JPS6185341A - 2-methylbutyloxyalkane derivative - Google Patents
2-methylbutyloxyalkane derivativeInfo
- Publication number
- JPS6185341A JPS6185341A JP20690984A JP20690984A JPS6185341A JP S6185341 A JPS6185341 A JP S6185341A JP 20690984 A JP20690984 A JP 20690984A JP 20690984 A JP20690984 A JP 20690984A JP S6185341 A JPS6185341 A JP S6185341A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- group
- optically active
- liquid crystal
- 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
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 33
- -1 sulfonyloxy Chemical group 0.000 abstract description 11
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 239000003377 acid catalyst Substances 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 150000001340 alkali metals Chemical class 0.000 abstract description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 2
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 2
- 125000005278 alkyl sulfonyloxy group Chemical group 0.000 abstract 2
- 229910052736 halogen Chemical group 0.000 abstract 2
- 150000002367 halogens Chemical group 0.000 abstract 2
- 125000005279 aryl sulfonyloxy group Chemical group 0.000 abstract 1
- 150000001721 carbon Chemical group 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- HPEVJTNZYIMANV-UHFFFAOYSA-N 2-methylbutyl 4-methylbenzenesulfonate Chemical compound CCC(C)COS(=O)(=O)C1=CC=C(C)C=C1 HPEVJTNZYIMANV-UHFFFAOYSA-N 0.000 description 1
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010010071 Coma Diseases 0.000 description 1
- 206010011878 Deafness Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000087799 Koma Species 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 150000001218 Thorium Chemical class 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 231100000895 deafness Toxicity 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 208000016354 hearing loss disease Diseases 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical class O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 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〕
本発明はアルカン誘導体に関するものであり、さらに詳
しくは式ＣＤ
〔式中、ｍは１〜１５の整数を、Ｘは水酸基、置換基を
有してもよいスルホニルオキシ基、アルキルヌルホニル
オキシ基、ハロゲン原イを示す。〕
で示される新規アルカン読導体に関するものであり、各
種液晶化合物を造るＩｌｌ １１１１体として利用でき
るものでちる。Detailed Description of the Invention [Industrial Application Field] The present invention relates to an alkane derivative, and more specifically to an alkane derivative of the formula CD [where m is an integer of 1 to 15, and X is a hydroxyl group or has a substituent Indicates a sulfonyloxy group, an alkylnulfonyloxy group, and a halogen group that may be substituted. ] This relates to a new alkane reading conductor shown in the following, which can be used as an Ill 1111 substance for producing various liquid crystal compounds.
従来、液晶化合物として、
（ＸはＩｉ、Ｃ］−１ＣＮを、ＹはＣ１、Ｃ２１１，を
、＊印は不斉炭素原子を示す。）
や、
（Ｆ ｅ ｒ ｒ ｏ ｅ ］−１ｅ ｃ工ｊｃｓ、２
４．（１９８０）ｓ０９゜ＭＯ］、、ＣＩ”ｙＳｔ、Ｌ
’ｉｇ、ＣＴ’、ｙｓｌ、、＋＋＋ｏｔ’ｔ、ｅｒ８２
１１９８２）６］ ）
捷だ、
（上記三什合物において、１１は９または１０である）
がＢ、Ｔ、０ｓｔｒｏｖｓｋｊｉによって造られた。Conventionally, as liquid crystal compounds, (X is Ii, C]-1CN, Y is C1, C211, and * indicates an asymmetric carbon atom. jcs, 2
4. (1980) s09゜MO], , CI”ySt, L
'ig, CT', ysl, +++ot't, er82
11982) 6] ) 杷田, (In the above three-compound, 11 is 9 or 10) was created by B, T, 0strovskji.
さらに、Ｍ（’ｌ］、、 （！ｒｙｓ’ｔ＋ 、 Ｔ−
１ｇ 、 ｃｒ ｙ Ｓ Ｉ−、、Ｉ８７、（１９７６
）１８９にビフェニルエステル系化合物が報告され、公
知となっている。Furthermore, M('l],, (!rys't+, T-
1g, cry SI-,, I87, (1976
) 189, biphenyl ester compounds have been reported and are well known.
しかしながら、これら公知の液晶化合物は広い？都度範
囲でカイラルスメクチック相を呈するものが少く、壕だ
、あったとしても安定性の点において問題があった。However, are these known liquid crystal compounds wide-ranging? There were few cases where the chiral smectic phase was observed, and even if there were, there were problems in terms of stability.
本発明は、上にのべたような従来１支術（でおける問題
点を解決するための各種欣晶仕合物を提供するのに必要
なＱｉＣＦｌとなる中間化合物を提供するものである。The present invention provides an intermediate compound that becomes QiCFl, which is necessary for providing various citrate compounds to solve the problems in the conventional method as described above.
すなわち、各種液晶化合物を提（１（する上で、その化
合物における光、学活＋′１部分を担うのに必要な原料
となる新規なアルカン銹導体を提供する。That is, we provide a new alkane conductor that is a necessary raw material for producing various liquid crystal compounds and playing a role in optical and academic activities in the compounds.
本発明の目的化合物は次の合成式で製造することができ
る。The target compound of the present invention can be produced by the following synthetic formula.
「合成式１」
〔式中、Ｘ１ハハロゲン、アルキルスルホニルオギシ基
、置換基を有してもよいアリールスルホニルオキシ基な
どを、ｈは水素、ヘンジルノ、（、又はテトラヒｌ−ヒ
ラニルＪ１（、ベンゾイル又はアセチルなどのアシルノ
人を、ｒｎは２〜］０の整数を、木印は不斉炭素原イを
示す。〕
ここにおいて、式〔層〕で示される化合物はグリコール
化合物を必要に応じ通常の方法、たとえばジヒドロピラ
ンと酸触媒に反応せしめることにより、ベンシルハ”ノ
イ］・との反応により、さらにハ［Ｉゲン化アシルとの
反応などにより、容↓）、に得るこＬができる。"Synthetic formula 1" [In the formula, or an acyl group such as acetyl, rn is an integer from 2 to ]0, and the wooden seal indicates an asymmetric carbon atom. For example, by reacting dihydropyran with an acid catalyst, by reacting with benzyl([I]), and further by reacting with acyl((I)), L can be obtained.
かくしてｆ！ｌ Ｃ＞ Ｊ上る式〔１〕で示される化合
物と、式〔履〕で示さｈる化合物とを無溶謀又はＩ）
Ｍ Ｓ Ｏ。Thus f! l C> J The compound represented by the above formula [1] and the compound represented by the formula [h] are melt-free or I)
M.S.O.
Ｌ）Ｍ Ｉｉ’ 、グリコールジアルキルエーテル類な
どの１Ｖ性溶媒を用いて、アルカリ金属の存在１・に室
温 〜】５０Ｃで縮合せしめることにより、目的化合物
式（Ｍ）をえることができる。L)M Ii' The target compound formula (M) can be obtained by condensation with the presence of an alkali metal (1) at room temperature ~]50C using a 1V solvent such as glycol dialkyl ethers.
捷た、次のようにしても造ることができる。It can also be created as follows.
［合成式２−１
（式中、Ｘ、 ’ｄ、ハｌ」ゲン、アルキルスルホニル
オギシノＩ（、置換］、（を有してもよいアリールスル
ホニルオキシ基、（などを示し、Ｒ，ｍ、＊印は前Ｓ己
と同じ。〕
式（Ｖ）で示される化合物はグリコール化合物を必要に
応じ、通常の方法でジヒドロピラン、ベンジルハライド
、アセチルハライド、ベンゾイルハライドと反応させた
のち、式（Ｄで示される化合物を造る方法に準じてＸ基
に変換すればよい。[Synthetic formula 2-1 (in the formula, , *marks are the same as those above.] The compound represented by formula (V) can be prepared by reacting a glycol compound with dihydropyran, benzyl halide, acetyl halide, or benzoyl halide, if necessary, using a conventional method. It may be converted to the X group according to the method for producing the compound represented by D.
式（ＩＦ）で示される化合物と式（Ｖ）で示さカる化合
物との反応は、前記したところと同様に行えばよい。The reaction between the compound represented by formula (IF) and the compound represented by formula (V) may be carried out in the same manner as described above.
合成式１及び２に従って造られた式〔狛〕で示される化
合物は適宜溶媒中、酸触媒、接触還元、アルカリ存在下
加水分解などによって、ＯＲ基をＯＨ基にかえたのち、
必要に応じ他の基にかえることができる。例えば、式〔
］〕で示される化合物の中Ｘがハロゲン原子のものを得
るには、ＸがＯＨの化合物を塩化チオニル、三臭化リン
、五」を化リンなどでハロゲン化を行ってもよいし、Ｘ
がＯＩ−１である化合物を一旦、スルホニル化し、クリ
コールジアルキルエーテル
ｉ−） ０ ％アセト／、メチルエチルケＩ−ンナトの
溶媒中、アルカリ金属ハライド（たとえば、１．５１１
ｒ 、 ｔｉｎ、 Ｔなど）と反応させればよい。The compound represented by the formula [Koma] prepared according to Synthetic Formulas 1 and 2 is converted into an OH group by converting the OR group into an OH group in an appropriate solvent, using an acid catalyst, catalytic reduction, hydrolysis in the presence of an alkali, etc.
It can be changed to other bases if necessary. For example, the expression [
]] In order to obtain a compound in which X is a halogen atom, a compound in which X is OH may be halogenated with thionyl chloride, phosphorus tribromide, phosphorus chloride, etc.
The compound in which is OI-1 is once sulfonylated, and an alkali metal halide (for example, 1.511
r, tin, T, etc.).
木全明［１的化合物ＣＩ個の不斉炭素原子をそσ）分子
中に持っているので、光学異性体が件するが、これらは
すべて本発明の範囲に含捷れる。Since the compound has CI asymmetric carbon atoms in its molecule, it is subject to optical isomers, but all of these are included within the scope of the present invention.
本発明し１藺止合物は光学活性体であるだめ、これを用
いて成品化合物を製造すれば、光学活性な液晶化合物を
得ることができる。Since the fixed compound of the present invention is an optically active compound, an optically active liquid crystal compound can be obtained by producing a finished compound using it.
以十゛本発明を１１体的に説明するため実施例をあげる
。Examples will now be given to specifically explain the present invention.
実施例１゜
光学Ｒ性な４− ｆ ２’−メチルブチルオキシ）−ブ
タン−１，−オールの合成：
８００ ｍｌのフラスコに１・４−ブタンジオール５２
ｇ、金属す１−リウム４．６ｆを入れ、８０°〜９０°
で、金属すトリウムが消失する捷で反応した。次いで４
０°〜５０°に冷却し、光学ｉｆｔ 性アミルシアルコ
ール（（α）含５−−４．４６（ｎｅａｔ ））とｐ
−１−ルエンヌルホン酸クロリドとから合成したｐ−ト
ルエンヌルホン酸２−メチルブチルエステル５０ｇを滴
下した。Example 1 Synthesis of optically R-property 4-f2'-methylbutyloxy)-butan-1,-ol: 52 mL of 1,4-butanediol was added to an 800 ml flask.
g, add 4.6f of metal 1-lium, 80° to 90°
Then, the metal strium reacted at the same time as it disappeared. then 4
Cooled to 0° to 50°, optically ift amyl sialic alcohol ((α) containing 5−4.46(neat)) and p
50 g of p-toluene-nulphonic acid 2-methylbutyl ester synthesized from -1-ruene-nulphonic acid chloride was added dropwise.
滴下後９０°〜１００°で８時間反応した。After dropping, the mixture was reacted at 90° to 100° for 8 hours.
反応終了後、氷水に加え入れ、イソプロピルエーテルで
反応物を抽出した。有機層は、よく水洗し、乾燥したの
ち、有機溶媒を留去し、頭記化合物を川た。 得ｉ
８０ｑ
〔α）ｏ−十１．２８°（ｎｅａｔ、ｌ（光学純度不明
）ｂ、ｐ １２２〜１２８°／２４問ＩＴダニＲｙ−
ヘ’ｔ ）ｚｌｚ ？ ｍ’λ：ｍｊｒ、−ｍ ’）
：８：３０ｎ、１４６０゜】３８０．１１１５
実施例２゜
光学活性なｐ −１−／Ｌ’エンスルホン酸２−メチル
ブチルオキシブチルエステルの合成：１００ｍ１のフラ
スコに、光学活性な４−（２′−メチルブチルオキシ）
ブタン−Ｊ−オ− ／ｌ／ ５ ｆ／と乾燥ピリジン３
５ｍ１を加えた。次いｆ、ｐ−トルエンスルホン酸クロ
ライド′６ｇを水冷下に、ゆっくりと加えた。４時間反
応させた後内容物を氷水にあけ、イソプロピルエーテル
で抽出した。有ｉ層は、水、希塩酸水溶液、水、飽和度
酸水素ナトリウム溶液、水と順次洗浄したのち、乾燥し
、有機溶媒を留去して題紀化合物を得た。 畳量 ７１
１Ｒヌベクトル９島↓ｍ（ｒｓ ’ｌ：］６００．１
８６２゜］］ＦＩＯ，１１］０
実施例３゜
光学活性な８− （２’−メチルブチルオキシ）−プｆ
ノパンー１−オールの合成：
１０００ｍ／フラスコに、金属すトリウム１９４ｆ１１
．８−トリメチレングリコール】８６ｇを入れすトリウ
ム塩とした。これに光学活性ア ミルアルコ −／Ｖ
（〔α）Ｄ＝−４，４６（ｎｅａｔ ））とＴ） −ト
ルエンメルホニルクロライドトカラ造ツｆｃ 光学活性
なｐ−トルエンスルホン酸２−メチルブチルエステ／Ｉ
／２００ｙをゆっくリド滴下した。室温で３時間反応し
たのち、ゆっくりと反応温度を８０°に上げ、更に９時
間反応した。反応終了後、氷水に加え入れ、イソプロピ
ルエーテルで反応物を抽出した。有機層は、よく水洗し
、乾燥したのち、有機溶媒を留去した。題記化合物を得
た。After the reaction was completed, it was added to ice water, and the reaction product was extracted with isopropyl ether. The organic layer was thoroughly washed with water, dried, and then the organic solvent was distilled off to remove the above compound. Profit i
80q [α) o-11.28° (neat, l (optical purity unknown) b, p 122-128°/24 questions IT tick Ry-
He't )zlz? m'λ: mjr, -m')
:8:30n, 1460゜】380.1115 Example 2゜Synthesis of optically active p-1-/L'enesulfonic acid 2-methylbutyloxybutyl ester: In a 100 ml flask, optically active 4-(2 ’-methylbutyloxy)
Butane-J-O-/l/5 f/ and dry pyridine 3
Added 5ml. Next, 6 g of f,p-toluenesulfonic acid chloride' was slowly added under water cooling. After reacting for 4 hours, the contents were poured into ice water and extracted with isopropyl ether. The layer I was washed with water, a dilute aqueous hydrochloric acid solution, water, a saturated sodium hydrogen oxide solution, and water in this order, then dried, and the organic solvent was distilled off to obtain the title compound. Tatami amount 71
1R Nuvector 9 islands ↓m (rs 'l:] 600.1
862゜]]FIO,11]0 Example 3゜Optically active 8-(2'-methylbutyloxy)-pf
Synthesis of nopan-1-ol: 1000m/flask, metal sodium 194f11
．． 8-trimethylene glycol] 86g was added to prepare a thorium salt. In addition, optically active amylalco-/V
([α)D=-4,46(neat)) and T) -Toluenemelphonyl chloride Tokarazukuritsu fc Optically active p-toluenesulfonic acid 2-methylbutyl ester/I
/200y was slowly dripped. After reacting at room temperature for 3 hours, the reaction temperature was slowly raised to 80° and the reaction was continued for an additional 9 hours. After the reaction was completed, it was added to ice water, and the reaction product was extracted with isopropyl ether. The organic layer was thoroughly washed with water, dried, and then the organic solvent was distilled off. The title compound was obtained.
得１８７ｇ （α〕Ｄ−月、３９°（ｎｅａ、ｔ ）
（光学純度不明）ｂ、ｐ １０４〜Ｉ ０９ Ｃｌ
２ ａｙｙＴ−１１ｆｉ１ｍ −１
１Ｆ＋ヌベクトル９ （側 ）：３．４００．］
４６５゜ａＸ
’Ｈ−Ｎ 、Ｍ Ｊ？’、 ｙ、 ヘクｌ−１（６０Ｍ
Ｈｚ ＣＤＣｌ、／ＴＭＳｉｎｔ）
ＳＩＴＥｐｍ）： ８．７２−１ ｔ 、 ２Ｈ，−Ｃ
Ｉ＋、 −０−１８，５０、ｉ ｔ／、 ２Ｈ−Ｃ
Ｉ（２−０−ｊ３１８、 ＩＣＥ 、 Ｃ１，２Ｈ，−
ＣＴＴ−Ｃ１１２〜○−）２．６１ 、 ｆ ｔ 、
］ Ｈ，−０１（＋実施例４゜
光学活性な０− トルエンスルホ７トセ２−メチルブチ
ルオキシプ［−１ピルエステルの合成：８００ｍＪのフ
ラスコに、光学活ｎ す３−（２′−メチルブチルオキ
シ）−ゾロパン−１−〕−ル４０ｇ、乾燥ピリジン８０
ｍｅを加えた。次いＴ、１ｌ−１ルエンスルホン酸りＩ
Ｉライド５２． ｌ Ｆ／を水冷下加え入れ２時間反応
した。反応終了後、通常のｈ法により単離して頭記仕合
物を？（）だ。 得鼠 ７７６ｇ１゛）１ｍ −１
１１しベクトルｙ’ｍａｘ （ｃｍ １：１６００．
１４６０゜１３６５．１１７８．１］２０
’Ｉｆ−Ｎ、Ｍ、Ｉ＋、スヘクｔ−＃ （６０Ｍ１１ｚ
、 Ｃ１）Ｃ］３／ｉ’Ｍｓ ｉｎｔ、 １ｒ（ｐ１
＋ｍ ）： ７．８６． ｆｄ 、２［（、ｉ’香Ｆ
Ｊ水、４（）？、３５．（ｄ、２Ｈ，芳香環水素）
４．１４ （ｔ、２＋１．−ＣＨ２−０−１８，３９ｆ
ｔ、２１１，４；ＩＩ、 −０−１ａ、］ ４ ｆｄ
、ｄ ２１１．−Ｃ）Ｊ−Ｃ１１２−０〜）２．４２１
Ｓ 、 ３１１．−〇［（３１ｇ（旧ｏｎ）：８．Ｆ
ｌｌ は、４１１．−Ｃ１１□−〇−Ｘ２１実施例５
光学活性な】−プロ化−８−（２’−ノー１−ルブチル
メキシ）プロパンの合成：
（イ） ５００ｍ１のフラスコに光学活ｔ１な３−（２
′−メチルブチルオキシン）−プロパン−１−オー／Ｌ
／２４．５ ｆ／ 、乾燥ピリジン４゜７３ｇ、乾燥ｒ
−−’ｊ ／ｖ２５０ ｍｌを加えた。Obtained 187g (α] D-month, 39° (nea, t)
(Optical purity unknown) b, p 104-I 09 Cl
2 ayyT-11fi1m -1 1F + Nuvector 9 (side): 3.400. ]
465゜aX'H-N, M J? ', y, hec l-1 (60M
Hz CDCl, /TMSint) SITEpm): 8.72-1 t, 2H, -C
I+, -0-18,50, it/, 2H-C
I(2-0-j318, ICE, C1,2H,-
CTT-C112~○-)2.61, f t,
] H, -01 (+Example 4゜Synthesis of optically active 0-toluenesulfo7tose2-methylbutyloxyp[-1 pyl ester: In an 800 mJ flask, optically active n 3-(2'-methyl butyloxy)-zolopane-1-]-l 40g, dry pyridine 80g
added me. Then T, 1l-1 luenesulfonic acid I
I ride 52. 1 F/ was added under water cooling and reacted for 2 hours. After the reaction is completed, isolate the above product using the usual H method. ()is. 776g1゛)1m-1 11 vector y'max (cm 1:1600.
1460゜1365.1178.1] 20 'If-N, M, I+, Shekt-# (60M11z
, C1)C]3/i'Ms int, 1r(p1
+m): 7.86. fd, 2 [(, i' incense F
J water, 4()? , 35. (d, 2H, aromatic ring hydrogen) 4.14 (t, 2+1.-CH2-0-18,39f
t, 211,4; II, -0-1a, ] 4 fd
, d 211. -C) J-C112-0~)2.421
S, 311. -〇 [(31g (old on): 8.F
ll is 411. -C11
'-Methylbutyloxine)-propane-1-oh/L
/24.5 f/, dry pyridine 4゜73g, dry r
--'j/v250 ml was added.
これに、水冷下、五泉化リン１６２ｇを滴「し、５時間
反応した。反Ｌ［−１終了後、内容物を氷水中にあけ、
エチル：［−チル抽出した。有機層を水、２規定Ｊｑ酸
飽和炭酸水諧すトリウノ、水溶液、飽和食塩水でｌｌ［
ｒｆ次洗浄し乾燥した。溶聾を■７大して頭側化合物を
得た。 （！′ｆｔｄ １１．６ ｇｂｙｐ、９５〜
１０４Ｃ／２１屑ｒｙｒｌＩＱｆｊ１ｍ 〜Ｉ
ＩＲスペクトルＱｍ、、ｘ ｆｃ’ｍ １：ｌ４（ｉ
ｎ、１８７５．１１１５
’ＩＩ−Ｎ、Ｍ、Ｒヌベクトル（６０Ｍｔｌｚ 、 （
月）Ｃ１３／ＴＭＳ ５ ｒａｔ、 ）
＝１２−
千誌捕不士 ６女す）
（”” ５００ ｍｌ′のフラス：１に、光学活＋１
．なｌ、−１ルエンスルホノ酸２−メチルブチルオキシ
プ１’７ ビ ル コ−ス ブー ル ６ ５ ｇ
、 臭、化 リ チ １ン ム ］ ９．８ｆ／
、 ＜１．燥ｒ士１ン２００Ｉｎｌを入れ、還流１−’
４時間反応１７４．γ。反応終了後、内容物を氷水に
加え人Ｊ１１、エチルエーテル抽出した。To this, 162 g of Gosenka phosphorus was added dropwise under water cooling, and the reaction was carried out for 5 hours.
Ethyl:[-thyl extracted. The organic layer was mixed with water, 2N Jq acid saturated carbonated water, an aqueous solution, and saturated saline.
It was then RF washed and dried. The cephalic compound was obtained by increasing the deafness by 7 times. (!'ftd 11.6 gbyp, 95~
104C/21 scrap ryrlIQfj1m ~I IR spectrum Qm,,x fc'm 1:l4(i
n, 1875.1115 'II-N, M, R Nuvector (60Mtlz, (
Month) C13/TMS 5 rat, ) = 12- Senshi Torfuji 6 women) ("" 500 ml' frass: 1, optical activity + 1
．． 2-methylbutyloxypyl, -1 luenesulfonate 1'7 6 5 g
, odor, chemical richness] 9.8f/
, <1. Add 200 l of dry water and reflux 1-'
4 hour reaction 174. γ. After the reaction was completed, the contents were added to ice water and extracted with ethyl ether.
有機層は、ｒとりＩ″ｌｌ ７．々酸欠−湘すトリウム
水溶／ｌｙ 。The organic layer contains r and I''ll.7.
水、飽和食塩水で順次洗浄１７乾燥した。エチルニーデ
ルを留去し頭側化合物を得た。Washed successively with water and saturated saline and dried for 17 days. Ethyl needle was distilled off to obtain the head compound.
？ｊ＋！ｉｌ ８７．６ Ｑ
ｂ、ｐ、 Ｈ＜スベク１／Ｉ／、’［＋−Ｎ、Ｍ、［
−ｉスベク１−ルは（イ）で得たものと同一であった。? j+! il 87.6 Q b, p, H<subek1/I/,'[+-N,M,[
The −i subvector was the same as that obtained in (a).
特π１−出願人 帝国化学産業株式会＋１丁ノＩツム
’ｌ’ｌ ｔｊ ル 百 （ツノ Ｊ〜）１ 事件の
表示
昭和５９年特許願第 ２０６ ！ｌ Ｏ４１号２ 発明
の名称
２−メチルブチＪレオキシアルカン誘導体３ 補正をす
る者
事＋１との関係 特許出願人
名称 帝国化学産業株式会判
４ 補市命令の１１付
昭和６０年］Ｊ１２９１１（発送日）
［昭和６０年６月２５１：Ｉ（不受理通知・発送Ｆｌ）
］
５ 補ＩＦの対象
］）願訃
２）願書のｒ ＋’＋ｉｉ記以外の発明者」の住所の欄
３）明細書
６ｈｌｉ ＋Ｉ・の内容
１）別紙の通り（浄叫）
とあるを
７番地の／１．１
ど＋ｆｌ’ Ｉｆ：する。Special π1-Applicant: Teikoku Kagaku Sangyo Co., Ltd.
'l'l tj Le Hundred (Tsuno J~) 1 Incident Display 1981 Patent Application No. 206! l O41 No. 2 Name of the invention 2-Methylbuty-J leoxyalkane derivative 3 Relationship with the person making the amendment + 1 Name of patent applicant Teikoku Kagaku Sangyo Co., Ltd. Court of Appeals 4 Supplementary City Ordinance No. 11 of 1985] J12911 (Shipping date ) [June 251, 1985: I (Notice of non-acceptance/dispatch Fl)
] 5 Subject of Supplementary IF]) Application 2) Column for the address of "inventor other than r + '+ ii" in the application 3) Description 6 hli + Contents of I. 1) As shown in the attached sheet (purification) 7 /1.1 of the address+fl' If: Yes.
Claims (1)
有してもよいスルホニルオキシ基、アルキルスルホニル
オキシ基、ハロゲン原子を示す。〕 で示される２−メチルブチルオキシアルカン誘導体。[Claims] Formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, m is an integer of 1 to 15, and , indicates a halogen atom. ] A 2-methylbutyloxyalkane derivative represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20690984A JPS6185341A (en) | 1984-10-01 | 1984-10-01 | 2-methylbutyloxyalkane derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20690984A JPS6185341A (en) | 1984-10-01 | 1984-10-01 | 2-methylbutyloxyalkane derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6185341A true JPS6185341A (en) | 1986-04-30 |
Family
ID=16531079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20690984A Pending JPS6185341A (en) | 1984-10-01 | 1984-10-01 | 2-methylbutyloxyalkane derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6185341A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002263988A (en) * | 2001-03-06 | 2002-09-17 | Brother Ind Ltd | Tool mounting detector |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5063134A (en) * | 1972-04-24 | 1975-05-29 |
-
1984
- 1984-10-01 JP JP20690984A patent/JPS6185341A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5063134A (en) * | 1972-04-24 | 1975-05-29 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002263988A (en) * | 2001-03-06 | 2002-09-17 | Brother Ind Ltd | Tool mounting detector |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| GB2027021A (en) | Pinen derivatives their preparation prising them | |
| JPS5912654B2 (en) | Optically active norpinene derivative and method for producing the same | |
| FR2642065A1 (en) | BENZOCYCLOALCENYL DIHYDROXY ALKANOIC ACID DERIVATIVES, PREPARATION METHOD AND MEDICAMENTS CONTAINING SAME | |
| US3778450A (en) | Certain bicyclic lactones | |
| Beracierta et al. | Stereoselective total syntheses of the (±)-di-O-methyl ethers of agatharesinol, sesquirin-A, and hinokiresinol, and of (±)-tri-O-methylsequirin-E, characteristic norlignans of coniferae | |
| EP0009892B1 (en) | Cyclopentenone and cyclopentenol derivatives and processes for their preparation | |
| CA1103663A (en) | Fluoro-prostaglandins and process for their preparation | |
| Adams et al. | Structure of Gossypol. XXIII. Attempts to Prepare Desapogossypolone Tetramethyl Ether. Condensation of Hexadiene-2, 4 with Dibenzoylethylene | |
| HU189582B (en) | Process for preparing 7-/4-substituted cyclopent-2-en-1-on-2-yl/-hept-2-trans-enoates, 2-arylthio-alkane-dicarboxylic acids and furyl derivatives thereof | |
| US4175201A (en) | Chemical synthesis | |
| JPS606653A (en) | Antihypercholesteremic 5-thiaalkanoic acid derivative | |
| US2673212A (en) | Process for preparing beta-methyl glutaconic acid esters from alkyl isodehydroacetates | |
| Macbeth et al. | 540. Reactions of αβ-unsaturated cyclic aldehydes and ketones. Part IX.(–)-cis-and (+)-trans-Piperitol from (–)-piperitone | |
| HU210180B (en) | Process for preparing halogeneted polybasic esters | |
| CA1152504A (en) | Prostaglandin derivatives of the .delta.2-pgf.sub.2 and .delta.2-pge.sub.2 series and process for their manufacture | |
| JP2750874B2 (en) | (-)-3- (p-tolyl) glycidol | |
| JPS59167542A (en) | Optically active liquid crystal | |
| JPS6242947A (en) | Novel benzoic acid derivative, medicament containing same and method for producing this compound | |
| JPS5921864B2 (en) | Fluoroprostaglandins and their production method | |
| US4425359A (en) | Fluoro-prostaglandins and process for their preparation | |
| AT338755B (en) | PROCESS FOR THE PRODUCTION OF OPTICALLY ACTIVE CIS-2- (2-HYDROXYATHYL) -3-CYCLOPENTEN-1-OL | |
| JPS5813551A (en) | 13-azathromboxane analogus compound, its preparation, and remedy for disease caused by thromboxane comprising it as active ingredient | |
| KR840001569B1 (en) | Process for the preparation of prostaglandine derivatives of 2-pge2 2-pgf2 series | |
| JPH0359097A (en) | Perfume composition containing 2-cyclohexylpropyl acetate | |
| JPS62226934A (en) | Norbornene derivative |