JPH04217670A - Ester derivative - Google Patents
Ester derivativeInfo
- Publication number
- JPH04217670A JPH04217670A JP2320305A JP32030590A JPH04217670A JP H04217670 A JPH04217670 A JP H04217670A JP 2320305 A JP2320305 A JP 2320305A JP 32030590 A JP32030590 A JP 32030590A JP H04217670 A JPH04217670 A JP H04217670A
- Authority
- JP
- Japan
- Prior art keywords
- pyrimidine
- phenyl
- hydroxyphenyl
- compound
- formula
- 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.)
- Granted
Links
- 150000002148 esters Chemical class 0.000 title claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 18
- 150000001875 compounds Chemical class 0.000 abstract description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 abstract description 14
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 abstract description 10
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 abstract description 9
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 abstract description 6
- 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 abstract description 5
- YQLMHXJICJZZFV-UHFFFAOYSA-N [amino-(4-ethoxycarbonylphenyl)methylidene]azanium;chloride Chemical compound [Cl-].CCOC(=O)C1=CC=C(C([NH3+])=N)C=C1 YQLMHXJICJZZFV-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000543 intermediate Substances 0.000 abstract description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 abstract description 4
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 abstract description 4
- SAHOFALKZHLHPA-UHFFFAOYSA-N butan-2-yl 4-[5-(2-hydroxyphenyl)pyrimidin-2-yl]benzoate Chemical compound C1=CC(C(=O)OC(C)CC)=CC=C1C1=NC=C(C=2C(=CC=CC=2)O)C=N1 SAHOFALKZHLHPA-UHFFFAOYSA-N 0.000 abstract description 4
- NRPFNQUDKRYCNX-UHFFFAOYSA-N 4-methoxyphenylacetic acid Chemical compound COC1=CC=C(CC(O)=O)C=C1 NRPFNQUDKRYCNX-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 230000008030 elimination Effects 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- 125000006239 protecting group Chemical group 0.000 abstract 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 36
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 36
- -1 -Methylhexanol Chemical compound 0.000 description 24
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- BTANRVKWQNVYAZ-BYPYZUCNSA-N (2S)-butan-2-ol Chemical compound CC[C@H](C)O BTANRVKWQNVYAZ-BYPYZUCNSA-N 0.000 description 8
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- JYVLIDXNZAXMDK-YFKPBYRVSA-N (2s)-pentan-2-ol Chemical compound CCC[C@H](C)O JYVLIDXNZAXMDK-YFKPBYRVSA-N 0.000 description 2
- ZPKPJIUKYONDSL-UHFFFAOYSA-N 1,1,1-trifluorononan-2-ol Chemical compound CCCCCCCC(O)C(F)(F)F ZPKPJIUKYONDSL-UHFFFAOYSA-N 0.000 description 2
- BWHYGTUWYAKAGS-UHFFFAOYSA-N 1-fluorooctan-1-ol Chemical compound CCCCCCCC(O)F BWHYGTUWYAKAGS-UHFFFAOYSA-N 0.000 description 2
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 2
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 2
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 2
- NGDNVOAEIVQRFH-UHFFFAOYSA-N 2-nonanol Chemical compound CCCCCCCC(C)O NGDNVOAEIVQRFH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010511 deprotection reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- YFVHSPAONQXAIB-UHFFFAOYSA-N 1,1,1-trifluoroheptan-2-ol Chemical compound CCCCCC(O)C(F)(F)F YFVHSPAONQXAIB-UHFFFAOYSA-N 0.000 description 1
- XEFMITHAWQJMRT-UHFFFAOYSA-N 1,1,1-trifluorohexan-2-ol Chemical compound CCCCC(O)C(F)(F)F XEFMITHAWQJMRT-UHFFFAOYSA-N 0.000 description 1
- INAIBHXNHIEDAM-UHFFFAOYSA-N 1,1,1-trifluorooctan-2-ol Chemical compound CCCCCCC(O)C(F)(F)F INAIBHXNHIEDAM-UHFFFAOYSA-N 0.000 description 1
- XJHGAJLIKDAOPE-UHFFFAOYSA-N 2-(4-phenylmethoxyphenyl)acetic acid Chemical compound C1=CC(CC(=O)O)=CC=C1OCC1=CC=CC=C1 XJHGAJLIKDAOPE-UHFFFAOYSA-N 0.000 description 1
- ACUZDYFTRHEKOS-SNVBAGLBSA-N 2-Decanol Natural products CCCCCCCC[C@@H](C)O ACUZDYFTRHEKOS-SNVBAGLBSA-N 0.000 description 1
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 1
- UEBHTEIKXIPNGN-UHFFFAOYSA-N 2-fluoroheptan-1-ol Chemical compound CCCCCC(F)CO UEBHTEIKXIPNGN-UHFFFAOYSA-N 0.000 description 1
- LRKCNYYCJZXSHR-UHFFFAOYSA-N 2-fluorononan-1-ol Chemical compound CCCCCCCC(F)CO LRKCNYYCJZXSHR-UHFFFAOYSA-N 0.000 description 1
- PXUHUAWWMDRECM-UHFFFAOYSA-N 2-fluorooctan-1-ol Chemical compound CCCCCCC(F)CO PXUHUAWWMDRECM-UHFFFAOYSA-N 0.000 description 1
- UTIMESSLYFMSPO-UHFFFAOYSA-N 2-methylbutyl 3-[4-[(4-decoxyphenyl)methylideneamino]phenyl]prop-2-enoate Chemical compound C1=CC(OCCCCCCCCCC)=CC=C1C=NC1=CC=C(C=CC(=O)OCC(C)CC)C=C1 UTIMESSLYFMSPO-UHFFFAOYSA-N 0.000 description 1
- QZESEQBMSFFHRY-UHFFFAOYSA-N 2-methylheptan-1-ol Chemical compound CCCCCC(C)CO QZESEQBMSFFHRY-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- ANEAPXSTNOCXJW-UHFFFAOYSA-N CCOC(=O)C1=CC=C(C=C1)C2=NC=C(C=N2)C3=CC=CC=C3OC Chemical compound CCOC(=O)C1=CC=C(C=C1)C2=NC=C(C=N2)C3=CC=CC=C3OC ANEAPXSTNOCXJW-UHFFFAOYSA-N 0.000 description 1
- RXXGBBKFGRJHPG-UHFFFAOYSA-N CCOC(=O)C1=CC=C(C=C1)C2=NC=C(C=N2)C3=CC=CC=C3OCC4=CC=CC=C4 Chemical compound CCOC(=O)C1=CC=C(C=C1)C2=NC=C(C=N2)C3=CC=CC=C3OCC4=CC=CC=C4 RXXGBBKFGRJHPG-UHFFFAOYSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- IUPHSIZBMWJSSV-UHFFFAOYSA-N FC(C(CO)CCCCC)(F)F Chemical compound FC(C(CO)CCCCC)(F)F IUPHSIZBMWJSSV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 229910019213 POCl3 Inorganic materials 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- OAIVIYSBZFEOIU-UHFFFAOYSA-N chloroform;propan-2-one Chemical compound CC(C)=O.ClC(Cl)Cl OAIVIYSBZFEOIU-UHFFFAOYSA-N 0.000 description 1
- 238000006264 debenzylation reaction Methods 0.000 description 1
- ACUZDYFTRHEKOS-UHFFFAOYSA-N decan-2-ol Chemical compound CCCCCCCCC(C)O ACUZDYFTRHEKOS-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 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
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Liquid Crystal Substances (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明はエステル誘導体に関する。詳しくは、液晶組成
物とくに強誘電性液晶組成物の成分として使用される液
晶性化合物を製造する際に、中間体として有用な新規な
エステル誘導体に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to ester derivatives. Specifically, the present invention relates to a novel ester derivative useful as an intermediate in producing a liquid crystal compound used as a component of a liquid crystal composition, particularly a ferroelectric liquid crystal composition.
(従来の技術)
液晶化合物が電気光学表示装置に利用されて以来、数多
くの液晶化合物が、合成され、ネマチック液晶またはネ
マチック−コレステリック液晶が、STN型表示素子、
コレステリック−ネマチック相転移型表示素子またはゲ
スト−ホスト効果利用表示素子などに広く利用されてい
る。(Prior Art) Since liquid crystal compounds were used for electro-optic display devices, many liquid crystal compounds have been synthesized, and nematic liquid crystals or nematic-cholesteric liquid crystals are used for STN type display elements,
It is widely used in cholesteric-nematic phase transition type display elements or display elements using guest-host effect.
しかし、これらの表示素子の応答速度は最高でも数m
secのオーダーであるために液晶表示素子の応用範囲
に限界があるとされてきたが、最近に至り、強誘電性液
晶を用いるとμ secオーダーの高速で応答が得られ
る事が分かってきた。However, the response speed of these display elements is several meters at most.
It has been thought that there is a limit to the application range of liquid crystal display elements because of the response speed on the order of seconds, but recently it has been found that using ferroelectric liquid crystals can provide high-speed responses on the order of microseconds.
従来知られている強誘電性液晶の例としては、1975
年にR.B.Meyer等によって合成された4−(4
’−n−デシルオキシベンジリデンアミノ)ケイ皮酸−
2−メチルブチルエステル(DOBAMBC)があげら
れる。この物質はそのカイラルスメクチックC相におい
て強誘電性を示す事を特徴としている(J.Physi
que.、36巻、P69(1975)参照)。An example of a conventionally known ferroelectric liquid crystal is the 1975
R. B. 4-(4
'-n-decyloxybenzylideneamino)cinnamic acid-
2-methylbutyl ester (DOBAMBC) is mentioned. This material is characterized by exhibiting ferroelectricity in its chiral smectic C phase (J. Physi
que. , vol. 36, p. 69 (1975)).
1980年に至り、N.A.Clark等がDOBAM
BCを使用した薄膜セルにおいて、μ secオーダー
の高速応答を見いだして以来(Appl.Phys.L
et.、36巻、P89(1980))、多くの強誘電
性液晶の合成研究がなされてきたにもかかわらず、物性
的要求の全てを単一化合物で満たす強誘電性液晶化合物
は見い出されておらず、何種類かの強誘電性液晶化合物
を組み合わせた組成物として用いることによって目的を
達成している。In 1980, N. A. Clark et al. DOBAM
Since we discovered a high-speed response on the μ sec order in a thin film cell using BC (Appl. Phys.
etc. , Vol. 36, P. 89 (1980)). Despite much research on the synthesis of ferroelectric liquid crystals, no ferroelectric liquid crystal compound has been found that satisfies all physical requirements in a single compound. This objective has been achieved by using a composition that combines several types of ferroelectric liquid crystal compounds.
(発明が解決しようとする課題)
本発明は、このような要求を満たす液晶組成物を構成す
る成分として使用される物質を製造する際に、中間体と
して有用な新規エステル誘導体を提供する事を目的とす
るものである。(Problems to be Solved by the Invention) The present invention aims to provide a novel ester derivative useful as an intermediate when producing a substance used as a component constituting a liquid crystal composition that satisfies such requirements. This is the purpose.
(課題を解決するための手段)
即ち本発明は、一般式[I]
(式中XはCH3、CF3、Fを表し、n及びmは0〜
10の整数を表し、C*は光学活性な炭素原子を表す)
で表されるエステル誘導体に関するものである。(Means for Solving the Problems) That is, the present invention solves the problem using the general formula [I] (wherein X represents CH3, CF3, F, and n and m are 0 to
represents an integer of 10, and C* represents an optically active carbon atom)
This relates to an ester derivative represented by
以下に本発明を詳細に説明する。The present invention will be explained in detail below.
前記[I]式で表される本発明のエステル誘導体におい
て、特に好ましいのはn=0、m=1〜10で表される
光学活性な2−アルカノールのエステル誘導体であり、
例えば光学活性な2−ブタノール、2−ペンタノール、
2−ヘキサノール、2−ヘプタノール、2−オクタノー
ル、2−ノナノール、2−デカノール、1−トリフルオ
ロメチルペンタノール、1−トリフルオロメチルヘキサ
ノール、1−トリフルオロメチルヘプタノール、1−ト
リフルオロメチルオクタノールであるエステル誘導体あ
るいは、n=1、m=1〜10で表される光学活性な2
−置換−1−アルコールのエステル誘導体であり、例え
ば2−メチルブタノール、2−メチルペンタノール、2
−メチルヘキサノール、2−メチルヘプタノール、2−
トリフルオロメチル−1−オクタノール、2−トリフル
オロメチル−1−ヘプタノール、2−フルオロ−1−オ
クタノール、2−フルオロ−1−ノナノール、2−フル
オロ−1−ヘプタノールであるエステル誘導体等が挙げ
られる。Among the ester derivatives of the present invention represented by the formula [I], particularly preferred are optically active 2-alkanol ester derivatives represented by n = 0 and m = 1 to 10,
For example, optically active 2-butanol, 2-pentanol,
2-hexanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 1-trifluoromethylpentanol, 1-trifluoromethylhexanol, 1-trifluoromethylheptanol, 1-trifluoromethyloctanol A certain ester derivative or optically active 2 represented by n = 1 and m = 1 to 10
-Ester derivatives of substituted-1-alcohols, such as 2-methylbutanol, 2-methylpentanol, 2-methylpentanol,
-Methylhexanol, 2-methylheptanol, 2-
Examples include ester derivatives such as trifluoromethyl-1-octanol, 2-trifluoromethyl-1-heptanol, 2-fluoro-1-octanol, 2-fluoro-1-nonanol, and 2-fluoro-1-heptanol.
本発明の[I]式で表されるエステル誘導体の具体例と
しては、例えば以下の化合物を挙げる事ができる。Specific examples of the ester derivative represented by formula [I] of the present invention include the following compounds.
5−(ヒドロキシフェニル)−2−[4−(1−メチル
プロピルオキシカルボニル)フェニル]ピリミジン、5
−(ヒドロキシフェニル)−2−[4−(1−メチルブ
チルオキシカルボニル)フェニル]ピリミジン、5−(
ヒドロキシフェニル)−2−[4−(1−メチルペンチ
ルオキシカルボニル)フェニル]ピリミジン、5−(ヒ
ドロキシフェニル)−2−[4−(1−メチルヘキシル
オキシカルボニル)フェニル]ピリミジン、5−(ヒド
ロキシフェニル)−2−[4−(1−メチルヘプチルオ
キシカルボニル)フェニル]ピリミジン、5−(ヒドロ
キシフェニル)−2−[4−(1−メチルオクチルオキ
シカルボニル)フェニル]ピリミジン、5−(ヒドロキ
シフェニル)−2−[4−(1−メチルノニルオキシカ
ルボニル)フェニル]ピリミジン、5−(ヒドロキシフ
ェニル)−2−[4−(1−トリフルオロメチルプロピ
ルオキシカルボニル)フェニル]ピリミジン、5−(ヒ
ドロキシフェニル)−2−(4−(1−トリフルオロメ
チルブチルオキシカルボニル)フェニル]ピリミジン、
5−(ヒドロキシフェニル)−2−4−(1−トリフル
オロメチルペンチルオキシカルボニル)フェニル]ピリ
ミジン、5−(ヒドロキシフェニル)−2−[4−(1
−トリフルオロメチルヘキシルオキシカルボニル)フェ
ニル]ピリミジン、5−(ヒドロキシフェニル)−2−
[4−(1−トリフルオロメチルヘプチルオキシカルボ
ニル)フェニル]ピリミジン、5−(ヒドロキシフェニ
ル)−2−[4−(1−トリフルオロメチルオクチルオ
キシカルボニル)フェニル]ピリミジン、5−(ヒドロ
キシフェニル)−2−[4−(2−メチルブチルオキシ
カルボニル)フェニル]ピリミジン、5−(ヒドロキシ
フェニル)−2−[4−(2−メチルペンチルオキシカ
ルボニル)フェニル]ピリミジン、−(ヒドロキシフェ
ニル)−2−[4−(2−メチルヘキシルオキシカルボ
ニル)フェニル]ピリミジン、5−(ヒドロキシフェニ
ル)−2−[4−(2−メチルヘプチルオキシカルボニ
ル)フェニル]ピリミジン、5−(ヒドロキシフェニル
)−2−[4−(2−メチルオクチルオキシカルボニル
)フェニル]ピリミジン、5−(ヒドロキシフェニル)
−2−[4−(2−フルオロベンチルオキシカルボニル
)フェニル]ピリミジン、5−(ヒドロキシフェニル)
−2−[4−(2−フルオロヘキシルオキシカルボニル
)フェニル]ピリミジン、5−(ヒドロキシフェニル)
−2−[4−(2−フルオロヘプチルオキシカルボニル
)フェニル]ピリミジン、5−(ヒドロキシフェニル)
−2−[4−(2−フルオロオクチルオキシカルボニル
)フェニル]ピリミジン、5−(ヒドロキシフェニル)
−2−14−(2−フルオロノニルオキシカルボニル)
フェニル]ピリミジン。5-(hydroxyphenyl)-2-[4-(1-methylpropyloxycarbonyl)phenyl]pyrimidine, 5
-(hydroxyphenyl)-2-[4-(1-methylbutyloxycarbonyl)phenyl]pyrimidine, 5-(
hydroxyphenyl)-2-[4-(1-methylpentyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)-2-[4-(1-methylhexyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl) )-2-[4-(1-methylheptyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)-2-[4-(1-methyloctyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)- 2-[4-(1-methylnonyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)-2-[4-(1-trifluoromethylpropyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)- 2-(4-(1-trifluoromethylbutyloxycarbonyl)phenyl)pyrimidine,
5-(hydroxyphenyl)-2-4-(1-trifluoromethylpentyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)-2-[4-(1
-trifluoromethylhexyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)-2-
[4-(1-trifluoromethylheptyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)-2-[4-(1-trifluoromethyloctyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)- 2-[4-(2-methylbutyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)-2-[4-(2-methylpentyloxycarbonyl)phenyl]pyrimidine, -(hydroxyphenyl)-2-[ 4-(2-methylhexyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)-2-[4-(2-methylheptyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)-2-[4- (2-methyloctyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)
-2-[4-(2-fluorobentyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)
-2-[4-(2-fluorohexyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)
-2-[4-(2-fluoroheptyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)
-2-[4-(2-fluorooctyloxycarbonyl)phenyl]pyrimidine, 5-(hydroxyphenyl)
-2-14-(2-fluorononyloxycarbonyl)
phenyl]pyrimidine.
[I]式で示される本発明のエステル誘導体は、後記実
施例に具体的に示すように、例えば次の工程により製造
される。The ester derivative of the present invention represented by the formula [I] is produced, for example, by the following steps, as specifically shown in the Examples below.
即ち、p−メトキシフェニル酢酸[II]にオキシ塩化
リン、ジメチルホルムアミド、次いで、過塩素酸マグネ
シウムを作用させ、[III]を得る。That is, p-methoxyphenylacetic acid [II] is reacted with phosphorus oxychloride, dimethylformamide, and then magnesium perchlorate to obtain [III].
[以下余白]
1)POCl3/DMF
2)Mg(Clo4)2
ついで[III]にp−エチルオキシカルボニルベンズ
アミジン塩酸塩を塩基性条件下に作用させ、[IV]を
得る。[Left below] 1) POCl3/DMF 2) Mg(Clo4)2 Next, [III] is treated with p-ethyloxycarbonylbenzamidine hydrochloride under basic conditions to obtain [IV].
更に[IV]を臭化水素水および酢酸で処理することに
より[V]を得る。Furthermore, [V] is obtained by treating [IV] with aqueous hydrogen bromide and acetic acid.
[V]を無水酢酸によりアセチル化し、ついで例えば塩
化チオニルで酸クロライドとし、これを更に三級アミン
の存在下、前記の光学活性なアルコールを反応せしめ[
VI]を得る。[V] is acetylated with acetic anhydride, then made into an acid chloride using, for example, thionyl chloride, and this is further reacted with the optically active alcohol described above in the presence of a tertiary amine [
VI].
最後に[VI]にベンジルアミンを作用させることによ
り脱保護基反応を行い、[I]式で示される本発明のエ
ステル誘導体を得る。Finally, [VI] is subjected to a deprotection reaction by reacting with benzylamine to obtain the ester derivative of the present invention represented by the formula [I].
上記の反応工程以外の工程として以下の工程を例示する
ことができる。The following steps can be exemplified as steps other than the above reaction steps.
ついで[VII]にp−エチルオキシカルボニルベンズ
アミジン塩酸塩を塩基性条件下に作用させ、[IX]を
得る。[VII] is then treated with p-ethyloxycarbonylbenzamidine hydrochloride under basic conditions to obtain [IX].
更に[IX]をエタノール中、水酸化カリウムで加水分
解することにより[X]を得る。Furthermore, [X] is obtained by hydrolyzing [IX] with potassium hydroxide in ethanol.
[X]を例えば塩化チオニルで酸クロライドとし、これ
を更に三級アミンの存在下、前記の光学活性なアルコー
ルを反応せしめ[XI]を得る。[X] is converted into an acid chloride using, for example, thionyl chloride, and this is further reacted with the optically active alcohol described above in the presence of a tertiary amine to obtain [XI].
最後に[XI]にパラジウム・カーボンを作用させるこ
とにより脱保護基反応を行い、[I]式で示される本発
明のエステル誘導体を得る。Finally, [XI] is subjected to a deprotection reaction by reacting with palladium-carbon to obtain the ester derivative of the present invention represented by the formula [I].
このようにして得られた本発明のエステル誘導体は、常
法の反応方法に従い、例えば特開平2−69440号な
どに記載の光学活性液晶化合物、液晶組成物に誘導する
ことができる。The ester derivative of the present invention thus obtained can be converted into an optically active liquid crystal compound or liquid crystal composition described in, for example, JP-A-2-69440, according to a conventional reaction method.
(実施例)
以下、実施例により本発明の化合物につき更に詳細に説
明するが、本発明はこれに限定されるものではない。(Examples) Hereinafter, the compounds of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
実施例1
5−(ヒドロキシフェニル)−2−[4−(1−メチル
プロピルオキシカルボニル)フェニル]ピリミジンの合
成
(第1段)
ジメチルホルムアミド81.6g(1.1ミリモル)に
、オキシ塩化リン102.6(0.67ミリモル)を0
℃で滴下し、ついでp−メトキシフェニル酢酸66gを
−10℃の温度で少しずつ加えた。混合物を20℃で1
時間、60℃で2時間、および80℃で5時間攪拌した
。ジメチルホルムアミドを減圧留去し、残査を冷却し、
過塩素酸マグネシウムの飽和水溶液に投入した。析出し
た結晶を濾別し、エーテルで洗浄して、過塩素酸塩61
g(収率81.2%)を得た。Example 1 Synthesis of 5-(hydroxyphenyl)-2-[4-(1-methylpropyloxycarbonyl)phenyl]pyrimidine (first stage) To 81.6 g (1.1 mmol) of dimethylformamide, 102 phosphorus oxychloride was added. .6 (0.67 mmol) to 0
C. and then 66 g of p-methoxyphenylacetic acid was added little by little at a temperature of -10.degree. Mixture at 20℃
The mixture was stirred at 60°C for 2 hours and at 80°C for 5 hours. Dimethylformamide was distilled off under reduced pressure, the residue was cooled,
It was poured into a saturated aqueous solution of magnesium perchlorate. The precipitated crystals were filtered, washed with ether, and perchlorate 61
g (yield: 81.2%).
この塩23.9g(72ミリモル)とp−エトキシカル
ボニルベンズアミジン塩酸塩をナトリウムエチラート1
4.8g(0.2モル)の存在下、エタノール250m
l中で8時間加熱還流した。23.9 g (72 mmol) of this salt and p-ethoxycarbonylbenzamidine hydrochloride were mixed with 1 ml of sodium ethylate.
250 m of ethanol in the presence of 4.8 g (0.2 mol)
The mixture was heated under reflux for 8 hours.
反応終了後、エタノールを減圧留去し、酢酸18g(0
.3モル)を含む水溶液500mlを加え攪拌した、沈
澱物を濾別し、水洗、乾燥後5−(メトキシフェニル)
−2−[4−(1−エトキシカルボニル)フェニル]ピ
リミジ15.2g(収率63%)を得た。After the reaction, ethanol was distilled off under reduced pressure and 18 g of acetic acid (0
.. 500 ml of an aqueous solution containing 5-(methoxyphenyl) was added and stirred, and the precipitate was filtered, washed with water, and dried.
15.2 g (yield: 63%) of -2-[4-(1-ethoxycarbonyl)phenyl]pyrimidine was obtained.
(第2段)
5−(メトキシフェニル)−2−[4−(1−エトキシ
カルボニル)フェニル]ピリミジン7.6g(23ミリ
モル)、臭化水素酸50g、酢酸100mlの混合物を
60時間還流した。酢酸の大部分を減圧留去したのち、
水を加えた。沈澱物を充分に水洗し、乾燥して5−(ヒ
ドロキシフェニル)−2−14−(1−カルボキシ)フ
ェニル]ピリミジン7.1g(収率99%)を得た。(Second Stage) A mixture of 7.6 g (23 mmol) of 5-(methoxyphenyl)-2-[4-(1-ethoxycarbonyl)phenyl]pyrimidine, 50 g of hydrobromic acid, and 100 ml of acetic acid was refluxed for 60 hours. After removing most of the acetic acid under reduced pressure,
Added water. The precipitate was thoroughly washed with water and dried to obtain 7.1 g (yield: 99%) of 5-(hydroxyphenyl)-2-14-(1-carboxy)phenyl]pyrimidine.
(第3段)
5−(ヒドロキシフェニル)−2−[4−(1−カルボ
キシ)フェニル]ピリミジン31g(106ミリモル)
、ピリジン310ml、無水酢酸38g(350ミリモ
ル)の混合物を70℃で10時間反応させたのち、10
0mlの氷水を加えた。析出した沈澱を濾別、水洗、乾
燥後、5−(アセチルオキシフェニル)−2−(4−(
1−カルボキシ)フェニル]ピリミジンを32g(収率
90%)を得た。得られた5−(アセチルオキシフェニ
ル)−2−[4−(1−カルボキシ)フェニル]ピリミ
ジン32g(95ミリモル)を塩化チオニル100ml
中に懸濁し、15時間加熱還流後、過剰の塩化チオニル
を減圧留去した、酸クロライドを単離することなくピリ
ジン80mlを加え、更に(S)−2−ブタノール8.
9g(120ミリモル)を加え 5時間反応させた。反
応混合物にクロロホルム300mlを加え5%塩酸水溶
液、水、10%炭酸ナトリウム水溶液で洗浄後、有機層
を硫酸マグネシウムで乾燥し、ベンジルアミン10.4
g(150ミリモル)を加えた。室温で20時間攪拌し
、脱アセトキシ化を行った。反応混合溶媒を濃縮後、シ
リカゲルクロマトグラフィー(CHCl3アセトン=1
5:1)で精製し、5−(ヒドロキシフェニル)−2−
[4−(1−メチルプロピルオキシカルボニル)フェニ
ル]ピリミジン21g(収率71%)を得た。(Third stage) 5-(hydroxyphenyl)-2-[4-(1-carboxy)phenyl]pyrimidine 31 g (106 mmol)
, 310 ml of pyridine, and 38 g (350 mmol) of acetic anhydride were reacted at 70°C for 10 hours.
Added 0 ml of ice water. After separating the precipitate by filtration, washing with water and drying, 5-(acetyloxyphenyl)-2-(4-(
32 g (yield: 90%) of 1-carboxy)phenyl]pyrimidine was obtained. 32 g (95 mmol) of the obtained 5-(acetyloxyphenyl)-2-[4-(1-carboxy)phenyl]pyrimidine was added to 100 ml of thionyl chloride.
After heating under reflux for 15 hours, excess thionyl chloride was distilled off under reduced pressure, 80 ml of pyridine was added without isolating the acid chloride, and 80 ml of (S)-2-butanol was added.
9 g (120 mmol) was added and reacted for 5 hours. After adding 300 ml of chloroform to the reaction mixture and washing with 5% aqueous hydrochloric acid, water, and 10% aqueous sodium carbonate, the organic layer was dried over magnesium sulfate, and benzylamine 10.4
g (150 mmol) was added. Deacetoxylation was performed by stirring at room temperature for 20 hours. After concentrating the reaction mixture solvent, silica gel chromatography (CHCl3acetone=1
5:1) and purified with 5-(hydroxyphenyl)-2-
21 g (yield 71%) of [4-(1-methylpropyloxycarbonyl)phenyl]pyrimidine was obtained.
得られた5−(ヒドロキシフェニル)−2−[4−(1
−メチルプロピルオキシカルボニル)フェニル]ピリミ
ジンの比旋光度ならびにNMRスペクトルの分析結果は
次のとうりであった。The obtained 5-(hydroxyphenyl)-2-[4-(1
The analysis results of the specific rotation and NMR spectrum of -methylpropyloxycarbonyl)phenyl]pyrimidine were as follows.
比旋光度[α]D(20℃)=+31.2゜(CHCl
3、C=1.1)
NMRスペクトル300MHz(CDCl3);ppm
=1.00(t,3H),1.31(d,2H),1.
60(m,1H),1.73(m、1H)、5.18(
m、1H)、6.62(brs、1H)、6.98(d
,2H),7.49(d,2H),8.14(d,2H
),8.52(d,2H),8.97(s、2H)
実施例2
5−(ヒドロキシフェニル)−2−[4−(1−メチル
ブチルオキシカルボニル)フェニル]ピリミジンの合成
(S)−2−ブタノールの代わりに(S)−2−ペンタ
ノールを用いること以外は実施例1と同様の操作を行い
、5−(ヒドロキシフェニル)−2−[4−(1−メチ
ルブチルオキシカルボニル)フェニル]ピリミジン25
g(収率81%)を得た。Specific optical rotation [α] D (20°C) = +31.2° (CHCl
3, C=1.1) NMR spectrum 300MHz (CDCl3); ppm
=1.00 (t, 3H), 1.31 (d, 2H), 1.
60 (m, 1H), 1.73 (m, 1H), 5.18 (
m, 1H), 6.62 (brs, 1H), 6.98 (d
, 2H), 7.49 (d, 2H), 8.14 (d, 2H
), 8.52 (d, 2H), 8.97 (s, 2H) Example 2 Synthesis of 5-(hydroxyphenyl)-2-[4-(1-methylbutyloxycarbonyl)phenyl]pyrimidine (S) The same operation as in Example 1 was carried out except that (S)-2-pentanol was used instead of -2-butanol, and 5-(hydroxyphenyl)-2-[4-(1-methylbutyloxycarbonyl) phenyl]pyrimidine 25
g (yield 81%) was obtained.
得られた5−(ヒドロキシフェニル)−2−[4−(1
−メチルブチルオキシカルボニル)フェニル]ピリミジ
ンの比旋光度ならびにNMRスペクトルの分析結果は次
のとうりであった。The obtained 5-(hydroxyphenyl)-2-[4-(1
The analysis results of the specific rotation and NMR spectrum of -methylbutyloxycarbonyl)phenyl]pyrimidine were as follows.
比旋光度[α]D(20℃)=+30.8゜(CHCl
3、C=1.2)
NMRスペクトル300MHz(CDCl3);ppm
=0.94(t,3H),1.33(d,3H),1.
42(m,2H),1.59(m,1H),1.74(
m,1H)5.20(m,1H),6.62(brs,
1H),6.98(d,2H),7.49(d,2H)
,8.14(d,2H),8.52(d、2H)、8.
97(s、2H)実施例3
5−(ヒドロキシフェニル)−2−[4−(1−メチル
ヘプチルオキシカルボニル)フェニル]ピリミジンの合
成
(S)−2−ブタノールの代わりに(S)−2−オクタ
ノールを用いること以外は実施例1と同様の操作を行い
、5−(ヒドロキシフェニル)−2−14−(1−メチ
ルヘプチルオキシカルボニル)フェニル)ピリミジン2
4g(収率79%)を得た。Specific optical rotation [α] D (20°C) = +30.8° (CHCl
3, C=1.2) NMR spectrum 300MHz (CDCl3); ppm
=0.94 (t, 3H), 1.33 (d, 3H), 1.
42 (m, 2H), 1.59 (m, 1H), 1.74 (
m, 1H) 5.20 (m, 1H), 6.62 (brs,
1H), 6.98 (d, 2H), 7.49 (d, 2H)
, 8.14 (d, 2H), 8.52 (d, 2H), 8.
97(s, 2H) Example 3 Synthesis of 5-(hydroxyphenyl)-2-[4-(1-methylheptyloxycarbonyl)phenyl]pyrimidine (S)-2- instead of (S)-2-butanol The same operation as in Example 1 was carried out except for using octanol, and 5-(hydroxyphenyl)-2-14-(1-methylheptyloxycarbonyl)phenyl)pyrimidine 2
4 g (yield 79%) was obtained.
得られた5−(ヒドロキシフェニル)−2−[4−(1
−メチルヘプチルオキシカルボニル)フェニル]ピリミ
ジンの比旋光度ならびにNMRスペクトルの分析結果は
次のとうりであった。The obtained 5-(hydroxyphenyl)-2-[4-(1
The analysis results of the specific rotation and NMR spectrum of -methylheptyloxycarbonyl)phenyl]pyrimidine were as follows.
比旋光度[α]D(20℃)=+21.2゜(CHCl
3、C=1.0)
NMRスペクトル300MHz(CDCl3);ppm
=0.85(t、3H)、1.28(brs、8H)、
136(d、3H)、1.62(m,1H),1.73
(m,1H),5.18(m,1H],6.49(br
s,1H),6.98(d,2H),7.49(d,2
H),814(d,2H)、8.52(d、2H)、8
.97(s、2H)実施例4
5−(ヒドロキシフェニル)−2−[4−(2−メチル
ブチルオキシカルボニル)フェニル]ピリミジンの合成
(S)−2−ブタノールの代わりに(S)−2−メチル
ブタノールを用いること以外は実施例1と同様の操作を
行い、5−(ヒドロキシフェニル)−2−[4−(2−
メチルブチルオキシカルボニル)フェニル]ピリミジン
26g(収率83%)を得た。Specific optical rotation [α] D (20°C) = +21.2° (CHCl
3, C=1.0) NMR spectrum 300MHz (CDCl3); ppm
=0.85 (t, 3H), 1.28 (brs, 8H),
136 (d, 3H), 1.62 (m, 1H), 1.73
(m, 1H), 5.18 (m, 1H], 6.49 (br
s, 1H), 6.98 (d, 2H), 7.49 (d, 2
H), 814 (d, 2H), 8.52 (d, 2H), 8
.. 97(s, 2H) Example 4 Synthesis of 5-(hydroxyphenyl)-2-[4-(2-methylbutyloxycarbonyl)phenyl]pyrimidine (S)-2- instead of (S)-2-butanol The same operation as in Example 1 was performed except for using methylbutanol, and 5-(hydroxyphenyl)-2-[4-(2-
26 g (yield: 83%) of methylbutyloxycarbonyl)phenyl]pyrimidine was obtained.
5−(ヒドロキシフェニル)−2−[4−(2−メチル
ブチルオキシカルボニル)フェニル]ピリミジンの比旋
光度ならびにNMRスペクトルの分析結果は次のとうり
であった。The specific optical rotation and NMR spectrum analysis results of 5-(hydroxyphenyl)-2-[4-(2-methylbutyloxycarbonyl)phenyl]pyrimidine were as follows.
比旋光度[α]D(20℃)=+3.8゜(CHCl3
、C=1.5)
NMRスペクトル300MHz(CDCl3);ppm
=0.93(t,3H),0.97(d,2H),1.
28(m,1H),1.50(m、1H)、1.86(
m、1H)、4.20(m、2H)、5.98(brs
、1H)、6.98(d、2H)、7.49(d、2H
)、8.14(d、2H)、8.52(d、2H)、8
.97(s、2H)実施例5
5−(ヒドロキシフェニル)−2−[4−(2−フルオ
ロオクチルオキシカルボニル)フェニル]ピリミジンの
合成
(S)−2−ブタノールの代わりに(S)−2−フルオ
ロ−1−オクタノールを用いること以外は実施例1と同
様の操作を行い、5−(ヒドロキシフェニル)−2−[
4−(2−フルオロオクチルオキシカルボニル)フェニ
ル]ピリミジン26g(収率83%)を得た。Specific optical rotation [α] D (20°C) = +3.8° (CHCl3
, C=1.5) NMR spectrum 300 MHz (CDCl3); ppm
=0.93 (t, 3H), 0.97 (d, 2H), 1.
28 (m, 1H), 1.50 (m, 1H), 1.86 (
m, 1H), 4.20 (m, 2H), 5.98 (brs
, 1H), 6.98 (d, 2H), 7.49 (d, 2H
), 8.14 (d, 2H), 8.52 (d, 2H), 8
.. 97(s, 2H) Example 5 Synthesis of 5-(hydroxyphenyl)-2-[4-(2-fluorooctyloxycarbonyl)phenyl]pyrimidine (S)-2- instead of (S)-2-butanol The same operation as in Example 1 was performed except for using fluoro-1-octanol, and 5-(hydroxyphenyl)-2-[
26 g (yield: 83%) of 4-(2-fluorooctyloxycarbonyl)phenyl]pyrimidine was obtained.
得られた5−(ヒドロキシフェニル)−2−[4−(2
−フルオロオクチルオキシカルボニル)フェニル]ピリ
ミジンの比旋光度ならびにNMRスペクトルの分析結果
は次とうりであった。The obtained 5-(hydroxyphenyl)-2-[4-(2
The analysis results of the specific rotation and NMR spectrum of -fluorooctyloxycarbonyl)phenyl]pyrimidine were as follows.
比旋光度[a]D(20℃)=+8.5゜(CHCl3
、C=1.3)
NMRスペクトル300MHz(CDCl3);ppm
=0.86(t,3H),1.27(brs,8H),
1.32 ̄1.83(m,2H),4.45(m,2H
),4.62(m,0.5H),4.88(m,0.5
H),6.98(d,2H),7.49(d,2H),
8.14(d,2H),8.52(d、2H)、8.9
7(d、2H)実施例6
5−(ヒドロキシフェニル)−2−[4−(1−メチル
プロピルオキシカルボニル)フェニル]ピリミジンの合
成
(第1段)
ジメチルホルムアミド81.6g(1.1ミリモル)に
、オキシ塩化リン102.6(0.67ミリモル)を0
℃で滴下し、ついでp−ベンジルオキシフェニル酢酸6
6g(290ミリモル)を−10℃の温度で少しずつ加
えた。混合物を20℃で1時間、60℃で2時間、およ
び80℃で5時間攪拌した。ジメチルホルムアミドを減
圧留去し、残査を冷却し、過塩素酸マグネシウムの飽和
水溶液に投入した。析出した結晶を濾別し、エーテルで
洗浄して、過塩素酸塩61g(収率52%)を得た。Specific optical rotation [a] D (20°C) = +8.5° (CHCl3
, C=1.3) NMR spectrum 300 MHz (CDCl3); ppm
=0.86 (t, 3H), 1.27 (brs, 8H),
1.32 ̄1.83 (m, 2H), 4.45 (m, 2H
), 4.62 (m, 0.5H), 4.88 (m, 0.5
H), 6.98 (d, 2H), 7.49 (d, 2H),
8.14 (d, 2H), 8.52 (d, 2H), 8.9
7(d,2H) Example 6 Synthesis of 5-(hydroxyphenyl)-2-[4-(1-methylpropyloxycarbonyl)phenyl]pyrimidine (first stage) 81.6 g (1.1 mmol) of dimethylformamide 102.6 (0.67 mmol) of phosphorus oxychloride was added to 0
℃, and then p-benzyloxyphenylacetic acid 6
6 g (290 mmol) were added in portions at a temperature of -10°C. The mixture was stirred at 20°C for 1 hour, 60°C for 2 hours, and 80°C for 5 hours. Dimethylformamide was distilled off under reduced pressure, and the residue was cooled and poured into a saturated aqueous solution of magnesium perchlorate. The precipitated crystals were filtered and washed with ether to obtain 61 g (yield: 52%) of perchlorate.
この塩23.9g(58.5ミリモル)とp−エトキシ
カルボニルベンズアミジン塩酸塩をナトリウムエチラー
ト14.8g(64.7ミリモル)の存在下、エタノー
ル250ml中で8時間加熱還流した。23.9 g (58.5 mmol) of this salt and p-ethoxycarbonylbenzamidine hydrochloride were heated under reflux in 250 ml of ethanol for 8 hours in the presence of 14.8 g (64.7 mmol) of sodium ethylate.
反応終了後、エタノールを減圧留去し、酢酸18g(0
.3モル)を含む水溶液500mlを加え攪拌した。沈
澱物を濾別し、水洗、乾燥後5−(ベンジルオキシフェ
ニル)−2−[4−(1−エトキシカルボニル)フェニ
ル]ピリミジ15.2g(収率63.4%)を得た。After the reaction, ethanol was distilled off under reduced pressure and 18 g of acetic acid (0
.. 500 ml of an aqueous solution containing 3 mol) was added and stirred. The precipitate was separated by filtration, washed with water, and dried to obtain 15.2 g of 5-(benzyloxyphenyl)-2-[4-(1-ethoxycarbonyl)phenyl]pyrimidine (yield: 63.4%).
(第2段)
5−(ベンジルオキシフェニル)−2−[4−(1−エ
トキシカルボニル)フェニル]ピリミジン7.6g(1
8.5ミリモル)、1規定水酸化カリウムを含むエタノ
ール500mlの混合物500mlを10時間還流した
、反応終了後、エタノールの大部分を減圧留去したのち
、水を加えた、沈澱物を充分に水洗し、乾燥して5−(
ベンジルオキシフェニル)−2−[4−(1−カルボキ
シ)フェニル]ピリミジン7.1g(収率99%)を得
た。(Second stage) 7.6 g (1
8.5 mmol), 500 ml of ethanol containing 1N potassium hydroxide was refluxed for 10 hours. After the reaction, most of the ethanol was distilled off under reduced pressure, and water was added. The precipitate was thoroughly washed with water. 5-(
7.1 g (yield: 99%) of benzyloxyphenyl)-2-[4-(1-carboxy)phenyl]pyrimidine was obtained.
(第3段)
5−(ベンジルオキシフェニル)−2−[4−(1−カ
ルボキシ)フェニル]ピリミジン31g(81.2ミリ
モル)を塩化チオニル100ml中に懸濁し、15時間
加熱還流後、過剰の塩化チオニルを減圧留去した。(Third stage) 31 g (81.2 mmol) of 5-(benzyloxyphenyl)-2-[4-(1-carboxy)phenyl]pyrimidine was suspended in 100 ml of thionyl chloride, and after heating under reflux for 15 hours, excess Thionyl chloride was distilled off under reduced pressure.
酸クロライドを単離することなくピリジン80mlを加
え、更に(S)−2−ブタノール8.9g(120ミリ
モル)を加え5時間反応させた。反応混合物にクロロホ
ルム300mlを加え5%塩酸水溶液、水、10%炭酸
ナトリウム水溶液で洗浄後、有機層を硫酸マグネシウム
で乾燥し濃縮後、500mlのテトラヒドロフランに溶
解し、5%Pd/C3gを添加し水素気流下、20時間
撹拌し、接触水添による脱ベンジル化を行った。反応混
合溶媒を瀘過、濃縮後、シリカゲルクロマトグラフィー
(CHCl3:アセトン=15:1)で精製し、5−(
ヒドロキシフェニル)−2−[4−(1−メチルプロピ
ルオキシカルボニル)フェニル]ピリミジン21g(収
率74.3%)を得た。80 ml of pyridine was added without isolating the acid chloride, and then 8.9 g (120 mmol) of (S)-2-butanol was added and the mixture was reacted for 5 hours. After adding 300 ml of chloroform to the reaction mixture and washing with 5% aqueous hydrochloric acid, water, and 10% aqueous sodium carbonate, the organic layer was dried over magnesium sulfate and concentrated, then dissolved in 500 ml of tetrahydrofuran, 3 g of 5% Pd/C was added, and hydrogen was added. The mixture was stirred for 20 hours under a stream of air to perform debenzylation by catalytic hydrogenation. After filtering and concentrating the reaction mixture solvent, it was purified by silica gel chromatography (CHCl3:acetone=15:1) to obtain 5-(
21 g (yield: 74.3%) of hydroxyphenyl)-2-[4-(1-methylpropyloxycarbonyl)phenyl]pyrimidine was obtained.
得られた5−(ヒドロキシフェニル)−2−[4−(1
−メチルプロピルオキシカルボニル)フェニル]ピリミ
ジンの比旋光度ならびにNMRスペクトルの分析結果は
次のとうりであった。The obtained 5-(hydroxyphenyl)-2-[4-(1
The analysis results of the specific rotation and NMR spectrum of -methylpropyloxycarbonyl)phenyl]pyrimidine were as follows.
比旋光度[α]D(20℃)=+3120(CHCl3
、C=1.1)
NMRスペクトル300MHz(CDCl3):ppm
=1.00(t,3H),1.31(d,2H),1.
60(m,1H),1.73(m、1H)、5.18(
m、1H)、6.62(brs、1H)、6.98(d
,2H),7.49(d,2H),8.14(d,2H
),8.52(d,2H)8.97(s、2H)
実施例7
5−(ヒドロキシフェニル)−2−[4−(1−メチル
ブチルオキシカルボニル)フェニル]ピリミジンの合成
(S)−2−ブタノールの代わりに(S)−2−ペンタ
ノールを用いること以外は実施例6と同様の操作を行い
、5−(ヒドロキシフェニル−2−[4−(1−メチル
ブチルオキシカルボニル)フェニル]ピリミジン25g
(収率81%)を得た。Specific optical rotation [α] D (20°C) = +3120 (CHCl3
, C=1.1) NMR spectrum 300MHz (CDCl3): ppm
=1.00 (t, 3H), 1.31 (d, 2H), 1.
60 (m, 1H), 1.73 (m, 1H), 5.18 (
m, 1H), 6.62 (brs, 1H), 6.98 (d
, 2H), 7.49 (d, 2H), 8.14 (d, 2H
), 8.52 (d, 2H) 8.97 (s, 2H) Example 7 Synthesis of 5-(hydroxyphenyl)-2-[4-(1-methylbutyloxycarbonyl)phenyl]pyrimidine (S)- The same operation as in Example 6 was performed except that (S)-2-pentanol was used instead of 2-butanol, and 5-(hydroxyphenyl-2-[4-(1-methylbutyloxycarbonyl)phenyl] 25g pyrimidine
(yield 81%).
得られた5−(ヒドロキシフェニル)−2−[4−(1
−メチルブチルオキシカルボニル)フェニル]ピリミジ
ンの比旋光度ならびにNMRスペクトルの分析結果は次
のとうりであった。The obtained 5-(hydroxyphenyl)-2-[4-(1
The analysis results of the specific rotation and NMR spectrum of -methylbutyloxycarbonyl)phenyl]pyrimidine were as follows.
比旋光度[α]D(20℃)=+30.8゜(CHCl
3、C=1.2)
NMRスペクトル300MHz(CDCl3);ppm
=0.94(t.3H),1.33(d,3H),1.
42(m,2H),1.59(m,1H),1.74(
m,1H)5.20(m,1H),6.62(brs,
1H),6.98(d,2H),7.49(d,2H)
,8【4(d,2H),8.52(d、2H)、8.9
7(s、2H)実施例8
5−(ヒドロキシフェニル)−2−(4−(1−メチル
ヘプチルオキシカルボニル)フェニル]ピリミジンの合
成
(S)−2−ブタノールの代わりに(S)−2−オクタ
ノールを用いること以外は実施例6と同様の操作を行い
、5−(ヒドロキシフェニル)−2−[4−(1−メチ
ルヘプチルオキシカルボニル)フェニル]ピリミジン2
4g(収率79%)を得た。Specific optical rotation [α] D (20°C) = +30.8° (CHCl
3, C=1.2) NMR spectrum 300MHz (CDCl3); ppm
=0.94 (t.3H), 1.33 (d, 3H), 1.
42 (m, 2H), 1.59 (m, 1H), 1.74 (
m, 1H) 5.20 (m, 1H), 6.62 (brs,
1H), 6.98 (d, 2H), 7.49 (d, 2H)
,8[4(d,2H),8.52(d,2H),8.9
7(s,2H) Example 8 Synthesis of 5-(hydroxyphenyl)-2-(4-(1-methylheptyloxycarbonyl)phenyl]pyrimidine (S)-2- instead of (S)-2-butanol) The same operation as in Example 6 was carried out except for using octanol, and 5-(hydroxyphenyl)-2-[4-(1-methylheptyloxycarbonyl)phenyl]pyrimidine 2
4 g (yield 79%) was obtained.
得られた5−(ヒドロキシフェニル)−2−[4−(1
−メチルヘプチルオキシカルボニル)フェニル]ピリミ
ジンの比旋光度ならびにNMRスペクトルの分析結果は
次のとうりであった。The obtained 5-(hydroxyphenyl)-2-[4-(1
The analysis results of the specific rotation and NMR spectrum of -methylheptyloxycarbonyl)phenyl]pyrimidine were as follows.
比旋光度[α]D(20℃)=+21.2゜(CHCl
3、C=1.0)
NMRスペクトル300MHz(CDCl3):ppm
=0.85(t、3H)、1.28(brs、8H)、
1.36(d、3H)、1.62(m,1H),1.7
3(m,1H),5.18(m,1H),6.49(b
rs,1H),6.98(d,2H),7.49(d,
2H),8.14(d,2H)、8.52(d、2H)
、8.97(s、2H)実施例9
5−(ヒドロキシフェニル)−2−[4−(2−メチル
ブチルオキシカルボニル)フェニル]ピリミジンの合成
(S)−2−ブタノールの代わりに(S)−2−メチル
ブタノールを用いること以外は実施例6と同様の操作を
行い、5−(ヒドロキシフェニル)−2−[4−(2−
メチルブチルオキシカルボニル)フェニル]ピリミジン
26g(収率83%)を得た。Specific optical rotation [α] D (20°C) = +21.2° (CHCl
3, C=1.0) NMR spectrum 300MHz (CDCl3): ppm
=0.85 (t, 3H), 1.28 (brs, 8H),
1.36 (d, 3H), 1.62 (m, 1H), 1.7
3 (m, 1H), 5.18 (m, 1H), 6.49 (b
rs, 1H), 6.98 (d, 2H), 7.49 (d,
2H), 8.14 (d, 2H), 8.52 (d, 2H)
, 8.97 (s, 2H) Example 9 Synthesis of 5-(hydroxyphenyl)-2-[4-(2-methylbutyloxycarbonyl)phenyl]pyrimidine (S) in place of (S)-2-butanol The same operation as in Example 6 was carried out except for using -2-methylbutanol, and 5-(hydroxyphenyl)-2-[4-(2-
26 g (yield: 83%) of methylbutyloxycarbonyl)phenyl]pyrimidine was obtained.
5−(ヒドロキシフェニル)−2−[4−(2−メチル
ブチルオキシカルボニル)フェニル]ピリミジンの比旋
光度ならびにNMRスペクトルの分析結果は次のとうり
であった。The specific optical rotation and NMR spectrum analysis results of 5-(hydroxyphenyl)-2-[4-(2-methylbutyloxycarbonyl)phenyl]pyrimidine were as follows.
比旋光度[α]D(20℃)=+3.8゜(CHCl3
、C=1.5)
NMRスペクトル300MHz(CDCl3);ppm
=0.93(t,3H),0.97(d,2H),1.
28(m,1H),1.50(m、1H)、1.86(
m、1H)、4.20(m、2H]、5.98(brs
、1H)、6.98(d、2H)、7.49(d、2H
)、8.14(d、2H)、8.52(d、2H)、8
.97(s、2H)実施例10
5−(ヒドロキシフェニル)−2−[4−(2−フルオ
ロオクチルオキシカルボニル)フェニル]ピリミジンの
合成
(S)−2−ブタノールの代わりに(S)−2−フルオ
ロ−1−オクタノールを用いること以外は実施例6と同
様の操作を行い、5−(ヒドロキシフェニル)−2−[
4−(2−フルオロオクチルオキシカルボニル)フェニ
ル]ピリミジン26g(収率83%)を得た。Specific optical rotation [α] D (20°C) = +3.8° (CHCl3
, C=1.5) NMR spectrum 300 MHz (CDCl3); ppm
=0.93 (t, 3H), 0.97 (d, 2H), 1.
28 (m, 1H), 1.50 (m, 1H), 1.86 (
m, 1H), 4.20 (m, 2H], 5.98 (brs
, 1H), 6.98 (d, 2H), 7.49 (d, 2H
), 8.14 (d, 2H), 8.52 (d, 2H), 8
.. 97(s,2H) Example 10 Synthesis of 5-(hydroxyphenyl)-2-[4-(2-fluorooctyloxycarbonyl)phenyl]pyrimidine (S)-2- instead of (S)-2-butanol The same operation as in Example 6 was performed except for using fluoro-1-octanol, and 5-(hydroxyphenyl)-2-[
26 g (yield: 83%) of 4-(2-fluorooctyloxycarbonyl)phenyl]pyrimidine was obtained.
得られた5−(ヒドロキシフェニル)−2−[4−(2
−フルオロオクチルオキシカルボニル)フェニル]ピリ
ミジンの比旋光度ならびにNMRスペクトルの分析結果
は次とうりであった。The obtained 5-(hydroxyphenyl)-2-[4-(2
The analysis results of the specific rotation and NMR spectrum of -fluorooctyloxycarbonyl)phenyl]pyrimidine were as follows.
比旋光度[α]D(20℃)=+8.5゜(CHCl3
、C=1.3)
NMRスペクトル300MHz(CDCl3);ppm
=0.86(t,3H),1.27(brs,8H),
1.32 ̄1.83(m,2H),4.45(m,2H
),4.62(m,0.5H),4.88(m,0.5
H),6.98(d,2H),7.49(d,2H),
8.14(d,2H),8.52(d、2H)、8.9
7(d、2H)(発明の効果)
本発明によれば、本発明のエステル誘導体を原料として
使用することにより強誘電性液晶として有用な種々の液
晶中間体を容易かつ安価に合成することができるという
効果が奏せられる。Specific optical rotation [α] D (20°C) = +8.5° (CHCl3
, C=1.3) NMR spectrum 300 MHz (CDCl3); ppm
=0.86 (t, 3H), 1.27 (brs, 8H),
1.32 ̄1.83 (m, 2H), 4.45 (m, 2H
), 4.62 (m, 0.5H), 4.88 (m, 0.5
H), 6.98 (d, 2H), 7.49 (d, 2H),
8.14 (d, 2H), 8.52 (d, 2H), 8.9
7(d, 2H) (Effects of the Invention) According to the present invention, various liquid crystal intermediates useful as ferroelectric liquid crystals can be easily and inexpensively synthesized by using the ester derivative of the present invention as a raw material. The effect of being able to do this is achieved.
特許出願人 荒川化学工業株式会社Patent applicant: Arakawa Chemical Industry Co., Ltd.
Claims (1)
〜10の整数を表し、C*は光学活性な炭素原子を表す
)で表されるエステル誘導体。[Claims] General formula [I] (wherein, X represents CH3, CF3, F, and n and m are 0
An ester derivative represented by (representing an integer of ~10, C* represents an optically active carbon atom).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2-244671 | 1990-09-14 | ||
JP24467190 | 1990-09-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04217670A true JPH04217670A (en) | 1992-08-07 |
JP2971129B2 JP2971129B2 (en) | 1999-11-02 |
Family
ID=17122219
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