JPH111452A - Production of 2-(2-phenyl-2-propenyl)indane-1,3-dione compounds - Google Patents
Production of 2-(2-phenyl-2-propenyl)indane-1,3-dione compoundsInfo
- Publication number
- JPH111452A JPH111452A JP9156432A JP15643297A JPH111452A JP H111452 A JPH111452 A JP H111452A JP 9156432 A JP9156432 A JP 9156432A JP 15643297 A JP15643297 A JP 15643297A JP H111452 A JPH111452 A JP H111452A
- Authority
- JP
- Japan
- Prior art keywords
- group
- lower alkyl
- alkyl group
- atom
- 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
- -1 2-(2-phenyl-2-propenyl)indane-1,3-dione compounds Chemical class 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- 150000001361 allenes Chemical class 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract 4
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- UHKAJLSKXBADFT-UHFFFAOYSA-N 1,3-indandione Chemical class C1=CC=C2C(=O)CC(=O)C2=C1 UHKAJLSKXBADFT-UHFFFAOYSA-N 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 150000001555 benzenes Chemical class 0.000 abstract description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 3
- CBEKYPINWJEJBP-UHFFFAOYSA-N 2-ethylindene-1,3-dione Chemical compound C1=CC=C2C(=O)C(CC)C(=O)C2=C1 CBEKYPINWJEJBP-UHFFFAOYSA-N 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract description 2
- 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 2
- JRGGUPZKKTVKOV-UHFFFAOYSA-N 1-bromo-3-chlorobenzene Chemical compound ClC1=CC=CC(Br)=C1 JRGGUPZKKTVKOV-UHFFFAOYSA-N 0.000 abstract 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 125000001309 chloro group Chemical group Cl* 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 description 1
- 125000006650 (C2-C4) alkynyl group Chemical group 0.000 description 1
- QBELEDRHMPMKHP-UHFFFAOYSA-N 1-bromo-2-chlorobenzene Chemical compound ClC1=CC=CC=C1Br QBELEDRHMPMKHP-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- SMBVYDNMCNDGCZ-UHFFFAOYSA-N 2-[2-(3-chlorophenyl)prop-2-enyl]-2-ethylindene-1,3-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C1(CC)CC(=C)C1=CC=CC(Cl)=C1 SMBVYDNMCNDGCZ-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000551547 Dione <red algae> Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241001460678 Napo <wasp> Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005278 alkyl sulfonyloxy group Chemical group 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002633 crown compound Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- FXORZKOZOQWVMQ-UHFFFAOYSA-L dichloropalladium;triphenylphosphane Chemical compound Cl[Pd]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FXORZKOZOQWVMQ-UHFFFAOYSA-L 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- LIXPXSXEKKHIRR-UHFFFAOYSA-M tetraethylphosphanium;bromide Chemical compound [Br-].CC[P+](CC)(CC)CC LIXPXSXEKKHIRR-UHFFFAOYSA-M 0.000 description 1
- FBOJNMRAZJRCNS-UHFFFAOYSA-M tetraethylphosphanium;chloride Chemical compound [Cl-].CC[P+](CC)(CC)CC FBOJNMRAZJRCNS-UHFFFAOYSA-M 0.000 description 1
- WKSYTZHMRBAPAO-UHFFFAOYSA-M tetraethylphosphanium;iodide Chemical compound [I-].CC[P+](CC)(CC)CC WKSYTZHMRBAPAO-UHFFFAOYSA-M 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明はインダン-1,3- ジオン類
の製造法に存し、特に、医薬、または特開平2-304043号
公報等に示される農薬の中間体として有用な、2-(2-フ
ェニル-2- プロペニル)インダン-1,3- ジオン類の製造
する方法に存するものである。BACKGROUND OF THE INVENTION The present invention relates to a process for producing indane-1,3-diones, and particularly useful as a pharmaceutical or an intermediate for agrochemicals described in JP-A-2-304043. -(2-phenyl-2-propenyl) indan-1,3-diones.
【0002】[0002]
【従来の技術】従来、2-(2-置換-2- プロペニル)イン
ダン-1,3- ジオン類の製造法としては、反応式(1) に表
される2. Description of the Related Art Conventionally, a method for producing 2- (2-substituted-2-propenyl) indan-1,3-diones is represented by a reaction formula (1).
【0003】[0003]
【化4】 Embedded image
【0004】一般式 [I'] で表されるインダン-1,3- ジ
オン類(式中、R6は低級アルキル基等を示す。)に、一
般式 [IV] (式中、Y は塩素、臭素、ヨウ素等のハロゲ
ン原子、アルキルスルホニルオキシ基、フェニルスルホ
ニルオキシ基、ヒドロキシル基、又はR7CO2 (式中、R7
は低級アルキル基、低級アルコキシ基を示す。))で示
される化合物を、塩基存在下、酸触媒下、またはパラジ
ウム触媒下反応させる製造法が知られている。一般式
[IV] で表される化合物の合成法は特開平2-304043号、
特開平7-061945号の各公報、特願平7-264058、特願平8-
001322、特願平7-338940等に記載されている方法があ
る。[0004] Indane-1,3-diones represented by the general formula [I '] (wherein R 6 represents a lower alkyl group or the like) are represented by the general formula [IV] (where Y is chlorine , A bromine atom, a halogen atom such as iodine, an alkylsulfonyloxy group, a phenylsulfonyloxy group, a hydroxyl group, or R 7 CO 2 (wherein R 7
Represents a lower alkyl group or a lower alkoxy group. A production method is known in which a compound represented by)) is reacted in the presence of a base, under an acid catalyst, or under a palladium catalyst. General formula
The method for synthesizing the compound represented by [IV] is described in JP-A-2-304043,
Japanese Unexamined Patent Publications Nos. 7-061945, 7-264058, 8-
001322, and a method described in Japanese Patent Application No. 7-338940.
【0005】[0005]
【発明が解決しようとする課題】このように、公知の方
法によって2-(2-フェニル-2- プロペニル)インダン-
1,3- ジオン類を合成する場合、工程数が多く、収率も
満足のいく方法ではない等の理由により、他の工業的に
有用な製造法が望まれていた。本発明は従来の問題点を
解決し、2-(2-フェニル-2- プロペニル)インダン-1,3
- ジオン類を選択的、効率的かつ高収率で製造する方法
を提供することを目的とする。As described above, 2- (2-phenyl-2-propenyl) indan-
In the case of synthesizing 1,3-diones, other industrially useful production methods have been desired, for example, because the number of steps is large and the yield is not a satisfactory method. The present invention solves the conventional problems and provides 2- (2-phenyl-2-propenyl) indan-1,3.
-To provide a method for producing diones selectively, efficiently and with high yield.
【0006】[0006]
【課題を解決するための手段】本発明者らは従来の課題
を解決するために鋭意検討した結果、2-(2-置換-2-プ
ロペニル)インダン-1,3- ジオン類の製造法として、一
般式 [I]で表されるインダン-1,3- ジオン類と一般式
[II] で表されるベンゼン類と、アレンを塩基およびパ
ラジウム触媒存在下において反応させ、一工程で一般式
[III]で表される目的化合物を収率良く得ることを特徴
とする2-(2-フェニル-2- プロペニル)インダン-1,3-
ジオンの製造法を見いだし、本発明に至った。即ち、本
発明の要旨は、一般式 [I]Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the conventional problems, and as a result, as a method for producing 2- (2-substituted-2-propenyl) indan-1,3-diones. -1,3-diones represented by the general formula [I] and the general formula
A benzene represented by the formula [II] is reacted with an allene in the presence of a base and a palladium catalyst to obtain a compound represented by the general formula
2- (2-phenyl-2-propenyl) indane-1,3-characterized in that the target compound represented by [III] is obtained in good yield.
The present inventors have found a method for producing dione, which has led to the present invention. That is, the gist of the present invention is represented by the general formula [I]
【0007】[0007]
【化5】 Embedded image
【0008】(式中、R1は水素原子、低級アルキル基、
低級アルケニル基及び低級アルキニル基を表し、R2及び
R3はそれぞれ独立して水素原子、ハロゲン原子、低級ア
ルキル基を示す。)で示される、インダン-1,3- ジオン
類に一般式 [II]Wherein R 1 is a hydrogen atom, a lower alkyl group,
Represents a lower alkenyl group and a lower alkynyl group, R 2 and
R 3 each independently represents a hydrogen atom, a halogen atom, or a lower alkyl group. ), Indane-1,3-diones have the general formula [II]
【0009】[0009]
【化6】 Embedded image
【0010】(式中、A は臭素原子、ヨウ素原子、OSO2
R4(式中、R4はハロゲン原子、ハロゲンで置換されてい
てもよい低級アルキル基、置換されていてもよいアリル
基を示す。)、又はOP(=O)(OR5)2(式中R5は低級アルキ
ル基、アリル基を示す。)を示し、X1,X2 はそれぞれ独
立して、水素原子、ハロゲン原子、低級アルキル基、低
級ハロアルキル基を示す。)で示される置換ベンゼン類
と、アレンを塩基およびパラジウム触媒存在下にて反応
させることを特徴とする一般式 [III](Where A is a bromine atom, an iodine atom, OSO 2
R 4 (in the formula, R 4 represents a halogen atom, a lower alkyl group optionally substituted by halogen, an allyl group optionally substituted), or OP ((O) (OR 5 ) 2 (formula Wherein R 5 represents a lower alkyl group or an allyl group), and X 1 and X 2 each independently represent a hydrogen atom, a halogen atom, a lower alkyl group, or a lower haloalkyl group. Wherein the substituted benzene represented by the formula) is reacted with an allene in the presence of a base and a palladium catalyst [III]
【0011】[0011]
【化7】 Embedded image
【0012】(式中、R1、R2、R3、X1およびX2は一般式
(I) 及び(II)で定義したとおり。)で示される2-(2-フ
ェニル-2- プロペニル)インダン-1,3- ジオン類の製造
法に存する。(Wherein R 1 , R 2 , R 3 , X 1 and X 2 are a general formula
As defined in (I) and (II). )) To produce 2- (2-phenyl-2-propenyl) indan-1,3-diones.
【0013】[0013]
【発明の実施の形態】以下、本発明の好ましい具体的実
施態様について説明する。一般式(I) で示されるインダ
ン-1,3- ジオン類において、R1は水素原子、低級アルキ
ル基、低級アルケニル基及び低級アルキニル基を示す。
低級アルキル基としてはC1〜C4のアルキル基、具体的に
はメチル基、エチル基、n-プロピル基、n-ブチル基等が
挙げられる。低級アルケニル基としては、C2〜C4のアル
ケニル基、具体的にはビニル基、アリル基、ブチレン基
等が挙げられる。低級アルキニル基としてはC2〜C4のア
ルキニル基、具体的にはエチニル基、プロパルギル基等
が挙げられる。中でも、メチル基、アリル基、プロパル
ギル基、ベンジル基が好ましい。R2,R3 はそれぞれ独立
して、水素原子、塩素原子、臭素原子等のハロゲン原
子、C1〜C4のアルキル基、具体的にはメチル基、エチル
基、n-プロピル基、n-ブチル基等を示す。中でもメチル
基、塩素原子が好ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred specific embodiments of the present invention will be described below. In the indane-1,3-diones represented by the general formula (I), R 1 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a lower alkynyl group.
Lower alkyl group of C 1 -C 4 as groups, such as methyl, ethyl, n- propyl and n- butyl. Examples of the lower alkenyl group include a C 2 -C 4 alkenyl group, specifically, a vinyl group, an allyl group, and a butylene group. The lower alkynyl group includes a C 2 -C 4 alkynyl group, specifically, an ethynyl group, a propargyl group and the like. Among them, a methyl group, an allyl group, a propargyl group, and a benzyl group are preferred. R 2 and R 3 are each independently a hydrogen atom, a chlorine atom, a halogen atom such as a bromine atom, a C 1 -C 4 alkyl group, specifically a methyl group, an ethyl group, an n-propyl group, an n- Shows a butyl group and the like. Among them, a methyl group and a chlorine atom are preferable.
【0014】一般式 [II] で示されるベンゼン類におい
て、A は臭素原子、ヨウ素原子、OSO2R4又はOP(=O)(O
R5)2を示す。R4はフッ素原子等のハロゲン原子、ハロゲ
ンで置換されていてもよい低級アルキル基、置換されて
いてもよいアリル基を示す。低級アルキル基としては、
C1〜C4のアルキル基を示し、R4としては、メチル基、エ
チル基、n-プロピル基、n-ブチル基、及びこれらのハロ
ゲン置換体、例えばトリフルオロメチル基等が挙げられ
る。置換されていてもよいアリル基としてはフェニル
基、p-メチルフェニル基、p-クロロフェニル基が挙げら
れる。In the benzenes represented by the general formula [II], A is a bromine atom, an iodine atom, OSO 2 R 4 or OP (= O) (O
R 5 ) 2 is indicated. R 4 represents a halogen atom such as a fluorine atom, a lower alkyl group optionally substituted with halogen, or an allyl group optionally substituted. As the lower alkyl group,
C 1 represents an alkyl group -C 4, as is R 4, a methyl group, an ethyl group, n- propyl group, n- butyl group, and their halogen substituents, trifluoromethyl group and the like, for example. Examples of the optionally substituted allyl group include a phenyl group, a p-methylphenyl group, and a p-chlorophenyl group.
【0015】R5での低級アルキル基は、メチル基、エチ
ル基、n-プロピル基、n-ブチル基等C1〜C4のアルキル基
が挙げられる。アリル基としてはフェニル基等が挙げら
れる。X1,X2 はそれぞれ独立して、水素原子、塩素原
子、フッ素原子等のハロゲン原子、メチル基、エチル
基、n-プロピル基、n-ブチル基等のC1〜C4のアルキル
基、トリクロロメチル基、トリフルオロメチル基等のC1
〜C3のハロアルキル基を示す。中でも少なくとも一方が
ハロゲン原子であることが好ましく、特にA に対してメ
タ位に置換していることが好ましく、これが塩素原子で
あればなお好ましい。The lower alkyl group for R 5 includes a C 1 -C 4 alkyl group such as a methyl group, an ethyl group, an n-propyl group and an n-butyl group. Examples of the allyl group include a phenyl group. X 1 and X 2 are each independently a hydrogen atom, a chlorine atom, a halogen atom such as a fluorine atom, a methyl group, an ethyl group, a n-propyl group, a C 1 to C 4 alkyl group such as an n-butyl group, C 1 such as trichloromethyl group and trifluoromethyl group
A haloalkyl group of ~C 3. Among them, at least one is preferably a halogen atom, particularly preferably substituted at the meta position with respect to A 1, and more preferably a chlorine atom.
【0016】本発明方法に用いるアレンは、数回に分け
て反応中に分割して仕込むこともできる。また反応系内
にガスの状態で連続的に吹き込むこともできる。副反応
を抑えるためには、連続的に吹き込む方法が好ましい。
アレンは市販ガス状体として、又Organic synthesis V.
22に記載の様に2,3-ジククロブロベンより調製してもよ
い。The allene used in the method of the present invention can be charged in several portions during the reaction. Further, it can be continuously blown into the reaction system in a gas state. In order to suppress a side reaction, a method of continuously blowing is preferable.
Allen is a commercially available gaseous substance, and Organic synthesis V.
It may be prepared from 2,3-diclocloben as described in 22.
【0017】このような一般式(I) で示されるインダン
-1,3- ジオン類と、一般式(II)で示されるベンゼン類と
ともに反応させる塩基としては任意のものが使用出来、
具体的にはNaOH,KOH,K2CO3,NaCO3,NaH等の無機塩、NaPO
4,K3PO4 等のリン酸塩、NaOR 5,KOR5(式中R5はC1〜C6の
アルキル基を示す)トリエチルアミン、ピリジン等の有
機塩基が挙げられるが、これらに限定されるものではな
い。反応に供される塩基の量は特に限定されるものでは
ないが、0.5 〜5 当量、好ましくは1.0 〜3.0当量であ
る。The indan represented by the general formula (I)
-1,3-diones and benzenes represented by the general formula (II)
Any base can be used for the reaction together,
Specifically, NaOH, KOH, KTwoCOThree, NaCOThree, NaH and other inorganic salts, NaPO
Four, KThreePOFourEtc. phosphate, NaOR Five, KORFive(Where RFiveIs C1~ C6of
(Indicating an alkyl group) such as triethylamine and pyridine
But not limited to these.
No. The amount of the base subjected to the reaction is not particularly limited.
But 0.5 to 5 equivalents, preferably 1.0 to 3.0 equivalents
You.
【0018】又、反応に供されるパラジウム触媒として
は、0価及び2価のパラジウム触媒を用いる。具体的に
は Pd(dppe)(dppeは(diphenylphohino)ethane を表
す)、Pd(PPh3)4,PdCl2(PPh)2,Pd2(dba)3 (dba はdibe
nzylideneacetoneを表す)、PdZ1 2 (式中Z1は塩素原
子、臭素原子、ヨウ素原子、アセトキシ基を表す。)、
Pd[P(Ph-Z2)(Ph-Z3)(Ph-Z4)]4 (式中Z2、Z3、Z4は、ス
ルホン酸または水素原子を表すがZ2=Z3=Z4=水素原子
の場合を除く)等が挙げられるが、これらに限定される
ものではない。またこれらの触媒は単独で用いることも
できるが、PPh3,dba,dppe,P(Ph-Z2)(Ph-Z3)(Ph-Z4)(式
中Z2、Z3、Z4は前述した通り)等の配位子となりうる化
合物共存下で用いることもできる。パラジウム触媒の量
は特に限定されるものではないが、0.001 〜0.1 当量、
好ましくは0.001 〜0.05当量である。As the palladium catalyst used for the reaction, zero-valent and divalent palladium catalysts are used. Specifically, Pd (dppe) (dppe represents (diphenylphohino) ethane), Pd (PPh 3 ) 4 , PdCl 2 (PPh) 2 , Pd 2 (dba) 3 (dba is dibe
represents a nzylideneacetone), PdZ 1 2 (wherein Z 1 represents a chlorine atom, a bromine atom, an iodine atom, an acetoxy group.)
Pd [P (Ph-Z 2 ) (Ph-Z 3 ) (Ph-Z 4 )] 4 (wherein Z 2 , Z 3 and Z 4 represent a sulfonic acid or a hydrogen atom, but Z 2 = Z 3 = Z 4 = hydrogen atom), but are not limited thereto. These catalysts can be used alone, but PPh 3 , dba, dppe, P (Ph-Z 2 ) (Ph-Z 3 ) (Ph-Z 4 ) (where Z 2 , Z 3 , Z 4 Can be used in the co-presence of a compound which can be a ligand such as described above). Although the amount of the palladium catalyst is not particularly limited, it is 0.001 to 0.1 equivalent,
Preferably it is 0.001-0.05 equivalent.
【0019】本発明においては通常、溶媒を使用する
が、具体的にはDMF,THF,DMSO, アセトン, アセトニトリ
ル, トルエン, 水等が挙げられる。但し、これらに限定
されるものではない。これらの溶媒は2種以上の溶媒を
混合して用いることもできる。溶媒の量は特に限定され
るものではないが、反応に用いる一般式(II)で表される
化合物に対し1 〜30倍量、好ましくは3 〜20倍量を用い
る。In the present invention, a solvent is generally used, and specific examples thereof include DMF, THF, DMSO, acetone, acetonitrile, toluene, water and the like. However, it is not limited to these. These solvents may be used as a mixture of two or more solvents. The amount of the solvent is not particularly limited, but it is 1 to 30 times, preferably 3 to 20 times the amount of the compound represented by the formula (II) used in the reaction.
【0020】本発明は相間移動触媒存在下にて行うこと
ができる。相間移動触媒としては、4級アンモニウム
塩、4級ホスホニウム塩等のオニウム塩類及びクラウン
化合物等が挙げられる。具体的には4級ホスホニウム塩
として、塩化テトラエチルホスホニウム、臭化テトラエ
チルホスホニウム、ヨウ化テトラエチルホスホニウム等
が挙げられ、4級アンモニウム塩としては塩化テトラブ
チルアンモニウム、臭化テトラブチルアンモニウム、ヨ
ウ化テトラブチルアンモニウム、臭化トリエチルベンジ
ルアンモニウム、テトラブチルアンモニウムハイドロゲ
ンサルフェート等が挙げられ、クラウン化合物としては
18- クラウン-6、ジシクロヘキシル-18-クラウン-6等が
挙げられる。反応に供される相間移動触媒の量は特に限
定されるものではないが、0.01〜0.1 当量、好ましくは
0.005 〜0.02当量である。The present invention can be carried out in the presence of a phase transfer catalyst. Examples of the phase transfer catalyst include onium salts such as quaternary ammonium salts and quaternary phosphonium salts, and crown compounds. Specifically, quaternary phosphonium salts include tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium iodide, and the like, and quaternary ammonium salts include tetrabutylammonium chloride, tetrabutylammonium bromide, and tetrabutylammonium iodide. , Triethylbenzylammonium bromide, tetrabutylammonium hydrogen sulfate and the like.
18-crown-6, dicyclohexyl-18-crown-6 and the like. The amount of the phase transfer catalyst used for the reaction is not particularly limited, but is preferably 0.01 to 0.1 equivalent, preferably
0.005 to 0.02 equivalents.
【0021】本発明における反応温度は20〜90℃、中で
も50〜80℃の範囲で行なうのが好ましい。反応終了後
は、系内の無機物を濾過あるいは水洗等の方法により除
去した後、溶媒を留去後、結晶化し目的物を得ることが
できる。また反応系に水を加えて結晶化を行い、目的物
を得ることもできる。水洗あるいは水溶媒から結晶化す
る際にP(Ph-Z2)(Ph-Z3)(Ph-Z4)(式中Z2、Z3、Z4は前述
した通り)等の水溶性の配位子を水に溶解しておくこと
により、系内に残存するパラジウムを除去することもで
きる。[0021] The reaction temperature in the present invention is preferably in the range of 20 to 90 ° C, especially 50 to 80 ° C. After completion of the reaction, inorganic substances in the system are removed by a method such as filtration or washing with water, and then the solvent is distilled off, followed by crystallization to obtain the desired product. Crystallization can also be performed by adding water to the reaction system to obtain the desired product. Water-soluble such as P (Ph-Z 2 ) (Ph-Z 3 ) (Ph-Z 4 ) (where Z 2 , Z 3 and Z 4 are as described above) when rinsing with water or crystallizing from an aqueous solvent By dissolving the ligand in water, palladium remaining in the system can be removed.
【0022】[0022]
【実施例】以下に実施例及び比較例を挙げて本発明をよ
り具体的に説明するが、本発明はその要旨を越えない限
り、以下の実施例に限定されるものではない。 実施例1 2-[2-(3-クロロフェニル)-2-プロペニル]-2-エチルイン
ダン-1,3- ジオンの調製 2-エチルインダン-1,3- ジオン8.71g (0.05mol) 、m-ブ
ロモクロロベンゼン 9.58g (0.05mol)、炭酸カリウム2
0.8g (0.15mol) 、テトラブチルアンモニウムブロマイ
ド0.32g (0.001mol)、ビス(トリフェニルホスフィンパ
ラジウム(II)ジクロリド0.07g 、DMF60ml の混合溶媒
を80℃に加温し、窒素気流下Organic synthesis V 、p2
2 に記載の方法で発生させたアレンを30分間吹き込ん
だ。反応系を放冷した後、水60mlを加えて撹拌し、静置
し、下層の水層を除去した後、水60mlとトリフェニルホ
スフィンをスルホン化した化合物0.2gを加えて水洗した
後、水30mlを加え撹拌しながら結晶化を行い、析出した
結晶を濾取し、乾燥、2-[2- (3-クロロフェニル)-2-
プロペニル]-2-エチルインダン-1,3- ジオン 8.10gを得
た。更に母液に酢酸エチルを加えて抽出し、有機層を濃
縮し、得られた残渣にヘキサンを加えて結晶化し、2-[2
-(3-クロロフェニル)-2-プロペニル]-2-エチルインダン
-1,3- ジオン 3.29gを得た。EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist. Example 1 Preparation of 2- [2- (3-chlorophenyl) -2-propenyl] -2-ethylindane-1,3-dione 8.71 g (0.05 mol) of 2-ethylindane-1,3-dione, m- 9.58 g (0.05 mol) of bromochlorobenzene, potassium carbonate 2
A mixed solvent of 0.8 g (0.15 mol), 0.32 g (0.001 mol) of tetrabutylammonium bromide, 0.07 g of bis (triphenylphosphinepalladium (II) dichloride, and 60 ml of DMF was heated to 80 ° C., and Organic synthesis V was added under a nitrogen stream. p2
Allene generated by the method described in 2 was blown for 30 minutes. After allowing the reaction system to cool, 60 ml of water was added and stirred, and the mixture was left to stand.The lower aqueous layer was removed.60 ml of water and 0.2 g of a compound obtained by sulfonating triphenylphosphine were added. Crystallization was performed while adding 30 ml and stirring, and the precipitated crystals were collected by filtration, dried and dried with 2- [2- (3-chlorophenyl) -2-.
8.10 g of [propenyl] -2-ethylindane-1,3-dione were obtained. Further, ethyl acetate was added to the mother liquor to perform extraction, the organic layer was concentrated, and hexane was added to the obtained residue for crystallization to give 2- [2
-(3-Chlorophenyl) -2-propenyl] -2-ethylindane
3.29 g of -1,3-dione was obtained.
【0023】[0023]
【発明の効果】以上詳述した通り、本発明の製造法によ
れば、医薬、農薬の中間体として有用な 2-(2-置換-2-
プロペニル) インダン-1,3- ジオン類を、高収率で容易
に得ることが可能となる。As described above in detail, according to the production method of the present invention, 2- (2-substituted-2-yl) useful as an intermediate for medicines and agricultural chemicals is used.
Propenyl) indane-1,3-dione can be easily obtained in high yield.
Claims (2)
ル基及び低級アルキニル基を表し、R2及びR3はそれぞれ
独立して水素原子、ハロゲン原子、低級アルキル基を示
す。)で示される、インダン-1,3- ジオン類に一般式
[II] 【化2】 (式中、A は臭素原子、ヨウ素原子、OSO2R4(式中、R4
はハロゲン原子、ハロゲンで置換されていてもよい低級
アルキル基、置換されていてもよいアリル基を示
す。)、又はOP(=O)(OR5)2(式中R5は低級アルキル基、
アリル基を示す。)を示し、X1,X2 はそれぞれ独立し
て、水素原子、ハロゲン原子、低級アルキル基、低級ハ
ロアルキル基を示す。)で示される置換ベンゼン類と、
アレンを塩基およびパラジウム触媒存在下にて反応させ
ることを特徴とする一般式 [III] 【化3】 (式中、R1、R2、R3、X1およびX2は一般式(I) 及び(II)
で定義したとおり。)で示される2-(2-フェニル-2- プ
ロペニル)インダン-1,3- ジオン類の製造法。1. A compound of the general formula [I] (In the formula, R 1 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group and a lower alkynyl group, and R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, or a lower alkyl group.) General formula for indane-1,3-diones
[II] embedded image (Where A is a bromine atom, an iodine atom, OSO 2 R 4 (wherein R 4
Represents a halogen atom, a lower alkyl group optionally substituted by halogen, or an allyl group optionally substituted by halogen. ) Or OP (= O) (OR 5 ) 2 (wherein R 5 is a lower alkyl group,
Indicates an allyl group. ) And X 1 and X 2 each independently represent a hydrogen atom, a halogen atom, a lower alkyl group, or a lower haloalkyl group. ), And
General formula [III] characterized in that allene is reacted in the presence of a base and a palladium catalyst. (Wherein, R 1 , R 2 , R 3 , X 1 and X 2 represent the general formulas (I) and (II)
As defined in. ), A method for producing 2- (2-phenyl-2-propenyl) indan-1,3-diones.
徴とする請求項1に記載の製造法。2. The method according to claim 1, wherein the reaction is performed in the presence of a phase transfer catalyst.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9156432A JPH111452A (en) | 1997-06-13 | 1997-06-13 | Production of 2-(2-phenyl-2-propenyl)indane-1,3-dione compounds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9156432A JPH111452A (en) | 1997-06-13 | 1997-06-13 | Production of 2-(2-phenyl-2-propenyl)indane-1,3-dione compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH111452A true JPH111452A (en) | 1999-01-06 |
Family
ID=15627630
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9156432A Pending JPH111452A (en) | 1997-06-13 | 1997-06-13 | Production of 2-(2-phenyl-2-propenyl)indane-1,3-dione compounds |
Country Status (1)
Country | Link |
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JP (1) | JPH111452A (en) |
-
1997
- 1997-06-13 JP JP9156432A patent/JPH111452A/en active Pending
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