JPH02237964A - Tropolone derivative - Google Patents

Tropolone derivative

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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
Application number
JP5777689A
Other languages
Japanese (ja)
Inventor
Hitoshi Takeshita
竹下 齊
Akira Mori
章 森
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Shokubai Co Ltd
Original Assignee
Nippon Shokubai Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Shokubai Co Ltd filed Critical Nippon Shokubai Co Ltd
Priority to JP5777689A priority Critical patent/JPH02237964A/en
Publication of JPH02237964A publication Critical patent/JPH02237964A/en
Pending legal-status Critical Current

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

NEW MATERIAL:The compound of formula I [R1 is 1-20C alkyl; R2 is H, -OCH3 or group of formula II (R3 is 1-8C alkyl, 1-20C alkoxy or -CN)]. EXAMPLE:5-(4-Dodecyloxycarbonyltetrafluorophenoxy)tropolone. USE:Raw material for agricultural chemicals such as fungicide. Synthetic interme diate for pharmaceuticals. PREPARATION:The objective compound of formula I can be produced by adding pentafluorobenzoic acid, dodecyl alcohol and sulfuric acid to benzene. reacting the components to obtain pentafluorobenzoic acid dodecyl ester of formula III, separately adding 5-hydroxy-tropolone and sodium hydride to hexamethyl phosphoric triamide and reacting the reaction product with the compound of formula III.

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)

【特許請求の範囲】 1、一般式( I )で示されるトロポロン誘導体。 ▲数式、化学式、表等があります▼( I ) 〔ただし、式中、R_1は炭素数1〜20のアルキル基
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
). ]
JP5777689A 1989-03-13 1989-03-13 Tropolone derivative Pending JPH02237964A (en)

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)

* Cited by examiner, † Cited by third party
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

Cited By (1)

* Cited by examiner, † Cited by third party
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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