JPS63185942A - Production of tribenzylamine - Google Patents
Production of tribenzylamineInfo
- Publication number
- JPS63185942A JPS63185942A JP62016493A JP1649387A JPS63185942A JP S63185942 A JPS63185942 A JP S63185942A JP 62016493 A JP62016493 A JP 62016493A JP 1649387 A JP1649387 A JP 1649387A JP S63185942 A JPS63185942 A JP S63185942A
- Authority
- JP
- Japan
- Prior art keywords
- benzylamine
- benzyl alcohol
- reaction
- tribenzylamine
- reaction system
- 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.)
- Pending
Links
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 57
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 10
- 239000007868 Raney catalyst Substances 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 229910000564 Raney nickel Inorganic materials 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000706 filtrate Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- -1 Raney nickel Chemical compound 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000003939 benzylamines Chemical class 0.000 description 1
- 125000000440 benzylamino group Chemical group [H]N(*)C([H])([H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FHYUCVWDMABHHH-UHFFFAOYSA-N toluene;1,2-xylene Chemical group CC1=CC=CC=C1.CC1=CC=CC=C1C FHYUCVWDMABHHH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、トリベンジルアミンの製造方法に関し、詳し
くはベンジルアミンとベンジルアルコールとの反応によ
りトリベンジルアミンを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing tribenzylamine, and more particularly to a method for producing tribenzylamine by reacting benzylamine with benzyl alcohol.
トリベンジルアミンは、各種合成反応において有用な原
料である。Tribenzylamine is a useful raw material in various synthetic reactions.
（従来の技術）
従来、トリベンジルアミンは、安価なベンジルアミンと
ベンジルアルコールとの反応より製造されるのが、一般
的である。この反応は、適当な触媒の存在下気相反応も
しくは、液相反応で行なわれるが、例えば米国特許第８
，２２３，７８４号（１９６５年）によれば、あらかじ
め反応器内にベンジルアミン及びベンジルアルコールを
それぞれ全量ならびに水中共沸する有機溶媒を仕込み、
水素化触媒の存在下で常圧下生成する水を共沸脱水によ
り糸外へ除去しながら反応を行うことによりトリベンジ
ルアミンを得ている。しかしこの従来方法では種々の副
反応例えば、ベンジルアミン同志の反応などが起こり、
収率が７７．１％と必ずしも高い収率とはいえない。(Prior Art) Tribenzylamine has conventionally been generally produced by reacting inexpensive benzylamine with benzyl alcohol. This reaction is carried out in the presence of a suitable catalyst in a gas phase reaction or in a liquid phase reaction, for example in US Pat.
, No. 223, 784 (1965), the entire amount of benzylamine and benzyl alcohol as well as an organic solvent that is azeotropic in water are charged in advance in a reactor.
Tribenzylamine is obtained by carrying out the reaction in the presence of a hydrogenation catalyst while removing water produced under normal pressure from the fibers by azeotropic dehydration. However, in this conventional method, various side reactions occur, such as reactions between benzylamines,
The yield was 77.1%, which is not necessarily a high yield.
（発明が解決しようとする問題点）
本発明者は上記のごとき不利を改善すべく鋭意研究を重
ね、ベンジルアミン及びベンジルアルコールの反応性に
着目した結果、はからずも水素化触媒の存在下に、ベン
ジルアミンとベンジルアルコールとを反応系内へ供給し
、生成する水を系外へ除きながら反応を行なうことによ
り、副反応を抑制しトリベンジルアミンを収率良く製造
することを見出し本発明を完成するに到った。(Problems to be Solved by the Invention) The present inventor has conducted intensive research to improve the above-mentioned disadvantages and has focused on the reactivity of benzylamine and benzyl alcohol. The present invention has been completed by discovering that by supplying amine and benzyl alcohol into the reaction system and conducting the reaction while removing the water produced from the system, side reactions can be suppressed and tribenzylamine can be produced in good yield. reached.
（問題点を解決する手段）
本発明は、ベンジルアミンとベンジルアルコールとを水
素化触媒の存在下に、生成する水を反応系外に除去しな
がら反応させてトリベンジルアミンを製造するにあたり
、ベンジルアミン及びベンジルアルコールを反応系内に
供給しながら反応させることを特徴とするトリベンジル
アミンの製造方法である。(Means for Solving the Problems) The present invention provides benzylamine and benzyl alcohol in the presence of a hydrogenation catalyst to produce tribenzylamine by reacting while removing the produced water from the reaction system. This is a method for producing tribenzylamine, which is characterized in that the reaction is carried out while supplying an amine and benzyl alcohol into a reaction system.
本発明の方法を実施するにあたり、ベンジルアミン及び
ベンジルアルコールを反応系内に供給しながら反応させ
ることが重要である。本発明のベンジルアミン及びベン
ジルアルコールを供給するには、■ベンジルアミン及び
ベンジルアルコールの各全使用量を供給するか、または
■該両原料の全使用量の一部をあらかじめ反応器に仕込
み、残量を供給する方法のいずれでも実施することがで
きる。前記■の供給方法において、あらかじめ反応器内
に仕込む両原料の量は両原料共に全使用量の１〜３０重
量％好ましくは５〜１５重量％である。この比率が高く
なると、収率が低下する傾向にある。ベンジルアミン及
びベンジルアルコールは、それぞれ別々に供給してもあ
るいは両者の混合液を供給してもよい。In carrying out the method of the present invention, it is important to react while supplying benzylamine and benzyl alcohol into the reaction system. In order to supply the benzylamine and benzyl alcohol of the present invention, either (1) supply the entire amount of each of benzylamine and benzyl alcohol, or (2) charge a part of the total amount of both raw materials to the reactor in advance and leave the remainder. Any method of supplying the amount can be carried out. In the supply method (2) above, the amount of both raw materials charged into the reactor in advance is 1 to 30% by weight, preferably 5 to 15% by weight of the total amount used. As this ratio increases, the yield tends to decrease. Benzylamine and benzyl alcohol may be supplied separately, or a mixture of the two may be supplied.
生成する水を反応系外に除去する方法としては、通常は
水と共沸する有機溶媒を用いた共沸脱水による方法が採
用できるが、本発明はこれに限定するものではなく、米
国特許第３，２２８，７３４号明細魯に詳述された公知
方法例えば、ガスを反応系に導入してガスと共に生成水
を除去する方法、減圧下で反応を行い生成水を除去する
方法なども採用できる。かかる有機溶媒は本反応に不活
性なものであればよいが、有機溶媒を効率よく使用する
点から水に不溶なものが好ましい。具体的にはベンゼン
、トルエン、キシレン等の芳香族炭化水素類、ヘキサン
、シクロヘキサン等の炭化水素類が挙げられ、共沸組成
比率の高いトルエンキシレンが好ましい。As a method for removing the produced water from the reaction system, azeotropic dehydration using an organic solvent that is azeotropic with water can usually be adopted, but the present invention is not limited to this. Known methods detailed in Lu, No. 3,228,734, such as a method in which gas is introduced into the reaction system and water produced together with the gas is removed, a method in which the reaction is carried out under reduced pressure and water produced are removed, etc. can also be employed. . Such an organic solvent may be one that is inert to this reaction, but from the viewpoint of efficient use of the organic solvent, one that is insoluble in water is preferred. Specific examples include aromatic hydrocarbons such as benzene, toluene, and xylene, and hydrocarbons such as hexane and cyclohexane, with toluene-xylene having a high azeotropic composition ratio being preferred.
溶媒量としては特に制限はないが、単なる共沸溶媒であ
るため両原料の合計量に対し５〜５０重量％の範囲が好
ましい。The amount of solvent is not particularly limited, but since it is a simple azeotropic solvent, it is preferably in the range of 5 to 50% by weight based on the total amount of both raw materials.
本発明に用いる水素化触媒としては、通常使用される水
素化触媒が挙げられるが、具体例としては、ラネーニッ
ケルやラネーコバルトなどのラネー触媒、安定化ニッケ
ル及び貴金属触媒などが挙げられる。水素化触媒の使用
量はベンジルアミンに対し２〜５０重量％の範囲が反応
効率、触媒効率などの面から好ましい。The hydrogenation catalyst used in the present invention includes commonly used hydrogenation catalysts, and specific examples include Raney catalysts such as Raney nickel and Raney cobalt, stabilized nickel, and noble metal catalysts. The amount of hydrogenation catalyst used is preferably in the range of 2 to 50% by weight based on benzylamine from the viewpoint of reaction efficiency, catalyst efficiency, etc.
ベンジルアミンとベンジルアルコールのモル比は、理論
量の１対２で良いが、トリベンジルアミンを収率良く得
るため１対２〜４が好ましい。The molar ratio of benzylamine to benzyl alcohol may be the theoretical amount of 1:2, but is preferably 1:2 to 4 in order to obtain tribenzylamine in a good yield.
反応は通常１４０〜２００ ”Ｃ好ましくは１５０〜１
８０″Ｃにて好適に進行する。ベンジルアミンとベンジ
ルアルコールとを供給する時間としては、２〜１０時間
の短時間で十分であり、未反応ベンジルアミンはほとん
ど残らず、反応を完結させるための熟成時間は２〜５時
間で十分である。上記方法で得られるトリベンジルアミ
ンは一般的な単離精製手段、例えば反応液から熱時濾過
により水素化触媒を除去し、Ｐ液を蒸留精製するか、ま
たは、ｐ液に晶出溶媒を加え晶出させＦ遇することによ
り容易に高純度の目的物が得られる。The reaction temperature is usually 140 to 200"C, preferably 150 to 1
The reaction proceeds suitably at 80"C. A short time of 2 to 10 hours is sufficient for supplying benzylamine and benzyl alcohol, leaving almost no unreacted benzylamine and allowing the reaction to complete. A maturing time of 2 to 5 hours is sufficient.Tribenzylamine obtained by the above method can be purified using general isolation and purification methods, such as removing the hydrogenation catalyst from the reaction solution by hot filtration, and distilling and purifying the P solution. Alternatively, a highly pure target product can be easily obtained by adding a crystallization solvent to the p liquid and performing crystallization.
（発明の効果）
本発明によれば、ベンジルアミンとベンジルアルコール
を反応系内に供給しながら反応させることにより、従来
法に比べて高い収率でトリベンジルアミンを製造するこ
とができる。例えば、比較例−１ではトリベンジルアミ
ンの収率は７４．２％である。(Effects of the Invention) According to the present invention, by reacting benzylamine and benzyl alcohol while feeding them into the reaction system, tribenzylamine can be produced in a higher yield than in the conventional method. For example, in Comparative Example-1, the yield of tribenzylamine is 74.2%.
一方、本発明（実施例１．２）では収率９６％以上と非
常に高くなる。次に本発明の方法を実施例により説明す
るが、本発明はそれらに限定されるものではない。On the other hand, in the present invention (Example 1.2), the yield is extremely high at 96% or more. Next, the method of the present invention will be explained using Examples, but the present invention is not limited thereto.
実施例−１
務
１１ガラス反応器にベンジルアミノ１６ （０，１５
本
だ。撹拌、昇温し、１６０〜１６５°Ｃになると同量で
８時間で反応器内に供給し、この間反応温度を１６０〜
１６５”Ｃに保ちながら生成する水をトルエン共沸で系
外へ除去した。ベンジルアミン、ベンジルアルコールの
混合液の供給終了後生成すろ水がなくなるまで反応を続
けるのに４時間の熟成時間を必要とした。反応少溶媒の
トルエンを留９９．９％、収率９２．７％）を得た。さ
らにＰ液をアミンの総収率は９６．７％であった。Example-1 Benzyl amino 16 (0,15
is book. After stirring and raising the temperature to 160-165°C, the same amount was fed into the reactor over 8 hours, and during this time the reaction temperature was kept at 160-165°C.
The produced water was removed from the system by toluene azeotropy while maintaining the temperature at 165"C. After the supply of the mixed solution of benzylamine and benzyl alcohol was completed, 4 hours of aging time was required to continue the reaction until the produced filtrate disappeared. The reaction minor solvent, toluene, was distilled to 99.9%, yield 92.7%).Furthermore, P solution was used to obtain amine with a total yield of 96.7%.
実施例−２
実施例−１においてベンジルアミン、ベンジルアルコー
ルの混合液の供給時間を４時間にした他ジルアミン１１
．２（収率３．９％）を得た。トリベンジルアミンの総
収率は９６．１％であった。Example-2 In addition to changing the supply time of the mixed solution of benzylamine and benzyl alcohol to 4 hours in Example-1, Zylamine 11
．． 2 (yield 3.9%) was obtained. The total yield of tribenzylamine was 96.1%.
実施例−３
実施例−１においてラネーニッケルの代わりに滲
安定化ニッケル２０ を使用した他は同様に反応、後処
理を行ない、白色結晶のトリペンシルアミン２４２．５
（Ｇ、Ｃ１純度９９．９％、収率８４．５％）をン
の総収率は８９．３％であった。Example 3 The reaction and post-treatment were carried out in the same manner as in Example 1, except that effusion stabilized nickel 20 was used instead of Raney nickel, and white crystal tripencylamine 242.5 was obtained.
(G, C1 purity 99.9%, yield 84.5%) The total yield was 89.3%.
実施例−４
実施例−１においてあらかじめ反応器に仕込んトリベン
ジルアミンの総収率は、９２．０％であった。Example 4 In Example 1, the total yield of tribenzylamine charged into the reactor in advance was 92.0%.
昇温し、反応温度を１６０〜１６５°Ｃに保ちながら生
成してくる水をトルエン共沸で系外へ除去しｔこ 。The temperature is raised, and while maintaining the reaction temperature at 160 to 165°C, the water produced is removed from the system using toluene azeotropy.
Claims (1)
存在下に、生成する水を反応系外に除去しながら反応さ
せてトリベンジルアミンを製造するにあたり、ベンジル
アミン及びベンジルアルコールを反応系内に供給しなが
ら反応させることを特徴とするトリベンジルアミンの製
造方法。When producing tribenzylamine by reacting benzylamine and benzyl alcohol in the presence of a hydrogenation catalyst while removing the produced water from the reaction system, while supplying benzylamine and benzyl alcohol into the reaction system. A method for producing tribenzylamine, which comprises reacting it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62016493A JPS63185942A (en) | 1987-01-26 | 1987-01-26 | Production of tribenzylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62016493A JPS63185942A (en) | 1987-01-26 | 1987-01-26 | Production of tribenzylamine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63185942A true JPS63185942A (en) | 1988-08-01 |
Family
ID=11917811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62016493A Pending JPS63185942A (en) | 1987-01-26 | 1987-01-26 | Production of tribenzylamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63185942A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014115433A (en) * | 2012-12-10 | 2014-06-26 | Sharp Corp | Manufacturing method of photoreceptor, photoreceptor, and image forming apparatus including photoreceptor |
-
1987
- 1987-01-26 JP JP62016493A patent/JPS63185942A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014115433A (en) * | 2012-12-10 | 2014-06-26 | Sharp Corp | Manufacturing method of photoreceptor, photoreceptor, and image forming apparatus including photoreceptor |
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