 6.33 Examples 2 to 6 In place of n-dodecyl alcohol in Example 1,
Each tropolone derivative was obtained in the same manner as in Example 1 except that the alcohols shown in Table 1 below were used. These physical properties are shown below.
裏腹斑主鬼上企宜
’Ｈ−ＮＭＲ （ＣＤＣ ｌ ｘ）
６３．９４（３Ｈ．ｓ）， ６．８０（２Ｈ，ｂｒｄ．
Ｊ＝１１．０Ｈｚ），７．２７（２Ｈ．ｂｒｄ．Ｊ＝１
１．ＯＩＩｚ）１３Ｃ−ＮＭＲ （ＣＤ（Ｉ！．！）
δ５３．３， ９５．３， １０６．５， １２０．６
， １２５．９，１４０．８（ＪｃＦ”２６５．１Ｈｚ
）， １４５．３（Ｊｃｙ＝２５３．３Ｈｚ），１５９
．３， １７２．０． １８０．１”Ｆ−ＮＭＲ （Ｃ
ＤＣｊ！ ！）
δ７．８． ２２．６ （１：１）
ＭＳ ｓ／ｚ ３４３（Ｍ”−１）， ３４４（Ｍ”）
． ６９（ｂｐ．）ＩＲ （ＫＢｒ．ｄｉｓｃ）
ν３５００−３２００． １７２５． １４８５． １
４３５， １３９０． １３２５，１２２５． １１６
０ ｃｍ＋一肌
ス１劃１ノ■を釦拠
融点 ９４℃
置トＮ朋 （ＣＤＣ Ｉ． ｓ）
６０．８８（３Ｈ．ｔ．Ｊ−７．０Ｈｚ）． １．２−
１．５（ＩＯＨ，ａ＋）．１．７７（２Ｈ．ｑｕｉｎｔ
．Ｊ−７．０Ｈｚ）． ４．４０（２Ｈ，ｔ，Ｊ．６．
６Ｈｚ），７．１４（２Ｈ，ｄｍ．Ｊ＝１２．１１｛ｚ
）． ７．２９（２Ｈ，ｄｍ，Ｊ＝１２．１Ｈｚ）”Ｃ
−ＮＭＲ （ＣＤＣｌ３）
δ １４．１． ２２．６． ２５．８． ２Ｂ．５．
２９．１０． ２９．１４．３１．８． ６７．１，
１０９．８， １２３．３， １２５．５， １３５
．１．１４１．２（Ｊｃｒ−２４５．５Ｈｚ），１４５
．６（Ｊｃｙ・２５３．３Ｈｚ）．１５５．７， １
５９．２， １７０．０ＩｑＦ−ＮＭＲ （ＣＤ（
Ｊ コ）
δ ９，０． ２３．６ （１：１）ＭＳ ｔａ／
ｚ ４４２（Ｍつ， ４４３（Ｍ”＋１）．ＩＲ （
ＫＢｒ，ｄｉｓｃ）
ν ３５００−３０００． ２９００， ２８３０．
１７３０． １６３０， １６１０．１５７０．
１４９０， １４２０， １３３０， １２３０． ９
９０ ｃｍ−’Ｅｌｅｍｅｎｔａｌ ａｎａｌｙｓｉｓ
ｆｏｒ ＣＢＨｔｔＯｓＦ４Ｃａｌｃｄ （％）
Ｃ ５９．７３ Ｈ ５．０１Ｆｏｕｎｄ
（％） Ｃ ５９．８０ Ｈ ５．２１実１
１ｕＪ回し九血
融点 ｉ ｏ ｏ ’ｃ
’Ｈ−ＮＭＲ （ＣＤＣ ｆ Ｍ＞
６ ０．８８（３Ｈ．ｔ．Ｊ＝７．０Ｈｚ）． １．
２−１．５（１４Ｈ，ｏ＋），１．７２（２Ｈ，ｑｕｉ
ｎｔ，Ｊ＝７．０Ｈｚ）， ４．４０（２Ｈ．ｔ，Ｊ＝
６．６Ｈｚ），７．１４（２Ｈ，ｄａ，Ｊ−１２．３Ｈ
ｚ）． ７．３０（２Ｈ．ｄｍ，Ｊ＝１２．３Ｈｚ）
” Ｃ−ＮＭＲ （ＣＤＣ ｊ！ ｓ）δ １４．１
． ２２，７． ２５．８． ２Ｂ．５． ２
９．２． ２９．３． ２９．４９，２９．５２．
３１．９． ６７．１， １０９．９， １
２３．３， １２５．５．１３５．３， １４１．
２（Ｊｃｒ’２４４．５Ｈｚ）． １４５．６（ＪＣ
Ｆ＝２５２．４ＨＺ）． １５５．７， １５９．
３， １７０．０’”Ｆ４ＭＲ （ＣＤＣｆ ：ｌ
）
δ ９．０， ２３．６ （１：１）ＭＳ ｍＨ
ｚ ４６Ｂ（Ｍ”−２）． ４６９（Ｍ”−１）．
４７０（Ｍ”）ＩＲ （ＫＢｒ，ｄｉｓｃ）
ν ３５００−３０００． ２９００． ２８３０
． １？３０． １６３０， １６１０．１５７
０， １４９０． １４２０． １３３０，
１２３０． ９９０ ｃｍ−’Ｅｌｅｍｅｎｔａｌ
ａｎａｌｙｓｉｓ ｆｏｒ Ｃｚ４Ｈｚ１ｌＯｓ
ＰｎＣａｌｃｄ （％） Ｃ ６１，２７
Ｈ ５．５７Ｆｏｕｎｄ （％） Ｃ ６１
．３２ Ｈ ５．７８次ｌ！ｌＪ８レ釦血
融点 １０日゜Ｃ
’Ｈ−ＮＭＲ （ＣＤＣ ｌ ２）
６ ０．８８（３Ｈ，ｔ，Ｊ＝７．０Ｈｚ）， １．
２−１．５（２２Ｈ，ａ＋），１．７７（２Ｈ．ｑｕｉ
ｎｔ，Ｊ−７．０Ｈｚ）． ４．４０（２Ｈ，ｔ，Ｊ
＝６．６Ｈｚ）．？．１４（２Ｈ．ｄｍ．Ｊ＝１２．５
Ｈｚ）． ７．３０（２１１，ｄｍ，Ｊ＝１２．５Ｈ
ｚ）” Ｃ−ＮＭＲ （ＣＤＣ ｊ！ ｓ）δ １４
．１． ２２．７． ２５．８， ２８．５．
２９．２， ２９．４． ２９．５．２９．６．
２９．７． ３１．９， ６７．１， １０
９．９， １２３．３，１２５．５，１３５．３，１
４１．２（Ｊｃｙ■２４５．５Ｈｚ），１４５．６（Ｊ
ＣＦ−２５０．４８Ｚ）， １５５．７， １５９
．２， １７０．０’ ”Ｐ−ＮＭＲ （ＣＤＣ
１ ｓ）δ ９．０． ２３．６ （１：１）ＭＳ
ｒａ／ｚ ５２７（Ｍ”）
ＩＲ （ｌＢｒ．ｄｉｓｃ）
ν ３５００−３０００．２９００．２８３０．１？３
０，１６３０，１６１０．１５７０，１４９０，１４２
０，１３３０．１２３０．９９０ ｃｍ−’ｔ！ｌｅｍ
ｅｎｔａｌ ａｎａｌｙｓｉｓ ｆｏｒ Ｃｇｓ
Ｈｓ４０ｓＦ４Ｃａｌｃｄ （％） Ｃ ６３
．８７ Ｈ ６．５１Ｆｏｕｎｄ （％）
Ｃ ６４．１６ ８ ６．７９尖覇漫１口１ζ１
皇
融点 １０７゜Ｃ
’Ｈ−ＮＭＲ （ＣＤ（／！ ！）
６ ０．８８（３Ｈ．ｔ．Ｊ−６．９Ｈｚ）． ｉ，
２−１．５（２６｝１，ｍ）．１．７６（２Ｈ．ｑｕｉ
ｎｔ．Ｊ■６．９Ｈｚ）， ４．４０（２Ｈ．ｔ，Ｊ
＝６．６Ｈｚ），？．１３（２Ｈ．ｄｍ．Ｊ＝１２．１
Ｈｚ）． ７．２９（２Ｈ，ｄｍ，Ｊ−１２．１Ｈｚ
）” Ｃ−ＮＭＲ （ＣＤＣ Ｉ．ｚ）δ １４．１
． １５．３， ２２．７． ２５．８． ２
８．５， ２９．１． ２９．４，２９．５，
２９．６． ２９．７． ３１．９． ６７．１
， １０９．９， １２３．３，１２５．５，１３
５．３，１４１．１（Ｊｃｒ■２４４．５Ｈｚ），１４
５．６（Ｊｃｙ■２５３．３Ｈｚ）．１５５．７，１５
９．３， １７０．０”Ｆ−ＮＭＲ （ＣＤＣｊ！
ｓ）
δ ９．０， ２３．６ （１：１）ＭＳ ｒａ／
ｚ ５５４（Ｍ”）． ５５５（Ｍ”＋１）ＩＲ
（ＫＢｒ，ｄｉｓｃ）
ν ３５００−３０００．２９００．２Ｂ３０．１７３
０．１６３０．１６１０．１５７０．１４９０．１４２
０．１３３０．１２３０．９９０ ｃｍ−’Ｅｌｅｍｅ
ｎｔａｌ ａｎａｌｙｓｉｓ ｆｏｒ Ｃ３０Ｈ
３１１０５Ｆ４Ｃａｌｃｄ （％） Ｃ ６４
．９７ Ｈ ６．９１Ｆｏｕｎｄ （％）
Ｃ ６４．８９ Ｈ ６．９３実施例７
精製されたＨＭＰＡ Ｂｍｌ中に、５−ヒドロキシ−
２−メトキシトロポン２５■（０． １ ６０１１１０
１）（０． １ ８ｍｓ＋ｏｌ）を加え、窒素気流下Ｏ
℃で約１時間溶液の色が濃紫色になるまで撹拌した．そ
の後、ペンタフルオロ安息香酸メチルを過剰量加え、窒
素気流下室温で２４時間撹拌した．
反応溶液をＯ’Ｃ２Ｎ−塩酸水溶液中に加え、反応を停
止させ、酢酸エチルで抽出した。有機層を再び水で洗浄
し、硫酸マグネシウムで乾燥し、減圧下溶媒を留去した
。H-NMR (CDClx) 63.94 (3H.s), 6.80 (2H,brd.
J=11.0Hz), 7.27(2H.brd.J=1
1. OIIz) 13C-NMR (CD(I!.!) δ53.3, 95.3, 106.5, 120.6
, 125.9, 140.8 (JcF”265.1Hz
), 145.3 (Jcy=253.3Hz), 159
．． 3, 172.0. 180.1"F-NMR (C
DCj! ! ) δ7.8. 22.6 (1:1) MS s/z 343 (M"-1), 344 (M")
．． 69 (bp.) IR (KBr. disc) ν3500-3200. 1725. 1485. 1
435, 1390. 1325, 1225. 116
0 cm + 1 section 1 button Melting point 94℃ (CDC I.s) 60.88 (3H.t.J-7.0Hz). 1.2-
1.5 (IOH, a+). 1.77 (2H.quint
．． J-7.0Hz). 4.40 (2H, t, J.6.
6Hz), 7.14 (2H, dm.J=12.11{z
). 7.29 (2H, dm, J=12.1Hz)"C
-NMR (CDCl3) δ 14.1. 22.6. 25.8. 2B. 5.
29.10. 29.14.31.8. 67.1,
109.8, 123.3, 125.5, 135
．． 1.141.2 (Jcr-245.5Hz), 145
．． 6 (Jcy・253.3Hz). 155.7, 1
59.2, 170.0IqF-NMR (CD(
J Co) δ 9,0. 23.6 (1:1) MS ta/
z 442 (M, 443 (M”+1).IR (
KBr, disc) ν 3500-3000. 2900, 2830.
1730. 1630, 1610.1570.
1490, 1420, 1330, 1230. 9
90 cm-'Elemental analysis
for CBHttOsF4Calcd (%)
C 59.73 H 5.01Found
(%) C 59.80 H 5.21 Fruit 1
1 uJ cycle 9 blood melting point io o'c'H-NMR (CDC f M> 6 0.88 (3H.t.J=7.0Hz). 1.
2-1.5 (14H, o+), 1.72 (2H, qui
nt, J=7.0Hz), 4.40(2H.t, J=
6.6Hz), 7.14(2H, da, J-12.3H
z). 7.30 (2H.dm, J=12.3Hz)
"C-NMR (CDC j! s) δ 14.1
．． 22,7. 25.8. 2B. 5. 2
9.2. 29.3. 29.49, 29.52.
31.9. 67.1, 109.9, 1
23.3, 125.5.135.3, 141.
2 (Jcr'244.5Hz). 145.6 (JC
F=252.4HZ). 155.7, 159.
3, 170.0'”F4MR (CDCf :l
) δ 9.0, 23.6 (1:1) MS mH
z 46B (M"-2). 469 (M"-1).
470 (M”) IR (KBr, disc) ν 3500-3000. 2900. 2830
．． 1?30. 1630, 1610.157
0, 1490. 1420. 1330,
1230. 990 cm-'Elemental
analysis for Cz4Hz1lOs
PnCalcd (%) C 61,27
H 5.57 Found (%) C 61
．． 32 H 5.78th l! lJ8rebutton Blood melting point 10 days °C'H-NMR (CDC l2) 6 0.88 (3H, t, J = 7.0Hz), 1.
2-1.5 (22H, a+), 1.77 (2H.qui
nt, J-7.0Hz). 4.40 (2H, t, J
=6.6Hz). ? ．． 14 (2H.dm.J=12.5
Hz). 7.30 (211, dm, J=12.5H
z)” C-NMR (CDC j! s) δ 14
．． 1. 22.7. 25.8, 28.5.
29.2, 29.4. 29.5.29.6.
29.7. 31.9, 67.1, 10
9.9, 123.3, 125.5, 135.3, 1
41.2 (Jcy■245.5Hz), 145.6 (J
CF-250.48Z), 155.7, 159
．． 2, 170.0' ”P-NMR (CDC
1 s) δ 9.0. 23.6 (1:1)MS
ra/z 527(M”) IR (lBr.disc) ν 3500-3000.2900.2830.1?3
0,1630,1610.1570,1490,142
0,1330.1230.990 cm-'t! lem
mental analysis for Cgs
Hs40sF4Calcd (%) C 63
．． 87 H 6.51 Found (%)
C 64.16 8 6.79 Tsubasaman 1 bite 1ζ1
Melting point 107°C'H-NMR (CD(/!!) 6 0.88 (3H.t.J-6.9Hz).i,
2-1.5 (26}1, m). 1.76 (2H.qui
nt. J■6.9Hz), 4.40(2H.t, J
=6.6Hz),? ．． 13 (2H.dm.J=12.1
Hz). 7.29 (2H, dm, J-12.1Hz
)” C-NMR (CDC I.z) δ 14.1
．． 15.3, 22.7. 25.8. 2
8.5, 29.1. 29.4, 29.5,
29.6. 29.7. 31.9. 67.1
, 109.9, 123.3, 125.5, 13
5.3,141.1 (Jcr■244.5Hz),14
5.6 (Jcy■253.3Hz). 155.7,15
9.3, 170.0"F-NMR (CDCj!
s) δ 9.0, 23.6 (1:1) MS ra/
z 554 (M”). 555 (M”+1) IR
(KBr, disc) ν 3500-3000.2900.2B30.173
0.1630.1610.1570.1490.142
0.1330.1230.990 cm-'Eleme
ntal analysis for C30H
31105F4Calcd (%) C 64
．． 97 H 6.91 Found (%)
C 64.89 H 6.93 Example 7 In purified HMPA Bml, 5-hydroxy-
2-Methoxytropone 25■ (0.1 601110
1) Add (0.18ms+ol) and o
The mixture was stirred at ℃ for about 1 hour until the color of the solution turned deep purple. Thereafter, an excess amount of methyl pentafluorobenzoate was added, and the mixture was stirred at room temperature under a nitrogen stream for 24 hours. The reaction solution was added to an aqueous O'C2N-hydrochloric acid solution to stop the reaction, and the mixture was extracted with ethyl acetate. The organic layer was washed again with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.
残渣をシリカゲルカラムクロマトグラフィー（酢酸エチ
ル）で分離精製し、５−（４−メトキシカルボニルテト
ラフルオロフエノキシ）−２−メトキシトロポンを収量
５６■、収率９８％で得た。The residue was separated and purified by silica gel column chromatography (ethyl acetate) to obtain 5-(4-methoxycarbonyltetrafluorophenoxy)-2-methoxytropone in a yield of 56 cm and 98%.
このものの物性を下記に示す。The physical properties of this product are shown below.
融点 ８５゜Ｃ
’１１−ＮＭＲ （ＣＤＣ ｌ ｓ”）６３．９１（
３Ｈ，ｓ）． ４．００（３１１，ｓ）． ６．５３（
ＩＨ．ｄ＋ｍ，Ｊ−１１Ｈｚ），６．６０（ＩＨ，ｄ＠
，Ｊ＝１１Ｈｚ）， ７．２６−７．２９（２｝１．１
１）”Ｃ−ＮＭＲ （ＣＤＣｊ！ｓ）
δ ５３．５． ５６．４， １１０．４， １
１４．６， １３０．１， １３７．５，１５５．
３， １６３．０． １７９．２” Ｆ−ＮＭＲ
（ＣＤＣ ｊ！ ｓ）δ ９．１． ２３．８
（１：１）ＭＳ ｍ／ｚ ３５８（Ｍ”．ｂｐ．）
， ３５９（Ｍ”＋１）ＩＲ （ＣＨＣ ｆ ３）
ｖ １７４０． １５８０． １４９５， １
３３０． １１６０ ｃｗ．−’Ｅ１ｅ＋ｗｅｎｔａ
ｌ ａｎａｌｙｓｉｓ ｆｏｒ Ｃ．＆ＨＩＯＯ
ＳＦ４Ｃａｌｃｄ （％） Ｃ ５３．６４
｝１ ２．８１Ｆｏｕｎｄ （％） Ｃ
５３．８０ Ｈ ２．８７υＶ （ＣＨ３０８）
λ−−− （ｅ） ２２８ｒｖ（３２３１２），
３２４ｎｓ＋（１３５７２）実施例８
実施例７において、ペンタフルオロ安息香酸メチルの代
りに、ペンタフルオロ安息香酸デシルエステルを用いた
以外実施例１と同様に操作して、５−（４−デシルオキ
シカルボニルテトラフルオロフェノキシ）−２−メトキ
シトロボンを得た．二のものの物性を下記に示す．
融点 ８４゜Ｃ
’Ｈ−ＮＭＲ （ＣＤＣ Ｉｌ３）
６０．８８（３Ｈ，ｔ，Ｊ＝７．０１ｌｚ）， １．２
−１．６（１８｝１．ｓ），１．７７（２Ｈ，ｑｕｉｎ
ｔ，Ｊ＝７．０！｛ｚ）． ３．９２（３Ｈ，ｓ）．６
．５２（ＩＨ．ｄｍ．Ｊ＝１１．０Ｈｚ）， ６．６０
（１１Ｉ．ｄｍ，Ｊ−１１．０Ｈｚ）．７．２７−７．
３０（２Ｂ，＋＋＋）
目Ｃ−ＮＭＲ （ＣＤＣｊ！ｓ）
δ１４．１， ２２．７， ２５．８． ２８．５．
２９．１． ２９．３， ２９．４７．２９．５５．
２９．６． ３１．９， ５６．４， ６７．１， ９
６．１， １１０．３，１１４．４， １３０．１，
１３７．５， １５５．３， １５９．３， １６３．
０．１７９．２
”Ｆ−ＮＭＲ （ＣＤＣ ｌ ！）
δ９．０， ２３．５ （１：１）
ＭＳ ｔａ／ｚ ５５０（Ｍ”）． ５５ＨＭ”＋１）
， ２０７（ｂｐ．）ＩＲ （ＣＨＣ ｆ ３）
ν２９３０． ２Ｂ６５， １７３０． １５Ｂ０．
１４９０， １３２５， １１５５．１１２０ ａｍ−
’
Ｅｌｅｍｅｎｔａｌ ａｎａｌｙｓｉｓ ｆｏｒ
Ｃｚｔｌｌ３ｚＯｓＦ４Ｃａｌｃｄ （％）
Ｃ ６３．２７ Ｈ ６．２９Ｐｏｕｎｄ （
％） Ｃ ６３．５４ Ｈ ６．４０実施例
９
精製されたビリジン２ｍｌに５−（４−デシルオキシカ
ルボニルテトラフルオロフエノキシ）トロポロン６０■
（０．１２一ｍｏｌ） 、４−ペンチルベンゾイルクロ
ライド３４■（０． １ ６ｖｗｏｌ）および触媒量の
４−ジメチルアミノピリジンを加え、窒素気流下室温で
２４時間撹拌した．反応後、反応液を冷２Ｎ一塩酸水溶
液中に加え、酢酸エチルで抽出後、水洗し、硫酸マグネ
シウムで乾燥し、減圧下溶媒を留去する．残渣をシリカ
ゲルカラムクロマトグラフィー（酢酸エチルで流出）で
分離精製し、５−（４−デシルオキシカルボニルテトラ
フルオロフェノキシ）−２− （４−ペンチルベンゾイ
ルオキシ）トロボンを収率６９％で得た。Melting point 85°C '11-NMR (CDCl s'') 63.91 (
3H,s). 4.00 (311,s). 6.53(
IH. d+m, J-11Hz), 6.60(IH, d@
, J=11Hz), 7.26-7.29(2}1.1
1)"C-NMR (CDCj!s) δ 53.5. 56.4, 110.4, 1
14.6, 130.1, 137.5, 155.
3, 163.0. 179.2”F-NMR
(CDC j! s) δ 9.1. 23.8
(1:1) MS m/z 358 (M”.bp.)
, 359(M”+1)IR (CHC f 3) v 1740. 1580. 1495, 1
330. 1160 cw. -'E1e+wenta
l analysis for C. &HIOO
SF4Calcd (%) C 53.64
}1 2.81Found (%) C
53.80 H 2.87υV (CH308) λ--- (e) 228rv (32312),
324ns+(13572) Example 8 In Example 7, 5-(4-decyloxycarbonyltetra Fluorophenoxy)-2-methoxytrobone was obtained. The physical properties of the second one are shown below. Melting point 84°C'H-NMR (CDC Il3) 60.88 (3H, t, J=7.01lz), 1.2
-1.6 (18}1.s), 1.77 (2H, quin
t, J=7.0! {z). 3.92 (3H, s). 6
．． 52 (IH.dm.J=11.0Hz), 6.60
(11I.dm, J-11.0Hz). 7.27-7.
30 (2B, +++) C-NMR (CDCj!s) δ14.1, 22.7, 25.8. 28.5.
29.1. 29.3, 29.47.29.55.
29.6. 31.9, 56.4, 67.1, 9
6.1, 110.3, 114.4, 130.1,
137.5, 155.3, 159.3, 163.
0.179.2 "F-NMR (CDCl!) δ9.0, 23.5 (1:1) MS ta/z 550 (M"). 55HM”+1)
, 207 (bp.) IR (CHC f 3) ν2930. 2B65, 1730. 15B0.
1490, 1325, 1155.1120 am-
'Elemental analysis for
Cztll3zOsF4Calcd (%)
C 63.27 H 6.29Pound (
%) C 63.54 H 6.40 Example 9 5-(4-decyloxycarbonyltetrafluorophenoxy)tropolone 60 μm to 2 ml of purified pyridine
(0.121 mol), 34 µ (0.16 vwol) of 4-pentylbenzoyl chloride, and a catalytic amount of 4-dimethylaminopyridine were added, and the mixture was stirred at room temperature under a nitrogen stream for 24 hours. After the reaction, the reaction solution is added to a cold 2N aqueous monohydrochloric acid solution, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and the solvent is distilled off under reduced pressure. The residue was separated and purified by silica gel column chromatography (elution with ethyl acetate) to obtain 5-(4-decyloxycarbonyltetrafluorophenoxy)-2-(4-pentylbenzoyloxy)trobone in a yield of 69%.
このものの物性を下記に示す．
無色液体
’Ｈ−ＮＭＲ （ＣＤＣｌ ３）
６ ０．８９（３１冒，ｔ，Ｊ＝６．６Ｈｚ）． １
．２−１．５（１８Ｈ，ｓ） ，１．５−１．７（２１
１，ｓ）． １．７６（２｝１，ｍ），２．６９（２
Ｈ，ｔ，Ｊ−８．１Ｈｚ）， ４．４１（２１１，ｔ，
Ｊ．６．６Ｈｚ）．６．３（ＩＨ．ｂｒｓ）， ７．２
９（２Ｈ．ｄｍ，Ｊ＝８．４Ｈｚ）．７．３（３１１，
ｂｒｓ）． ８．０７（２１１，ｄｓｉ，Ｊ＝８．４Ｈ
ｚ）” Ｃ−ＮＭＲ （ＣＤＣ ｌ ｓ）δ １４．
０． １４．１， ２２．５． ２２，７， ２５．８
． ２Ｂ．５． ２９．１．２９．３， ２９．４７．
２９．５０， ３０．８， ３１．４， ３１．９．
３６．１． ６７．２， １１０．８， １２６．１
． １２８．７， １３０．６，１３３．９，１４１
．１（Ｊｃｒ＝２４０．６１１ｚ），１４９．７，１５
９．３，１６４．０
”Ｆ−ＮＭＲ （ＣＤＣ１３）
δ ９．８， ２４．０ （１：１）
ＭＳ ｍＨｚ ６４４（Ｍ”−１）， ６４５（
Ｍ”）実施例１０
実施例９において、５−（４−ドデシルカルボニルテト
ラフルオロフェノキシ）トロポロンの代りに５−（４−
デシルカルボニルテトラフルオロフエノキシ）トロポロ
ン６３．６■（０． １ ３ｍｓ＋ｏｌ）を用いた以外
実施例９と同様に操作して５−（４一デシルオキシカル
ボニルテトラフルオロフエノキシ） −２− （４−ペ
ンチルベンゾイルオキシ）トロポンを得た．
このものの物性を下記に示す．
無色液体
諺Ｈ〜ＮＭＲ （ＣＤＣ ｆ ｘ）
６０．８９（６Ｈ，ｔ，Ｊ−７．２Ｈｚ）， １．２−
１．５（１８１｛，ｍ），１．６６（２Ｈ，ｑｕｉｎｔ
，Ｊ−７．５Ｈｚ） ．１．７５（２Ｈ，ｑｕｉｎｔ，
Ｊ−７．２Ｈｚ） ．２．６８（２Ｈ，ｔ．Ｊ＝７．７
Ｈｚ）． ４．４０（２Ｈ．ｔ．Ｊ＝６．６Ｈｚ）．６
．３（ＩＨ．ｂｒｓ）． ７．２９（２Ｈ，ｄｍ．Ｊ
−８．２Ｈｚ）．７．３（３Ｂ，ｂｒｓ）， ８．０７
（２Ｈ，ｄｗ．Ｊ−８．２Ｈｚ）” Ｃ−ＮＭＲ （Ｃ
ＤＣ Ｉ． ２）δ１４，０， １４．１． ２２．５
， ２２．７． ２５．８． ２Ｂ．５． ２９．２．
２９．４． ２９．５． ２９．５７． ２９．６４．
３０．８． ３１．４，３１．９． ３６．１． ６
７．２， １１０．６， １２６．１． １２８．７，
？３０．６， １３３．９， １４１．０（ＪＣＦ
■２４５．５Ｈｚ），１４５．４（Ｊｃｒ−２６３．
ＩＨＺ），１４９．７， １５９．３， １６４．
０” Ｆ−ＮＭＲ （ＣＤＣ ｌ ｓ）δ ９．８．
２４．０ （１：１）ＭＳ ｍＨｚ ６７２
（Ｍ”−１）， ６７３（Ｍ”）ＩＲ（ｎｅａｔ）
ν ２９００． ２８５０． １？２５． １５８
５， １４８５． １３１５． １２１０．１１
５０． １０？０． ９９５ ｃｔａ−’Ｅ１ｅｓ
＋ｅｎｔａｌ ａｎａｌｙｓｉｓ ｆｏｒ Ｃ
ｘｓＨ４４０ｈＦ４Ｃａｌｃｄ （％） Ｃ
６７．８４ Ｈ ６．５９Ｆｏｕｎｄ （％）
Ｃ ６７．５９ Ｈ ６．７２実施例１１〜
１３
実施例９において、４−ペンチルベンゾイルクロライド
の代りに下記表２の酸塩化物を用いた以外は実施例９と
同様に操作してそれぞれのトロポロン誘導体を得た．
これらのものの物性を下記に示す．
１隻班土上坐化立１
無色液体
’Ｈ−ＮＭＲ （ＣＤＣ ｊ！ ｓ）６０．８８（３
Ｈ．ｔ．Ｊ−７．１１１ｚ）， １．２−１．５（１８
１１，ｍ）．１．７６（２Ｈ，ｑｕｉｎｔ．Ｊ−７．１
Ｈｚ）． ３．８９（３Ｈ，ｓ）．４．４０（２１１．
ｔ．Ｊ−６．６Ｈｚ）， ６．３（１Ｂ，ｂｒｄ，Ｊ−
１０．５Ｈｚ），６．９６（２Ｈ．ｄｅｇ．Ｊ−８．８
Ｈｚ）． ７．１５（ＩＨ，ｂｒｄ．Ｊ−１０．５Ｈｚ
），７．２６（２Ｈ．ｂｒｓ）． ８．１１（２８，ｄ
ｓ．Ｊ＝８．８Ｈｚ）１３Ｃ−ＮＭＲ （ＣＤＣＩｌコ
）
δ１４．１． ２２．７， ２５．８． ２８．５．
２９．１， ２９．３， ２９．５，２９．５６． ２
９．６３． ３１．９． ５５．５， ６７．２， １
１０．７，１１３，９， １２０．９， １３２．７，
１３３．１， １５９．２， １６３．７，１６４．
２．
薯啼Ｆ−Ｎ阿Ｒ （ＣＤＣ ｊ！３）δ９．８， ２
４．０ （１：１）
ＩＲ （ＫＢｒ．ｎｅａｔ）
ν２９１０． ２８４０． １？３５． １５９５．
１４９０． １３１５． １２５０．１２１０． １１
５０． １０７５． １０２０． １０００ ｃｍ−’
ｆ！ｌｅｍｅｎｔａｌ ａｎａｌｙｓｉｓ ｆｏｒ
ＣｓａＨ３ｈＯＪａＣａｌｃｄ （％） Ｃ
６４．５５ １１ ５．７４Ｆｏｕｎｄ （％）
Ｃ ６４．５９ Ｈ ５．９１１２の 人
融点 ５７゜Ｃ
’Ｈ−ＮＭＲ （ＣＤＣ Ｉｌ３）
６０．８８（６８，ｔ，Ｊ＝６．６Ｈｚ）， １．２−
１．５（３６Ｈ，ｍ）．１．７−１．９（４１１，ｍ）
， ４．０２（２Ｈ，ｔ，Ｊ＝６．６Ｈｚ）．４．４１
（２Ｈ，ｔ，Ｊ＝６．６Ｈｚ）， ６．３（ＩＨ．ｂｒ
ｄ，Ｊ＝１０．８｝１ｚ），６．９４（２Ｈ．ｄｍ．Ｊ
＝８．８１１ｚ）． ７．１５（ｉｌｌ，ｂｒｄ，Ｊ＝
１０．８１ｌｚ）．７．３５（２１，ｂｒｓ）． ８．
１０（２Ｈ，ｄｍ，Ｊ＝８．８Ｈｚ）” Ｃ−ＮＭＲ
（ＣＤＣ ｌ ｘ）
δ１４．１， ２２，７， ２５．８， ２６．０．
２Ｂ．５． ２９．０９．２９．１４． ２９．４．
２９．５． ２９．５６， ２９．６０， ２９．６４
，３１．９． ６７．２． ６８．３， １１０．８，
１１４．３， １２０．６．１３２．７， １３３．
９， １５９．２， １６３．７， １６３．８１叩一
ＮＭＲ （ＣＤＣＩｌ３）
δ９．８． ２４．０ （１：１）
ＭＳ ｍＨｚ ７８７（Ｍつ． ７８８（Ｍ”＋
１）ｆｉｌｅｌＩｅｎｔａｌ ａｎａｌｙｓｉｓ ｆｏ
ｒ Ｃ４ＳＨＳｌＯ？Ｆ４Ｃａｌｃｄ （％） Ｃ
６８．６８ ＩＩ ？．４３Ｆｏｕｎｄ （％）
Ｃ ６Ｂ．８８ ８ ７．４７実施例１３の
ヒ八物
融点 ７５゜Ｃ
’Ｈ−ＮＭＲ （ＣＤＣ Ｉ！ ｓ）６０．８８（３
８，ｔ．Ｊ＝７．１Ｈｚ）， １．２−１．５（１８Ｈ
，ｍ）．１．７６（２｝１，ｑｕｔｎｔ．Ｊ＝７．１Ｈ
ｚ）． ４．４１（２Ｈ．ｔ．Ｊ＝６．６Ｈｚ）．６．
７（ＬＨ．ｂｒｓ）， ７．２６（１８，ｂｒｓ），
７．３１（２８，ｂｒｓ），７．８０（２Ｈ．ｄａ＋．
Ｊ＝８．６Ｈｚ）， ８．２６（２Ｈ，ｄｓ＋．Ｊ＝８
．６Ｈｚ）’ ”Ｃ−ＮＭＲ （ＣＤＣ ｆ ３）δ１
４．１． ２２．７， ２５．８， ２８．５， ２９
．１， ２９．３． ２９．４７．２９．５４． ２９
．６， ３１．９， ６７．３， １１０．９， １１
７，２．１１７．８， １３０．９， １３２．４，
１３３．７．１４１．１（ＪＣＦ−２４１．６０２），
１４５．５（ＪＣＦ＝２５９．２ＨＺ），１５９．１
， １５９．７， １６２．４”Ｆ−ＮＭＲ （ＣＤＣ
ｆｓ）
δ９．８， ２４．２ （１：１）The physical properties of this material are shown below. Colorless liquid 'H-NMR (CDCl 3) 6 0.89 (31 Hz, t, J = 6.6 Hz). 1
．． 2-1.5 (18H, s), 1.5-1.7 (21
1,s). 1.76 (2}1, m), 2.69 (2
H, t, J-8.1Hz), 4.41 (211, t,
J. 6.6Hz). 6.3 (IH.brs), 7.2
9 (2H.dm, J=8.4Hz). 7.3 (311,
brs). 8.07 (211, dsi, J=8.4H
z)” C-NMR (CDCl s) δ 14.
0. 14.1, 22.5. 22,7, 25.8
．． 2B. 5. 29.1.29.3, 29.47.
29.50, 30.8, 31.4, 31.9.
36.1. 67.2, 110.8, 126.1
．． 128.7, 130.6, 133.9, 141
．． 1 (Jcr=240.611z), 149.7, 15
9.3, 164.0 "F-NMR (CDC13) δ 9.8, 24.0 (1:1) MS mHz 644 (M"-1), 645 (
M”) Example 10 In Example 9, 5-(4-dodecylcarbonyltetrafluorophenoxy)tropolone was replaced with 5-(4-
5-(4-decyloxycarbonyltetrafluorophenoxy) -2- ( 4-Pentylbenzoyloxy)tropone was obtained. The physical properties of this material are shown below. Colorless liquid proverb H~NMR (CDC f x) 60.89 (6H, t, J-7.2Hz), 1.2-
1.5 (181{, m), 1.66 (2H, quint
, J-7.5Hz). 1.75 (2H, quint,
J-7.2Hz). 2.68 (2H, t.J=7.7
Hz). 4.40 (2H.t.J=6.6Hz). 6
．． 3 (IH.brs). 7.29 (2H, dm.J
-8.2Hz). 7.3 (3B, brs), 8.07
(2H, dw.J-8.2Hz)” C-NMR (C
D.C.I. 2) δ14,0, 14.1. 22.5
, 22.7. 25.8. 2B. 5. 29.2.
29.4. 29.5. 29.57. 29.64.
30.8. 31.4, 31.9. 36.1. 6
7.2, 110.6, 126.1. 128.7,
? 30.6, 133.9, 141.0 (JCF
■245.5Hz), 145.4 (Jcr-263.
IHZ), 149.7, 159.3, 164.
0” F-NMR (CDCl s) δ 9.8.
24.0 (1:1) MS mHz 672
(M”-1), 673(M”)IR(neat) ν 2900. 2850. 1?25. 158
5, 1485. 1315. 1210.11
50. 10?0. 995 cta-'E1es
+mental analysis for C
xsH440hF4Calcd (%) C
67.84 H 6.59 Found (%)
C 67.59 H 6.72 Example 11~
13 Each tropolone derivative was obtained in the same manner as in Example 9, except that the acid chloride shown in Table 2 below was used instead of 4-pentylbenzoyl chloride. The physical properties of these materials are shown below. 1 ship group Dojo zakatate 1 Colorless liquid 'H-NMR (CDC j!s) 60.88 (3
H. t. J-7.111z), 1.2-1.5 (18
11, m). 1.76 (2H, quint. J-7.1
Hz). 3.89 (3H, s). 4.40 (211.
t. J-6.6Hz), 6.3(1B,brd,J-
10.5Hz), 6.96 (2H.deg.J-8.8
Hz). 7.15 (IH,brd.J-10.5Hz
), 7.26 (2H.brs). 8.11 (28, d
s. J=8.8Hz) 13C-NMR (CDCIl) δ14.1. 22.7, 25.8. 28.5.
29.1, 29.3, 29.5, 29.56. 2
9.63. 31.9. 55.5, 67.2, 1
10.7, 113, 9, 120.9, 132.7,
133.1, 159.2, 163.7, 164.
2.薯啼F-N阿R (CDC j!3) δ9.8, 2
4.0 (1:1) IR (KBr.neat) ν2910. 2840. 1?35. 1595.
1490. 1315. 1250.1210. 11
50. 1075. 1020. 1000 cm-'
f! elemental analysis for
CsaH3hOJaCalcd (%) C
64.55 11 5.74Found (%)
Human melting point of C 64.59 H 5.9112 57°C'H-NMR (CDC Il3) 60.88 (68, t, J=6.6Hz), 1.2-
1.5 (36H, m). 1.7-1.9 (411, m)
, 4.02 (2H, t, J=6.6Hz). 4.41
(2H, t, J=6.6Hz), 6.3(IH.br
d, J=10.8}1z), 6.94 (2H.dm.J
=8.811z). 7.15(ill,brd,J=
10.81lz). 7.35 (21,brs). 8.
10 (2H, dm, J=8.8Hz)” C-NMR
(CDC l x) δ14.1, 22,7, 25.8, 26.0.
2B. 5. 29.09.29.14. 29.4.
29.5. 29.56, 29.60, 29.64
, 31.9. 67.2. 68.3, 110.8,
114.3, 120.6.132.7, 133.
9, 159.2, 163.7, 163.81 NMR (CDCIl3) δ9.8. 24.0 (1:1) MS mHz 787 (M) 788 (M”+
1) FileIental analysis fo
rC4SHSIO? F4Calcd (%) C
68.68 II? ．． 43 Found (%)
C 6B. 88 8 7.47 Melting point of the compound of Example 13 75°C 'H-NMR (CDC I!s) 60.88 (3
8,t. J=7.1Hz), 1.2-1.5(18H
, m). 1.76(2}1, qutnt.J=7.1H
z). 4.41 (2H.t.J=6.6Hz). 6.
7(LH.brs), 7.26(18,brs),
7.31 (28, brs), 7.80 (2H.da+.
J=8.6Hz), 8.26(2H, ds+.J=8
．． 6Hz)' ”C-NMR (CDC f 3) δ1
4.1. 22.7, 25.8, 28.5, 29
．． 1, 29.3. 29.47.29.54. 29
．． 6, 31.9, 67.3, 110.9, 11
7, 2.117.8, 130.9, 132.4,
133.7.141.1 (JCF-241.602),
145.5 (JCF=259.2HZ), 159.1
, 159.7, 162.4"F-NMR (CDC
fs) δ9.8, 24.2 (1:1)
Claims (1)
を表わし、Ｒ＿２はＨ、−ＯＣＨ＿３または▲数式、化
学式、表等があります▼（ただしＲ＿３は炭素数１〜８
のア ルキル基、炭素数１〜２０のアルコキシ基または−ＣＮ
を表わす）を表わす。〕[Claims] 1. Tropolone derivative represented by general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [However, in the formula, R_1 represents an alkyl group having 1 to 20 carbon atoms, R_2 is H, -OCH_3, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼( However, R_3 has 1 to 8 carbon atoms.
an alkyl group, an alkoxy group having 1 to 20 carbon atoms, or -CN
). ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5777689A JPH02237964A (en) | 1989-03-13 | 1989-03-13 | Tropolone derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5777689A JPH02237964A (en) | 1989-03-13 | 1989-03-13 | Tropolone derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02237964A true JPH02237964A (en) | 1990-09-20 |
Family
ID=13065269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5777689A Pending JPH02237964A (en) | 1989-03-13 | 1989-03-13 | Tropolone derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02237964A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4045025A4 (en) * | 2019-10-16 | 2023-11-22 | Kinesid Therapeutics, Inc. | Tropolone derivatives and tautomers thereof for iron regulation in animals |
-
1989
- 1989-03-13 JP JP5777689A patent/JPH02237964A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4045025A4 (en) * | 2019-10-16 | 2023-11-22 | Kinesid Therapeutics, Inc. | Tropolone derivatives and tautomers thereof for iron regulation in animals |
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