JPS5941986B2

JPS5941986B2 - New nematic liquid crystal compound

Info

Publication number: JPS5941986B2
Application number: JP15645077A
Authority: JP
Inventors: 久人佐藤; 晴義高津
Original assignee: Dainippon Ink and Chemicals Co Ltd
Current assignee: DIC Corp
Priority date: 1977-12-27
Filing date: 1977-12-27
Publication date: 1984-10-11
Also published as: JPS5498744A

Description

【発明の詳細な説明】本発明は電気光学的表示材料として有用な新規ネマチツ
ク液晶化合物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel nematic liquid crystal compounds useful as electro-optic display materials.

本発明によつて提供される新規ネマチツク液晶化合物は
一般式〔式中、Ｒ，は炭素原子数３〜８の直鎖状アルキル基を
表わし、Ｒ２は炭素原子数３、６又は７の直鎖状アルキ
ル基を表わす（但し、Ｒ２が炭素原子数３の直鎖状アル
キル基である場合、Ｒ１は炭素原子数３及び７の直鎖状
アルキル基を含まない。The novel nematic liquid crystal compound provided by the present invention has the general formula: (However, when R2 is a linear alkyl group having 3 carbon atoms, R1 does not include a linear alkyl group having 3 or 7 carbon atoms.

）。以下同様〕の化合物である。). The same applies hereafter].

式（１）の化合物は、そのいずれもが弱い正の誘率異方
性をもち、ネマチツク液晶性を呈する化合物である。All of the compounds of formula (1) have weak positive dielectric anisotropy and exhibit nematic liquid crystallinity.

従つて、式（１）の化合物は、該化合物単独の形態で、
或は該化合物相互の混合物の形態で、或は該化合物と他
のネマチツク液晶化合物及び／又は非ネマチツク液晶化
合物との混合物の形態で、液晶表示セル例えばエム・シ
ヤツト（Ｍ．Ｓｃｈａｄｔ）等〔ＡＰＰＬＩＥＤＰＨＹ
ＳＩＣＳＬＥＴＴＥＲＳｌ８ｌ２７〜１２８（１９７１
）〕によつて提案された電界効果型セル（フイールド・
ェフエクト・モード・セル）又はジ一・エイチ・ハイル
マイヤ一（Ｇ．Ｈ．Ｈｅｉｌｍｅｉｅｒ）等〔ＰＲＯＣ
ＥＥＤＩＮＧＯＦＴＨＥＩ．Ｅ．Ｅ．Ｅ？１１６２〜１
１７１（１９６８）〕によつて提案された動的光散型セ
ル（ダイナミツク・スキヤツタリング・モード・セル）
に適用することができる。更に、式（１）の化合物は化
学的に安定であつて水分、光等によつて分解せず、低粘
度であり、閾値電圧が低く、然も無色乳白色といつた幾
多の優れた特性を有しているため、式（１）の化合物を
用いれば、長寿命で低電圧駆動及び高速応答が可能であ
り然も表示が極めて鮮明な液晶表示セルを製作すること
ができる。Therefore, the compound of formula (1) in the form of the compound alone,
Alternatively, in the form of mixtures of the compounds with each other or with other nematic and/or non-nematic liquid crystal compounds, liquid crystal display cells such as M. Schadt etc. [APPLIED PHY
SICSLETTERSl8l27~128 (1971
)] proposed a field-effect cell (field effect cell)
effect mode cell) or G.H. Heilmeier, etc. [PROC
EEDINGOFTTHEI. E. E. E? 1162-1
171 (1968)].
It can be applied to Furthermore, the compound of formula (1) is chemically stable, does not decompose due to moisture, light, etc., has a low viscosity, has a low threshold voltage, and has many excellent properties such as being colorless and milky white. Therefore, by using the compound of formula (1), it is possible to manufacture a liquid crystal display cell that has a long life, is capable of low-voltage driving, high-speed response, and has an extremely clear display.

次に、式（）の化合物の物理特性を第１表に掲げる。Next, the physical properties of the compound of formula () are listed in Table 1.

本発明によれば、式（１）の化合物は次の製造方法に従
つて製造される。According to the present invention, the compound of formula (1) is produced according to the following production method.

第１段階一式（）の化合物にハロゲン化剤を反応させて
式（つの化合物（式中、ＸはＦ、Ｂｒ，．Ｃｌ．Ｉ等の
ハロゲン原子である。In the first step, the compound of formula () is reacted with a halogenating agent to form a compound of the formula (where X is a halogen atom such as F, Br, .Cl.I, etc.).

）を製造する。式（りの化合物において好ましいＸは塩
素原子であり、ハロゲン化剤としては塩化チオニルを用
いればよい。反応は常圧及び反応混合物の還流温度で行
なう。反応によつて生成した混合物から式（りの化合物
を単離する必要なく、過剰のハロゲン化剤を除去するだ
けでよい。第２段階一第１段階で製造された粗製の式（
りの化合物と式（）の化合物を不活性有機溶媒中で反応
させる。) is manufactured. In the compound of the formula (R), X is preferably a chlorine atom, and thionyl chloride may be used as the halogenating agent.The reaction is carried out at normal pressure and the reflux temperature of the reaction mixture. It is only necessary to remove the excess halogenating agent without the need to isolate the compound of .
A compound of formula () is reacted with a compound of formula () in an inert organic solvent.

不活性有機溶媒としては例えばジエチルエーテル、テト
ラヒドロフラン、ジメチルホルムアミド、ベンゼン等を
用いればよい。反応中に遊離したハロゲン化水素を反応
系外に除くために、上記不活性有機溶媒中にピリジン、
第３級アミン等の塩基性物質を含ませることが望ましい
。反応は常圧及び−１０℃から室温までの温度で行なう
。反応生成物に対して溶剤抽出、水洗、乾燥、再結晶等
の一連の精製処理を施すことによつて目的とする式（１
）の化合物を単離することができる。原料となる式（）
の化合物は次の製造方法に従つて製造される。As the inert organic solvent, for example, diethyl ether, tetrahydrofuran, dimethylformamide, benzene, etc. may be used. In order to remove the hydrogen halide liberated during the reaction from the reaction system, pyridine,
It is desirable to include a basic substance such as a tertiary amine. The reaction is carried out at normal pressure and at temperatures from -10°C to room temperature. By subjecting the reaction product to a series of purification treatments such as solvent extraction, water washing, drying, and recrystallization, the desired formula (1
) can be isolated. Raw material formula ()
The compound is produced according to the following production method.

初３１段階一式（ａ）の化合物にハロゲン化剤を反応させ
て式（ｂ）の化合物を製造する。In the first 31 steps, a compound of formula (a) is reacted with a halogenating agent to prepare a compound of formula (b).

ハロゲン化剤としては塩化チオニルを用いればよい。反
応によつて生成した混合物から式（ｂ）の化合物を単離
する必要はなく、過剰のハロゲン化剤を除去するだけで
よい。″５２段階一第１段階で製造された粗製の式（ｂ
）の化合物に不活性有機溶媒の存在下又は不存在下で臭
素を反応させて式（ｃ）の化合物を製造する。Thionyl chloride may be used as the halogenating agent. It is not necessary to isolate the compound of formula (b) from the mixture produced by the reaction, it is only necessary to remove excess halogenating agent. ``52 Steps - Crude formula (b) produced in the first step
The compound of formula (c) is prepared by reacting the compound of formula (c) with bromine in the presence or absence of an inert organic solvent.

不活性有機溶媒としては四塩化炭素、クロロホルム、ジ
クロルエタンの如き低級炭化水素の塩素化物を用いれば
よい。反応によつて生成した混合物はそのまま次の第３
段階に供給される。第３段階一第２段階の反応によつて
生成した混合物に過剰の低級アルコールを反応させた後
、過剰のアルコールを溜去し、次いで反応生成物に対し
て溶剤抽出、水洗、乾燥等の一連の精製処理を施して式
（ｄ）の化合物（式中、ビは低級アルキル基である。As the inert organic solvent, chlorinated lower hydrocarbons such as carbon tetrachloride, chloroform, and dichloroethane may be used. The mixture produced by the reaction is directly used in the following third step.
supplied to the stage. 3rd step - After reacting an excess of lower alcohol with the mixture produced by the reaction of the 2nd step, the excess alcohol is distilled off, and then the reaction product is subjected to a series of solvent extraction, water washing, drying, etc. The compound of formula (d) (wherein, bi is a lower alkyl group) is obtained by purification treatment.

）を単離する。第４段階一第３段階で製造された式（ｄ
）の化合物にアルコール中で脱ハロゲン化剤を反応させ
た後、アルコールを溜去し、次いで反応生成物に対して
溶斉胎出、水洗、乾燥、蒸溜等の一連の精製処理を施し
て式（ｅ）の化合物を単離する。) is isolated. The formula (d
) is reacted with a dehalogenating agent in alcohol, the alcohol is distilled off, and the reaction product is subjected to a series of purification treatments such as elution, washing with water, drying, and distillation to obtain the formula Isolate the compound (e).

脱ハロゲン化剤としては１・８−ジアザビシクロ（５・
４・Ｏ）ウンデセンー７が特に好ましい。第５段階一第
４段階で製造された式（ｅ）の化合物をアルカリ性アル
コール水で加水分解し、反応生成物をメタノール水から
再結晶させて式（）の化合物を製造する。As a dehalogenating agent, 1,8-diazabicyclo (5.
4.O) undecene-7 is particularly preferred. Step 5 - The compound of formula (e) produced in step 4 is hydrolyzed with alkaline alcoholic water, and the reaction product is recrystallized from methanol water to produce the compound of formula ().

斯くして製造される式（）の化合物はネマチツク液晶化
合物であり、その物理特性を第２表に掲げる。The compound of formula () thus produced is a nematic liquid crystal compound, and its physical properties are listed in Table 2.

第１段階一反応溶媒として水を用い、式（ｆ）の化合物
に塩酸を反応させて塩酸塩とした後、これに亜硝酸塩を
低温下で反応させて式（ｇ）の化合物を製造する。First step: Using water as a reaction solvent, the compound of formula (f) is reacted with hydrochloric acid to form a hydrochloride salt, and then reacted with nitrite at low temperature to produce the compound of formula (g).

第２段階一第１段階の反応によつて生成した混合物を加
熱されたキサントゲン酸塩水溶液に徐徐に加えて反応さ
せた後、反応生成物を抽出して式（ｈ）の化合物を製造
する。Second Step - The mixture produced by the first step reaction is gradually added to the heated xanthate aqueous solution to react, and the reaction product is extracted to prepare the compound of formula (h).

第３段階一第２段階で製造された式（ｈ）の化合物をア
ルカリ性アルコールで加水分解し、分解液を酸性とした
後、これに溶剤抽出、水洗、乾燥、蒸溜等の一連の精製
処理を施して式（）の化合物を単離する。Step 3 - After hydrolyzing the compound of formula (h) produced in Step 2 with alkaline alcohol and making the decomposition solution acidic, it is subjected to a series of purification treatments such as solvent extraction, water washing, drying, and distillation. to isolate a compound of formula ().

式（１）の化合物は、電気光学的表示材料として用いる
場合には、該化合物相互の混合物或は該化合物と他のネ
マチツク液晶化合物及び／又は非ネマチツク液晶化合物
との混合物の形態で用いることが望ましく、特に共晶組
成の混合物の形態で用いることが望ましい。When the compound of formula (1) is used as an electro-optical display material, it can be used in the form of a mixture of the compounds or a mixture of the compound and other nematic liquid crystal compounds and/or non-nematic liquid crystal compounds. It is desirable to use it, especially in the form of a mixture of eutectic composition.

９ｆ荀−５６−？ヌ＝＝蜂；：ツク液晶化合物を例示する。9f Xun-56-? Nu==bee;： The following is an example of a liquid crystal compound.

〔式中、Ｒ及びビは夫々ＮＣｍＨ２ｍ＋１−、ＮＣ−０−のいずれかを表わす（但し、ｍは１〜１０の整
数）。[In the formula, R and Bi each represent either N CmH2m+1- or N C-0- (however, m is an integer from 1 to 10).

〕〔式中、Ｒはｎ−ＣｍＨ２ｍ＋１ｎｃｍＨ２ｍ＋１−０−、ｎ−ＣｍＨ２ｍ＋１−０−Ｃ−のいずれか
を表わし、ｗはｎ−ＣｍＨ２ｍ＋１−、ＮＣ−０−のい
ずれかを表わす（但し、ｍは１〜１０の整数）。[In the formula, R represents either n-CmH2m+1 n cmH2m +1-0-, n-CmH2m+1-0-C-, and w represents either n-CmH2m+1- or NC-0- (however, m is an integer from 1 to 10).

〕〔式中、Ｒ及びＲ′は不々ｎ−ＣｍＨ２ｍ＋ＨｎＯ−
のいずれかを表わす（但し、ｍは１〜１０の整数）。[In the formula, R and R' are n-CmH2m+HnO-
(However, m is an integer from 1 to 10).

〕〔式中、Ｒ及びＲ′は夫々ＮＣｍＨ２ｍ＋１−、Ｎｎ−ＣｍＨ２ｍ＋１−Ｃ−０−のいずれかを表わす（但
し、ｍは１〜１０の整数）。] [In the formula, R and R' each represent either N CmH2m+1- or N n-CmH2m+1-C-0- (however, m is an integer from 1 to 10).

〕〔式中、Ｒ及びｋは夫々ｎ−ＣｍＨ２ｍ＋１−、ＮＣ
ｍＨ２ｍ＋１−０−のいずれかを表わす（但し、ｍは１
〜１０の整数）。[In the formula, R and k are respectively n-CmH2m+1-, NC
mH2m+1-0- (where m is 1
~10 integers).

〕〔式中、Ｒはｎ−ＣｍＨ２ｍ＋１−、ｎ−ＣｍＨ２＋ＣｍＨ２ｍ＋１−Ｃ−０−のいずれかを表わす（但し、
ｍは１〜１０の整数）。[In the formula, R represents either n-CmH2m+1-, n-CmH2+ CmH2m+1-C-0- (However,
m is an integer from 1 to 10).

〕〔式中、Ｒはｎ−ＣｍＨ２ｍ＋１を表わす（但し、ｍ
は１〜１０の整数）。] [In the formula, R represents n-CmH2m+1 (however, m
is an integer from 1 to 10).

〕〔式中、Ｒはｎ−ＣｍＨ２ｍ＋１−、ｎ−ＣｍＨ２ｍ
＋１−０−のいずれかを表わす（但し、ｍは１〜１０の
整数）。[In the formula, R is n-CmH2m+1-, n-CmH2m
Represents either +1-0- (where m is an integer from 1 to 10).

〕〔式中、Ｒはｎ−Ｃｎｌｌ［２ｍ＋１−、ｎ−ＣｍＨ
２ｍ＋１−０−のいずれかを表わす（但し、ｍは１〜１
０の整数）。] [Wherein, R is n-Cnll[2m+1-, n-CmH
Represents either 2m+1-0- (where m is 1 to 1
0 integer).

〕〔式中、Ｒはｎ−ＣｍＨ２ｍ＋１−、ＮｃｍＨ２ｍ＋１−０−、ｎ−ＣｎｌＨ２ｍ＋１−ｃ−０−のいずれ
かを表わす（但し、ｍは１〜１０の整数）。] [In the formula, R represents either n-CmH2m+1-, N cmH2m +1-0-, or n-CnlH2m+1-c-0- (however, m is an integer from 1 to 10).

〕〔式中、Ｒはｎ−ＣｍＨ２ｍ＋１−、ｎ−ＣｍＨ２ｍ
＋１−０−のいずれかを表わす（但し、ｍは１〜１０の
整数）。〕〔式中、Ｒはｎ−ＣｍＨ２ｍ＋１−、ｎ−Ｃ
ｍＨ２ｍ＋１−０−のいずれかを表わす（但し、ｍは１
〜１０の整数）。[In the formula, R is n-CmH2m+1-, n-CmH2m
Represents either +1-0- (where m is an integer from 1 to 10). [In the formula, R is n-CmH2m+1-, n-C
mH2m+1-0- (where m is 1
~10 integers).

〕〔式中、Ｒはｎ−ＣｍＨ２ｍ＋１−を表わす（但し、
ｍは１〜１０の整数）。] [In the formula, R represents n-CmH2m+1- (however,
m is an integer from 1 to 10).

〕〔式中、Ｒはｎ−ＣｍＨ２ｍ＋１−を表わし、ＸはＦ
．Ｃｌ．Ｂｒ、のいずれかを表わす（但し、ｍは１〜８
の整数）。[In the formula, R represents n-CmH2m+1-, and X is F
．． Cl. Br (however, m is 1 to 8)
integer).

〕〔式中、Ｒはｎ−ＣｍＨ２ｍ＋１を表わし、ＸはＦｌ
Ｃｌ．Ｂｒ．Ｉのいずれかを表わす（但し、ｍは１〜８
の整数）。[In the formula, R represents n-CmH2m+1, X is Fl
Cl. Br. I (however, m is 1 to 8)
integer).

］また、式（１）の化合物を前記他のネマチツク液晶化
合物及び／又は非ネマチツク液晶化合物との混合物との
形態で用いる場合、更に必要に応じて該混合物に粘度低
下剤、配向剤その他の助剤を添加しても一向に差支えな
い。] Furthermore, when the compound of formula (1) is used in the form of a mixture with the other nematic liquid crystal compound and/or non-nematic liquid crystal compound, if necessary, the mixture may be further added with a viscosity reducing agent, an aligning agent and other aids. There is no problem in adding agents.

次に本発明を原料製造例及び実施例をもつて具体的に説
明する。Next, the present invention will be specifically explained with reference to raw material production examples and examples.

原料製造例１式ｎ−Ｃ３Ｈ７−＜》−ＣＯＯＨの化合物１７０７
（１モル）を塩化チオニル５００７に溶解し、この混合
物を還流下で１時間攪拌した後、過剰の塩化チオニルを
溜去した。Raw material production example 1 Compound 1707 of formula n-C3H7-<>>-COOH
(1 mol) was dissolved in thionyl chloride 5007 and the mixture was stirred under reflux for 1 hour, after which excess thionyl chloride was distilled off.

次に、得られた反応生成物に温度７０〜８０℃で臭素２
７０ｔを徐々に滴下し、この混合物を同温度で２０時間
攪拌した後、これをメタノール５００ｍ１に加え、この
混合物を還流下で１時間攪拌し、その後過剰のメタノー
ルを溜去した。得られた反応生成物をエーテルで抽出し
、抽出液を水洗後無水芒硝で乾燥し、その後この抽出液
からエーテルを溜去した。次に、得られた反応生成物を
１・８−ジアザービシクロ（５・４・０）ウンデセンー
７の５０％メタノール溶液３００ｙに溶解し、この混合
物を還流下で５時間攪拌した後、メタノールを溜去した
。得られた混合物をエーテルで抽出し、抽出液を水洗後
無水芒硝で乾燥し、抽出液からエーテルを溜去し、反応
生成物を真空下で蒸溜した。次に、その主溜分とアルカ
リ件メタノール水溶液３５０ｙ（２５％苛性ソーダ３２
０ｆ＋メタノール３０ｔ）との混合物を還流下で１時間
撹拌し、希塩酸で酸性としてから反応生成物をエーテル
抽出し、抽出液を水で洗浄した後、無水芒硝で乾燥し、
しかる後抽出液からエーテルを溜去した。得られた反応
生成物を８０％メタノール水から再結晶させて式ｎ−Ｃ
３Ｈ７−〈〉》−ＣＯＯＨの化合物１３０７２Ｃハ料
製造例２〜６原料製造例１における式１−Ｃ３Ｈ７−×、、７，＞−一ＣＯＯＨの化合物１
モルに（えて下記の化合物１モルを夫々用いる以外は同
？造例と同様にして第３表に示す化合物を得た。Next, the obtained reaction product was added with bromine 2 at a temperature of 70 to 80°C.
70 t was gradually added dropwise, and the mixture was stirred at the same temperature for 20 hours, then added to 500 ml of methanol, the mixture was stirred under reflux for 1 hour, and then excess methanol was distilled off. The obtained reaction product was extracted with ether, the extract was washed with water and dried over anhydrous sodium sulfate, and then the ether was distilled off from the extract. Next, the obtained reaction product was dissolved in 300 y of a 50% methanol solution of 1,8-diazabicyclo(5.4.0) undecene-7, and this mixture was stirred under reflux for 5 hours. Distilled away. The resulting mixture was extracted with ether, the extract was washed with water and dried over anhydrous sodium sulfate, the ether was distilled off from the extract, and the reaction product was distilled under vacuum. Next, the main distillate and alkaline methanol aqueous solution 350 y (25% caustic soda 32
After stirring the mixture with 0f + 30 t of methanol for 1 hour under reflux and acidifying with dilute hydrochloric acid, the reaction product was extracted with ether, the extract was washed with water, and then dried over anhydrous sodium sulfate.
Thereafter, ether was distilled off from the extract. The obtained reaction product was recrystallized from 80% methanol water to give the formula n-C.
Compound 1 of 3H7-〈〉》》-COOH 13072C Halogen Production Examples 2-6 Formula 1-C3H7-x,, 7,>-COOH Compound 1 in Raw Material Production Example 1
The compounds shown in Table 3 were obtained in the same manner as in the same procedure except that 1 mole of each of the following compounds was used instead.

原料製造例７式ｎ−Ｃ３Ｈ７←《》←ＮＨ２の化合
物１３５７（１モル）と水２００ＣＣを混合し、この混
合物に濃塩酸２１５ＣＣ（２．５モル）を徐々に滴下し
、滴下終了後この混合物を５０〜６０℃で３０分間反応
させた。Raw material production example Compound 1357 (1 mol) of formula 7 n-C3H7←《》←NH2 and 200 cc of water were mixed, 215 cc of concentrated hydrochloric acid (2.5 mol) was gradually added dropwise to this mixture, and after the completion of the dropping, this mixture was reacted at 50-60°C for 30 minutes.

次に、この反応液に９７％亜硝酸ナトリウム７１．１７
（１モル）を水２００ＣＣに溶解した溶液を滴下し、滴
下終了後この混合物を１時間反応させた。この際反応温
度を５℃以下に保つた。次いで、キサントゲン酸カリウ
ム３２１７（２モル）を水４００ＣＣに溶解し、この溶
液に温度を４５〜５０℃に保ちながら上記反応液を３時
間かけて滴下し、滴下終了後この混合物を同温度で１時
間反応させた。その後、反応生成物をエーテルで抽出し
、抽出液を３％水酸化ナトリウムメタノール溶液で洗浄
し、続いて無水芒硝で乾燥しＬ−秘．１１：１１出前よ
りエ一子ルｋ溜尖１，≠一〃いで徂られた反応生成物
をエタノール１０００ｍ１に溶解し、この溶液に還流下
で水酸化ナトリウム２２４．４７（４モル）を徐々に添
加し、添加終了後これらを３．５時間反応させた。反応
液よりエタノールを溜去し、次いでこれに水を加え、更
に６Ｎ硫酸を加えて酸件にした後、この液より反応生成
物をエーテルで抽出した。抽出液を水洗し、無水芒硝で
乾燥した後、これを蒸溜して下記化合物９２７（０．６
１モル）を得た。収率６１％原料製造例８原料製造例７におけるＮＣ３Ｈ７｛｝２１モルに代えて式ｎ−Ｃ６Ｈｌ３−《》−ＮＨ２の化合物１モルを用い
る以外は同製造例と同様にして下記の化合物１１１７（
０．５７２モル）を得た。Next, add 97% sodium nitrite 71.17 to this reaction solution.
A solution of (1 mol) dissolved in 200 cc of water was added dropwise, and after the dropwise addition was completed, the mixture was allowed to react for 1 hour. At this time, the reaction temperature was kept below 5°C. Next, potassium xanthate 3217 (2 mol) was dissolved in 400 cc of water, and the above reaction solution was added dropwise to this solution over 3 hours while keeping the temperature at 45 to 50°C. Allowed time to react. Thereafter, the reaction product was extracted with ether, the extract was washed with 3% sodium hydroxide methanol solution, and then dried over anhydrous sodium sulfate. 11:11 After delivery, the reaction product was dissolved in 1,000 ml of ethanol, and 224.47 (4 mol) of sodium hydroxide was gradually added to this solution under reflux. After addition, these were allowed to react for 3.5 hours. Ethanol was distilled off from the reaction solution, water was then added thereto, 6N sulfuric acid was added to make the solution acidic, and the reaction product was extracted from this solution with ether. The extract was washed with water, dried over anhydrous sodium sulfate, and then distilled to obtain the following compound 927 (0.6
1 mol) was obtained. Yield 61% Raw Material Production Example 8 The following compound was produced in the same manner as in Raw Material Production Example 7, except that 1 mol of a compound of the formula n-C6Hl3-《》-NH2 was used instead of 1 mol of N C3H7{}2 in Raw Material Production Example 7. 1117(
0.572 mol) was obtained.

収率５７．２％＼〜ｔ）？？―−１−―原料製造例９原料製造例７における式ＮＣ３Ｈべ「ＹＮＨ２ｌモルに代えて式ＮＣ７Ｈｌ５−《／−ＮＨ２の化合物１モルを用いる以
外は同製造例と同様にして下記の化合物１２５７（０．
６０１モル）を得た。Yield 57.2%\~t)? ? --1--Raw material production example 9 The following procedure was carried out in the same manner as in raw material production example 7 except that 1 mol of a compound of the formula N C7Hl5-<</-NH2 was used instead of 1 mol of the formula Compound 1257 (0.
601 mol) was obtained.

収率６２．２％実施例１式ｎ−Ｃ４Ｈ９−く診−Ｃ
ＯＯＨの化合物１８．２７（０．１モル）を塩化チオニ
ル５０７に溶解し、この混合物を還流下で１時間反応さ
せた後、過剰の塩化チオニルを溜去した。Yield 62.2% Example Formula 1 n-C4H9-K Diagnosis-C
OOH compound 18.27 (0.1 mol) was dissolved in thionyl chloride 507 and the mixture was reacted under reflux for 1 hour, after which excess thionyl chloride was distilled off.

次に、得られた反応生成物をエーテル５０ｍ１に溶解し
、この溶液にＯ℃で式ｎ−Ｃ３Ｈ７−《》−ＳＨの化
合物１５．２７（０，１モル）を加え、続いて−１０℃
で更にピリジン２０７を滴下し、滴下終了後室温にて反
応を更に１時間続行させた。次に、この反応液を希塩酸
及び水で洗浄後、無水芒硝で乾燥し、しかる後この反応
液からエーテルを溜去した。得られた反応生成物をメタ
ノールから再結晶させて下記化合物２０．０７（０．０
６３３モル）を得た。収率６３．３％実施例２〜４実施例１における式ＮＣ４Ｈ９べ》；ＣＯＯＨの化合物１モルに【代えて下記の化合物１モルを夫々用いる以外は同実施
例と同様にして第４表に示す化合物を得た。The resulting reaction product was then dissolved in 50 ml of ether, and to this solution was added 15.27 (0.1 mol) of the formula n-C3H7-《》-SH at 0 °C, followed by -10 °C.
Further, pyridine 207 was added dropwise, and after the dropwise addition was completed, the reaction was continued for another 1 hour at room temperature. Next, this reaction solution was washed with dilute hydrochloric acid and water, dried over anhydrous sodium sulfate, and then ether was distilled off from this reaction solution. The obtained reaction product was recrystallized from methanol to obtain the following compound 20.07 (0.0
633 mol) was obtained. Yield: 63.3% Examples 2 to 4 The formula N C4H9 in Example 1 The compound shown in was obtained.

実施例５式ｎ−Ｃ３Ｈ７−く？−ＣＯＯＨの化合物
１６．８７（０．１モル）を塩化チオニル５０（ｉｌに
溶解し、この混合物を還流下で１時間反応させた後、過
剰の塩化チオニルを溜去した。Example 5 Formula n-C3H7-? -COOH compound 16.87 (0.1 mol) was dissolved in 50 (il) thionyl chloride and the mixture was reacted under reflux for 1 hour, after which excess thionyl chloride was distilled off.

次に、得られた反応生成物をエーテル５０ｍ１に溶解し
、この溶液にＯ゛Ｃで式ＮＣ６Ｈｌ３−く、ョ２−ＳＨ
の化合物１９．４、笑７（０．１モル）を加え、続いて
−１０℃で更にピリジン２０７を滴下し、滴下終了後室
温にて反応を更に１時間続行させた。Next, the obtained reaction product was dissolved in 50 ml of ether, and this solution was heated with O
Compound 19.4, 7 (0.1 mol) was added thereto, and then pyridine 207 was further added dropwise at -10°C, and after the dropwise addition was completed, the reaction was continued for an additional hour at room temperature.

次に、この反応液を希塩酸及び水で洗浄後、無水芒硝で
乾燥し、しかる後この反応液からエーテルを溜去した。
得られた反応生成物をメタノールから再結晶させて下記
化合物２１．７７（０．０６３１モル）を得た。収率６
３．１％実施例６〜１０実施例５における式ｎ−Ｃ３Ｈ７−〈，Σ−ＣＯＯＨの化合物１モルに代
えて下記の化合物１モルを夫々用いる以外は同実施例と
同様にして第５表に示す化合物を得た。Next, this reaction solution was washed with dilute hydrochloric acid and water, dried over anhydrous sodium sulfate, and then ether was distilled off from this reaction solution.
The obtained reaction product was recrystallized from methanol to obtain the following compound 21.77 (0.0631 mol). Yield 6
3.1% Examples 6 to 10 Table 5 was carried out in the same manner as in Example 5 except that 1 mol of each of the following compounds was used in place of 1 mol of the compound of the formula n-C3H7-<,Σ-COOH in Example 5. The compound shown in was obtained.

実施例１１式ｎ−Ｃ３Ｈ７パトＣＯＯＨの化合物１
６．８ｙ（０．１モル）を塩化チオニル５０ｙに溶解
し、この混合物を還流下で１時間反応させた後、過剰の
塩化チオニルを溜去した。Example 11 Compound 1 of formula n-C3H7-COOH
6.8y (0.1 mol) was dissolved in 50y of thionyl chloride, and the mixture was reacted under reflux for 1 hour, and then excess thionyl chloride was distilled off.

次に、得られた反応生成物をエーテル５０ｍ１に溶解し
、この溶液にｏ℃で式ｎ−Ｃ７Ｈ，５入トＳＨの化合
物２０．８ｙ（０．１モル）を加え、続いて−１０℃
で更にピリジン２０Ｖを滴下し、滴下終了後室温にて反
応を更に１時間続行させた。次に、この反応液を希塩酸
及び水で洗浄後、無水芒硝で乾燥し、しかる後この反応
液からエーテルを溜去した。得られた反応生成物をメタ
ノールから再結晶させて下記化合物２３．０ｙ（０．
０６４２モル）を得た。収率６４．２％実施例１２〜
１６実施例１１における式ｎ−Ｃ３Ｈ７べＹＣＯＯＨの化合物１モルに代えて下
記の化合物１モルを夫々用いる以外は同実施例と同様に
して第６表に示す化合物を得た。The resulting reaction product was then dissolved in 50 ml of ether, and to this solution was added 20.8y (0.1 mol) of a compound of the formula n-C7H,5-SH at 0°C, followed by -10°C.
Then, 20 V of pyridine was further added dropwise, and after the addition was completed, the reaction was continued for another 1 hour at room temperature. Next, this reaction solution was washed with dilute hydrochloric acid and water, dried over anhydrous sodium sulfate, and then ether was distilled off from this reaction solution. The obtained reaction product was recrystallized from methanol to obtain the following compound 23.0y (0.
0642 mol) was obtained. Yield 64.2% Example 12~
16 The compounds shown in Table 6 were obtained in the same manner as in Example 11, except that 1 mol of each of the following compounds was used in place of 1 mol of the compound having the formula n-C3H7beYCOOH in Example 11.

Claims

[Scope of Claims] 1 General formula [wherein R_1 represents a linear alkyl group having 3 to 8 carbon atoms, and R_2 represents a linear alkyl group having 3, 6 or 7 carbon atoms (provided that , R_2 is a linear alkyl group having 3 carbon atoms, R_1 is a straight chain alkyl group having 3 and 7 carbon atoms.
Contains no straight chain alkyl group. ). ] compound. 2. A compound according to claim 1 having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 3. A compound according to claim 1 having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 4. The compound according to claim 1 having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 5. The compound according to claim 1, having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 6. The compound according to claim 1 having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 7. The compound according to claim 1 having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 8. The compound according to claim 1 having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 9. A compound according to claim 1 having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 10. The compound according to claim 1 having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 11. The compound according to claim 1 having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 12. The compound according to claim 1 having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 13. The compound according to claim 1 having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 14. The compound according to claim 1 having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 15. The compound according to claim 1 having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 16. The compound according to claim 1 having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 17. The compound according to claim 1 having the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 18 General formula ▲ Numerical formula, chemical formula, table, etc. are available ▼ [In the formula, R_1 represents a linear alkyl group having 3 to 8 carbon atoms, and X represents a halogen atom. ] Compounds with general formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_2 represents a linear alkyl group having 3, 6 or 7 carbon atoms. [In the formula, R_1 and R_2 each represent the same meaning as above (However, if R_2 is a linear alkyl group with 3 carbon atoms, In some cases, R_1 does not contain a linear alkyl group having 3 or 7 carbon atoms.