JPH0429951A - Biphenyl derivative - Google Patents
Biphenyl derivativeInfo
- Publication number
- JPH0429951A JPH0429951A JP13680690A JP13680690A JPH0429951A JP H0429951 A JPH0429951 A JP H0429951A JP 13680690 A JP13680690 A JP 13680690A JP 13680690 A JP13680690 A JP 13680690A JP H0429951 A JPH0429951 A JP H0429951A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- biphenyl derivative
- general formula
- group
- 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 49
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 8
- 229910052794 bromium Inorganic materials 0.000 abstract description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- -1 n-octyl group Chemical group 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- 238000000921 elemental analysis Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- LMTMMYPZXZQEJM-UHFFFAOYSA-N (2-fluoro-4-iodophenyl) benzoate Chemical compound C(C1=CC=CC=C1)(=O)OC1=C(C=C(C=C1)I)F LMTMMYPZXZQEJM-UHFFFAOYSA-N 0.000 description 1
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- 101100231510 Caenorhabditis elegans ceh-7 gene Proteins 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 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
- 239000007789 gas Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は新規なビフェニル誘導体に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to novel biphenyl derivatives.
［従来の技術］
本出願人は、ビフェニル系液晶化合物に関し、特願平１
−３０３８５０号にて出願している。[Prior Art] The present applicant has filed a patent application for biphenyl-based liquid crystal compounds in Japanese Patent Application No.
The application has been filed under No.-303850.
［発明が解決しようとする課題］
本発明は、このものを含む種々の液晶化合物の中間体と
して有用であり、かつ医薬、農薬等の中＝１−
量体としても利用できる新規なビフェニル誘導体を提供
することを目的とする。[Problems to be Solved by the Invention] The present invention provides a novel biphenyl derivative that is useful as an intermediate for various liquid crystal compounds including this biphenyl derivative, and can also be used as a monomer of pharmaceuticals, agricultural chemicals, etc. The purpose is to provide.
［課題を解決するための手段］
本発明者らは、上記目的を達成すべく鋭意検討を行った
結果、新規なビフェニル誘導体を得て、本発明に到達し
た。すなわち本発明は、一般式％式％（１）
〔式中、Ｘは臭素原子またはロウ素原子を、Ｘｌはフッ
素原子または塩素原子を、Ｙは一〇−または−Ｓ−を、
Ｒは水素原子または炭素数１〜１８のアルキル基を表す
〕で示されるビフェニル誘導体である。[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the present inventors obtained a novel biphenyl derivative and arrived at the present invention. That is, the present invention is based on the general formula % formula % (1) [wherein,
R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms].
一般式（１）において、Ｒとしては水素原子、メチル基
、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ペン
チル基、ｎ−ヘキシル基、ｎ−へブチル基、ｎ−オクチ
ル基、ｎ−ノニル基、 ｎ−デシル基、ｎ−ウンデシル
基、ｎ−ドデシル基、ｎ−テトラデシル基、ｎ−ヘキサ
デシル基、ｎ−オクタデシル基、などが挙げられる。In general formula (1), R is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-hebutyl group, an n-octyl group, Examples include n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, and the like.
これらのうち、好ましいものは水素原子および炭素数２
〜１４のアルキル基である。Among these, preferred are hydrogen atoms and 2 carbon atoms.
~14 alkyl groups.
Ｘｌは好ましくはフッ素原子である。Xl is preferably a fluorine atom.
Ｙは好ましくは一〇−である。Y is preferably 10-.
一般式（１）で示される化合物の具体例としては、表−
１に示すような基を有する化合物が挙げられる。As a specific example of the compound represented by the general formula (1), Table-
Examples include compounds having groups as shown in 1.
表一 １中、各記号はそれぞれ以下の基を表す。Table 1 1, each symbol represents the following group.
ＭＥＴ ； Ｃｔ１３−
ＥＴＨ； Ｃ２Ｈ３−
ＰＲＯ； ｎ−Ｃ３ｔ１７−
ＢＬＩＴ ； ｎ−Ｃ，Ｈｇ−
ＰＥＮ ； ｎ−Ｃ３Ｈ７，−
ＨＥＸ ； ｎ−ＣａＢｒ２−
１（ＥＰ ； ｎ−Ｃ７■ｌ５−
ＯＣＴ″ｎ−Ｃ３Ｈ，７−
ＮＯＮ ｎ−Ｃｇ Ｈｌ ｇ −
ＤＥＣｎ−ＣＩＢＨ２，−
ＵＮＤ ｎ−Ｃ２，Ｈ２３−
ＤＯＤ ｎ−ｃ１２１（２６−
ＴＥＤ ｎ−Ｃ１４Ｈ２９−
一般式（１）に含まれる化合物は、例えば次の工程を経
て合成できる（下記式中、ｘ、 ｘ’、ＹおよびＲは一
般式（１）の場合と同一である）。MET; Ct13- ETH; C2H3- PRO; n-C3t17- BLIT; n-C,Hg- PEN; n-C3H7,-HEX; n-CaBr2- 1(EP; ,7- NON n-Cg Hl g - DECn-CIBH2, - UND n-C2,H23- DOD n-c121 (26- TED n-C14H29- The compound included in the general formula (1) can be prepared by, for example, the following step. (In the following formula, x, x', Y and R are the same as in general formula (1)).
（Ｉ）Ｒが水素原子の場合。(I) When R is a hydrogen atom.
×１
ｘ２−ｄ−ｖ−ｏ （２）（Ｘ２； Ｃ
１，Ｂｒ ｏｒ Ｉ）
ｘ−ｏ−ｄ−ｙ−ｕ
（１ａ）
一般式（４）の化合物と式（５）の化合物を、不活性ガ
ス雰囲気下、塩基（例えば炭酸ナトリウム）存在下、０
価または２価のパラジウム触媒あるいは０価または２価
ニッケル触媒を用いてクロスカッ−リングさせることに
より、一般式（６）の化合物を得る。×1 x2-d-v-o (2) (X2; C
1,Br or I)
A compound of general formula (6) is obtained by cross-curling using a valent or divalent palladium catalyst or a zero or divalent nickel catalyst.
一般式（６）の化合物を、Ｘ２（臭素あるいはヨウ素）
を用いてハロゲン化し、一般式（８）の化合物を得る。The compound of general formula (6), X2 (bromine or iodine)
is halogenated to obtain a compound of general formula (8).
一般式（８）の化合物を塩基（例えば水酸化ナトリウム
）で加水分解することにより、本発明の化合物である一
般式（１ａ）で示されるビフェニル誘導体を得ることが
できる。By hydrolyzing the compound of general formula (8) with a base (eg, sodium hydroxide), a biphenyl derivative represented by general formula (1a), which is a compound of the present invention, can be obtained.
（ＩＦ） Ｒがアルキル基の場合。(IF) When R is an alkyl group.
すなわち、一般式（１ａ）の化合物を塩基（例えば水酸
化ナトリウム）の存在下、一般式（９）のアルキル化剤
（例えばハロゲン化アルキル）と反応させることにより
、本発明の化合物である一般式（１ｂ）で示されるビフ
ェニル誘導体を得ることができる。That is, by reacting a compound of general formula (1a) with an alkylating agent (for example, an alkyl halide) of general formula (9) in the presence of a base (for example, sodium hydroxide), a compound of the general formula (1a), which is a compound of the present invention, can be prepared. A biphenyl derivative represented by (1b) can be obtained.
また、一般式（１ｂ）で示されるビフェニル誘導体は、
次のような工程を経ても合成可能である。In addition, the biphenyl derivative represented by the general formula (1b) is
It can also be synthesized through the following steps.
Ｘ２−ｄ−Ｙ−１（
（Ｘ２； Ｃｌ、Ｂｒ ｏｒ １）
すなわち、−最大（２）の化合物を塩基（例えば水酸化
ナトリウム）の存在下、−最大（９）のアルキル化剤（
例えばハロゲン化アルキル）と反応させることにより、
−最大（１０）の化合物を得る。X2-d-Y-1 ( (X2; Cl, Br or 1) i.e. - the compound of up to (2) is treated in the presence of a base (e.g. sodium hydroxide) - the alkylating agent of up to (9) (
For example, by reacting with alkyl halides),
- Obtain maximum (10) compounds.
一般式（１０）の化合物に金属マグネシウムを作用しグ
リニヤール試薬としたのち、パラジウムあるいはニッケ
ル触媒存在下、−最大（１１）で示されるジハロゲノベ
ンゼン誘導体とクロスカップリングさせることにより、
本発明の化合物である一般式（１ｂ）で示されるビフェ
ニル誘導体を得ることができる。The compound of general formula (10) is treated with metallic magnesium to form a Grignard reagent, and then cross-coupled with a dihalogenobenzene derivative represented by -maximum (11) in the presence of a palladium or nickel catalyst.
A biphenyl derivative represented by general formula (1b), which is a compound of the present invention, can be obtained.
本発明のビフェニル誘導体は、種々の液晶化合物の中間
体として有用であり、かつ医薬、農薬等の中間体として
も利用することができる。The biphenyl derivative of the present invention is useful as an intermediate for various liquid crystal compounds, and can also be used as an intermediate for medicines, agricultural chemicals, and the like.
例えば本発明のビフェニル誘導体を中間体として、下記
のような液晶化合物を得ることができる。For example, the following liquid crystal compounds can be obtained using the biphenyl derivative of the present invention as an intermediate.
ＣｅＨ７？−Ｃ＝ｃ−０−ｄ−ｏ−ｃ、ｕ、ａ （
１２）Ｃ４゜８２、−０−ｄ−０−Ｃｏ Ｈｔ ３（１
３）上記化合物は例えば次のような工程を経て合成でき
る。CeH7? -C=c-0-d-o-c, u, a (
12) C4゜82, -0-d-0-Co Ht 3(1
3) The above compound can be synthesized, for example, through the following steps.
１−０−ｄ−ＯＨ（１４）
すなわち、本発明の化合物（１４）を水酸化ナトリウム
存在下ヘキシルブロマイド（１５）と反応させて化合物
（１６）を得る。1-0-d-OH (14) That is, compound (14) of the present invention is reacted with hexyl bromide (15) in the presence of sodium hydroxide to obtain compound (16).
化合物（１６）と化合物（１７）を、トリエチルアミン
中不活性ガス雰囲気下、０価または２価のパラジウム触
媒およびヨウ化鋼を用いて反応させることにより、化合
物（１２）を得ることができる。Compound (12) can be obtained by reacting compound (16) and compound (17) in triethylamine in an inert gas atmosphere using a zero- or divalent palladium catalyst and iodized steel.
さらに、化合物（１２）をパラジウムカーボン存在下水
素添加することにより、化合物（１３）を得ることがで
きる。Furthermore, compound (13) can be obtained by hydrogenating compound (12) in the presence of palladium carbon.
化合物（１２）、（１３）の液晶としての有用性の指標
として、これらの化合物の相転移温度を表−２に示す。As an indicator of the usefulness of compounds (12) and (13) as liquid crystals, the phase transition temperatures of these compounds are shown in Table 2.
表−２ 表−２中各記号はそれぞれ以下の相を表す。Table-2 Each symbol in Table 2 represents the following phase.
Ｃｒｙ；結晶相
Ｓｌ ；未同定スメクチック相
Ｓｃ；スメクチックＣ相
Ｉｓｏ；等方性液体相
［実施例コ
以下、本発明を製造例および実施例により更に説明する
が、本発明はこれに限定されない。Cry; crystalline phase Sl; unidentified smectic phase Sc; smectic C phase Iso; isotropic liquid phase [Examples] The present invention will be further explained below with reference to production examples and examples, but the present invention is not limited thereto.
製造例−１
表−１中Ｎ ｏ、２の化合物の製造
■０−フルオローｐ−ヨードフェノール３０．０ｇを無
水トルエン３００ｍ１に溶かし、ピリジン１６…１を加
え室温で攪拌した。これにベンゾイルクロリド１７．６
ｍｌを１５分間かけて滴下し、そのまま室温で２４時間
攪拌した。反応混合物を水、ＩＮ塩酸、飽和炭酸水素ナ
トリウム水溶液、水で順次洗浄後、トルエンを留去した
。得られた固体をメタノールから再結晶することにより
、ｐ−ベンゾイルオキシ−ｍ−フルオロヨードベンゼン
３８．２ｇを得た。Production Example 1 Production of Compound No. 2 in Table 1 30.0 g of 0-fluoro-p-iodophenol was dissolved in 300 ml of anhydrous toluene, 16...1 of pyridine was added, and the mixture was stirred at room temperature. To this, benzoyl chloride 17.6
ml was added dropwise over 15 minutes, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was washed successively with water, IN hydrochloric acid, a saturated aqueous sodium bicarbonate solution, and water, and then toluene was distilled off. The obtained solid was recrystallized from methanol to obtain 38.2 g of p-benzoyloxy-m-fluoroiodobenzene.
■ｐｐ−ベンゾイルオキシ−ｍ−フルオロラードベンゼ
ン１．８ｇをトルエン５０ｍ１に溶かし、２Ｍ炭酸ナト
リウム水溶液２５ｍ１を加え室温で攪拌した。これに不
活性ガス雰囲気下、テトラキストリフェニルホスフィン
パラジウム８６０ｍｇ、フェニルホウ酸５．０ｇのエタ
ノール溶液３０ｍ１を加え、５時間加熱還流を行った。(2) 1.8 g of pp-benzoyloxy-m-fluororade benzene was dissolved in 50 ml of toluene, 25 ml of a 2M aqueous sodium carbonate solution was added, and the mixture was stirred at room temperature. To this was added 30 ml of an ethanol solution containing 860 mg of tetrakistriphenylphosphine palladium and 5.0 g of phenylboric acid under an inert gas atmosphere, and the mixture was heated under reflux for 5 hours.
放冷後、３０％過酸化水素水３ｍｌで反応を止め、トル
エンで抽出、水洗後、トルエンを留去した。得られた固
体をヘキサンから再結晶することにより、下記化合物（
１８）７．０ｇを得た。After cooling, the reaction was stopped with 3 ml of 30% hydrogen peroxide solution, extracted with toluene, washed with water, and then the toluene was distilled off. By recrystallizing the obtained solid from hexane, the following compound (
18) 7.0g was obtained.
■■で得られた化合物（１８）２．８ｇを酢酸３５ｍ１
に溶かし、これに硫酸１ ｍ Ｉ ｓメタ過ヨウ素酸５
５０ｍｇ、およびヨウ素１．２ｇを加え、９０℃で１０
時間攪拌した。2.8 g of compound (18) obtained in ■■ was added to 35 ml of acetic acid.
and add 1 ml of sulfuric acid to 5 ml of metaperiodic acid.
Add 50 mg and 1.2 g of iodine, and heat at 90°C for 10
Stir for hours.
放冷後、反応混合物を氷水２００ｍ１に注ぎ、亜硫酸水
素ナトリウムで過剰のヨウ素を還元した後、析出した固
体をろ取した。これをトルエンから再結晶することによ
り、下記化合物（１９）１．７ｇを得た。After cooling, the reaction mixture was poured into 200 ml of ice water, excess iodine was reduced with sodium bisulfite, and the precipitated solid was collected by filtration. By recrystallizing this from toluene, 1.7 g of the following compound (19) was obtained.
■■で得られた化合物（１９）１．７ｇをエタノール３
０ｍ１に懸濁させ、これに水酸化ナトリウム４９０ｍｇ
を加え、１時間加熱還流を行った。放冷後、エタノール
を留去し得られた固体を水４０ｍ１に溶かした。この溶
液に炭酸ガスを吹き込み、析出した固体をろ取すること
により、本発明の化合物である表−１中Ｎ００２の化合
物１．２ｇを得た。1.7 g of compound (19) obtained in ■■ was added to 3 mL of ethanol.
Suspend in 0ml and add 490mg of sodium hydroxide to this.
was added and heated under reflux for 1 hour. After cooling, the ethanol was distilled off and the resulting solid was dissolved in 40 ml of water. By blowing carbon dioxide gas into this solution and filtering off the precipitated solid, 1.2 g of the compound of the present invention, No. 002 in Table 1, was obtained.
実施例−１
製造例−１により得た表−１中Ｎ００２の化合物の構造
を、ＮＭＲ（核磁気共鳴スペクトル分析）、ＭＳ（質量
分析）、ＩＲ（赤外吸収スペクトル分析）および元素分
析により確認した。この化合物の元素分析値を下記に示
す。またこの化合物のＩＲスペクトル、Ｈ−ＮＭＲスペ
クトルおよびＦ−ＮＭＲスペクトルをそれぞれ第１図、
第２図および第３図に示す。Example-1 The structure of the compound N002 in Table-1 obtained in Production Example-1 was confirmed by NMR (nuclear magnetic resonance spectroscopy), MS (mass spectrometry), IR (infrared absorption spectroscopy), and elemental analysis. did. The elemental analysis values of this compound are shown below. In addition, the IR spectrum, H-NMR spectrum, and F-NMR spectrum of this compound are shown in Figure 1, respectively.
Shown in FIGS. 2 and 3.
元素分析値： 理論値（％） 実測値（％）Ｃ：８
２．３Ｉ Ｃ：８２．１１Ｈ： ９．３１
Ｈ： ９．４６Ｆ： ４．６５ Ｆ
： ４．７５［発明の効果コ
（１）本発明により種々の液晶化合物の中間体として有
用であり、かつ各種医薬、農薬の中間体としても利用す
ることのできる新規なビフェニル誘導体を提供すること
ができた。Elemental analysis value: Theoretical value (%) Actual value (%) C: 8
2.3I C: 82.11H: 9.31
H: 9.46F: 4.65F
: 4.75 [Effects of the Invention (1) The present invention provides a novel biphenyl derivative that is useful as an intermediate for various liquid crystal compounds and can also be used as an intermediate for various medicines and agricultural chemicals. was completed.
（２）本発明のビフェニル誘導体は合成ルートが短く、
かつ収率の高い方法で製造できるので有用である。(2) The biphenyl derivative of the present invention has a short synthetic route;
It is also useful because it can be produced with a high yield.
（３）本発明のビフェニル誘導体を中間体として用いる
ことにより、従来知られていた製造法では得ることので
きない新規な液晶化合物を得ることが可能となった。(3) By using the biphenyl derivative of the present invention as an intermediate, it has become possible to obtain a novel liquid crystal compound that cannot be obtained by conventionally known production methods.
第１図、第２図および第３図はそれぞれ実施例−１で得
られた化合物のＩＲ，Ｈ−ＮＭＲおよびＦ−ＮＭＲスペ
クトルを示す。FIG. 1, FIG. 2, and FIG. 3 show IR, H-NMR, and F-NMR spectra of the compound obtained in Example-1, respectively.
Claims (1)
ッ素原子または塩素原子を、Ｙは−Ｏ−または−Ｓ−を
、Ｒは水素原子または炭素数１〜１８のアルキル基を表
す〕で示されるビフェニル誘導体。[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) [In the formula, X is a bromine atom or an iodine atom, X^1 is a fluorine atom or a chlorine atom, and Y is - A biphenyl derivative represented by O- or -S-, and R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13680690A JPH0429951A (en) | 1990-05-25 | 1990-05-25 | Biphenyl derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13680690A JPH0429951A (en) | 1990-05-25 | 1990-05-25 | Biphenyl derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0429951A true JPH0429951A (en) | 1992-01-31 |
Family
ID=15183949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13680690A Pending JPH0429951A (en) | 1990-05-25 | 1990-05-25 | Biphenyl derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0429951A (en) |
-
1990
- 1990-05-25 JP JP13680690A patent/JPH0429951A/en active Pending
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