JPH0466576A - Production of optically active phenylpyrimidine derivative - Google Patents
Production of optically active phenylpyrimidine derivativeInfo
- Publication number
- JPH0466576A JPH0466576A JP2173140A JP17314090A JPH0466576A JP H0466576 A JPH0466576 A JP H0466576A JP 2173140 A JP2173140 A JP 2173140A JP 17314090 A JP17314090 A JP 17314090A JP H0466576 A JPH0466576 A JP H0466576A
- Authority
- JP
- Japan
- Prior art keywords
- formulas
- formula
- optically active
- catalyst
- tables
- 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
- OXPDQFOKSZYEMJ-UHFFFAOYSA-N 2-phenylpyrimidine Chemical class C1=CC=CC=C1C1=NC=CC=N1 OXPDQFOKSZYEMJ-UHFFFAOYSA-N 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 150000004820 halides Chemical class 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 abstract description 4
- LFZLXMOEJYCWSP-UHFFFAOYSA-N 2-(4-bromophenyl)-5-decoxypyrimidine Chemical compound N1=CC(OCCCCCCCCCC)=CN=C1C1=CC=C(Br)C=C1 LFZLXMOEJYCWSP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 abstract description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 abstract description 3
- FFOHUXSIRBSYNC-UHFFFAOYSA-N 4-[4-(5-decoxypyrimidin-2-yl)phenyl]but-3-en-2-yl acetate Chemical compound N1=CC(OCCCCCCCCCC)=CN=C1C1=CC=C(C=CC(C)OC(C)=O)C=C1 FFOHUXSIRBSYNC-UHFFFAOYSA-N 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 150000007514 bases Chemical class 0.000 abstract 1
- LYWCPTCPTWCZSZ-UHFFFAOYSA-N but-3-en-2-yl acetate Chemical compound C=CC(C)OC(C)=O LYWCPTCPTWCZSZ-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- 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 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 3
- -1 and the like Chemical compound 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 2
- 150000001495 arsenic compounds Chemical class 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical group C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- OAMZXMDZZWGPMH-UHFFFAOYSA-N ethyl acetate;toluene Chemical compound CCOC(C)=O.CC1=CC=CC=C1 OAMZXMDZZWGPMH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229940093920 gynecological arsenic compound Drugs 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000010898 silica gel chromatography 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
- 239000007858 starting material Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- BPLUKJNHPBNVQL-UHFFFAOYSA-N triphenylarsine Chemical compound C1=CC=CC=C1[As](C=1C=CC=CC=1)C1=CC=CC=C1 BPLUKJNHPBNVQL-UHFFFAOYSA-N 0.000 description 1
- FEVFLQDDNUQKRY-UHFFFAOYSA-N tris(4-methylphenyl) phosphite Chemical compound C1=CC(C)=CC=C1OP(OC=1C=CC(C)=CC=1)OC1=CC=C(C)C=C1 FEVFLQDDNUQKRY-UHFFFAOYSA-N 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
- Liquid Crystal Substances (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は強誘電性液晶化合物もしくは、その中間体とし
て有用な光学活性なフェニルピリミジン誘導体の製造法
に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing a ferroelectric liquid crystal compound or an optically active phenylpyrimidine derivative useful as an intermediate thereof.
〈従来の技術〉
一般式（［１）
キル基、
炭素数２〜２０のアルコキシアルキル基（式中、Ｒ５は
炭素数１〜２ｏのアルキル基を示し、Ｙは−ｏ−−−ｃ
ｏｏ−または−〇Ｃｏ−をＲ２は水素原子、炭素数１〜
２ｏのアルキル基、炭素数２〜２ｏのアルコキシアルキ
ル基またはアルキルカルボニル基を示す。Ｘは水素原子
またはフッ素原子を示し、ｍはＯまたは１を、ｎは０〜
１０の整数を示し、＊印は不斉炭素原子を表わす。<Prior art> General formula ([1) Kyl group, alkoxyalkyl group having 2 to 20 carbon atoms (in the formula, R5 represents an alkyl group having 1 to 2 o carbon atoms, and Y is -o---c
oo- or -〇Co-, R2 is a hydrogen atom, carbon number 1-
It represents a 2o alkyl group, an alkoxyalkyl group having 2 to 2o carbon atoms, or an alkylcarbonyl group. X represents a hydrogen atom or a fluorine atom, m represents O or 1, and n represents 0 to 1.
An integer of 10 is shown, and the * mark represents an asymmetric carbon atom.
で示される光学活性なフェニルピリミジン誘導体は、強
誘電性液晶化合物もしくはその中間体として有用である
。この光学活性なフェニルピリミジン誘導体（ＩＩＩ）
は、光学活性な側鎖とコア部が直接炭素−炭素結合して
いるものであり、このような結合様式を有するフェニル
ピリミ１．；ン誘導体は、化合物のみならずその一般的
な型造法ムこつぃてもあまり知られていない
〈発明が解決しようとする課題〉
このようなことがら、強誘電性液晶化合物もしくハソノ
中間体として有用な光学活性なフェニルピリミジン誘導
体の優れた製造方法が望まれていた。The optically active phenylpyrimidine derivative represented by is useful as a ferroelectric liquid crystal compound or an intermediate thereof. This optically active phenylpyrimidine derivative (III)
is one in which the optically active side chain and the core part are directly bonded to carbon-carbon, and phenylpyrimi 1. has such a bonding mode. However, not only the compound but also the general molding method thereof is not well known. (Problem to be solved by the invention) An excellent method for producing optically active phenylpyrimidine derivatives useful as phenylpyrimidine derivatives has been desired.
〈課題を解決するための手段〉
本発明者らは、上記、光学活性なフェニルピリミジン誘
導体の製造法について鋭意検削の結果、本発明に至った
。<Means for Solving the Problems> The present inventors have arrived at the present invention as a result of intensive research into the method for producing the above-mentioned optically active phenylpyrimidine derivative.
すなわち、本発明は、−船人（１）
％式％（１）
（式中、Ｒ，は炭素数１〜２ｏのアルキル基を示し、Ｙ
は−〇−−ｃｏｏ−または−ｏｃ〇−をＺは臭素または
沃素原子を示し、ｍば０また１才ｌである。）
でホされるハロゲン化物と一般式（ｎ）（式中、Ｒ２は
水素原子、炭素数１〜２０のアルキル基、炭素数２〜２
０のアルコキシアルキル基またはアルキルカルボニル基
を示し、Ｘは水素原子またはフッ素原子を示し、ｎはＯ
〜］Ｏの整数を示し、＊印は不斉炭素原子を表わす。）
で示される光学活性なアルコール誘導体とを、触媒の存
在下、反応させることにより、前記−船人（Ｉ［Ｉ）で
示される光学活性なフェニルピリミジン誘導体を得る製
造法を提供するものである。That is, the present invention provides - Shipman (1) % formula % (1) (wherein, R represents an alkyl group having 1 to 2 carbon atoms, and Y
is -〇--coo- or -oc〇-, Z represents a bromine or iodine atom, and m is 0 or 1. ) and the general formula (n) (wherein, R2 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and 2 to 2 carbon atoms)
0 represents an alkoxyalkyl group or an alkylcarbonyl group, X represents a hydrogen atom or a fluorine atom, and n represents O
~] represents an integer of O, and * represents an asymmetric carbon atom. )
The present invention provides a production method for obtaining an optically active phenylpyrimidine derivative represented by the above-mentioned -Funenin (I[I) by reacting the optically active alcohol derivative represented by the following in the presence of a catalyst.
以下、本発明について詳しく説明する。The present invention will be explained in detail below.
−Ｃ式（ＩＩＩ）で示される光学活性なフェニルピノミ
ジン誘導体は、−船人（１）で示されるハロゲン化物と
、−ｍ式（Ｉｔ）で示される光学活性なアルコール誘導
体とを金属触媒と塩基性物質の存在下に反応させること
により得られる。The optically active phenylpinomidine derivative represented by the -C formula (III) is prepared by combining a halide represented by the -Funenin (1) and an optically active alcohol derivative represented by the -m formula (It) with a metal catalyst. Obtained by reaction in the presence of a basic substance.
上記−Ｃ式（１）および（ＩＩ）で示される原料化合物
は、文献記載の方法に本して製造することができる。上
記反応に用いる光学活性なアルコル誘導体（ＩＩ）の使
用量は、ハロゲン化物（１）に対して通常０．９〜１０
侑当量であるが好ましくは、１〜３倍当量である。The starting compounds represented by the above -C formulas (1) and (II) can be produced by methods described in literature. The amount of the optically active alcohol derivative (II) used in the above reaction is usually 0.9 to 10% relative to the halide (1).
It is preferably 1 to 3 times equivalent.
上記反応に用いられる金属触媒としては、パラジウム系
では塩化パラジウム、酢酸パラジウム、トリフェニルホ
スフィンパラジウム錯体、パラジウム／炭素などが用い
られ、ニッケル系およびロジウム系についても前記と同
様な触媒が用いられる。As the metal catalyst used in the above reaction, palladium-based catalysts include palladium chloride, palladium acetate, triphenylphosphine palladium complex, palladium/carbon, and the like, and nickel-based and rhodium-based catalysts are also used.
これらの金属触媒の使用量は、原料ハロゲン化物（１）
に対して１ｏ−３〜１ｏ−１倍当量の範囲である。The amount of these metal catalysts used is the raw material halide (1)
The range is 10-3 to 10-1 times the equivalent amount.
この反応では上記金属触媒の他に、助触媒として、３価
のリン化合物または３価のヒ素化合物が必要であり、そ
れらとしては、−船人（ＩＶ）２３−貝−、（ＩＶ）
（式中、Ｍはリン原子またはヒ素原子を示し、Ｒ５、Ｒ
４およびＲ３は同一または相異なり、アルキル基、アリ
ール基、アルコキシ基、アリールオキシ基またはハロゲ
ン原子を示す、）
で示される化合物であって、具体的にはトリーｎ−ブチ
ルホスフィン、トリフェニルホスフィン、トリーロート
リルホスフィン、トリー〇−トリルホスファイト、三塩
化リン、トリフェニルヒ素などが例示される。In addition to the above-mentioned metal catalyst, this reaction requires a trivalent phosphorus compound or a trivalent arsenic compound as a co-catalyst. In the formula, M represents a phosphorus atom or an arsenic atom, R5, R
4 and R3 are the same or different and represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom), specifically tri-n-butylphosphine, triphenylphosphine, Examples include tri-rotolylphosphine, tri-tolylphosphite, phosphorus trichloride, triphenyl arsenic, and the like.
これらのリン化合物またはヒ素化合物の使用量は、上記
の金属触媒に対して０．５〜５０倍当量、好ましくは１
０〜３０倍当量である。The amount of these phosphorus compounds or arsenic compounds used is 0.5 to 50 times equivalent to the above metal catalyst, preferably 1
It is 0 to 30 times equivalent.
前記塩基性物質としては、アルカリ金属の炭酸塩、カル
ボン酸塩、アルコキサイド、水酸化物、有機塩基等が挙
げられ、好ましくは、アルカリ金属の炭酸塩または３級
アミン（有機塩基）が好ましく用いられ、これらとして
は炭酸ナトリウム、炭酸水素ナトリウム、トリエチルア
ミン、ジ−イソプロピルエチルアミン、トリーｎ−ブチ
ルアミン、Ｎ、Ｎ、Ｎ’ 、Ｎ −テトラメチルエチ
レンジアミン、ジメチルアニリンなどが例示される。Examples of the basic substance include alkali metal carbonates, carboxylates, alkoxides, hydroxides, organic bases, etc., and alkali metal carbonates or tertiary amines (organic bases) are preferably used. Examples of these include sodium carbonate, sodium hydrogencarbonate, triethylamine, di-isopropylethylamine, tri-n-butylamine, N,N,N',N-tetramethylethylenediamine, and dimethylaniline.
塩基性物質の使用量は、ハロゲン化物（１）に対して１
〜５倍当量である。The amount of basic substance used is 1 for halide (1).
~5 times equivalent.
必要により、例えばアセトニトリル、テトラヒドロフラ
ン、Ｎ、Ｎ−ジメチルホルムアミド、ヘキサメチルホス
ホリルアミド、Ｎ−メチルピロリドン、メタノールなど
を反応溶媒として使用することもできる。If necessary, for example, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, hexamethylphosphorylamide, N-methylpyrrolidone, methanol, etc. can be used as a reaction solvent.
これらの反応溶媒の使用量は特に制限されない。The amount of these reaction solvents used is not particularly limited.
尚、本反応は通常窒素、アルゴン等の不活性ガス中で行
われる。Note that this reaction is usually carried out in an inert gas such as nitrogen or argon.
本方法においては、反応温度を高めることにより目的と
する光学活性なフェニルピリミジン誘導体（Ｉ［ｌ）の
収率を向上させることができるが、あまり高温では副生
物が増加するので、通常反応温度は１５〜１９０°Ｃで
あり、好ましくは１００〜１５０°Ｃである。In this method, the yield of the desired optically active phenylpyrimidine derivative (I[l) can be improved by increasing the reaction temperature, but if the temperature is too high, by-products will increase, so the reaction temperature is usually The temperature is 15-190°C, preferably 100-150°C.
反応終了後、抽出、蒸留、再結晶等の通常の手段により
目的化合物（Ｉ［ｌ）を得ることができる。After the reaction is completed, the target compound (I[l) can be obtained by conventional means such as extraction, distillation, recrystallization, etc.
〈発明の効果〉
本発明により一般式（ＩＩＩ）で示される光学活性なフ
ェニルピリミジン誘導体を効率よく製造することができ
、該誘導体は強誘電性液晶もしくはその中間体として有
用である。<Effects of the Invention> According to the present invention, an optically active phenylpyrimidine derivative represented by the general formula (III) can be efficiently produced, and the derivative is useful as a ferroelectric liquid crystal or an intermediate thereof.
〈実施例〉
以下、実施例により本発明を更に詳細に説明するが、本
発明はこれら実施例に限定されるものではない。<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例１
攪拌装置、温度計を装着した４つロフラスコに、２−（
４−ブロモフェニル）−５−デシルオキシピリミジン７
．８ｇ （０，０２モル）、（−）−２トリウム５ｇお
よびＮ−メチルピロリドン１０ｄを仕込み、窒素雰囲気
中トリフェニルホスフィン０．１６ｇと酢酸パラジウム
０．０６ｇを加えて、１１０〜１２０°Ｃで２０時間加
熱攪拌した。Example 1 2-(
4-Bromophenyl)-5-decyloxypyrimidine 7
．． 8 g (0.02 mol), 5 g of (-)-2 thorium and 10 d of N-methylpyrrolidone were charged, 0.16 g of triphenylphosphine and 0.06 g of palladium acetate were added in a nitrogen atmosphere, and the mixture was heated at 110 to 120°C for 20 The mixture was heated and stirred for hours.
反応終了後、反応混合物を水２００ｄに注入し、トルエ
ン２００ｄで抽出した。得られたトルエン層は水洗のの
ち、減圧上濃縮して黒かっ色の残渣を得た。After the reaction was completed, the reaction mixture was poured into 200 d of water and extracted with 200 d of toluene. The obtained toluene layer was washed with water and then concentrated under reduced pressure to obtain a brownish black residue.
これをシリカゲルカラムクロマトグラフィー（溶離液：
トルエンー酢酸エチル）にて精製して、（−）−２−、
（４−（３−アセトキシ−１−ブテニル）フェニル）−
５−デシルオキシピリミジン（Ｉ［［−１） ３．６
ｇ （収率４２％）を得た。This was subjected to silica gel column chromatography (eluent:
Purification with toluene-ethyl acetate) to give (-)-2-,
(4-(3-acetoxy-1-butenyl)phenyl)-
5-decyloxypyrimidine (I[[-1) 3.6
g (yield 42%) was obtained.
（〔α〕シ’＝ ３．１ （Ｃ＝ １０． ＣＨＣ
ｌ５ ） １実施例２〜ｔ３
実施例１の２−（４−ブロモフェニル）−５デシルオキ
シピリミジンおよび８−ブテン−１オールを表−１に示
す化合物に代える以外は実施例１に準して、反応、後処
理をおこない、表−１に示す結果を得た。([α] C'= 3.1 (C= 10. CHC
l5) 1 Examples 2 to t3 The same procedure as in Example 1 was carried out except that 2-(4-bromophenyl)-5decyloxypyrimidine and 8-buten-1ol in Example 1 were replaced with the compounds shown in Table 1. , reaction, and post-treatment were performed, and the results shown in Table 1 were obtained.
Claims (1)
−Ｏ−、−ＣＯＯ−または−ＯＣＯ−を示し、Ａｒは、
▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、 ▲数式、化学式、表等があります▼または▲数式、化学
式、表等があります▼を示し、 Ｚは臭素または沃素原子を示し、ｍは０または１である
。） で示されるハロゲン化物と一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＿２は水素原子、炭素数１〜２０のアルキル
基、炭素数２〜２０のアルコキシアルキル基またはアル
キルカルボニル基を示し、Ｘは水素原子またはフッ素原
子を示し、ｎは０〜１０の整数を示し、＊印は不斉炭素
原子を表わす。） で示される光学活性なアルコール誘導体とを、触媒の存
在下、反応させることを特徴とする一般式▲数式、化学
式、表等があります▼ （式中、Ｒ＿１、Ｒ＿２、Ｘ、Ｙ、Ａｒ、ｍ、ｎ、およ
び＊印は前記と同じ意味を表わす。） で示される光学活性なフェニルピリミジン誘導体の製造
法。(1) General formula R_1-(Y)_m-A_r-Z (wherein, R_1 represents an alkyl group having 1 to 20 carbon atoms, Y represents -O-, -COO- or -OCO-, and Ar is
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, Z indicates a bromine or iodine atom, and m is 0 or 1. ) and the general formula ▲ Numerical formulas, chemical formulas, tables, etc. , X represents a hydrogen atom or a fluorine atom, n represents an integer from 0 to 10, and the * mark represents an asymmetric carbon atom.) in the presence of a catalyst, There are general formulas ▲mathematical formulas, chemical formulas, tables, etc. that are characterized by reactions▼ (In the formulas, R_1, R_2, The method for producing the optically active phenylpyrimidine derivative shown.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2173140A JPH0466576A (en) | 1990-06-29 | 1990-06-29 | Production of optically active phenylpyrimidine derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2173140A JPH0466576A (en) | 1990-06-29 | 1990-06-29 | Production of optically active phenylpyrimidine derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0466576A true JPH0466576A (en) | 1992-03-02 |
Family
ID=15954860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2173140A Pending JPH0466576A (en) | 1990-06-29 | 1990-06-29 | Production of optically active phenylpyrimidine derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0466576A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4211694B4 (en) * | 1992-04-08 | 2006-06-01 | Merck Patent Gmbh | Liquid crystalline compounds |
-
1990
- 1990-06-29 JP JP2173140A patent/JPH0466576A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4211694B4 (en) * | 1992-04-08 | 2006-06-01 | Merck Patent Gmbh | Liquid crystalline compounds |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4981992A (en) | Process for preparing optically active 3-hydroxybutanoic acid | |
| US6072073A (en) | Carbonyl arylations and vinylations using transition metal catalysts | |
| CN116589506A (en) | Tri-discoene metallocene compound and application thereof | |
| US6025503A (en) | Process for producing optically active titanium alkoxide complexes | |
| JPH0466576A (en) | Production of optically active phenylpyrimidine derivative | |
| JP3303327B2 (en) | Asymmetric induction catalyst | |
| JPH02183A (en) | Optically active phosphine compound | |
| US5756815A (en) | Process for the preparation arylamalonates | |
| JP5544596B2 (en) | Process for producing optically active cyclic ether compound and catalyst used therefor | |
| JP4024059B2 (en) | Binaphthol derivative, chiral zirconium catalyst and asymmetric heterodales alder reaction method | |
| IL211613A (en) | Method for producing optically active cyclopropane carboxylic acid ester compound, asymmetric copper complex and optically active salicylideneaminoalcohol compound | |
| KR102548050B1 (en) | Novel multi-fused heterocyclic compound and preparation method thereof | |
| JPS62281840A (en) | Production of cinnamic acid derivative | |
| JP5205971B2 (en) | Method for producing tetrahydropyran compound | |
| KR101404616B1 (en) | Method for Preparation of γ-fluorinated ketone derivatives | |
| JP4509327B2 (en) | Process for producing N, N-disubstituted-4-aminocrotonic acid ester | |
| JP2855221B2 (en) | Optically active 3,4-bisphosphinopyrrolidine compound | |
| JPH08245526A (en) | Optically active amines, optically active imines and their production | |
| CN115785166A (en) | Triplecene-bridged metallocene compound and application thereof | |
| CN112876515A (en) | Tripleene carbene allyl palladium compound and application thereof | |
| CN115947765A (en) | Triplecene double-bridged metallocene compound and application thereof | |
| CN116082265A (en) | One-pot method for preparing biaryl heterocyclic compound | |
| JP3804080B2 (en) | Method for producing triarylamine compound | |
| JPH0325421B2 (en) | ||
| JPH0317075A (en) | Preparation of 6-fluorochromone-2-carboxylic acid derivative |