JPH0229067B2 - - Google Patents
Info
- Publication number
- JPH0229067B2 JPH0229067B2 JP58013673A JP1367383A JPH0229067B2 JP H0229067 B2 JPH0229067 B2 JP H0229067B2 JP 58013673 A JP58013673 A JP 58013673A JP 1367383 A JP1367383 A JP 1367383A JP H0229067 B2 JPH0229067 B2 JP H0229067B2
- Authority
- JP
- Japan
- Prior art keywords
- methylaniline
- isopropyl
- methyl
- isopropylaniline
- reaction
- 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
- IGDKJXXPUDSVMV-UHFFFAOYSA-N 3-methyl-n-propan-2-ylaniline Chemical compound CC(C)NC1=CC=CC(C)=C1 IGDKJXXPUDSVMV-UHFFFAOYSA-N 0.000 claims description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 4
- FRCFWPVMFJMNDP-UHFFFAOYSA-N n-propan-2-ylaniline Chemical compound CC(C)NC1=CC=CC=C1 FRCFWPVMFJMNDP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- MKYJJJUJQHKWNM-UHFFFAOYSA-N 3-methyl-4-propan-2-ylaniline Chemical compound CC(C)C1=CC=C(N)C=C1C MKYJJJUJQHKWNM-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- DGQQLJUOIVFNLX-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1.CC1=CC=CC(N)=C1 DGQQLJUOIVFNLX-UHFFFAOYSA-N 0.000 description 19
- JJYPMNFTHPTTDI-UHFFFAOYSA-N meta-toluidine Natural products CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 16
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 239000011592 zinc chloride Substances 0.000 description 8
- 235000005074 zinc chloride Nutrition 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- SFTBLNXWRAQUHE-UHFFFAOYSA-N 3-methyl-n,n-di(propan-2-yl)aniline Chemical compound CC(C)N(C(C)C)C1=CC=CC(C)=C1 SFTBLNXWRAQUHE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- WWRCMNKATXZARA-UHFFFAOYSA-N 1-Isopropyl-2-methylbenzene Chemical compound CC(C)C1=CC=CC=C1C WWRCMNKATXZARA-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- WAMQUKAVKNSKAX-UHFFFAOYSA-N 2-methyl-4-nitro-1-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C([N+]([O-])=O)C=C1C WAMQUKAVKNSKAX-UHFFFAOYSA-N 0.000 description 1
- IJALWSVNUBBQRA-UHFFFAOYSA-N 4-Isopropyl-3-methylphenol Chemical compound CC(C)C1=CC=C(O)C=C1C IJALWSVNUBBQRA-UHFFFAOYSA-N 0.000 description 1
- ZSTKODDIHPJZBV-UHFFFAOYSA-N 4-chloro-2-methyl-1-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(Cl)C=C1C ZSTKODDIHPJZBV-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000007126 N-alkylation reaction Methods 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- RQZGOIJRSJWNRB-UHFFFAOYSA-N n-methyl-4-propan-2-ylaniline Chemical compound CNC1=CC=C(C(C)C)C=C1 RQZGOIJRSJWNRB-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- LRTFPLFDLJYEKT-UHFFFAOYSA-N para-isopropylaniline Chemical compound CC(C)C1=CC=C(N)C=C1 LRTFPLFDLJYEKT-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005932 reductive alkylation reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- -1 zinc chloride N-isopropyl-3-methylaniline Chemical compound 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【発明の詳細な説明】
本発明は３―メチル―４―イソプロピルアニリ
ンの製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 3-methyl-4-isopropylaniline.
さらに詳しくはＮ―イソプロピル―３―メチル
アニリンをプロピレン及びフリーデル・クラフツ
型触媒の存在下で加熱することを特徴とする３―
メチル―４―イソプロピルアニリンの製造方法に
関する。 More specifically, 3- is characterized in that N-isopropyl-3-methylaniline is heated in the presence of propylene and a Friedel-Crafts type catalyst.
The present invention relates to a method for producing methyl-4-isopropylaniline.
３―メチル―４―イソプロピルアニリンは農薬
中間体として重要であり、近年需要の増大がみこ
まれ、かつ経済的にもその価置が評価されてお
り、その円滑な供給が望まれているのである。 3-Methyl-4-isopropylaniline is important as an intermediate for agricultural chemicals, and its demand is expected to increase in recent years, and its value is evaluated economically, so its smooth supply is desired. .
３―メチル―４―イソプロピルアニリンを得る
方法として
(1) ２―イソプロピルトルエンをニトロ化し蒸留
分離して得られる３―メチル―４―イソプロピ
ルニトロベンゼンを水素還元等適当な方法で還
元する方法
(2) ３―メチル―４―イソプロピルフエノールの
アミノ化
(3) ３―メチル―４―イソプロピルクロルベンゼ
ンのアミノ化
(4) ３―メチルアニリンのイソプロピル化などが
挙げられるがこれらの方法はいずれも工業的に
有利な方法とはいえない。 Methods for obtaining 3-methyl-4-isopropylaniline include (1) a method of reducing 3-methyl-4-isopropylnitrobenzene obtained by nitration of 2-isopropyltoluene and distillation separation using an appropriate method such as hydrogen reduction (2) Examples include amination of 3-methyl-4-isopropylphenol (3), amination of 3-methyl-4-isopropylchlorobenzene (4), and isopropylation of 3-methylaniline, but all of these methods are industrially difficult. This is not an advantageous method.
例えば(1)ではニトロ化反応で生成する異性体間
の沸点が極めて近く蒸留法による分離が困難であ
り、２），３），４）では出発原料が得られにく
い、副生物が多い、収率が悪い、反応のコントロ
ール性が難しいなど経済的に又製造上も極めて不
利である。 For example, in (1), the boiling points of the isomers produced in the nitration reaction are extremely close and it is difficult to separate them by distillation, and in 2), 3), and 4), it is difficult to obtain starting materials, there are many by-products, and It is extremely disadvantageous economically and in terms of production, such as poor yield and difficulty in controlling the reaction.
従つて３―メチル―４―イソプロピルアニリン
を工業的に製造している例はほとんど知られてお
らず、わずかにZh.Obshch.Khim.33(8)2785〜９
（1963）．Zh.Organ.Khim.１（10），1838（1965）
あるいは特開昭57−203044等にその製造法の記
載があるのみである。 Therefore, there are almost no known examples of industrial production of 3-methyl-4-isopropylaniline, and only Zh.Obshch.Khim. 33 (8) 2785-9
(1963). Zh.Organ.Khim. 1 (10), 1838 (1965)
Alternatively, the manufacturing method is only described in JP-A-57-203044 and the like.
即ち，の文献には多量の85％〜94％硫酸中
で３―メチルアニリンをイソプロピルアルコール
でアルキル化する例が記載されている。この場合
の３―メチル―４―イソプロピルアニリンの生成
率は34.7％と悪く、さらに反応後の廃酸量が多い
ため後処理工程に問題が多い。の文献には３―
メチルアニリンをフツ化水素中プロピレンにてア
ルキル化する方法が記載されているが、反応時間
が長く転化率も一般に低く、また高転化率ではジ
イソプロピル―３―メチルアニリンが大量（10〜
23％）に生成する。さらに低沸点で腐食性の強い
フツ化水素を使用するため工業的に莫大な設備投
資を必要とする等の欠点を有する。 That is, the literature describes an example of alkylating 3-methylaniline with isopropyl alcohol in a large amount of 85% to 94% sulfuric acid. In this case, the production rate of 3-methyl-4-isopropylaniline is as low as 34.7%, and furthermore, the amount of waste acid after the reaction is large, causing many problems in the post-treatment process. In the literature, there are 3-
A method of alkylating methylaniline with propylene in hydrogen fluoride has been described, but the reaction time is long and the conversion rate is generally low.Also, at high conversion rates, a large amount of diisopropyl-3-methylaniline (10~
23%). Furthermore, since hydrogen fluoride, which has a low boiling point and is highly corrosive, is used, it has drawbacks such as requiring a huge industrial investment in equipment.
本発明者は３―メチル―４―イソプロピルアニ
リンの安価で効率的な合成法について鋭意検討を
重ねた結果Ｎ―イソプロピル―３―メチルアニリ
ンをプロピレン、フリーデル・クラフツ型触媒の
存在下で加熱することにより容易に３―メチル―
４―イソプロピルアニリンが得られることを見出
し本発明に至つた。 As a result of extensive research into a cheap and efficient method for synthesizing 3-methyl-4-isopropylaniline, the inventors of the present invention heated N-isopropyl-3-methylaniline in the presence of propylene and a Friedel-Crafts type catalyst. 3-methyl-
It was discovered that 4-isopropylaniline could be obtained, leading to the present invention.
本発明の原料となるＮ―イソプロピル―３―メ
チルアニリンは３―メチルアニリン（ｍ―トルイ
ジン）とアセトンとの還元アルキル化反応あるい
は３―メチルアニリンとイソプロピルハロゲナイ
トまたはイソプロピルアルコールによるＮ―アル
キル化など公知の方法で容易にかつ高収率で製造
することができる。本発明に使用する原料は必ず
しも高純度である必要はなく、例えば上記のよう
な製法によつた場合、Ｎ―イソプロピル―３―メ
チルアニリンに３―メチルアニリンを０〜30％含
有するものであつても本発明を実施する上で何ら
支障がない。 N-isopropyl-3-methylaniline, which is a raw material for the present invention, can be produced by a reductive alkylation reaction between 3-methylaniline (m-toluidine) and acetone, or by N-alkylation using 3-methylaniline and isopropylhalogenite or isopropyl alcohol. It can be produced easily and in high yield by known methods. The raw materials used in the present invention do not necessarily have to be of high purity; for example, when using the above manufacturing method, N-isopropyl-3-methylaniline containing 0 to 30% of 3-methylaniline can be used. However, there is no problem in implementing the present invention.
本発明に使用される触媒としては塩化アルミニ
ウム、塩化鉄、塩化錫、塩化亜鉛、塩化コバル
ト、塩化カドミウム、臭化アルミニウム、臭化鉄
の他フツ化ホウ素、フツ化水素、リン酸、硫酸等
のフリーデル・クラフツ型触媒が挙げられこれら
の触媒は単独であるいは２種以上混合して用いら
れる。その使用量は原料であるＮ―イソプロピル
―３―メチルアニリンの重量に対して５〜300％、
好適には10〜100％である。使用するプロピレン
の量は好適にはＮ―イソプロピル―３―メチルア
ニリン1molに対して0.1〜10molである。このプ
ロピレンは反応開始前に反応器の空間部にガス状
で圧入してもよく、反応中連続的に反応器に圧入
してもよい。反応は通常加圧下で行われる。 Catalysts used in the present invention include aluminum chloride, iron chloride, tin chloride, zinc chloride, cobalt chloride, cadmium chloride, aluminum bromide, iron bromide, boron fluoride, hydrogen fluoride, phosphoric acid, sulfuric acid, etc. Examples include Friedel-Crafts type catalysts, and these catalysts may be used alone or in combination of two or more. The amount used is 5 to 300% of the weight of the raw material N-isopropyl-3-methylaniline.
It is preferably 10-100%. The amount of propylene used is preferably from 0.1 to 10 mol per mol of N-isopropyl-3-methylaniline. This propylene may be pressurized into the space of the reactor in gaseous form before the start of the reaction, or may be continuously pressurized into the reactor during the reaction. The reaction is usually carried out under pressure.
反応温度はあまり低いと反応速度が小さく、転
化率が低くなるためある程度高くする方が好まし
いが反応温度を高くしすぎるとタール状高沸点分
が増加する。例えば100〜400℃であり、好適には
160〜250℃である。昇温の仕方は任意でよく短時
間に設定温度に上昇させてもゆつくりと時間をか
けて上昇させても反応自体にはほとんど影響がな
い。 If the reaction temperature is too low, the reaction rate will be low and the conversion rate will be low, so it is preferable to raise the reaction temperature to some extent, but if the reaction temperature is too high, tar-like high-boiling components will increase. For example, 100-400℃, preferably
The temperature is 160-250℃. The method of raising the temperature can be arbitrary, and the reaction itself is hardly affected whether the temperature is raised to the set temperature in a short time or slowly over time.
本反応は不活性溶媒の存在下または不存在下で
反応してもよい。使用する不活性溶媒はニトロベ
ンゼン、二硫化炭素などである。 This reaction may be carried out in the presence or absence of an inert solvent. Inert solvents used include nitrobenzene and carbon disulfide.
反応時間は反応温度、触媒種、触媒使用量、プ
ロピレン量により決定することができ、一般には
４〜10時間である。 The reaction time can be determined depending on the reaction temperature, catalyst species, amount of catalyst used, and amount of propylene, and is generally 4 to 10 hours.
反応生成物の取出しは反応終了後、反応器を所
定温度にまで冷却した後、水酸化ナトリウム水溶
液の入つた分解釜に反応液を圧送し、触媒を分
解、中和させ十分撹拌後、水層と油層を分離し油
層を蒸留釜に移液し、減圧蒸留を行う方法が好都
合である。初留分は主に３―メチルアニリン、Ｎ
―イソピロピル―３―メチルアニリン、主留分は
主に３―メチル―４―イソプロピルアニリン、後
留分は主にジイソプロピル―３―メチルアニリン
（以下ジイソプロピル体という）からなり蒸留残
査として極く少量のタール状高沸点分がある。こ
の初留分、後留分は回収して反応器に戻し循環使
用することによりさらに製造コストの低減が可能
である。この蒸留は大きな沸点差（３―メチルア
ニリン13mmHg86℃、Ｎ―イソプロピル―３―メ
チルアニリン13mmHg116℃、３―メチル―４―イ
ソプロピルアニリン13mmHg141〜５℃）を利用し
て分離するため蒸留段数は少なくてすみ操作が比
較的容易であり、蒸留に要する減圧度も厳しくな
いため、分離コストが安価となる利点を有する。 To take out the reaction product, after the reaction is completed, the reactor is cooled to a predetermined temperature, and then the reaction solution is pumped into a decomposition tank containing an aqueous sodium hydroxide solution, the catalyst is decomposed and neutralized, and after thorough stirring, the aqueous layer is removed. A convenient method is to separate the oil layer from the oil layer, transfer the oil layer to a distillation tank, and perform vacuum distillation. The first distillate is mainly 3-methylaniline, N
-Isopropyl-3-methylaniline, the main distillate is mainly 3-methyl-4-isopropylaniline, and the after-distillate is mainly diisopropyl-3-methylaniline (hereinafter referred to as diisopropyl substance), with a very small amount as a distillation residue. There is a tar-like high boiling point component. The production cost can be further reduced by recovering the first distillate and the second distillate and recycling them back to the reactor. This distillation uses a large boiling point difference (3-methylaniline 13mmHg 86℃, N-isopropyl-3-methylaniline 13mmHg 116℃, 3-methyl-4-isopropylaniline 13mmHg 141~5℃), so the number of distillation stages is small. It is relatively easy to operate, and the degree of vacuum required for distillation is not severe, so it has the advantage that separation costs are low.
以下に実施例をあげて本発明をさらに詳細に説
明するが、本発明はその要旨を越えないかぎりこ
れらに限定されるものではない。 The present invention will be described in more detail with reference to Examples below, but the present invention is not limited thereto unless it exceeds the gist thereof.
実施例 １
チタン製オートクレーブにＮ―イソプロピル―
３―メチルアニリン149.0ｇ（1mol）を仕込み、
塩化亜鉛50ｇを加えた。脱気して、プロピレン
0.2molを圧入した。つづいて撹拌しながらオー
トクレーブの温度を180℃まで30分間で上昇させ
た。180℃に達してから８時間同温度で撹拌した
後、冷却して反応液を水酸化ナトリウム29ｇを溶
解させた水500ｇの入つた分解槽に徐々に抜出し
た。静置してオイル分146.0ｇを得た。このオイ
ル分のガスクロマトグラフイーによる分析では３
―メチルアニリン5.9％、Ｎ―イソプロピル―３
―メチルアニリン10.7％、３―メチル―４―イソ
プロピルアニリン76.7％、ジイソプロピル体6.7
％であつた。Example 1 N-isopropyl in a titanium autoclave
Prepare 149.0g (1mol) of 3-methylaniline,
50g of zinc chloride was added. Degassed and propylene
0.2 mol was injected under pressure. Subsequently, the temperature of the autoclave was raised to 180°C over 30 minutes while stirring. After reaching 180° C., the mixture was stirred at the same temperature for 8 hours, cooled, and the reaction solution was gradually discharged into a decomposition tank containing 500 g of water in which 29 g of sodium hydroxide was dissolved. The mixture was allowed to stand still to obtain 146.0 g of oil. According to gas chromatography analysis of this oil content, 3
-Methylaniline 5.9%, N-isopropyl-3
-Methylaniline 10.7%, 3-methyl-4-isopropylaniline 76.7%, diisopropyl form 6.7%
It was %.
つづいて内径２cm、長さ30cmのマクマホン充填
塔を装備したフラスコにオイル分を入れ、還流比
３、減圧度14mmHgで蒸留した。初留（82〜135
℃）18.6ｇ（そのガスクロマトグラフイーによる
組成比、以下同じ、３―メチルアニリン44.1％、
Ｎ―イソプロピル―３―メチルアニリン49.4％、
３―メチル―４―イソプロピルアニリン6.5％）、
主留（135〜157℃）112.7ｇ（Ｎ―イソプロピル
―３―メチルアニリン3.0％、３―メチル―４―
イソプロピルアニリン95.2％、ジイソプロピル体
1.8％）、後留（157〜172℃）11.3ｇ（３―メチル
―４―イソプロピルアニリン31.7％、ジイソプロ
ピル体68.3％）、釜残1.9ｇ（３―メチル―４―イ
ソプロピルアニリン2.4％、ジイソプロピル体
97.6％）を得た。 Subsequently, the oil was placed in a flask equipped with a McMahon packed column with an inner diameter of 2 cm and a length of 30 cm, and distilled at a reflux ratio of 3 and a degree of vacuum of 14 mmHg. Hatsutome (82-135
℃) 18.6g (composition ratio as determined by gas chromatography, same hereinafter, 3-methylaniline 44.1%,
N-isopropyl-3-methylaniline 49.4%,
3-methyl-4-isopropylaniline 6.5%),
Main distillate (135-157℃) 112.7g (N-isopropyl-3-methylaniline 3.0%, 3-methyl-4-
Isopropylaniline 95.2%, diisopropyl form
1.8%), after distillation (157-172℃) 11.3g (3-methyl-4-isopropylaniline 31.7%, diisopropyl form 68.3%), bottom residue 1.9g (3-methyl-4-isopropylaniline 2.4%, diisopropyl form)
97.6%).
実施例 ２
実施例１で得た初留分18.6ｇと後留分11.3ｇお
よびＮ―イソプロピル―３―メチルアニリン
119.1ｇ、塩化亜鉛50ｇ、プロピレン0.2molをオ
ートクレーブに仕込み200℃で５時間反応させた。
この反応液を水酸化ナトリウム水溶液で分解、中
和してオイル分146.2ｇを得た。このオイル分の
ガスクロマトグラフイーによる分析では３―メチ
ルアニリン6.1％、Ｎ―イソプロピル―３―メチ
ルアニリン8.2％、３―メチル―４―イソプロピ
ルアニリン77.4％、ジイソプロピル体8.3％であ
つた。Example 2 18.6 g of the first distillate and 11.3 g of the later distillate obtained in Example 1 and N-isopropyl-3-methylaniline
119.1 g, 50 g of zinc chloride, and 0.2 mol of propylene were placed in an autoclave and reacted at 200°C for 5 hours.
This reaction solution was decomposed and neutralized with an aqueous sodium hydroxide solution to obtain 146.2 g of oil. Analysis of this oil by gas chromatography revealed that it was 6.1% 3-methylaniline, 8.2% N-isopropyl-3-methylaniline, 77.4% 3-methyl-4-isopropylaniline, and 8.3% diisopropyl.
このオイル分を蒸留すると主留分113.0ｇ（Ｎ
―イソプロピルアニリン2.5％、３―メチル―４
―イソプロピルアニリン95.3％、ジイソプロピル
体2.2％）を得た。 When this oil is distilled, the main distillate is 113.0g (N
-Isopropylaniline 2.5%, 3-methyl-4
- 95.3% isopropyl aniline, 2.2% diisopropyl form).
実施例 ３
塩化亜鉛30ｇとＮ―イソプロピル―３―メチル
アニリン149ｇ、プロピレン0.5molを実施例１で
使用したオートクレーブに仕込み220℃で４時間
反応させた。得られたオイル分のガスクロマトグ
ラフイーによる分析では３―メチルアニリン9.5
％、Ｎ―イソプロピル―３―メチルアニリン6.4
％、３―メチル―４―イソプロピルアニリン74.3
％、ジイソプロピル体9.8％であつた。Example 3 30 g of zinc chloride, 149 g of N-isopropyl-3-methylaniline, and 0.5 mol of propylene were charged into the autoclave used in Example 1 and reacted at 220° C. for 4 hours. Analysis of the obtained oil by gas chromatography revealed that 3-methylaniline was 9.5%.
%, N-isopropyl-3-methylaniline 6.4
%, 3-methyl-4-isopropylaniline 74.3
%, and the diisopropyl form was 9.8%.
実施例 ４
塩化亜鉛の代りに塩化アルミニウム30ｇを用い
たことを除いて実施例１の手順に従つてＮ―イソ
プロピル―３―メチルアニリンを反応させた。得
られたオイル分のガスクロマトグラフイーによる
分析では３―メチルアニリン5.2％、Ｎ―イソプ
ロピル―３―メチルアニリン18.6％、３―メチル
―４―イソプロピルアニリン72.1％、ジイソプロ
ピル体4.1％であつた。Example 4 N-isopropyl-3-methylaniline was reacted according to the procedure of Example 1, except that 30 g of aluminum chloride was used instead of zinc chloride. Analysis of the resulting oil by gas chromatography revealed that it contained 5.2% of 3-methylaniline, 18.6% of N-isopropyl-3-methylaniline, 72.1% of 3-methyl-4-isopropylaniline, and 4.1% of diisopropyl derivatives.
実施例 ５
塩化亜鉛50ｇの代りに塩化亜鉛25ｇ、塩化鉄25
ｇを用いたことを除いて実施例１の手順に従つて
Ｎ―イソプロピル―３―メチルアニリンを反応さ
せた。得られたオイル分のガスクロマトグラフイ
ーによる分析では３―メチルアニリン4.3％、Ｎ
―イソプロピル―３―メチルアニリン23.9％、３
―メチル―４―イソプロピルアニリン69.8％、ジ
イソプロピル体2.0％であつた。Example 5 25g of zinc chloride and 25g of iron chloride instead of 50g of zinc chloride
N-isopropyl-3-methylaniline was reacted according to the procedure of Example 1 except that g was used. Analysis of the obtained oil by gas chromatography revealed that 3-methylaniline was 4.3%, N
-Isopropyl-3-methylaniline 23.9%, 3
-Methyl-4-isopropylaniline was 69.8% and diisopropyl form was 2.0%.
実施例 ６
塩化亜鉛の代りに塩化スズ70ｇを用いたことを
除いて実施例１の手順に従つてＮ―イソプロピル
―３―メチルアニリンを反応させた。得られたオ
イル分のガスクロマトグラフイーによる分析では
３―メチルアニリン7.1％、Ｎ―イソプロピル―
３―メチルアニリン8.9％、３―メチル―４―イ
ソプロピルアニリン75.0％、ジイソプロピル体
9.0％であつた。Example 6 N-isopropyl-3-methylaniline was reacted according to the procedure of Example 1, except that 70 g of tin chloride was used instead of zinc chloride. Gas chromatography analysis of the obtained oil revealed 7.1% of 3-methylaniline and N-isopropyl.
3-methylaniline 8.9%, 3-methyl-4-isopropylaniline 75.0%, diisopropyl form
It was 9.0%.
実施例 ７
プロピレン1mol、塩化アルミニウム30ｇとＮ
―イソプロピル―３―メチルアニリン149ｇを加
え実施例１の手順に従つて反応させた。得られた
オイル分のガスクロマトグラフイーによる分析で
は３―メチルアニリン5.1％、Ｎ―イソプロピル
―３―メチルアニリン15.7％、３―メチル―４―
イソプロピルアニリン73.0％、ジイソプロピル体
6.2％であつた。Example 7 1 mol of propylene, 30 g of aluminum chloride and N
149 g of -isopropyl-3-methylaniline was added and reacted according to the procedure of Example 1. Analysis of the obtained oil content by gas chromatography revealed 5.1% of 3-methylaniline, 15.7% of N-isopropyl-3-methylaniline, and 3-methyl-4-
Isopropylaniline 73.0%, diisopropyl form
It was 6.2%.
実施例 ８
塩化亜鉛の代りに臭化アルミニウム50ｇを用い
たことを除いて実施例１の手順に従つてＮ―イソ
プロピル―３―メチルアニリンを反応させた。得
られたオイル分のガスクロマトグラフイーによる
分析では３―メチルアニリン8.5％、Ｎ―イソプ
ロピル―３―メチルアニリン4.1％、３―メチル
―４―イソプロピルアニリン75.6％、ジイソプロ
ピル体11.8％であつた。Example 8 N-isopropyl-3-methylaniline was reacted according to the procedure of Example 1, except that 50 g of aluminum bromide was used instead of zinc chloride. Analysis of the obtained oil by gas chromatography revealed that it contained 8.5% of 3-methylaniline, 4.1% of N-isopropyl-3-methylaniline, 75.6% of 3-methyl-4-isopropylaniline, and 11.8% of diisopropyl derivatives.
比較例 １
実施例１でプロピレンを用いないことを除いて
実施例１と同じ条件で反応を行つた。得られたオ
イル分のガスクロマトグラフイーによる分析では
３―メチルアニリン1.3％、Ｎ―イソプロピル―
３―メチルアニリン47.0％、３―メチル―４―イ
ソプロピルアニリン41.6％、ジイソプロピル体
6.9％、その他3.2％であつた。Comparative Example 1 A reaction was carried out under the same conditions as in Example 1 except that propylene was not used. Analysis of the obtained oil by gas chromatography revealed 1.3% of 3-methylaniline, N-isopropyl-
3-methylaniline 47.0%, 3-methyl-4-isopropylaniline 41.6%, diisopropyl form
6.9%, others 3.2%.
Claims (1)
ロピレン及びフリーデル・クラフツ型触媒の存在
下で加熱することを特徴とする３―メチル―４―
イソプロピルアニリンの製造方法。1 3-Methyl-4- characterized by heating N-isopropyl-3-methylaniline in the presence of propylene and a Friedel-Crafts type catalyst
A method for producing isopropylaniline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58013673A JPS59167545A (en) | 1983-02-01 | 1983-02-01 | Production of 3-methyl-4-isopropylaniline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58013673A JPS59167545A (en) | 1983-02-01 | 1983-02-01 | Production of 3-methyl-4-isopropylaniline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59167545A JPS59167545A (en) | 1984-09-21 |
| JPH0229067B2 true JPH0229067B2 (en) | 1990-06-27 |
Family
ID=11839707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58013673A Granted JPS59167545A (en) | 1983-02-01 | 1983-02-01 | Production of 3-methyl-4-isopropylaniline |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59167545A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5001263A (en) * | 1985-08-21 | 1991-03-19 | Air Products And Chemicals, Inc. | Formation of ortho-alkylated aromatic amines from N-alkylated aromatic amines |
| JP4541143B2 (en) * | 2002-07-11 | 2010-09-08 | 明治製菓株式会社 | Method for producing quinoline derivative |
-
1983
- 1983-02-01 JP JP58013673A patent/JPS59167545A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59167545A (en) | 1984-09-21 |
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