JPH0247994B2 - NNARUKIRU22CHENIRUKETONNOSEIZOHO - Google Patents
NNARUKIRU22CHENIRUKETONNOSEIZOHOInfo
- Publication number
- JPH0247994B2 JPH0247994B2 JP26713484A JP26713484A JPH0247994B2 JP H0247994 B2 JPH0247994 B2 JP H0247994B2 JP 26713484 A JP26713484 A JP 26713484A JP 26713484 A JP26713484 A JP 26713484A JP H0247994 B2 JPH0247994 B2 JP H0247994B2
- Authority
- JP
- Japan
- Prior art keywords
- thiophene
- carbon atoms
- alkyl
- general formula
- present
- 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.)
- Expired - Lifetime
Links
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 14
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- 229930192474 thiophene Natural products 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- -1 alkyl 2-thienyl ketone Chemical compound 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- WYJOVVXUZNRJQY-UHFFFAOYSA-N 2-Acetylthiophene Chemical compound CC(=O)C1=CC=CS1 WYJOVVXUZNRJQY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
〔発明の技術分野〕
本発明は電気的表示材料として用いられる液晶
物質をはじめ各種の有用な化合物の製造原料又は
製造中間として使用されるｎ−アルキル２−チエ
ニルケトンの製造法に関する。
〔発明の従来技術〕
ｎ−アルキル２−チエニルケトンの製造法とし
ては触媒として無水塩化第二錫を使用してチオフ
エンとｎ−アルキルカルボン酸塩化物を反応させ
る方法（G.M.Badger，H.J.Rodda.andW.H.F.
Sasse，J.C.S.，1954，4162）が知られている。
しかしこの方法は発煙性の無水塩化第二錫や毒
性の高いベンゼンを使用しなければならないとい
う欠点がある。
一方、チオフエンと無水酢酸を撹拌しながら少
量の過塩素酸を滴下してメチル２−チエニルケト
ンを製造する方法が知られている〔G.N.
Dorofeenko，Zhur.Vsesoyuz.Khim.
Obshchestvaim.D.I.Mendeleeva 5354（1960）；
Chem.Abstr.，54，22563g〕。
〔発明の目的〕
本発明者は上記公知例における無水酢酸の代り
に炭素数の多い無水ｎ−アルキルカルボン酸を使
用すれば、常温で目的とするｎ−アルキル２−チ
エニルケトンが高収率で得られることを見い出し
た。
本発明は以上のような知見に基づいてなされた
ものでｎ−アルキル２−チエニルケトンを容易に
製造する方法を提供することを目的とする。
〔発明の構成〕
すなわち本発明は、チオフエンと、
一般式（PCO）2O ………（）
（式中、Ｒは炭素原子数２〜７の直鎖アルキル基
を示す）
で表わされる無水ｎ−アルキルカルボン酸とを、
触媒として過塩素酸を用いて反応させ、
一般式
（式中、Ｒは前記と同一意味）
で表わされる化合物を得ることを特徴とするｎ−
アルキル２−チエニルケトンの製造法である。
式（）の化合物においてＲは炭素原子数２〜
７の直鎖アルキル基であり、特に炭素原子数４〜
７が好ましい。
本発明の方法においては、ベンゼン、エーテル
などの有機溶媒中で製造してもよいが、特に無溶
媒で行なうのが反応処理工程上好都合である。温
度は通常室温あるいはやや上昇した温度で行なう
が、いずれにしても外部からの加熱あるいは冷却
は必要としない。
また式（）の化合物はチオフエンに対し等モ
ル用いるのが好ましい。
〔発明の実施例〕
次に実施例を挙げて本発明を具体的に説明す
る。
実施例 １
チオフエン42ｇ（0.5モル）と無水プロピオン
酸〔（C2H5CO）2O〕75ｇ（0.5モル）の混合物に
撹拌下で60％過塩素酸10滴を室温で滴下して２時
間撹拌した。この混合物を水200mlに加え、有機
層を分離し、炭酸ナトリウム溶液で中和し、水洗
後無水芒硝で乾燥し、反応生成物を減圧下で蒸留
して下記の化合物62.5ｇを得た。収率89.3％。沸
点124〜125℃／30mmHg。
NMR（δ，CCl4）
1.20（ｔ，3H，−CH3）
2.88（ｑ，2H，−CH2−）
7.13（ｑ，1H，Hb）
7.55〜7.61（ｍ，2H，HaおよびHc）
実施例 ２〜６
実施例１における無水プロピオン酸
〔（C2H5CO）2O〕の代りに下記の化合物0.5モルを
各々用いる以外は同実施例と同様にして第１表に
示す化合物を得た。
（ｎ−C3H7CO）2O
（ｎ−C4H9CO）2O
（ｎ−C5H11CO）2O
（ｎ−C6H13CO）2O
（ｎ−C7H15CO）2O
[Technical Field of the Invention] The present invention relates to a method for producing n-alkyl 2-thienyl ketone, which is used as a raw material or intermediate in the production of various useful compounds, including liquid crystal substances used as electrical display materials. [Prior Art of the Invention] A method for producing n-alkyl 2-thienyl ketone is a method of reacting thiophene and n-alkylcarboxylic acid chloride using anhydrous tin chloride as a catalyst (GMBadger, HJRodda.andW.HF
Sasse, JCS, 1954 , 4162) is known. However, this method has the disadvantage of requiring the use of fuming anhydrous stannic chloride and highly toxic benzene. On the other hand, there is a known method for producing methyl 2-thienyl ketone by dropping a small amount of perchloric acid into thiophene and acetic anhydride while stirring [GN
Dorofeenko, Zhur.Vsesoyuz.Khim.
Obshchestvaim.DIMendeleeva 5354 (1960);
Chem.Abstr., 54, 22563g]. [Object of the Invention] The present inventor has discovered that by using n-alkyl carboxylic anhydride with a large number of carbon atoms instead of acetic anhydride in the above-mentioned known examples, the desired n-alkyl 2-thienyl ketone can be produced in high yield at room temperature. I found out what I can get. The present invention was made based on the above findings, and an object of the present invention is to provide a method for easily producing n-alkyl 2-thienyl ketone. [Structure of the Invention] That is, the present invention provides thiophene and an anhydride n represented by the general formula (PCO) 2 O (in the formula, R represents a straight-chain alkyl group having 2 to 7 carbon atoms). -alkyl carboxylic acid,
The reaction is carried out using perchloric acid as a catalyst, and the general formula (wherein R has the same meaning as above)
This is a method for producing alkyl 2-thienyl ketone. In the compound of formula (), R has 2 to 2 carbon atoms.
7 straight-chain alkyl groups, especially those having 4 to 4 carbon atoms.
7 is preferred. Although the method of the present invention may be produced in an organic solvent such as benzene or ether, it is particularly convenient to carry out the reaction process without a solvent. The temperature is usually room temperature or slightly elevated, but in any case no external heating or cooling is required. Further, it is preferable to use the compound of formula () in an equimolar amount to thiophene. [Examples of the Invention] Next, the present invention will be specifically explained with reference to Examples. Example 1 10 drops of 60% perchloric acid were added dropwise to a mixture of 42 g (0.5 mol) of thiophene and 75 g (0.5 mol) of propionic anhydride [(C 2 H 5 CO) 2 O] under stirring at room temperature for 2 hours. Stirred. This mixture was added to 200 ml of water, the organic layer was separated, neutralized with sodium carbonate solution, washed with water and dried over anhydrous sodium sulfate, and the reaction product was distilled under reduced pressure to obtain 62.5 g of the following compound. Yield 89.3%. Boiling point 124-125℃/30mmHg. NMR (δ, CCl 4 ) 1.20 (t, 3H, -CH 3 ) 2.88 (q, 2H, -CH 2 -) 7.13 (q, 1H, Hb) 7.55-7.61 (m, 2H, Ha and Hc) Examples 2-6 The compounds shown in Table 1 were obtained in the same manner as in Example 1, except that 0.5 mol of each of the following compounds was used instead of propionic anhydride [(C 2 H 5 CO) 2 O] in Example 1. . (n-C 3 H 7 CO) 2 O (n-C 4 H 9 CO) 2 O (n-C 5 H 11 CO) 2 O (n-C 6 H 13 CO) 2 O (n-C 7 H 15CO ) 2O
【表】【table】
本発明の方法によれば炭素原子数の多いアルカ
ノイル基をチオフエンの２位の位置に有するチオ
フエン誘導体が無溶媒かつ常温で容易に製造でき
る。
According to the method of the present invention, a thiophene derivative having an alkanoyl group having a large number of carbon atoms at the 2-position of thiophene can be easily produced without a solvent and at room temperature.
Claims (1)
を示す） で表わされる無水ｎ−アルキルカルボン酸とを、
触媒として過塩素酸を用いて反応させ、 一般式 （式中、Ｒは前記と同一意味） で表わされる化合物を得ることを特徴とするｎ−
アルキル２−チエニルケトンの製造法。[Scope of Claims] 1 Thiophene and an n-alkylcarboxylic anhydride represented by the general formula (RCO) 2 O (wherein R represents a straight-chain alkyl group having 2 to 7 carbon atoms),
The reaction is carried out using perchloric acid as a catalyst, and the general formula (wherein R has the same meaning as above)
Method for producing alkyl 2-thienyl ketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26713484A JPH0247994B2 (en) | 1984-12-17 | 1984-12-17 | NNARUKIRU22CHENIRUKETONNOSEIZOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26713484A JPH0247994B2 (en) | 1984-12-17 | 1984-12-17 | NNARUKIRU22CHENIRUKETONNOSEIZOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61143374A JPS61143374A (en) | 1986-07-01 |
| JPH0247994B2 true JPH0247994B2 (en) | 1990-10-23 |
Family
ID=17440545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26713484A Expired - Lifetime JPH0247994B2 (en) | 1984-12-17 | 1984-12-17 | NNARUKIRU22CHENIRUKETONNOSEIZOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0247994B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100455578C (en) * | 2003-12-17 | 2009-01-28 | 住友精化株式会社 | The preparation method of 2-acylthiophene compound |
-
1984
- 1984-12-17 JP JP26713484A patent/JPH0247994B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61143374A (en) | 1986-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE3881817T2 (en) | 3,5-Dihydroxy-6,8-nonadienoic acids and derivatives as hypocholesterolemic agents. | |
| JPS5940813B2 (en) | Magnesium compounds and their production method | |
| JPH0247994B2 (en) | NNARUKIRU22CHENIRUKETONNOSEIZOHO | |
| EP0187674A2 (en) | Process for the preparation of polyhalogenated carbinols | |
| US3910958A (en) | Process for preparing arylacetic acids and esters thereof | |
| US4080505A (en) | α-Chlorocarboxylic acids | |
| JPH0537140B2 (en) | ||
| US4596887A (en) | Process for preparing dihalovinylcyclopropanecarboxylates | |
| KATO et al. | Reaction of Ethyl 4-Halo-3-oxobutanoate with Diethyl Malonate, Methyl Cyanoacetate, and Malononitrile | |
| JP2527961B2 (en) | Benzoic acid ester derivative and method for producing the same | |
| JPS5838261A (en) | Novel 1,3-disubstituted imidazole derivative and its preparation | |
| JPS597135A (en) | Preparation of malonic acid ester | |
| US4649213A (en) | Process for producing an α-aromatic group substituted alkanoic acid derivative | |
| US5359110A (en) | Process for the preparation of a R-alpha cyclopentenones and R-alpha and R-omega cyclopentanoids | |
| JPS61106537A (en) | Production of cyclopentylacetic acid ester | |
| JPS6030678B2 (en) | Method for producing pyrazolooxazine carboxylic acid derivatives | |
| JPS58194837A (en) | Preparation of diphenylmethane derivative | |
| JPS5929052B2 (en) | Production method of triketone hydrate | |
| JPH026433A (en) | Optically active fluorine-containing malonic acid ester derivative and production thereof | |
| KR20020073751A (en) | Beta-substituted-gamma-butyrolactones and preparation process thereof | |
| WO1983003411A1 (en) | Pharmaceutical compound and process for the manufacture thereof | |
| JPH03127780A (en) | Anilinopyrimidine derivative | |
| JPS6124568A (en) | Method for producing dihydropyridine ester | |
| JPH0313225B2 (en) | ||
| JPH03153660A (en) | Sulfonic acid ester of 4-halo-3-hydroxybutane nitrile and preparation thereof |