JPH0489452A - Cyclic compound - Google Patents
Cyclic compoundInfo
- Publication number
- JPH0489452A JPH0489452A JP20422390A JP20422390A JPH0489452A JP H0489452 A JPH0489452 A JP H0489452A JP 20422390 A JP20422390 A JP 20422390A JP 20422390 A JP20422390 A JP 20422390A JP H0489452 A JPH0489452 A JP H0489452A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- cyclic
- compound
- group
- cyclic compound
- 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
- 150000001923 cyclic compounds Chemical class 0.000 title claims abstract description 10
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- -1 tetrahydro-2H-pyranyl group Chemical group 0.000 claims description 11
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 5
- 235000007586 terpenes Nutrition 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 125000001589 carboacyl group Chemical group 0.000 abstract description 5
- JAAJQSRLGAYGKZ-UHFFFAOYSA-N 1,2,3,4-tetrahydronaphthalen-1-ol Chemical class C1=CC=C2C(O)CCCC2=C1 JAAJQSRLGAYGKZ-UHFFFAOYSA-N 0.000 abstract description 3
- 125000002947 alkylene group Chemical group 0.000 abstract description 3
- 239000000463 material Substances 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000002260 anti-inflammatory agent Substances 0.000 description 2
- 229940121363 anti-inflammatory agent Drugs 0.000 description 2
- 239000000043 antiallergic agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 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 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241001265503 Pyrodinium Species 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Quinoline Compounds (AREA)
- Pyrane Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
この発明は新規な環式化合物に関し、詳細にはたとえば
下記構造式［Ａ］で示される１、２．３．４−テトラヒ
ドロ−１−ナフトール話導体などを製造する際の中間体
として有用な新規な環式化合物に関するものである。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a novel cyclic compound, and in particular, 1,2,3.4-tetrahydro-1-naphthol represented by the following structural formula [A]. The present invention relates to a novel cyclic compound useful as an intermediate in the production of speech conductors and the like.
［従来の技術］
上記化合物［Ａ］ は、たとえば特開昭６３−３０１８
４０号公報によって公知であり、この公報には該化合物
が抗炎症剤や抗アレルギー剤として有用なものであるこ
とも明らかにされている。[Prior Art] The above compound [A] is disclosed in, for example, JP-A No. 63-3018.
40, which also discloses that the compound is useful as an anti-inflammatory agent and an anti-allergic agent.
［発明の目的］
この発明の目的は、上記化合物［Ａ］ またはその類縁
化合物を工業的に収率良く製造し得る中間体として有用
であり、また他の用途への適用可能性を持った新規な環
式化合物を提供しようとするものである。[Objective of the Invention] The object of the present invention is to provide a novel intermediate which is useful as an intermediate for industrially producing the above compound [A] or its analogues in good yield, and which has applicability to other uses. The aim is to provide a cyclic compound with a unique structure.
［発明の構成コ
この発明の目的とする環式化合物は新規であり、下記−
形式［１］で表わすことができる。[Constitution of the Invention The cyclic compound targeted by this invention is novel and has the following -
It can be expressed in the format [1].
艶ｊ■Ｌ１
〔■〕
（ＩＩＩ）
［式中、Ａは、＝ｃ＝ｏまたは；ＣＨＯＲ３（Ｒ３は環
状テルペンオキシ（低級）アルカノイル基を表わす）、
Ｒ１は含酸素複素環式基または環状テルペンオキシ（低
級）アルカノイル基、Ｒ２は共に水素もしくは低級アル
キル基を表わす］この発明の環式化合物は、下記反応式
で例示される方法によって製造することができる。Gloss j■L1 [■] (III) [In the formula, A is =c=o or; CHOR3 (R3 represents a cyclic terpeneoxy (lower) alkanoyl group),
R1 represents an oxygen-containing heterocyclic group or a cyclic terpeneoxy (lower) alkanoyl group, and R2 both represent hydrogen or a lower alkyl group] The cyclic compound of the present invention can be produced by the method exemplified by the following reaction formula. can.
（Ｉａ）
（式中、Ｒ２は前記と同じ意味、Ｚは末端もしくは中間
に酸素原子が存在するアルキレン基を表わす）
製造法２
（ＩＶ） （Ｖ）
（Ｉｂ）（式中、Ｒ２およびＲ３は前記と同じ意味
、Ｘはハロゲンを表わす）
上記の種々の定義の好ましい例および詳細な説明を以下
に述べる。(Ia) (In the formula, R2 has the same meaning as above, Z represents an alkylene group having an oxygen atom at the end or in the middle) Production method 2 (IV) (V)
(Ib) (In the formula, R2 and R3 have the same meanings as above, and X represents a halogen.) Preferred examples and detailed explanations of the above various definitions are described below.
「低級」とは、特にことわりのない限り炭素原子１〜６
個を意味するものとする。"Lower" means 1 to 6 carbon atoms unless otherwise specified.
shall mean an individual.
Ｒ１て示される「含酸素複素環式基」の好ましい例とし
ては、環内に１個以上の酸素原子を有する単環式もしく
は多環式基を意味するものであり、例えばテトラヒドロ
フリル、テトラヒドロ−２Ｈ−ピラニル、３．４−ジヒ
ドロ−２Ｈ−クメニル等が挙げられる。Preferred examples of the "oxygen-containing heterocyclic group" represented by R1 mean a monocyclic or polycyclic group having one or more oxygen atoms in the ring, such as tetrahydrofuryl, tetrahydro- 2H-pyranyl, 3,4-dihydro-2H-cumenyl, and the like.
Ｒ２で示される「低級アルキル基」の好ましい例として
は、メチル、エチル、プロピル、イソプロピル、ブチル
、イソブチル、第３級ブチル、ペンチル、ネオペンチル
、ヘキシル等のような炭素原子１〜６個を有する直鎖ま
たは分岐のアルキル基が挙げられ、これらの中でも好ま
しいのはｎ−プロピル、ｎ−ブチル、ｎ−ペンチル、ｎ
−ヘキシル等の炭素原子３〜６個を有する直鎖アルキル
基であり、特に好ましいのはｎ−ブチルである。Preferred examples of the "lower alkyl group" represented by R2 include straight groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, neopentyl, hexyl, etc. Chain or branched alkyl groups are mentioned, and among these, preferred are n-propyl, n-butyl, n-pentyl, n-
- Straight-chain alkyl groups having 3 to 6 carbon atoms, such as hexyl, particularly preferred is n-butyl.
Ｒ３で示される「環状テルペンオキシ（低級）アルカノ
イル基」における「（低級）アルカノイル」部分の具体
例としては、ホルミル、アセチル、プロピオニル、ブチ
リル、イソブチリル、バレリル、インバレリル、ヘキサ
ノイル等のような炭素原子１〜６個を有する直鎮状また
は分岐状アルカノイル等が挙げられ、これらの中でも好
ましいのは炭素原子数１〜６個のアルカノイルである。Specific examples of the "(lower) alkanoyl" moiety in the "cyclic terpeneoxy (lower) alkanoyl group" represented by R3 include carbon atom 1 such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, invaleryl, hexanoyl, etc. Examples include straight or branched alkanoyl having 6 to 6 carbon atoms, and among these, preferred is alkanoyl having 1 to 6 carbon atoms.
また「環状テルペンオキシ（低級）アルカノイル基」に
おける「環状テルペン」部分の好ましいものとしてはメ
ンチル、ピネニル、トリシフレニル、リモネニル等が挙
げられ、これらの中でも好ましいのはメンチルである。Preferred examples of the "cyclic terpene" moiety in the "cyclic terpeneoxy (lower) alkanoyl group" include menthyl, pinenyl, tricifrenyl, limonenyl, etc. Among these, menthyl is preferred.
Ｚで示される「末端もしくは中間に酸素原子を有するア
ルキレン基」の好ましい例としては、−ＣＨ２ＣＨ２０
、−ＣＨ２ＣＨ２ＣＨ２０−等が挙げられる。Preferred examples of the "alkylene group having an oxygen atom at the end or in the middle" represented by Z include -CH2CH20
, -CH2CH2CH20-, and the like.
Ｘで示される「ハロゲン」としては塩素、ふっ素、臭素
、よう素等が挙げられ、これらの中でも好ましいのは塩
素、臭素である。Examples of the "halogen" represented by X include chlorine, fluorine, bromine, iodine, etc. Among these, chlorine and bromine are preferred.
次にこの発明の目的化合物［１Ｆの製造法を説明する。Next, a method for producing the object compound [1F of the present invention] will be explained.
製造法１
この製造法は、化合物［１１］に化合物［ＩＩＩ ］を
付加反応させることによって化合物［Ｉａ］を製造する
方法である。Production method 1 This production method is a method for producing compound [Ia] by subjecting compound [11] to addition reaction of compound [III].
この反応は、塩酸、硫酸、Ｐ−トルエンスルホン酸、Ｐ
−）ルエンスルホン酸ピリジニウム塩等の存在下で、冷
却下、常温もしくは加熱下に行なうことができ、この反
応は塩化メチレン、ジメチルホルムアミド、ジメチルス
ルホキシド、アセトン、エタノールの如き反応に悪影響
を及ぼさない常用の溶媒中で行なわれる。This reaction consists of hydrochloric acid, sulfuric acid, P-toluenesulfonic acid, P
-) The reaction can be carried out in the presence of pyridinium luenesulfonic acid salt, etc., under cooling, at room temperature, or under heating. It is carried out in a solvent.
製造法２
この製造法は、化合物［ｒＶ］に化合物［Ｖ］を反応さ
せて化合物［１ｂ ］を製造する方法である。Production method 2 This production method is a method for producing compound [1b] by reacting compound [rV] with compound [V].
この反応は、塩基の存在下に行なうのが好ましい。好適
な塩基としては、例えは水酸化ナトリウム、水酸化カリ
ウム、水酸化カルシウム等のアルカリ金属水酸化物また
はアルカリ土類金属水酸化物、例えば炭酸水素ナトリウ
ム、炭酸水素カリウム等のアルカリ金属炭酸水素塩、例
えば炭酸ナトリウム、炭酸カリウム、炭酸カルシウム等
のアルカリ金属炭酸塩またはアルカリ土類金属炭酸塩、
例えば燐酸二水素ナトリウム、燐酸二水素カリウム、燐
酸水素二ナトリウム、燐酸水素二カリウム等のアルカリ
金属燐酸塩のような無機塩基、あるいは例えばナトリウ
ムメトキシド、カリウムエトキシド等のアルカリ金属ア
ルコキシド、例えばトリエチルアミン、ピリジン、ルチ
ジン等のアミン類のような有機塩基が挙げられる。This reaction is preferably carried out in the presence of a base. Suitable bases include, for example, alkali metal hydroxides or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, alkali metal bicarbonates such as sodium bicarbonate, potassium bicarbonate, etc. , alkali metal carbonates or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate, calcium carbonate, etc.
Inorganic bases such as alkali metal phosphates such as sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, etc., or alkali metal alkoxides such as sodium methoxide, potassium ethoxide, etc., such as triethylamine, Examples include organic bases such as amines such as pyridine and lutidine.
反応は、たとえば冷却下、常温もしくは加熱下に、塩化
メチレン、アセトン、エタノール、ジメチルホルムアミ
ドの如き反応に悪影響を及ぼさない慣用の溶媒中で行な
われる。The reaction is carried out, for example, under cooling, at room temperature or under heating in a conventional solvent which does not adversely affect the reaction, such as methylene chloride, acetone, ethanol, dimethylformamide.
この発明の目的化合物［１］は分子中に不斉炭素原子を
有することがあり、これに基づく光学異性体の様な立体
異性体が包含されるが、この発明はその様な立体異性体
の混合物はもとより、それらを光学分割により単離した
ものもすへてこの発明の範囲内に含まれる。The object compound [1] of this invention may have an asymmetric carbon atom in the molecule, and stereoisomers such as optical isomers based on this are included. Not only mixtures but also those isolated by optical resolution are included within the scope of the present invention.
［発明の効果コ
この発明の目的化合物は、抗炎症剤や抗アレルギー剤と
して有用な例えば１，２，３．４−テトラヒドロ−１−
ナフトール誘導体［Ａ１等の合成中間体などとして有用
な化合物である。[Effects of the Invention] The object compound of the present invention is a compound useful as an anti-inflammatory agent or an anti-allergic agent, such as 1,2,3,4-tetrahydro-1-
Naphthol derivatives [Compounds useful as synthetic intermediates such as A1.
［実施例］
２．２−ジブチル−１，５−ジヒドロキシ−１，２，３
４−テトラヒドロ−ナフタリン２７．６ｇ（０，１モル
）を塩化メチレン２２０．８ｍｌに溶解し、１０℃以下
に冷却した後、ピリジン３９．６ｇ（０，５モル）を加
える。この溶液を０〜１０℃に保ち、これに、１メンチ
ルオキシ酢酸クロリド５８．２８ （０，２５モル）を
塩化メチレン５５．２ｍｌに溶かした溶液を２時間かけ
て滴下する。滴下終了後、同温度で２時間反応を行ない
、次いで水１３８ｍ１を加えてから攪拌し、静置後水層
を分離する。有機層を５％塩酸１３８ｍ１．８％炭酸水
素ナトリウム水溶液１３８ｍ１および水１３８ｍ１で順
次洗浄してから減圧濃縮する。残留物にイソプロピルア
ルコール３３１．２ｍｌを加え、加熱溶解した後冷却し
、内温４５℃で０．０１ｇの種晶を加えて結晶を析出さ
せ、３０℃まで冷却した後再度４０〜４５℃に加温して
から室温まで冷却し、同温度で３時間熟成した後結晶を
濾取する。得られた結晶をイソプロピルアルコール５５
．２ｍｌで洗浄してから一夜真空乾燥すると、（−）
２．２−ジブチル−２，５−ジ（メンタン−３−イル）
オキシアセチルオキシ−１，２，３，４−テトラヒドロ
ナフタリンの粗結晶２８．１ｇ（４２，０％）［（＋）
体０．８％を含む］を得る。[Example] 2.2-dibutyl-1,5-dihydroxy-1,2,3
27.6 g (0.1 mol) of 4-tetrahydro-naphthalene are dissolved in 220.8 ml of methylene chloride and, after cooling to below 10 DEG C., 39.6 g (0.5 mol) of pyridine are added. This solution is kept at 0 to 10 DEG C., and a solution of 58.28 (0.25 mol) of 1-menthyloxyacetic acid chloride dissolved in 55.2 ml of methylene chloride is added dropwise over 2 hours. After the dropwise addition was completed, the reaction was carried out at the same temperature for 2 hours, then 138 ml of water was added and stirred, and after standing still, the aqueous layer was separated. The organic layer is washed successively with 138 ml of 5% hydrochloric acid, 138 ml of 1.8% aqueous sodium bicarbonate solution and 138 ml of water, and then concentrated under reduced pressure. Add 331.2 ml of isopropyl alcohol to the residue, heat and dissolve, then cool, add 0.01 g of seed crystals at an internal temperature of 45°C to precipitate crystals, cool to 30°C, then heat again to 40-45°C. After heating, the mixture is cooled to room temperature, and after aging at the same temperature for 3 hours, the crystals are collected by filtration. The obtained crystals are mixed with isopropyl alcohol 55
．． After washing with 2ml and vacuum drying overnight, (-)
2.2-dibutyl-2,5-di(menthan-3-yl)
28.1 g (42.0%) of crude crystals of oxyacetyloxy-1,2,3,4-tetrahydronaphthalene [(+)
0.8%].
この粗結晶をイソプロピルアルコール２８１ｍ１に加熱
溶解した後、上記と同様にして再結晶を行なって精製す
ると、（−）体のみからなる結晶２５．２８（９３，４
％）が得られる。After heating and dissolving this crude crystal in 281 ml of isopropyl alcohol, the crystals were purified by recrystallization in the same manner as above, resulting in 25.28 (93,4
%) is obtained.
尚、光学純度の測定は、光学活性体用カラム“スミバッ
クＯＡ ２０００”“を用いたＨＰＬＣ法によって行な
う。The optical purity is measured by HPLC using an optically active substance column "Sumivac OA 2000".
ＩＲ（ヌショール） ： ２Ｂ６０．１７７０．１７
４０．１２００゜１１２０ ｃｍ−’
５−ヒドロキシ−α−テトラロン１６．２ｇ（０，１モ
ル）を塩化メチレン１３０＋ｎｌに溶解し、これに３．
４−ジヒドロ−２Ｈ−ピラン１２．６８（０，１５モル
）とｐ−ｔ−ルエンスルホン酸ピロジニウム塩２．５１
ｇ（０，０１モル）を加え、室温で一夜攪拌する。反応
終了後１モルの水酸化ナトリウム水溶液４０．５ｍｌを
加えて攪拌し、静置後有機層を分取する。次いて有機層
を１モルの水酸化ナトリウム水溶液４０．５ｍｌおよび
水４０．５ｍｌで順次洗浄した後、減圧下に濃縮乾固す
る。残留物にイソプロピルアルコール８１ｍ１を加えて
加熱溶解した後冷却し、３４〜３８℃で結晶を析出させ
た後再度４５〜５５℃に昇温してから水８１ｍ１を加え
、同温度で１０分間攪拌した後１０℃以下に冷却し、１
時間以上熟成してから析出結晶を濾取する。この結晶を
５０％含水イソプロピルアルコール３２．４ｍｌで洗浄
し、−夜真空乾燥すると、５−［２Ｈ−３，４，５，６
−チトラヒトロピランー２−イルオキシ］−α−テトラ
ロンよりなる結晶２２．１ｇ（９１，０％）が得られる
。IR (Nushor): 2B60.1770.17
40.1200°1120 cm-' 16.2 g (0.1 mol) of 5-hydroxy-α-tetralone was dissolved in 130+ nl of methylene chloride, and 3.
12.68 (0.15 mol) of 4-dihydro-2H-pyran and 2.51 pt-luenesulfonic acid pyrodinium salt
g (0.01 mol) and stirred overnight at room temperature. After the reaction is completed, 40.5 ml of a 1 molar aqueous sodium hydroxide solution is added and stirred, and after standing still, the organic layer is separated. Next, the organic layer is washed successively with 40.5 ml of a 1 molar aqueous sodium hydroxide solution and 40.5 ml of water, and then concentrated to dryness under reduced pressure. 81 ml of isopropyl alcohol was added to the residue, heated and dissolved, and then cooled. Crystals were precipitated at 34 to 38°C. After raising the temperature to 45 to 55°C again, 81 ml of water was added and stirred at the same temperature for 10 minutes. After that, cool to below 10℃,
After aging for more than an hour, the precipitated crystals are collected by filtration. The crystals were washed with 32.4 ml of 50% aqueous isopropyl alcohol and dried under vacuum overnight.
22.1 g (91.0%) of crystals consisting of -titrahytropyran-2-yloxy]-α-tetralone are obtained.
ＩＲ（ヌジョール） ： ２９５０．１６８０．１５
９５．１５９０゜９７０ ｃｍ−’
’Ｈ−ＮＭＲ： ７．６９（ＩＨ，ｄ、Ｊ−８）１２）
、 ７．２５（２Ｈ，ｍ）、 ５．４４（ＩＨｌｓ）、
３．８２（ＩＨ，ｍ）、３．６２（１）１９ｍ）、
２．９５（２Ｈ２ｔ、Ｊ−６Ｈｚ）、 ２．６２（２
Ｈ，ｔ、Ｊ−６Ｈｚ）。IR (Nujol): 2950.1680.15
95.1590°970 cm-'' H-NMR: 7.69 (IH, d, J-8) 12)
, 7.25 (2H, m), 5.44 (IHLs),
3.82 (IH, m), 3.62 (1) 19 m),
2.95 (2H2t, J-6Hz), 2.62 (2
H, t, J-6Hz).
２．１２ （２Ｈ，ｔ、Ｊ−６Ｈ２） 、１．９５ （
２）１．ｍ） 。2.12 (2H, t, J-6H2), 1.95 (
2)1. m).
１．７２−１．６２（４Ｈ，ｍ）1.72-1.62 (4H, m)
Claims (3)
▲数式、化学式、表等があります▼（Ｒ＾３ は環状テルペンオキシ（低級）アルカノイル基を表わす
）、Ｒ＾１は含酸素複素環式基または環状テルペンオキ
シ（低級）アルカノイル基、Ｒ＾２は共に水素もしくは
低級アルキル基を表わす］ で示されることを特徴とする環式化合物。(1) General formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^3 is a cyclic terpene oxy(lower)alkanoyl group), R^1 is an oxygen-containing heterocyclic group or a cyclic terpeneoxy(lower)alkanoyl group, and R^2 both represent hydrogen or a lower alkyl group. cyclic compound.
がテトラヒドロ−２Ｈ−ピラニル基、Ｒ＾２がいずれも
水素である請求項（１）記載の環式化合物。(2) A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R^1
The cyclic compound according to claim 1, wherein is a tetrahydro-2H-pyranyl group and R^2 is hydrogen.
＾ａは３−メンチルオキシアセチルを表わす）、Ｒ＾１
が３−メンチルオキシアセチル、Ｒ＾２がいずれもｎ−
ブチル基である請求項（１）記載の環式化合物。(3) A is a ▲ mathematical formula, chemical formula, table, etc. ▼ (R^3
^a represents 3-menthyloxyacetyl), R^1
is 3-menthyloxyacetyl, and R^2 is both n-
The cyclic compound according to claim (1), which is a butyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20422390A JPH0489452A (en) | 1990-07-31 | 1990-07-31 | Cyclic compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20422390A JPH0489452A (en) | 1990-07-31 | 1990-07-31 | Cyclic compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0489452A true JPH0489452A (en) | 1992-03-23 |
Family
ID=16486880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20422390A Pending JPH0489452A (en) | 1990-07-31 | 1990-07-31 | Cyclic compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0489452A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5655598A (en) * | 1995-09-19 | 1997-08-12 | Garriss; John Ellsworth | Apparatus and method for natural heat transfer between mediums having different temperatures |
| CN113474182A (en) * | 2019-02-28 | 2021-10-01 | 引能仕株式会社 | Petroleum aromatic-containing oil, rubber composition, tire, and method for producing tire |
-
1990
- 1990-07-31 JP JP20422390A patent/JPH0489452A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5655598A (en) * | 1995-09-19 | 1997-08-12 | Garriss; John Ellsworth | Apparatus and method for natural heat transfer between mediums having different temperatures |
| CN113474182A (en) * | 2019-02-28 | 2021-10-01 | 引能仕株式会社 | Petroleum aromatic-containing oil, rubber composition, tire, and method for producing tire |
| CN113474182B (en) * | 2019-02-28 | 2023-07-18 | 引能仕株式会社 | Oil containing petroleum aromatic, rubber composition, tire, and method for producing tire |
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