JPH07138209A - Production of halogen-containing aminomethyl compound - Google Patents
Production of halogen-containing aminomethyl compoundInfo
- Publication number
- JPH07138209A JPH07138209A JP5307411A JP30741193A JPH07138209A JP H07138209 A JPH07138209 A JP H07138209A JP 5307411 A JP5307411 A JP 5307411A JP 30741193 A JP30741193 A JP 30741193A JP H07138209 A JPH07138209 A JP H07138209A
- Authority
- JP
- Japan
- Prior art keywords
- halogen
- compound
- reaction
- ammonium
- nitrile compound
- 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
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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、含ハロゲンアミノメチ
ル化合物の製造法に関する。本発明に係る含ハロゲンア
ミノメチル化合物は、医薬、農薬等の分野、特に除草
剤、殺虫剤の中間体等として有用である。FIELD OF THE INVENTION The present invention relates to a method for producing a halogen-containing aminomethyl compound. INDUSTRIAL APPLICABILITY The halogen-containing aminomethyl compound according to the present invention is useful in the fields of medicine, agricultural chemicals, etc., especially as an intermediate for herbicides and insecticides.
【０００２】[0002]
【従来の技術】一般的に、ニトリル化合物を原料として
アミノメチル化合物を得る方法としては、ニトリル化合
物中のニトリル基を還元してアミノメチル基とし、相当
するアミノメチル化合物を得る方法がある。この還元反
応は、下記反応式に示すように、水素化金属類等の還元
剤を用いる方法と、水素添加による方法とに大別され
る。2. Description of the Related Art Generally, as a method of obtaining an aminomethyl compound from a nitrile compound as a raw material, there is a method of reducing a nitrile group in the nitrile compound to give an aminomethyl group and obtaining a corresponding aminomethyl compound. This reduction reaction is roughly classified into a method using a reducing agent such as a metal hydride and a method using hydrogenation, as shown in the following reaction formula.
【０００３】[0003]
【化１】 [Chemical 1]
【０００４】式中、Ｒは、メチル、エチル等のアルキ
ル；置換若しくは無置換の、フェニル、トリル、ナフチ
ル等のアリール（ａｒｙｌ）；置換若しくは無置換の、
ピリジル、フリル等の複素環基；又はこれらが結合した
化合物を表す。上記のうち、還元剤を用いる方法として
は、例えば、水素化アルミニウムリチウム（ＬｉＡｌＨ
4 ）、水素化アルミニウム（ＡｌＨ3 ）、水素化ホウ素
ナトリウム（ＮａＢＨ4 ）等の還元剤を用いる方法があ
る。また、水素添加による方法としては、例えば、Ｃｏ
Ｃｌ2 、Ｃｏ2 （ＣＯ）8等の均一系触媒を用いる水素
添加、ラネーニッケル、ラネーコバルト、パラジウムカ
ーボン等の不均一系触媒を用いる水素添加等の方法があ
る。In the formula, R is alkyl such as methyl or ethyl; substituted or unsubstituted aryl such as phenyl, tolyl or naphthyl; substituted or unsubstituted,
A heterocyclic group such as pyridyl or furyl; or a compound to which these are bonded. Among the above, as a method using a reducing agent, for example, lithium aluminum hydride (LiAlH
4 ), aluminum hydride (AlH 3 ), sodium borohydride (NaBH 4 ) and the like. In addition, as a method by hydrogen addition, for example, Co
There are methods such as hydrogenation using a homogeneous catalyst such as Cl 2 and Co 2 (CO) 8 and hydrogenation using a heterogeneous catalyst such as Raney nickel, Raney cobalt and palladium carbon.
【０００５】しかしながら、還元剤を用いる方法では、
還元剤が高価であり経済的な不利がある、還元剤の
多くは禁水物質であり取扱操作が煩雑である等の問題点
があり、小規模な一部医薬品等に利用されるのみで、一
般的な工業化規模での使用には不向きな方法である。こ
れに対して触媒による水素添加による方法では、触媒
が高価であり経済的に不利である、触媒反応のために
必須の高圧設備に投資が必要である、２級アミン等の
副生物の生成により収率を上げるのが技術的に難しい等
の問題点があった。However, in the method using a reducing agent,
There is a problem that the reducing agent is expensive and economically disadvantageous, many of the reducing agents are water-prohibited substances, and the handling operation is complicated. This method is not suitable for use on a general industrial scale. On the other hand, in the method using catalytic hydrogenation, the catalyst is expensive and economically disadvantageous, and it is necessary to invest in high-pressure equipment essential for the catalytic reaction. There was a problem that it was technically difficult to increase the yield.
【０００６】ところで、アミノメチル化合物のうち、化
合物中にアミノメチル基とともに塩素、臭素、ふっ素等
のハロゲン元素を有する含ハロゲンアミノメチル化合物
を、含ハロゲンニトリル化合物を原料として製造する方
法としては、上記した還元剤を用いる方法、触媒による
水素添加による方法等が知られている。しかしながら、
上記の場合、上述した問題点があるほか、そのハロゲン
自身も還元されたアミノメチル化合物（以下、脱ハロゲ
ン化物という）が副生し、目的物の収率が低下するとい
う問題点があった。Among the aminomethyl compounds, the method for producing a halogen-containing aminomethyl compound having a halogen element such as chlorine, bromine or fluorine together with an aminomethyl group in the compound using a halogen-containing nitrile compound as a raw material is as described above. A method using the reducing agent described above, a method using hydrogenation with a catalyst, and the like are known. However,
In the above case, in addition to the above-mentioned problems, there is a problem in that the halogen itself is also reduced to form an aminomethyl compound (hereinafter referred to as a dehalogenated compound) as a by-product, which lowers the yield of the target product.
【０００７】特に含ハロゲン芳香族ニトリル化合物を原
料とする場合には、そのハロゲンとシアノ基の置換位置
がオルト又はパラ配位の場合には、この脱ハロゲン化物
の副生が多くなる傾向があり、脱ハロゲン化物の副生を
抑制する有効な手段がなかった。In particular, when a halogen-containing aromatic nitrile compound is used as a raw material, and when the substitution position of the halogen and the cyano group is the ortho or para coordination, the dehalogenation by-product tends to increase. However, there is no effective means for suppressing the dehalogenation by-product.
【０００８】[0008]
【化２】 [Chemical 2]
【０００９】式中、Ｘは、ハロゲンを表す。ところで、
含ハロゲンニトリル化合物を還元して含ハロゲンアミノ
メチル化合物を製造する工程において、反応時にアンモ
ニアを添加物として使用すると、２級アミン化合物の副
生が抑えられることが知られていた。しかしながら、上
記脱ハロゲン化物の副生は、この方法を用いても抑制で
きなかった。上記の方法による含ハロゲンニトリル化合
物がクロロシアノピリジン類の場合の還元反応について
ＤＥ３７２６９９３明細書中に開示があるが、その収率
は５８％と極めて低く実用的なものとは言えない。In the formula, X represents halogen. by the way,
In the step of producing a halogen-containing aminomethyl compound by reducing a halogen-containing nitrile compound, it has been known that by-product of a secondary amine compound can be suppressed by using ammonia as an additive during the reaction. However, the dehalogenation by-product could not be suppressed even by using this method. Although the reduction reaction in the case where the halogen-containing nitrile compound is a chlorocyanopyridine compound by the above method is disclosed in DE3726993 specification, the yield thereof is as extremely low as 58%, which is not practical.
【００１０】[0010]
【発明が解決しようとする課題】上記に鑑み、本発明は
含ハロゲンニトリル化合物を原料として含ハロゲンアミ
ノメチル化合物を製造するにあたって、２級アミン化合
物の副生を阻止するとともに、脱ハロゲン化物の副生を
も抑制し、効率的に含ハロゲンアミノメチル化合物を得
る方法を提供することを目的とするものである。In view of the above, in the present invention, when a halogen-containing nitrile compound is used as a raw material to produce a halogen-containing aminomethyl compound, a secondary amine compound is prevented from being produced as a by-product, and a dehalogenation by-product is produced. It is an object of the present invention to provide a method for efficiently obtaining a halogen-containing aminomethyl compound by suppressing the growth of raw materials.
【００１１】[0011]
【課題を解決するための手段】本発明の要旨は、含ハロ
ゲンアミノメチル化合物を製造するにあたり、含ハロゲ
ンニトリル化合物を、不均一系触媒の存在下、アンモニ
ア及びアンモニウム塩を添加して水素添加反応を行い、
含ハロゲンニトリル化合物のニトリル基を還元するとこ
ろにある。以下、本発明を詳述する。The gist of the present invention is to prepare a halogen-containing aminomethyl compound by adding a halogen-containing nitrile compound in the presence of a heterogeneous catalyst with ammonia and an ammonium salt to carry out a hydrogenation reaction. And then
It is in the process of reducing the nitrile group of a halogen-containing nitrile compound. Hereinafter, the present invention will be described in detail.
【００１２】本発明において原料として使用される含ハ
ロゲンニトリル化合物としては、脂肪族炭化水素がハロ
ゲン及びニトリル基で置換された化合物、芳香族炭化水
素がハロゲン及びニトリル基で置換された化合物、複素
環式化合物がハロゲン及びニトリル基で置換された化合
物、上記脂肪族炭化水素、芳香族炭化水素、複素環式化
合物等が結合した化合物の一部がハロゲン及びニトリル
基で置換された化合物等が挙げられる。上記ハロゲンと
しては、塩素、臭素、ふっ素、よう素が挙げられる。The halogen-containing nitrile compound used as a raw material in the present invention includes a compound in which an aliphatic hydrocarbon is substituted with a halogen and a nitrile group, a compound in which an aromatic hydrocarbon is substituted with a halogen and a nitrile group, and a heterocycle. Examples include compounds in which the formula compound is substituted with halogen and a nitrile group, compounds in which a part of the compound to which the above-mentioned aliphatic hydrocarbon, aromatic hydrocarbon, heterocyclic compound, etc. are bound is substituted with a halogen and a nitrile group. . Examples of the halogen include chlorine, bromine, fluorine and iodine.
【００１３】上記含ハロゲンニトリル化合物として、例
えば、ｐ−クロロベンゾニトリル、ｏ−クロロベンゾニ
トリル、ｍ−クロロベンゾニトリル、１−クロロ−２−
シアノナフタレン、１−クロロ−４−シアノナフタレ
ン、ｏ−クロロベンジルシアニド、ｐ−クロロベンジル
シアニド、３−クロロフタロニトリル、４−クロロフタ
ロニトリル、２−クロロイソフタロニトリル、４−クロ
ロイソフタロニトリル、５−クロロイソフタロニトリ
ル、２−クロロテレフタロニトリル、２，４−ジクロロ
ベンゾニトリル、２，６−ジクロロベンゾニトリル、
３，５−ジクロロベンゾニトリル、２−クロロ−３−シ
アノピリジン、２−クロロ−４−シアノピリジン、２−
クロロ−５−シアノピリジン、２，６−ジクロロ−３−
シアノピリジン、２，６−ジクロロ−４−シアノピリジ
ン、クロロアセトニトリル、３−クロロプロピオニトリ
ル、２−クロロプロピオニトリル、２，３−ジクロロプ
ロピオニトリル、１−クロロ−１，２−エタンジシアニ
ド、ｐ−ブロモベンゾニトリル、ｏ−ブロモベンゾニト
リル、ｍ−ブロモベンゾニトリル、１−ブロモ−２−シ
アノナフタレン、１−ブロモ−４−シアノナフタレン、
ｏ−ブロモベンジルシアニド、ｐ−ブロモベンジルシア
ニド、３−ブロモフタロニトリル、４−ブロモフタロニ
トリル、２−ブロモイソフタロニトリル、４−ブロモイ
ソフタロニトリル、５−ブロモイソフタロニトリル、２
−ブロモテレフタロニトリル、２，４−ジブロモベンゾ
ニトリル、２，６−ジブロモベンゾニトリル、３，５−
ジブロモベンゾニトリル、２−ブロモ−３−シアノピリ
ジン、２−ブロモ−４−シアノピリジン、２−ブロモ−
５−シアノピリジン、２，６−ジブロモ−３−シアノピ
リジン、２，６−ジブロモ−４−シアノピリジン、ブロ
モアセトニトリル、３−ブロモプロピオニトリル、２−
ブロモプロピオニトリル、２，３−ジブロモプロピオニ
トリル、１−ブロモ−１，２−エタンジシアニド等が挙
げられる。Examples of the halogen-containing nitrile compound include p-chlorobenzonitrile, o-chlorobenzonitrile, m-chlorobenzonitrile and 1-chloro-2-
Cyanonaphthalene, 1-chloro-4-cyanonaphthalene, o-chlorobenzyl cyanide, p-chlorobenzyl cyanide, 3-chlorophthalonitrile, 4-chlorophthalonitrile, 2-chloroisophthalonitrile, 4-chloroisophthalo Nitrile, 5-chloroisophthalonitrile, 2-chloroterephthalonitrile, 2,4-dichlorobenzonitrile, 2,6-dichlorobenzonitrile,
3,5-dichlorobenzonitrile, 2-chloro-3-cyanopyridine, 2-chloro-4-cyanopyridine, 2-
Chloro-5-cyanopyridine, 2,6-dichloro-3-
Cyanopyridine, 2,6-dichloro-4-cyanopyridine, chloroacetonitrile, 3-chloropropionitrile, 2-chloropropionitrile, 2,3-dichloropropionitrile, 1-chloro-1,2-ethanedicyanide, p-bromobenzonitrile, o-bromobenzonitrile, m-bromobenzonitrile, 1-bromo-2-cyanonaphthalene, 1-bromo-4-cyanonaphthalene,
o-bromobenzyl cyanide, p-bromobenzyl cyanide, 3-bromophthalonitrile, 4-bromophthalonitrile, 2-bromoisophthalonitrile, 4-bromoisophthalonitrile, 5-bromoisophthalonitrile, 2
-Bromoterephthalonitrile, 2,4-dibromobenzonitrile, 2,6-dibromobenzonitrile, 3,5-
Dibromobenzonitrile, 2-bromo-3-cyanopyridine, 2-bromo-4-cyanopyridine, 2-bromo-
5-cyanopyridine, 2,6-dibromo-3-cyanopyridine, 2,6-dibromo-4-cyanopyridine, bromoacetonitrile, 3-bromopropionitrile, 2-
Examples include bromopropionitrile, 2,3-dibromopropionitrile, 1-bromo-1,2-ethanedicyanide, and the like.
【００１４】本発明で使用されるアンモニウム塩は、特
に限定されるものではなく、例えば、塩化アンモニウ
ム、臭化アンモニウム、硫酸アンモニウム、硝酸アンモ
ニウム等が挙げることができる。上記アンモニウム塩
は、本発明で使用される上記含ハロゲンニトリル化合物
のハロゲンと同一のハロゲンとアンモニウムとの塩であ
ることが好ましい。例えば、上記含ハロゲンニトリル化
合物中のハロゲンが塩素の場合には、塩化アンモニウム
を用い、該ハロゲンが臭素の場合には、臭化アンモニウ
ムを用いるのが好ましい。上記アンモニウム塩の使用量
は、上記含ハロゲンニトリル化合物に対して、０．１〜
５倍モルである。０．１倍モルより少ない場合には、目
的物の収率が低下したり脱ハロゲン化反応の進行が多く
なり、また５倍モルより多い場合には、反応後の分離、
精製が困難になるので好ましくない。The ammonium salt used in the present invention is not particularly limited, and examples thereof include ammonium chloride, ammonium bromide, ammonium sulfate and ammonium nitrate. The ammonium salt is preferably a salt of the same halogen and ammonium as the halogen of the halogen-containing nitrile compound used in the present invention. For example, when the halogen in the halogen-containing nitrile compound is chlorine, ammonium chloride is used, and when the halogen is bromine, ammonium bromide is preferably used. The amount of the ammonium salt used is 0.1 to 0.1 with respect to the halogen-containing nitrile compound.
It is 5 times the molar amount. When the amount is less than 0.1 times the molar amount, the yield of the desired product is lowered or the progress of the dehalogenation reaction increases, and when the amount is more than the 5 times molar amount, separation after the reaction,
It is not preferable because purification becomes difficult.
【００１５】本発明においては、反応時にアンモニアと
ともに、上記アンモニウム塩を添加する。上記アンモニ
アの反応系への添加は、反応溶媒へのガス吹込、アンモ
ニア水のような含水状態のいずれでもよく、またアンモ
ニアガスを有機溶媒に通気飽和させる等の方法により得
られる飽和アンモニア性有機溶媒を反応溶媒として使用
する方法でもよい。In the present invention, the above ammonium salt is added together with ammonia during the reaction. The addition of the above ammonia to the reaction system may be either gas blowing into the reaction solvent, or any of the water-containing states such as ammonia water, and a saturated ammoniacal organic solvent obtained by a method of saturating the ammonia gas by aeration with an organic solvent. May be used as a reaction solvent.
【００１６】本発明で使用される不均一系触媒として
は、ニトリル基を還元することのできる触媒であれば、
特に限定されず、例えば、ラネーニッケル、ラネーコバ
ルト、パラジウムカーボン等が挙げられる。なかでも、
ラネーニッケル、ラネーコバルトは、脱ハロゲン化物の
生成がより効果的に抑制されるため、好ましく用いられ
る。The heterogeneous catalyst used in the present invention is a catalyst capable of reducing a nitrile group,
It is not particularly limited, and examples thereof include Raney nickel, Raney cobalt, and palladium carbon. Above all,
Raney nickel and Raney cobalt are preferably used because the production of dehalogenated compounds is more effectively suppressed.
【００１７】本発明の反応時の圧力は特に限定されず、
通常は法規制上の問題及び設備投資等の経済的効果を考
慮して大気圧〜１０気圧（ゲージ）で行えば良い。反応
温度によっても変化するが、反応を１〜２時間で完了さ
せるためには、５〜９気圧で行うことが好ましい。The pressure during the reaction of the present invention is not particularly limited,
Usually, the atmospheric pressure to 10 atm (gauge) may be taken into consideration in consideration of legal restrictions and economic effects such as capital investment. Although it changes depending on the reaction temperature, in order to complete the reaction in 1 to 2 hours, it is preferable to carry out at 5 to 9 atm.
【００１８】上記反応の温度は、通常０〜８０℃、好ま
しくは１５〜６０℃である。反応温度が８０℃より高く
なるとタール状物が多く生成し、０℃より低いと反応速
度が遅くなり経済的でない。The temperature of the above reaction is usually 0 to 80 ° C, preferably 15 to 60 ° C. When the reaction temperature is higher than 80 ° C, a large amount of tar-like substances are produced, and when the reaction temperature is lower than 0 ° C, the reaction rate becomes slow, which is not economical.
【００１９】上記反応は溶媒中で行うことができる。上
記溶媒としては、基質を溶解する溶媒であれば特に限定
されず、例えば、アルコール系溶媒としてメタノール、
エタノール、ｉ−プロパノール等；エーテル系溶媒とし
てジエチルエーテル、ジイソプロピルエーテル、ジオキ
サン、ＴＨＦ等；炭化水素系溶媒としてヘキサン、シク
ロヘキサン、オクタン、トルエン、キシレン等；エステ
ル系溶媒として酢酸エチル、酢酸プロピル等が挙げられ
る。これら溶媒は、単独又は複数を混合して用いること
ができる。The above reaction can be carried out in a solvent. The solvent is not particularly limited as long as it is a solvent that dissolves a substrate, and for example, methanol as an alcohol solvent,
Ethanol, i-propanol, etc .; ether solvents such as diethyl ether, diisopropyl ether, dioxane, THF, etc .; hydrocarbon solvents such as hexane, cyclohexane, octane, toluene, xylene, etc .; ester solvents such as ethyl acetate, propyl acetate, etc. To be These solvents may be used alone or in combination of two or more.
【００２０】[0020]
【作用】以上のとおり、従来から２級アミン化合物の副
生を抑制するために反応時添加されていたアンモニアと
ともに、アンモニア塩を併用添加することにより相乗効
果がみられ、これにより、２級アミンの副生が更に大き
く抑制されるだけでなく、分子内の活性なハロゲンが還
元されてできる脱ハロゲン化物の副生も同時に抑制する
ことができる。As described above, a synergistic effect is observed by adding together an ammonia salt together with ammonia, which was conventionally added at the time of reaction in order to suppress the by-product of the secondary amine compound. Not only the by-product of the above is further suppressed, but also the by-product of the dehalogenation product formed by reducing the active halogen in the molecule can be suppressed at the same time.
【００２１】[0021]
【実施例】以下に本発明の実施例を掲げて更に詳しく説
明するが、本発明はこれら実施例に限定されるものでは
ない。 実施例１ ２−クロロ−５−シアノピリジン１０．７ｇ（０．０７
７モル）、塩化アンモニウム８．２ｇ（０．１５４モ
ル）を、アンモニアガスをメタノールに通気し飽和させ
て得た飽和アンモニア性メタノール１００ｍｌに溶解
し、ラネーニッケル５ｇをこれに加え、オートクレーブ
中で水素圧９ｋｇ／ｃｍ2 Ｇ、室温で１時間反応した。
触媒を濾過後、溶媒を留去した。濃縮物に３０％苛性ソ
ーダを加え中和し、酢酸エチルで抽出した。有機層を濃
縮後、減圧蒸留を行い、２−クロロ−５−アミノメチル
ピリジン９．７ｇ（収率８８．２％）を得た。このもの
の圧力２ｍｍＨｇにおける沸点は、１０２〜１０５℃の
範囲であった。またこのものをガスクロマトグラフィー
により分析したところ、２級アミンは面積百分率で０．
３％、脱クロロ体である３−アミノメチルピリジンは同
２．８％生成していることがわかった。The present invention will be described in more detail below with reference to examples of the present invention, but the present invention is not limited to these examples. Example 1 10.7 g (0.07) of 2-chloro-5-cyanopyridine
7 mol) and 8.2 g (0.154 mol) of ammonium chloride are dissolved in 100 ml of saturated ammoniacal methanol obtained by allowing ammonia gas to pass through and saturated with methanol. The reaction was performed at 9 kg / cm 2 G and room temperature for 1 hour.
After filtering the catalyst, the solvent was distilled off. The concentrate was neutralized with 30% sodium hydroxide and extracted with ethyl acetate. The organic layer was concentrated and then distilled under reduced pressure to obtain 9.7 g of 2-chloro-5-aminomethylpyridine (yield 88.2%). The boiling point of this product at a pressure of 2 mmHg was in the range of 102 to 105 ° C. When this product was analyzed by gas chromatography, secondary amine was found to have an area percentage of 0.
It was found that 3% and 3-aminomethylpyridine, which is a dechloroform, were produced at 2.8%.
【００２２】実施例２ ４−クロロベンゾニトリル１０．６ｇ（０．０７７モ
ル）、塩化アンモニウム８．２ｇ（０．１５４モル）を
飽和アンモニア性メタノール１００ｍｌに溶解し、ラネ
ーコバルト５ｇをこれに加え、オートクレーブ中で水素
圧９ｋｇ／ｃｍ2Ｇ、４０℃で１時間反応した。触媒を
濾過後、溶媒を留去した。濃縮物に３０％苛性ソーダを
加え中和し、酢酸エチルで抽出した。有機層を濃縮後、
減圧蒸留を行い、４−クロロベンジルアミン１０．０ｇ
（収率９１．７％）を得た。このものの圧力１５ｍｍＨ
ｇにおける沸点は、１０６〜１０７℃の範囲であった。Example 2 10.6 g (0.077 mol) of 4-chlorobenzonitrile and 8.2 g (0.154 mol) of ammonium chloride were dissolved in 100 ml of saturated ammoniacal methanol, and 5 g of Raney cobalt was added thereto. Reaction was carried out in an autoclave at a hydrogen pressure of 9 kg / cm 2 G and 40 ° C. for 1 hour. After filtering the catalyst, the solvent was distilled off. The concentrate was neutralized with 30% sodium hydroxide and extracted with ethyl acetate. After concentrating the organic layer,
Distilled under reduced pressure to give 4-chlorobenzylamine 10.0 g.
(Yield 91.7%) was obtained. The pressure of this thing is 15mmH
The boiling point at g was in the range of 106-107 ° C.
【００２３】実施例３ ４−ブロモベンゾニトリル１４．０ｇ（０．０７７モ
ル）、臭化アンモニウム１５．１ｇ（０．１５４モル）
を飽和アンモニア性メタノール１００ｍｌに溶解し、ラ
ネーニッケル５ｇをこれに加え、オートクレーブ中で水
素圧５ｋｇ／ｃｍ 2 Ｇ、室温で３時間反応した。触媒を
濾過後、溶媒を留去した。濃縮物に３０％苛性ソーダを
加え中和し、酢酸エチルで抽出した。有機層を濃縮後、
減圧蒸留を行い、４−ブロモベンジルアミン１１．２ｇ
（収率７８．３％）を得た。このものの圧力１５ｍｍＨ
ｇにおける沸点は、１２６〜１２７℃の範囲であった。Example 3 14.0 g (0.077 mol) of 4-bromobenzonitrile
), Ammonium bromide 15.1 g (0.154 mol)
Was dissolved in 100 ml of saturated ammoniacal methanol,
Add 5 g of Nanickel and water in an autoclave.
Element pressure 5kg / cm 2G, reacted at room temperature for 3 hours. Catalyst
After filtration, the solvent was distilled off. Add 30% caustic soda to the concentrate
The mixture was neutralized and extracted with ethyl acetate. After concentrating the organic layer,
Distillation under reduced pressure is carried out, and 11.2 g of 4-bromobenzylamine
(Yield 78.3%) was obtained. The pressure of this thing is 15mmH
The boiling point at g was in the range of 126-127 ° C.
【００２４】実施例４ ３−クロロプロピオニトリル６．９ｇ（０．０７７モ
ル）、塩化アンモニウム８．２ｇ（０．１５４モル）を
飽和アンモニア性メタノール１００ｍｌに溶解し、ラネ
ーニッケル５ｇをこれに加え、オートクレーブ中で水素
圧９ｋｇ／ｃｍ2Ｇ、室温で１時間反応した。触媒を濾
過後、溶媒を留去した。濃縮物に３０％苛性ソーダを加
え中和し、酢酸エチルで抽出した。有機層に塩化水素３
ｇを吹き込み、濾別乾燥し、３−クロロプロピルアミン
塩酸塩９．２ｇ（収率９２．０％）を得た。このものの
融点は、１４８〜１５０℃の範囲であった。Example 4 6.9 g (0.077 mol) of 3-chloropropionitrile and 8.2 g (0.154 mol) of ammonium chloride were dissolved in 100 ml of saturated ammoniacal methanol, and 5 g of Raney nickel was added thereto. The reaction was carried out in an autoclave at a hydrogen pressure of 9 kg / cm 2 G and room temperature for 1 hour. After filtering the catalyst, the solvent was distilled off. The concentrate was neutralized with 30% sodium hydroxide and extracted with ethyl acetate. Hydrogen chloride 3 in the organic layer
g was blown in, filtered and dried to obtain 9.2 g of 3-chloropropylamine hydrochloride (yield 92.0%). The melting point of this product was in the range of 148 to 150 ° C.
【００２５】比較例１ 塩化アンモニウムを添加しない以外は、実施例１と同様
の方法、及び条件にて反応を行った。その結果、２−ク
ロロ−５−アミノメチルピリジン６．３ｇ（収率５７．
３％）を得た。このものをガスクロマトグラフィーによ
り分析したところ、２級アミンは面積百分率で１５．２
％、脱クロロ体は同８．５％生成していることがわかっ
た。Comparative Example 1 The reaction was carried out by the same method and conditions as in Example 1 except that ammonium chloride was not added. As a result, 6.3 g of 2-chloro-5-aminomethylpyridine (yield 57.
3%) was obtained. This product was analyzed by gas chromatography to find that the secondary amine had an area percentage of 15.2.
%, And the dechloroform was produced at 8.5%.
【００２６】[0026]
【発明の効果】本発明によれば、含ハロゲンニトリル化
合物の還元反応において、反応時に、従来から用いられ
てきたアンモニアに加えて、アンモニウム塩を添加する
と、２級アミンの副生が一層少なくなり、更にアンモニ
アのみを添加する場合には抑制することができなかった
脱ハロゲン化物等の副生成物の生成を抑制し、極めて効
率的に含ハロゲンアミノメチル化合物を製造することが
できる。INDUSTRIAL APPLICABILITY According to the present invention, in the reduction reaction of a halogen-containing nitrile compound, when an ammonium salt is added in addition to ammonia which has been conventionally used during the reaction, the secondary amine by-product is further reduced. Further, the production of by-products such as dehalogenated compounds, which could not be suppressed when ammonia alone is added, can be suppressed, and the halogen-containing aminomethyl compound can be produced extremely efficiently.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｄ 213/61 // Ｃ０７Ｂ 61/00 ３００ (72)発明者 山本 幹生 兵庫県加古郡播磨町宮西346番地の１ 住 友精化株式会社第１研究所内─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 6 Identification number Internal reference number FI Technical indication C07D 213/61 // C07B 61/00 300 (72) Inventor Mikio Yamamoto Miyanishi, Kami-gun, Kako-gun Miyanishi No. 346 No. 1 Sumitomo Seika Co., Ltd. 1st Laboratory
Claims (7)
触媒の存在下、アンモニア及びアンモニウム塩を添加し
て水素添加反応を行い、含ハロゲンニトリル化合物のニ
トリル基を還元することを特徴とする含ハロゲンアミノ
メチル化合物の製造法。1. A halogen-containing nitrile compound, wherein ammonia and an ammonium salt are added in the presence of a heterogeneous catalyst to carry out a hydrogenation reaction to reduce the nitrile group of the halogen-containing nitrile compound. A method for producing an aminomethyl compound.
臭化アンモニウム、硫酸アンモニウム又は硝酸アンモニ
ウムである請求項１記載の製造法。2. The ammonium salt is ammonium chloride,
The production method according to claim 1, which is ammonium bromide, ammonium sulfate or ammonium nitrate.
ニトリル化合物に対して０．１〜５倍モルである請求項
１記載の製造法。3. The method according to claim 1, wherein the ammonium salt is added in an amount of 0.1 to 5 times the molar amount of the halogen-containing nitrile compound.
ネーコバルトである請求項１記載の製造法。4. The method according to claim 1, wherein the heterogeneous catalyst is Raney nickel or Raney cobalt.
ージ）である請求項１記載の製造法。5. The method according to claim 1, wherein the pressure range of the reduction reaction is 0 to 10 atm (gauge).
請求項１記載の製造法。6. The production method according to claim 1, wherein the reaction temperature of the reduction reaction is 0 to 80 ° C.
請求項１記載の製造法。7. The production method according to claim 1, wherein the reaction solvent for the reduction reaction is methanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5307411A JPH07138209A (en) | 1993-11-12 | 1993-11-12 | Production of halogen-containing aminomethyl compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5307411A JPH07138209A (en) | 1993-11-12 | 1993-11-12 | Production of halogen-containing aminomethyl compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07138209A true JPH07138209A (en) | 1995-05-30 |
Family
ID=17968737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5307411A Pending JPH07138209A (en) | 1993-11-12 | 1993-11-12 | Production of halogen-containing aminomethyl compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07138209A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000017138A1 (en) * | 1998-09-17 | 2000-03-30 | Asahi Glass Company Ltd. | Process for the preparation of fluorobenzyl derivatives |
| US6921828B2 (en) | 2000-08-25 | 2005-07-26 | Bayer Cropscience S.A. | Processes for the preparation of 2-aminomethlpyridines and the 2-cyanopyridines used in their preparation |
| JP2012179501A (en) * | 2011-02-28 | 2012-09-20 | Ne Chemcat Corp | Palladium-containing catalyst for nitrile compound hydrogenation and method of manufacturing primary amine using the same |
| US9988353B2 (en) * | 2013-11-15 | 2018-06-05 | Bayer Cropscience Aktiengesellschaft | Catalytic hydrogenation of nitriles |
| US10781176B2 (en) * | 2015-04-30 | 2020-09-22 | Bayer Cropscience Aktiengesellschaft | Catalytic hydrogenation of substituted cyanopyridines and process for preparing substituted pyridylmethylbenzamides |
-
1993
- 1993-11-12 JP JP5307411A patent/JPH07138209A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000017138A1 (en) * | 1998-09-17 | 2000-03-30 | Asahi Glass Company Ltd. | Process for the preparation of fluorobenzyl derivatives |
| US6452056B1 (en) * | 1998-09-17 | 2002-09-17 | Asahi Glass Company, Limited | Process for the preparation of fluorobenzyl derivatives |
| US6921828B2 (en) | 2000-08-25 | 2005-07-26 | Bayer Cropscience S.A. | Processes for the preparation of 2-aminomethlpyridines and the 2-cyanopyridines used in their preparation |
| US7321043B2 (en) | 2000-08-25 | 2008-01-22 | Bayer Cropscience S.A. | Processes for the preparation of 2-aminomethylpyridines and the 2-cyanopyridines used in their preparation |
| JP2012179501A (en) * | 2011-02-28 | 2012-09-20 | Ne Chemcat Corp | Palladium-containing catalyst for nitrile compound hydrogenation and method of manufacturing primary amine using the same |
| US9988353B2 (en) * | 2013-11-15 | 2018-06-05 | Bayer Cropscience Aktiengesellschaft | Catalytic hydrogenation of nitriles |
| US10414730B2 (en) | 2013-11-15 | 2019-09-17 | Bayer Cropscience Aktiengesellschaft | Catalytic hydrogenation of nitriles |
| US10781176B2 (en) * | 2015-04-30 | 2020-09-22 | Bayer Cropscience Aktiengesellschaft | Catalytic hydrogenation of substituted cyanopyridines and process for preparing substituted pyridylmethylbenzamides |
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