JPS6141336B2 - - Google Patents
Info
- Publication number
- JPS6141336B2 JPS6141336B2 JP53126379A JP12637978A JPS6141336B2 JP S6141336 B2 JPS6141336 B2 JP S6141336B2 JP 53126379 A JP53126379 A JP 53126379A JP 12637978 A JP12637978 A JP 12637978A JP S6141336 B2 JPS6141336 B2 JP S6141336B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- diphenylamines
- carbon atoms
- aluminum
- ethylene bond
- 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
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 22
- -1 aluminum halide Chemical class 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000005804 alkylation reaction Methods 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 230000002152 alkylating effect Effects 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229940100198 alkylating agent Drugs 0.000 description 4
- 239000002168 alkylating agent Substances 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- WONYVCKUEUULQN-UHFFFAOYSA-N 2-methyl-n-(2-methylphenyl)aniline Chemical compound CC1=CC=CC=C1NC1=CC=CC=C1C WONYVCKUEUULQN-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 description 2
- MHJCZOMOUCUAOI-UHFFFAOYSA-N n-tert-butyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C(C)(C)C)C1=CC=CC=C1 MHJCZOMOUCUAOI-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- YPIVUMUFTPSQHL-UHFFFAOYSA-N 4-phenyl-N-(4-phenyl-6-propan-2-ylidenecyclohexa-2,4-dien-1-yl)-6-propan-2-ylidenecyclohexa-2,4-dien-1-amine Chemical compound C1(=CC=CC=C1)C1=CC(C(C=C1)NC1C(C=C(C=C1)C1=CC=CC=C1)=C(C)C)=C(C)C YPIVUMUFTPSQHL-UHFFFAOYSA-N 0.000 description 1
- UUNBFTCKFYBASS-UHFFFAOYSA-N C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC Chemical compound C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC UUNBFTCKFYBASS-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- SRENRFDRXNVMKN-UHFFFAOYSA-N n-butyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCC)C1=CC=CC=C1 SRENRFDRXNVMKN-UHFFFAOYSA-N 0.000 description 1
- BYYFPVDBAHOLDX-UHFFFAOYSA-N n-dodecyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCCCCCC)C1=CC=CC=C1 BYYFPVDBAHOLDX-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 238000010626 work up procedure Methods 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は、エチレン結合を有する炭化水素を用
いてジフエニルアミン類をアルキル化する方法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for alkylating diphenylamines using a hydrocarbon having an ethylene bond.
芳香族化合物をエチレン結合を有する炭化水素
にてアルキル化する方法については、これまでに
も多くの報告があり、触媒としてもハロゲン化ア
ルミニウム、ハロゲン化ガリウムおよびハロゲン
化硼素などのルイス酸、硫酸およびｐ−トルエン
スルホン酸などのプロトン酸、アルミナ、シリカ
−アルミナなどの酸性触媒やカチオン交換樹脂な
どが知られている。（たとえば「有機合成化学協
会誌」Vol.36、No.6、426〜439頁）
しかしながら、これらの触媒をジフエニルアミ
ン類のエチレン結合を有する炭化水素によるアル
キル化反応に用いた場合には、反応収率が低いの
みならず、アルキル化剤の重合など好ましからざ
る副反応が同時に起こり、反応後の取扱いも複雑
となつて、工業的に実施する場合の大きな問題と
なつていた。 There have been many reports on methods of alkylating aromatic compounds with hydrocarbons having an ethylene bond, and Lewis acids such as aluminum halides, gallium halides and boron halides, sulfuric acid and Protonic acids such as p-toluenesulfonic acid, acidic catalysts such as alumina and silica-alumina, and cation exchange resins are known. (For example, "Journal of the Society of Organic Synthetic Chemistry," Vol. 36, No. 6, pp. 426-439) However, when these catalysts are used in the alkylation reaction of diphenylamines with a hydrocarbon having an ethylene bond, the reaction yield is low. Not only is the reaction rate low, but also undesirable side reactions such as polymerization of the alkylating agent occur simultaneously, and handling after the reaction is complicated, posing a major problem in industrial implementation.
またAlCl3−CH3NO2やAlCl3−C6H5NO2等の混
合触媒を用いる方法（たとえばJ.A.C.S Vol.84
1688頁やBull.Chem.Soc.Jap.Vol.40、115、119、
125頁）も知られているが、これらの方法におい
ては異性体の生成やトランスアルキル化反応は抑
えられるものの、アルキル化物の収率向上に関し
ては殆んど寄与しない。 In addition, methods using mixed catalysts such as AlCl 3 −CH 3 NO 2 and AlCl 3 −C 6 H 5 NO 2 (for example, JACS Vol. 84
1688 pages and Bull.Chem.Soc.Jap.Vol.40, 115, 119,
(p. 125) are also known, but although these methods suppress the production of isomers and transalkylation reactions, they hardly contribute to improving the yield of alkylated products.
このようなことから、本発明者らはジフエニル
アミン類のエチレン結合を有する炭化水素による
アルキル化反応を有利に行うべく鋭意研究の結
果、従来技術からはとうてい予期し得ざることで
はあるが、上記反応において触媒としてハロゲン
化アルミニウムとアルコールを併用使用すること
によりアルキル化物の収率が飛躍的に向上し、操
作的にも極めて簡単に目的物が得られることを見
出し、本発明に至つた。 For this reason, the present inventors have conducted intensive research to advantageously carry out the alkylation reaction of diphenylamines with a hydrocarbon having an ethylene bond. The inventors have discovered that by using aluminum halide and alcohol together as a catalyst, the yield of the alkylated product can be dramatically improved, and the desired product can be obtained with extremely simple operation, leading to the present invention.
すなわち本発明は、一般式
（式中、R1およびR2は同一または相異なつて水素
原子または炭素数１〜12のアルキル基を示す。）
で示されるジフエニルアミン類に、分子中にエチ
レン結合を１個有する炭素数４〜12の脂肪族また
は芳香族炭化水素を反応させてアルキル化を行な
うにあたり、触媒としてハロゲン化アルミニウム
と炭素数１〜８のアルコールを併用することを特
徴とするジフエニルアミン類のアルキル化方法で
ある。 That is, the present invention is based on the general formula (In the formula, R 1 and R 2 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.) Diphenylamines having 4 to 4 carbon atoms and having one ethylene bond in the molecule This is a method for alkylating diphenylamines, which is characterized by using aluminum halide and an alcohol having 1 to 8 carbon atoms together as a catalyst in performing alkylation by reacting 12 aliphatic or aromatic hydrocarbons.
本発明において用いられる前記一般式で示され
るジフエニルアミン類としては、たとえばジフエ
ニルアミン、オクチルジフエニルアミン、ジトリ
ルアミンおよびブチルジフエニルアミンなどが例
示される。 Examples of the diphenylamines represented by the above general formula used in the present invention include diphenylamine, octyldiphenylamine, ditolylamine, and butyldiphenylamine.
また、アルキル化剤として用いられる分子中に
エチレン結合を１個有する炭素数４〜12の脂肪酸
または芳香族炭化水素としては、たとえばイソブ
チレン、ヘキセン、シクロヘキセン、オクテン、
ノネン、ドデセン、スチレンおよびα−メチルス
チレンなどが例示される。 In addition, examples of fatty acids or aromatic hydrocarbons having 4 to 12 carbon atoms and having one ethylene bond in the molecule used as alkylating agents include isobutylene, hexene, cyclohexene, octene,
Examples include nonene, dodecene, styrene, and α-methylstyrene.
触媒として用いられるハロゲン化アルミニウム
とは塩化アルミニウムおよび臭化アルミニウム等
であり、炭素数１〜８のアルコールとしてはメタ
ノール、エタノール、ｎ−プロピルアルコール、
ｉ−プロピルアルコール、ｔ−ブチルアルコー
ル、ｎ−オクタノールおよび２−エチルヘキサノ
ールなどが例示される。 Aluminum halides used as catalysts include aluminum chloride and aluminum bromide, and alcohols having 1 to 8 carbon atoms include methanol, ethanol, n-propyl alcohol,
Examples include i-propyl alcohol, t-butyl alcohol, n-octanol, and 2-ethylhexanol.
本発明のアルキル化反応は、無溶媒下もしくは
反応に不活性な溶媒の存在下において、通常−10
〜300℃、好ましくは30〜150℃の温度にて実施さ
れる。また反応に使用されるエチレン結合を有す
る炭化水素は単一化合物であつても混合物であつ
ても良く、またあらかじめジフエニルアミン類に
一種のアルキル化剤を反応せしめた後、更に他の
アルキル化剤と反応せしめて同一分子中に異種の
アルキル基を導入せしめても良い。このアルキル
化反応においてハロゲン化アルミニウムの量は、
通常ジフエニルアミン類に対して0.1〜100重量
％、より好ましくは、５〜50重量％である。併用
されるアルコールの量はハロゲン化アルミニウム
に対して0.1モル倍以上であるが、好ましくは、
0.3〜2.5モル倍である。この反応において、さら
に酸性触媒を併用することも可能である。 The alkylation reaction of the present invention is usually carried out in the absence of a solvent or in the presence of a solvent inert to the reaction.
It is carried out at a temperature of ~300°C, preferably 30-150°C. In addition, the hydrocarbon having an ethylene bond used in the reaction may be a single compound or a mixture, and after reacting diphenylamine with one kind of alkylating agent, it may be reacted with another alkylating agent. Different types of alkyl groups may be introduced into the same molecule by reaction. In this alkylation reaction, the amount of aluminum halide is
It is usually 0.1 to 100% by weight, more preferably 5 to 50% by weight based on the diphenylamine. The amount of alcohol used in combination is at least 0.1 times the mole of aluminum halide, but preferably,
It is 0.3 to 2.5 times the mole. In this reaction, it is also possible to further use an acidic catalyst.
かくして、本発明の方法により製造されるアル
キル化ジフエニルアミン類としては、たとえば、
ｔ−ブチルジフエニルアミン、イソプロピルオク
チルジフエニルアミン、オクチルジフエニルアミ
ン、ジオクチルジフエニルアミンおよびノニルジ
メチルジフエニルアミンなどである。 Thus, the alkylated diphenylamines produced by the method of the present invention include, for example:
These include t-butyldiphenylamine, isopropyloctyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, and nonyldimethyldiphenylamine.
かかるアルキル化ジフエニルアミン類は、有機
化合物の安定剤として、また農薬、医薬や染料の
中間原料などとして有用な化合物である。 Such alkylated diphenylamines are useful compounds as stabilizers for organic compounds and as intermediate raw materials for agricultural chemicals, medicines, and dyes.
以下に実施例により本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例 １
ジイソブチレン290ｇ、ジフエニルアミン169
ｇ、塩化アルミニウム40ｇおよびイソブタノール
22.2ｇを温度計、還流冷却器および滴下ロートを
備えた１の４つ口フラスコに仕込み、130℃に
て８時間反応する。反応終了後塩化アルミニウム
を水、苛性ソーダにて分解し、充分有機層を水洗
後、未反応原料、モノオクチル体および低沸点成
分を蒸留することによりｐ、p′−ジオクチルフエ
ニルアミンが収率90％にて得られる。製品の純度
98％以上。沸点220℃（１mmHg）、融点105℃
参考例 １
イソブタノールを使用しない以外は実施例１と
全く同様にアルキル化反応を行なつたところｐ、
p′−ジオクチルジフエニルアミンが収率76％で得
られる。Example 1 290 g of diisobutylene, 169 g of diphenylamine
g, aluminum chloride 40 g and isobutanol
22.2 g was placed in a four-necked flask equipped with a thermometer, reflux condenser, and dropping funnel, and reacted at 130°C for 8 hours. After the reaction, aluminum chloride is decomposed with water and caustic soda, the organic layer is thoroughly washed with water, and unreacted raw materials, monooctyl compounds, and low-boiling components are distilled to give p,p'-dioctyl phenylamine in a yield of 90%. Obtained in %. Product purity
More than 98%. Boiling point: 220°C (1 mmHg), melting point: 105°C Reference Example 1 An alkylation reaction was carried out in exactly the same manner as in Example 1 except that isobutanol was not used.
p'-dioctyldiphenylamine is obtained with a yield of 76%.
実施例 ２
ジフエニルアミン21ｇ、α−メチルスチレン
44.2ｇ、塩化アルミニウム３ｇ、エタノール１ｇ
およびリグロイン100c.c.を200c.c.フラスコに仕込
み、100〜110℃にて５時間反応する。反応終了後
実施例１と同様の後処理を行なつて、収率85％に
てビス（４−フエニルイソプロピリデンフエニ
ル）アミンを得た。このものは純度98％以上の融
点97〜８℃の白色粉末である。Example 2 21 g of diphenylamine, α-methylstyrene
44.2g, aluminum chloride 3g, ethanol 1g
and 100 c.c. of ligroin were charged into a 200 c.c. flask and reacted at 100 to 110°C for 5 hours. After the reaction was completed, the same post-treatment as in Example 1 was carried out to obtain bis(4-phenylisopropylidenephenyl)amine in a yield of 85%. This product is a white powder with a purity of 98% or higher and a melting point of 97-8°C.
実施例 ３
ジフエニルアミンの代りにドデシルジフエニル
アミンを使用し、ジイソブチレンの代りにノネン
を使用する以外は実施例１と同様に反応を行な
い、同様の通常の後処理を実施することにより、
見掛収率99％にて褐色液体が得られる。ドデシル
フエニルノニルフエニルアミン80％を含む。Example 3 The reaction was carried out in the same manner as in Example 1, except that dodecyl diphenylamine was used instead of diphenylamine and nonene was used instead of diisobutylene, and by carrying out the same conventional work-up,
A brown liquid is obtained with an apparent yield of 99%. Contains 80% dodecyl phenyl nonylphenyl amine.
実施例 ４
ジーＯ−トリルアミン197.3ｇ、臭化アルミニ
ウム30ｇおよびｎ−オクタノール7.5ｇを温度
計、還流冷却器および滴下ロートを備えた４つ口
フラスコに仕込み、60℃に昇温する。140ｇのイ
ソブチレンを４時間を要して仕込む。反応終了
後、実施例１と同様の後処理を実施することによ
りビス（４−ｔ−ブチル−２−メチルフエニル）
アミン88％、ｐ−ｔ−ブチル−ジ−ｏ−トリルア
ミン９％を含む混合物301ｇが得られる。Example 4 197.3 g of di-O-tolylamine, 30 g of aluminum bromide and 7.5 g of n-octanol are charged into a four-necked flask equipped with a thermometer, reflux condenser and dropping funnel, and the temperature is raised to 60°C. It takes 4 hours to prepare 140g of isobutylene. After the reaction, bis(4-t-butyl-2-methylphenyl) was obtained by carrying out the same post-treatment as in Example 1.
301 g of a mixture containing 88% amine and 9% pt-butyl-di-o-tolylamine are obtained.
実施例 ５
ｔ−ブチルジフエニルアミン225ｇ、塩化アル
ミニウム40ｇおよびメタノール10ｇを温度計、還
流冷却器および滴下ロートを備えた１４つ口フ
ラスコに仕込む。130℃に昇温後、プロピレンテ
トラマー202ｇを６時間を要して滴下する。反応
終了後実施例１と同様の処理を実施することによ
り純度95％のドデシルフエニル−ｔ−ブチルフエ
ニルアミン395ｇが得られる。Example 5 225 g of t-butyldiphenylamine, 40 g of aluminum chloride and 10 g of methanol are charged into a 14-necked flask equipped with a thermometer, reflux condenser and addition funnel. After raising the temperature to 130°C, 202 g of propylene tetramer was added dropwise over a period of 6 hours. After the reaction was completed, the same treatment as in Example 1 was carried out to obtain 395 g of dodecylphenyl-t-butylphenylamine with a purity of 95%.
Claims (1)
原子または炭素数１〜12のアルキル基を示す。） で示されるジフエニルアミン類に、分子中にエチ
レン結合を１個有する炭素数４〜12の脂肪族また
は芳香族炭化水素を反応させてアルキル化を行な
うにあたり、触媒としてハロゲン化アルミニウム
と炭素数１〜８のアルコールを併用することを特
徴とするジフエニルアミン類のアルキル化方法。[Claims] 1. General formula (In the formula, R 1 and R 2 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.) Diphenylamines having 4 to 4 carbon atoms and having one ethylene bond in the molecule 1. A method for alkylating diphenylamines, which comprises using an aluminum halide and an alcohol having 1 to 8 carbon atoms together as a catalyst in carrying out the alkylation by reacting 12 aliphatic or aromatic hydrocarbons.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12637978A JPS5553249A (en) | 1978-10-13 | 1978-10-13 | Alkylation of diphenylamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12637978A JPS5553249A (en) | 1978-10-13 | 1978-10-13 | Alkylation of diphenylamines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5553249A JPS5553249A (en) | 1980-04-18 |
| JPS6141336B2 true JPS6141336B2 (en) | 1986-09-13 |
Family
ID=14933692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12637978A Granted JPS5553249A (en) | 1978-10-13 | 1978-10-13 | Alkylation of diphenylamines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5553249A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8332797D0 (en) * | 1983-12-08 | 1984-01-18 | Ciba Geigy Ag | Antioxidant production |
| US7390928B2 (en) | 2005-12-14 | 2008-06-24 | Chemtura Corporation | Alkylation of N′-phenyl-N-alkylphenylenediamines in ionic liquid, N′-phenyl-N-alkyl (alkylphenylene) diamines produced thereby, and lubricant compositions containing same |
| US7145038B1 (en) | 2005-12-14 | 2006-12-05 | Chemtura Corporation | Alkylation of a diphenylamine compound in ionic liquid |
| WO2011002038A1 (en) | 2009-06-30 | 2011-01-06 | 日本ゼオン株式会社 | Novel diarylamine compound, and anti-aging agent, polymer composition, crosslinked rubber product and molded article thereof, and method for producing diarylamine compound |
-
1978
- 1978-10-13 JP JP12637978A patent/JPS5553249A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5553249A (en) | 1980-04-18 |
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