JPH027941B2 - Manufacture of n-substituted-n-acetyl-2,6- dialkylaniline - Google Patents
Manufacture of n-substituted-n-acetyl-2,6- dialkylanilineInfo
- Publication number
- JPH027941B2 JPH027941B2 JP14930281A JP14930281A JPH027941B2 JP H027941 B2 JPH027941 B2 JP H027941B2 JP 14930281 A JP14930281 A JP 14930281A JP 14930281 A JP14930281 A JP 14930281A JP H027941 B2 JPH027941 B2 JP H027941B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- represented
- substituted
- dialkylaniline
- acetyl chloride
- 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
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 26
- 239000012346 acetyl chloride Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- -1 1,2-ethylene group Chemical group 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 3
- JJKWHOSQTYYFAE-UHFFFAOYSA-N 2-methoxyacetyl chloride Chemical compound COCC(Cl)=O JJKWHOSQTYYFAE-UHFFFAOYSA-N 0.000 description 3
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- YXWIRQHVEQIJOV-UHFFFAOYSA-N 2-ethyl-n-(1-methoxypropan-2-yl)-6-methylaniline Chemical compound CCC1=CC=CC(C)=C1NC(C)COC YXWIRQHVEQIJOV-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-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
- 238000006640 acetylation reaction Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 230000003032 phytopathogenic effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SMINYPCTNJDYGK-UHFFFAOYSA-N N-(2-ethyl-6-methylphenyl)-2-chloroacetamide Chemical compound CCC1=CC=CC(C)=C1NC(=O)CCl SMINYPCTNJDYGK-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は次式：
（式中、R1及びR2は互いに独立して各々メチ
ル基又はエチル基を表わし、R3は炭素原子数１
ないし３のアルキル基を表わし、Ａは１個又は２
個のメチル基で置換され得る１，２―エチレン
基、２―オキソ―１，２―エチレン基又は１―メ
チル―２―オキソ―１，２―エチレン基を表わ
す。）で表わされるＮ―置換―２，６―ジアルキ
ルアニリンと次式：
Ｘ―CH2―CO―Cl （）
（式中、Ｘは塩素原子または炭素原子数１ない
し３のアルコキシ基を表わす。）で表わされる塩
化アセチルとを反応させることにより次式：
（式中、R1，R2，R3、Ａ及びＸは前記と同じ
意味を表わす。）で表わされるＮ―置換―Ｎ―ア
セチル―２，６―ジアルキルアニリンを製造する
方法に関する。[Detailed description of the invention] The present invention is based on the following formula: (In the formula, R 1 and R 2 each independently represent a methyl group or an ethyl group, and R 3 has 1 carbon atom.
represents 1 to 3 alkyl groups, A is 1 or 2
represents a 1,2-ethylene group, a 2-oxo-1,2-ethylene group, or a 1-methyl-2-oxo-1,2-ethylene group which can be substituted with methyl groups. ) N-substituted- 2,6 -dialkylaniline represented by the following formula: By reacting with acetyl chloride represented by the following formula: The present invention relates to a method for producing N-substituted-N-acetyl-2,6-dialkylaniline represented by the formula (wherein R 1 , R 2 , R 3 , A and X have the same meanings as above).
式で表わされるＮ―置換―Ｎ―アセチル―
２，６―ジアルキルアニリンは、植物病因性微生
物に対する著しい作用を示し、それ故植物病因性
微生物に感染した裁培植物を保護するのに使用さ
れる。式で表わされるＮ―置換―Ｎ―アセチル
―２，６―ジアルキルアニリン及びその応用につ
いては例えば、米国特許第3952056号、第3937730
号、第4206228号及び第4200451号明細書に記載さ
れている。 N-substituted-N-acetyl- represented by the formula
2,6-Dialkylanilines exhibit a significant action against phytopathogenic microorganisms and are therefore used to protect cultivated plants infected with phytopathogenic microorganisms. For N-substituted-N-acetyl-2,6-dialkylanilines represented by the formula and their applications, see, for example, U.S. Pat.
No. 4206228 and No. 4200451.
式で表わされるＮ―置換―Ｎ―アセチル―
２，６―ジアルキルアニリンを、相当する式で
表わされるＮ―置換―２，６―ジアルキルアニリ
ンと式で表わされる塩化アセチルとの反応によ
り製造する方法は公知である。この反応は水酸化
ナトリウム、炭酸ナトリウム、Ｎ，Ｎ―ジメチル
アニリン及びトリエチルアミンの如き無機又は有
機塩基の存在下及び不存在下で行うことができ
る。しかしながら水性無機塩基の存在下でアセチ
ル化を実施するには、加水分解の結果、かなりの
量の塩化アセチルが失なわれるので、大過剰の塩
化アセチルが必要とされる。このことは一方では
非経済的であり、他方では加水分解の結果生成す
る酸を廃液から除去しなければならぬので、生態
学的な問題が起るという理由で望ましくない。大
過剰の塩化アセチルを使用するという不利益は、
実際には有機塩基を使用することによつて避ける
ことができるが、しかしこの場合には生成するそ
れぞれのアミン塩酸塩を分離し、更に対応するア
ミンを再生しなければならず、附加的経費の増加
をもたらす要因である。 N-substituted-N-acetyl- represented by the formula
Methods for preparing 2,6-dialkylanilines by reaction of N-substituted-2,6-dialkylanilines of the corresponding formula with acetyl chloride of the formula are known. This reaction can be carried out in the presence or absence of inorganic or organic bases such as sodium hydroxide, sodium carbonate, N,N-dimethylaniline and triethylamine. However, carrying out the acetylation in the presence of an aqueous inorganic base requires a large excess of acetyl chloride, since significant amounts of acetyl chloride are lost as a result of hydrolysis. This is undesirable because, on the one hand, it is uneconomical and, on the other hand, it causes ecological problems, since the acid produced as a result of the hydrolysis must be removed from the waste liquid. The disadvantage of using a large excess of acetyl chloride is that
In practice this can be avoided by using an organic base, but in this case each amine hydrochloride formed must be separated and the corresponding amine regenerated, resulting in additional costs. This is the factor that causes the increase.
アセチル化反応の中には塩基が存在せず、且つ
無溶媒で実施できるものがあるが、式で表わさ
れるＮ―置換―２，６―ジアルキルアニリンと式
で表わされる塩化アセチルとの反応は塩基が存
在しない場合には常に不活性溶媒の存在を必要と
する。溶媒が全く存在しないときには、取扱いの
難しい暗色の非常に粘稠な生成物が得られ、所望
の生成物は非常な低収率で得られるに過ぎない。 Some acetylation reactions do not require a base and can be carried out without a solvent, but the reaction between N-substituted-2,6-dialkylaniline represented by the formula and acetyl chloride represented by the formula requires a base. The presence of an inert solvent is required whenever an inert solvent is not present. When no solvent is present, a dark, very viscous product is obtained which is difficult to handle and the desired product is obtained only in very low yields.
式で表わされれるＮ―置換―２，６―ジアル
キルアニリンと式で表わされる塩化アセチルと
の反応を不活性溶媒中で塩基を使用せずに行う
と、反応中に生成した塩化水素を直ちにガス相と
して分離できるという利点がある。しかしながら
経済的理由から、実質的に等モル量の塩化アセチ
ルが使用されるので、反応を完全に遂行し、塩化
水素を完全に分離するためには長い反応時間が必
要とされる。概して、反応混合物を90ないし110
℃で数時間加熱することが必要であり、その結果
第二の反応と樹脂状の副生物の生成が促進され
る。これらの第二の反応の結果として、有効物質
の収量が減少する。 When the reaction between the N-substituted-2,6-dialkylaniline represented by the formula and the acetyl chloride represented by the formula is carried out in an inert solvent without the use of a base, the hydrogen chloride formed during the reaction is immediately released. It has the advantage that it can be separated as a gas phase. However, for economic reasons, substantially equimolar amounts of acetyl chloride are used, so that long reaction times are required to carry out the reaction completely and to completely separate off the hydrogen chloride. Generally, the reaction mixture is heated between 90 and 110
Heating for several hours at °C is necessary, thereby accelerating the secondary reaction and the formation of resinous by-products. As a result of these secondary reactions, the yield of active substance is reduced.
上記の方法はそれらに伴う不都合のために非経
済的なものである。それ故、本発明の目的は簡単
で経済的、しかも商業的規模において好収率で、
式で表わされるＮ―置換―Ｎ―アセチル―２，
６―ジアルキルアニリンを製造し得る方法を提供
することにある。 The above methods are uneconomical due to the disadvantages associated with them. Therefore, it is an object of the present invention to provide a simple, economical and efficient method with good yields on a commercial scale.
N-substituted-N-acetyl-2, represented by the formula
The object of the present invention is to provide a method for producing 6-dialkylaniline.
本発明者等は、式で表わされるＮ―置換―
２，６―ジアルキルアニリンと式で表わされる
塩化アセチルとの反応を、溶媒としての過剰の式
で表わされる塩化アセチル中で行うことによ
り、式で表わされるＮ―置換―Ｎ―アセチル―
２，６―ジアルキルアニリンが高収率、高純度で
製造し得ることを見出した。本発明による改良さ
れた製造方法は、式で表わされるＮ―置換―
２，６―ジアルキルアニリンと、該Ｎ―置換―
２，６―ジアルキルアニリン１モルあたり２ない
し20モルの式で表わされる塩化アセチルとを、
過剰量の式で表わされる塩化アセチルを唯一の
溶媒として、塩基の不存在下で反応せしめ、式
で表わされる過剰の塩化アセチルを溜去し、生成
した式で表わされるＮ―置換―Ｎ―アセチル―
２，６―ジアルキルアニリンを中性になる迄水洗
した後、得られた製品を乾燥することからなる。 The present inventors have discovered that N-substituted-
By carrying out the reaction of 2,6-dialkylaniline with acetyl chloride represented by the formula in excess acetyl chloride represented by the formula as a solvent, N-substituted-N-acetyl- represented by the formula
It has been found that 2,6-dialkylaniline can be produced in high yield and purity. The improved manufacturing method according to the present invention is characterized in that N-substituted-
2,6-dialkylaniline and the N-substituted-
2 to 20 mol of acetyl chloride represented by the formula per mol of 2,6-dialkylaniline,
Using an excess amount of acetyl chloride represented by the formula as the only solvent, the reaction is carried out in the absence of a base, and the excess acetyl chloride represented by the formula is distilled off to produce N-substituted-N-acetyl represented by the formula ―
The process consists of washing the 2,6-dialkylaniline with water until it becomes neutral, and then drying the resulting product.
本発明によれば、式で表わされるＮ―置換―
２，６―ジアルキルアニリン１モル当り、２ない
し20モル、好ましくは４ないし８モルの式で表
わされる塩化アセチルが使用される。70℃ないし
反応混合物の還流温度、好ましくは反応混合物の
還流温度で反応が都合よく進行する。 According to the present invention, N-substituted-
2 to 20 mol, preferably 4 to 8 mol, of acetyl chloride of the formula are used per mole of 2,6-dialkylaniline. The reaction conveniently proceeds from 70°C to the reflux temperature of the reaction mixture, preferably at the reflux temperature of the reaction mixture.
過剰の式で表わされる塩化アセチル溜去した
後、50ないし110℃の水で、得られた生成物を水
洗する。水洗を数回繰返すと有利である。洗浄水
にアルカリ、特に水酸化ナトリウム又は水酸化カ
リウムを、PHが４ないし10になるのに充分な量加
えるのも有利である。続いて生成物を、場合によ
り更に純水で洗浄した後、100ないし120℃で真空
乾燥する。 After distilling off the excess acetyl chloride, the product obtained is washed with water at 50 to 110°C. It is advantageous to repeat the washing several times. It is also advantageous to add an alkali, in particular sodium hydroxide or potassium hydroxide, to the wash water in an amount sufficient to bring the pH to between 4 and 10. The product is then optionally further washed with pure water and then vacuum dried at 100 to 120°C.
本発明の方法は回分的に行うことも、又連続的
に行うこともできる。 The method of the invention can be carried out batchwise or continuously.
本発明の方法は、式で表わされるＮ―置換―
２，６―ジアルキルアニリンを沸騰している式
で表わされる塩化アセチルの中に加え、反応完了
後、過剰の塩化アセチルを減圧下溜去することに
より、回分的に有利に行われる。 The method of the present invention provides N-substituted-
It is advantageously carried out batchwise by adding the 2,6-dialkylaniline to boiling acetyl chloride of the formula and, after the reaction is complete, removing excess acetyl chloride under reduced pressure.
本発明方法を連続的に実施するには、式で表
わされる塩化アセチルと式で表わされるＮ―置
換―２，６―ジアルキルアニリンとを同時に、反
応温度で、反応容器に仕込み、そのあとで直ぐ
に、混合物を真空濃縮するのが有利である。本発
明方法を実施するための連続的方法は２ないし４
段のカスケード反応器又は流下膜型反応器におい
て有利に遂行することができる。 To carry out the process of the invention continuously, acetyl chloride of the formula and an N-substituted-2,6-dialkylaniline of the formula are simultaneously charged into a reaction vessel at the reaction temperature, and then immediately , it is advantageous to concentrate the mixture in vacuo. The continuous method for carrying out the method of the invention is 2 to 4
It can advantageously be carried out in a stage cascade reactor or in a falling film reactor.
反応中に生成した塩化水素は気体状態で分離さ
れ、鋼製シリンダーに圧入されるか、水に溶解し
て濃塩酸とするか、又は酸化して塩素にする。 The hydrogen chloride produced during the reaction is separated in gaseous form and forced into a steel cylinder, dissolved in water to form concentrated hydrochloric acid, or oxidized to chlorine.
出発物質として使用され、式で表わされるＮ
―置換―２，６―ジアルキルアニリンの中では、
Ａが１，２―エチレン基、１―メチル―１，２―
エチレン基、又は１―メチル―２―オキソ―１，
２―エチレン基を表わし、R3がメチル基を表わ
すものが好ましい。式で表わされる出発物質と
して特に望ましいものは、Ｎ―（1′―メチル―
2′―メトキシエチル）―２―エチル―６―メチル
アニリン及びＮ―（1′―メトキシカルブニルエチ
ル）―２，６―ジメチルアニリンである。式で
表わされる塩化アセチルの中では塩化クロロアセ
チルと塩化メトキシアセチルが好ましい。 N used as a starting material and represented by the formula
Among the -substituted-2,6-dialkylanilines,
A is 1,2-ethylene group, 1-methyl-1,2-
Ethylene group, or 1-methyl-2-oxo-1,
Preferably, it represents a 2-ethylene group and R 3 represents a methyl group. A particularly desirable starting material of the formula is N-(1'-methyl-
They are 2'-methoxyethyl)-2-ethyl-6-methylaniline and N-(1'-methoxycarbunylethyl)-2,6-dimethylaniline. Among the acetyl chlorides represented by the formula, chloroacetyl chloride and methoxyacetyl chloride are preferred.
有害物質による環境汚染が最少限に減少される
ことが本発明方法の特に有利な点である。本発明
方法により得られる生成物は、純度が高く、生成
物の収率が優れている。式で表わされるＮ―置
換―２，６―ジアルキルアニリンと式で表わさ
れる塩化アセチルとの反応は極めて急速に進むの
で、反応器中の反応物の滞留時間を短かく保つこ
とができ、その結果、所定の量の生成物の製造の
ための反応器の大きさを比較的小さくしておくこ
とができる。式で表わされる塩化アセチルを反
応に再使用できるため、このもの損失が避けられ
る。最後に本発明の方法のもう一つの利点は、反
応物の量的比率を広い限定範囲内で変えても最終
生成物の品質に不利に影響しないことである。 It is a particular advantage of the process according to the invention that environmental pollution by harmful substances is reduced to a minimum. The product obtained by the method of the present invention has high purity and excellent product yield. Since the reaction between the N-substituted-2,6-dialkylaniline represented by the formula and the acetyl chloride represented by the formula proceeds very rapidly, the residence time of the reactants in the reactor can be kept short, resulting in , the size of the reactor for the production of a given amount of product can be kept relatively small. Since the acetyl chloride represented by the formula can be reused in the reaction, its loss is avoided. Finally, another advantage of the process according to the invention is that the quantitative proportions of the reactants can be varied within wide limits without adversely affecting the quality of the final product.
それ故本発明の方法によつて式で表わされる
Ｎ―置換―Ｎ―アセチル―２，６―ジアルキルア
ニリンを簡単な方法で、高収率、高純度で製造す
ることができる。 Therefore, by the method of the present invention, N-substituted-N-acetyl-2,6-dialkylaniline represented by the formula can be produced in a simple manner, in high yield, and with high purity.
本発明の方法を次の実施例によつて説明する。 The method of the invention is illustrated by the following example.
実施例 １
撹拌器、滴下漏斗、コンデンサーの付いた３
三つ口フラスコに塩化クロロアセチル1356g（12
モル）を入れ、沸騰する迄加熱する。次にＮ―
（2′―メトキシ―1′―メチルエチル）―２―エチ
ル―６―メチルアニリン207g（１モル）を、溶液
が均一に沸騰し、ガスを発生する状態を常に保て
る速さで滴下する。Ｎ―（2′―メトキシ―1′―メ
チルエチル）―２―エチル―６―メチルアニリン
を加えた後、過剰の塩化クロロアセチルを回転蒸
発器により、15mmHgの圧力で蒸発させる。この
ようにして得た粗製品を分液漏斗中で200mlの水
により洗浄する。このときのこの洗浄水は30％の
水酸化ナトリウム溶液を添加してPH８に調整して
おく。水相を分離した後、生成物を、先づ水で２
度洗い、次に110℃、15mmHgで30分間乾燥する。
Ｎ―（2′―メトキシ―1′―メチルエチル）―Ｎ―
クロロアセチル―２―エチル―６―メチルアニリ
ンの収量は273.8g（理論量の96.6％）である。Example 1 3 with stirrer, addition funnel and condenser
1356 g of chloroacetyl chloride (12
) and heat until it boils. Next N-
207 g (1 mol) of (2'-methoxy-1'-methylethyl)-2-ethyl-6-methylaniline is added dropwise at a rate that allows the solution to uniformly boil and gas to be generated. After adding the N-(2'-methoxy-1'-methylethyl)-2-ethyl-6-methylaniline, the excess chloroacetyl chloride is evaporated off in a rotary evaporator at a pressure of 15 mm Hg. The crude product thus obtained is washed with 200 ml of water in a separatory funnel. The washing water at this time is adjusted to pH 8 by adding 30% sodium hydroxide solution. After separating the aqueous phase, the product was first diluted with water.
Wash twice and then dry at 110℃ and 15mmHg for 30 minutes.
N-(2'-methoxy-1'-methylethyl)-N-
The yield of chloroacetyl-2-ethyl-6-methylaniline is 273.8 g (96.6% of theory).
実施例 ２
撹拌器、滴下漏斗、コンデンサーの付いた2l三
つ口フラスコに塩化メトキシアセチル868g（８モ
ル）を入れ沸騰する迄加熱する。次にＮ―（1′―
メトキシカルボニルエチル）―２，６―ジメチル
アニリン165.5g（0.8モル）を、溶液が均一に沸騰
し、ガスを発生する状態を常に保てる速さで滴下
する。Ｎ―（1′―メトキシカルボニルエチル）―
２，６―ジメチルアニリンを加えた後、過剰の塩
化メトキシアセチルを回転蒸発器により、15mm
Hgの圧力で蒸発させる。このようにして得た粗
生成物を水100mlにより80℃で洗浄する。このと
きのこの洗浄水は1Nの水酸化ナトリウムを添加
してPHを４に調整をしておく。水相を分離した
後、製品を先づ温水で２度洗浄し、次に110℃、
15mmHgで１時間乾燥する。Ｎ―（1′―メトキシ
カルボニルエチル）―Ｎ―メトキシアセチル―
２，６―メチルアニリンの収量は217.3g（理論量
の97.2％）である。Example 2 868 g (8 mol) of methoxyacetyl chloride is placed in a 2L three-necked flask equipped with a stirrer, dropping funnel, and condenser and heated until it boils. Next, N-(1'-
165.5 g (0.8 mol) of methoxycarbonylethyl-2,6-dimethylaniline is added dropwise at such a rate that the solution is uniformly boiled and gas is constantly evolved. N-(1'-methoxycarbonylethyl)-
After adding 2,6-dimethylaniline, excess methoxyacetyl chloride was removed by rotary evaporation to 15 mm
Evaporate at pressure of Hg. The crude product thus obtained is washed with 100 ml of water at 80°C. At this time, the pH of the washing water was adjusted to 4 by adding 1N sodium hydroxide. After separating the aqueous phase, the product was first washed twice with hot water, then heated at 110°C.
Dry at 15mmHg for 1 hour. N-(1'-methoxycarbonylethyl)-N-methoxyacetyl-
The yield of 2,6-methylaniline is 217.3 g (97.2% of theory).
Claims (1)
ル基又はエチル基を表わし、R3は炭素原子数１
ないし３のアルキル基を表わし、Ａは１個又は２
個のメチル基で置換され得る１，２―エチレン
基、２―オキソ―１，２―エチレン基又は１―メ
チル―２―オキソ―１，２―エチレン基を表わ
す。）で表わされるＮ―置換―２，６―ジアルキ
ルアニリンと、該Ｎ―置換―２，６―ジアルキル
アニリン１モルあたり２ないし20モルの次式： Ｘ―CH2―CO―Cl （） （式中、Ｘは塩素原子又は炭素原子数１ないし
３のアルコキシ基を表わす。）で表わされる塩化
アセチルとを、過剰量の式で表わされる塩化ア
セチルを唯一の溶媒として、塩基の不存在下で反
応せしめ、過剰の式で表わされる塩化アセチル
を蒸溜し、生成された次式： （式中、R1，R2，Ａ，R3及びＸは前記と同じ
意味を表わす。）で表わされるＮ―置換―Ｎ―ア
セチル―２，６―ジアルキルアニリンを中性にな
る迄水で洗浄した後に、生成物を乾燥することか
らなる前記の式で表わされるＮ―置換―Ｎ―ア
セチル―２，６―ジアルキルアニリンの製造方
法。 ２ 式で表わされるＮ―置換―２，６―ジアル
キルアニリン１モル当り４ないし８モルの式で
表わされる塩化アセチルを使用する特許請求の範
囲第１項記載の製造方法。 ３ 式で表わされるＮ―置換―２，６―ジアル
キルアニリンと式で表わされる塩化アセチルと
の反応が70℃ないし反応混合物の還流温度の温度
範囲で行われる特許請求の範囲第１項記載の製造
方法。 ４ 式で表わされるＮ―置換―２，６―ジアル
キルアニリンと式で表わされる塩化アセチルと
の反応が反応混合物の還流温度で行われる特許請
求の範囲第１項記載の製造方法。 ５ 過剰の式で表わされる塩化アセチルを蒸溜
によつて除去した後に得られる式で表わされる
Ｎ―置換―Ｎ―アセチル―２，６―ジアルキルア
ニリンを50ないし100℃の水で洗浄する特許請求
の範囲第１項記載の製造方法。 ６ 洗浄水のPHを４ないし10とするに十分な量の
アルカリが洗浄水に加えられる特許請求の範囲第
１項及び第５項記載の製造方法。[Claims] Primary formula: (In the formula, R 1 and R 2 each independently represent a methyl group or an ethyl group, and R 3 has 1 carbon atom.
represents 1 to 3 alkyl groups, A is 1 or 2
represents a 1,2-ethylene group, a 2-oxo-1,2-ethylene group, or a 1-methyl-2-oxo-1,2-ethylene group which can be substituted with methyl groups. ) of the following formula : where X represents a chlorine atom or an alkoxy group having 1 to 3 carbon atoms. By distilling the excess acetyl chloride, the following formula is produced: (In the formula, R 1 , R 2 , A, R 3 and A method for producing N-substituted-N-acetyl-2,6-dialkylaniline represented by the above formula, which comprises drying the product after washing. 2. The manufacturing method according to claim 1, wherein 4 to 8 moles of acetyl chloride represented by the formula are used per mole of N-substituted-2,6-dialkylaniline represented by the formula. 3. The production according to claim 1, wherein the reaction between the N-substituted-2,6-dialkylaniline represented by the formula and the acetyl chloride represented by the formula is carried out at a temperature ranging from 70°C to the reflux temperature of the reaction mixture. Method. 4. The production method according to claim 1, wherein the reaction between the N-substituted-2,6-dialkylaniline represented by the formula and the acetyl chloride represented by the formula is carried out at the reflux temperature of the reaction mixture. 5. A patent claim in which N-substituted-N-acetyl-2,6-dialkylaniline represented by the formula obtained after removing excess acetyl chloride represented by the formula by distillation is washed with water at 50 to 100°C The manufacturing method according to scope 1. 6. The manufacturing method according to claims 1 and 5, wherein a sufficient amount of alkali is added to the washing water to adjust the pH of the washing water to 4 to 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14930281A JPH027941B2 (en) | 1981-09-21 | 1981-09-21 | Manufacture of n-substituted-n-acetyl-2,6- dialkylaniline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14930281A JPH027941B2 (en) | 1981-09-21 | 1981-09-21 | Manufacture of n-substituted-n-acetyl-2,6- dialkylaniline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5862144A JPS5862144A (en) | 1983-04-13 |
| JPH027941B2 true JPH027941B2 (en) | 1990-02-21 |
Family
ID=15472176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14930281A Expired JPH027941B2 (en) | 1981-09-21 | 1981-09-21 | Manufacture of n-substituted-n-acetyl-2,6- dialkylaniline |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH027941B2 (en) |
-
1981
- 1981-09-21 JP JP14930281A patent/JPH027941B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5862144A (en) | 1983-04-13 |
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