JP2001233838A - Method for producing alkylamine fluoride compound - Google Patents
Method for producing alkylamine fluoride compoundInfo
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- JP2001233838A JP2001233838A JP2000357871A JP2000357871A JP2001233838A JP 2001233838 A JP2001233838 A JP 2001233838A JP 2000357871 A JP2000357871 A JP 2000357871A JP 2000357871 A JP2000357871 A JP 2000357871A JP 2001233838 A JP2001233838 A JP 2001233838A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、Ｆ（ＣＦ2）n（Ｃ
Ｈ2）mＮＨ2で表されるフッ化アルキルアミン化合物の
製造方法に関する。[0001] The present invention relates to F (CF 2 ) n (C
The present invention relates to a method for producing a fluorinated alkylamine compound represented by H 2 ) m NH 2 .
【０００２】[0002]
【従来の技術】Ｆ（ＣＦ2）n（ＣＨ2）mＮＨ2で表され
るフッ化アルキルアミン化合物は、各種有機化合物の合
成中間体として有用な化合物である。特にＣＦ3ＣＨ2Ｎ
Ｈ2は、医農薬の合成中間体として有用な化合物であ
る。2. Description of the Related Art Fluorinated alkylamine compounds represented by F (CF 2 ) n (CH 2 ) m NH 2 are useful as intermediates for synthesizing various organic compounds. Especially CF 3 CH 2 N
H 2 is a compound useful as a synthetic intermediate for medicinal and agricultural chemicals.
【０００３】Ｆ（ＣＦ2）n（ＣＨ2）mＸとアンモニアと
を反応させて、Ｆ（ＣＦ2）n（ＣＨ 2）mＮＨ2を製造す
る方法としては、（１）無水の不活性溶媒の存在下で、
ＣＦ3ＣＨ2Ｘに対して１〜３倍モルのＮＨ3を反応させ
てＣＦ3ＣＨ2ＮＨ2とする方法（ＵＳＰ４６１８７１
８）、（２）ＣＦ3ＣＨ2Ｃｌと濃アンモニア水とを反応
させてＣＦ3ＣＨ2ＮＨ2とする際に、ＣＦ3ＣＨ2Ｃｌに
対して１〜３倍モルのＮＨ3を用いる方法（ＵＳＰ２３
４８３２１）、（３）ＣＦ3ＣＨ2ＣｌまたはＣＦ3ＣＨ2
Ｂｒと濃アンモニア水とを反応させてＣＦ3ＣＨ2ＮＨ2
とする際に、ＣＦ3ＣＨ2ＣｌまたはＣＦ3ＣＨ2Ｂｒに対
して６．５倍モルのＮＨ3を用いる方法（Ｄｉｃｋｅｙ
ｅｔ ａｌ．，Ｉｎｄ．Ｅｎｇ．Ｃｈｅｍ．，４８，
２０９，１９５６）等が知られている。[0003] F (CFTwo)n(CHTwo)mX and ammonia
And react with F (CFTwo)n(CH Two)mNHTwoManufacture
(1) In the presence of an anhydrous inert solvent,
CFThreeCHTwo1 to 3 moles of NH with respect to XThreeReact
And CFThreeCHTwoNHTwo(USP 4,618,711)
8), (2) CFThreeCHTwoReaction between Cl and concentrated aqueous ammonia
Let me CFThreeCHTwoNHTwoAnd CFThreeCHTwoCl
1 to 3 moles of NHThreeUsing USP23 (USP23
48321), (3) CFThreeCHTwoCl or CFThreeCHTwo
The reaction between Br and concentrated aqueous ammoniaThreeCHTwoNHTwo
And CFThreeCHTwoCl or CFThreeCHTwoAgainst Br
6.5 moles of NHThree(Dickkey)
et al. , Ind. Eng. Chem. , 48,
209, 1956).
【０００４】[0004]
【発明が解決しようとする課題】しかし（１）の方法で
は、生成したＣＦ3ＣＨ2ＮＨ2の一部と副生するＨＸと
が反応してハロゲン化物塩（ＣＦ3ＣＨ2ＮＨ2・ＨＸ）
を形成し、ＣＦ3ＣＨ2ＮＨ2の収率が低くなる（７０〜
８７％程度）問題が認められた。また、生成したＣＦ3
ＣＨ2ＮＨ2・ＨＸをＣＦ3ＣＨ2ＮＨ2に変換して回収す
るためには、アルカリ水溶液を添加し、有機溶媒により
抽出を行った後、蒸留精製する必要があり、実工程数が
多く煩雑になる問題があった。さらに、生成したＣＦ3
ＣＨ2ＮＨ2の一部が、さらにＣＦ3ＣＨ2Ｘと反応して
［Ｆ（ＣＦ2）n（ＣＨ2）m］2ＮＨで表される第二アミ
ン化合物や［Ｆ（ＣＦ2）n（ＣＨ2）m］3Ｎで表される
第三アミン化合物が生成し、ＣＦ3ＣＨ2ＮＨ2の収率が
低くなる問題もあった。However, in the method (1), a part of the generated CF 3 CH 2 NH 2 reacts with the by-produced HX to form a halide salt (CF 3 CH 2 NH 2 .HX). )
And the yield of CF 3 CH 2 NH 2 is reduced (70-
(About 87%) A problem was observed. In addition, the generated CF 3
The CH 2 NH 2 · HX to recover converted to CF 3 CH 2 NH 2 may, adding an alkali aqueous solution, after extraction with an organic solvent, it is necessary to distillation purification, many actual number of steps There was a problem that became complicated. Furthermore, the generated CF 3
Part of CH 2 NH 2 further reacts with CF 3 CH 2 X to form a secondary amine compound represented by [F (CF 2 ) n (CH 2 ) m ] 2 NH or [F (CF 2 ) n There was also a problem that a tertiary amine compound represented by (CH 2 ) m ] 3 N was generated, and the yield of CF 3 CH 2 NH 2 was reduced.
【０００５】（２）や（３）の方法では、有機溶媒は用
いられず、濃アンモニア水が反応溶媒となっている。濃
アンモニア水にはＣＦ3ＣＨ2Ｘが溶解しにくいため、Ｎ
Ｈ3との反応性が低下し、収率が低くなる問題が認めら
れた。さらに、（２）や（３）の方法を実施する場合に
は、反応器が腐食する問題があり、ハステロイ等の耐酸
性の材質からなる高価な反応器を使用する必要があっ
た。In the methods (2) and (3), no organic solvent is used, and concentrated aqueous ammonia is used as a reaction solvent. Since CF 3 CH 2 X is difficult to dissolve in concentrated ammonia water,
There was a problem that the reactivity with H 3 was reduced and the yield was reduced. Further, when the methods (2) and (3) are performed, there is a problem that the reactor is corroded, and it is necessary to use an expensive reactor made of an acid-resistant material such as Hastelloy.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記の問題を
解決すべくなされたものであり、Ｆ（ＣＦ2）n（Ｃ
Ｈ 2）mＸ（ただし、Ｘは、塩素原子、臭素原子またはヨ
ウ素原子を示し、ｎおよびｍは、それぞれ独立して１以
上の整数を示す。）で表される化合物とＮＨ3とを反応
させてＦ（ＣＦ2）n（ＣＨ2）mＮＨ2（ｎおよびｍは、
前記と同じ意味を示す。）で表される化合物を製造する
方法において、Ｆ（ＣＦ2）n（ＣＨ2）mＸに対して４倍
モル以上のＮＨ3を用いて、有機溶媒を必須成分とする
反応溶媒の存在下に反応を行うことを特徴とするフッ化
アルキルアミン化合物の製造方法を提供する。The present invention solves the above problems.
It was made to solve, and F (CFTwo)n(C
H Two)mX (where X is a chlorine atom, a bromine atom or
Represents an iodine atom, and n and m are each independently 1 or more
Indicates the above integer. ) And NHThreeReact with
Let F (CFTwo)n(CHTwo)mNHTwo(N and m are
It has the same meaning as above. To produce the compound represented by
In the method, F (CFTwo)n(CHTwo)m4 times for X
More than mole of NHThreeUsing organic solvent as an essential component
Fluorination characterized by conducting the reaction in the presence of a reaction solvent
Provided is a method for producing an alkylamine compound.
【０００７】[0007]
【発明の実施の形態】本発明におけるＦ（ＣＦ2）n（Ｃ
Ｈ2）mＸにおいて、Ｘは入手しやすさや反応性等の点か
ら塩素原子が好ましい。また、ｎは１〜１６が好ましく
１〜８が特に好ましく、１がとりわけ好ましい。ｍは１
〜１０が好ましく、１〜５が特に好ましく、１がとりわ
け好ましい。Ｆ（ＣＦ2）n（ＣＨ2）mＸの具体例として
はつぎの化合物が挙げられる。DETAILED DESCRIPTION OF THE INVENTION F (CF 2 ) n (C
In H 2 ) m X, X is preferably a chlorine atom from the viewpoint of availability and reactivity. Further, n is preferably 1 to 16, particularly preferably 1 to 8, and particularly preferably 1. m is 1
10 is preferable, 1 to 5 is particularly preferable, and 1 is particularly preferable. Specific examples of F (CF 2 ) n (CH 2 ) m X include the following compounds.
【０００８】ＣＦ3ＣＨ2Ｃｌ、ＣＦ3ＣＨ2Ｂｒ、ＣＦ3
ＣＨ2Ｉ、ＣＦ3ＣＦ2ＣＨ2Ｃｌ、ＣＦ3ＣＦ2ＣＨ2Ｂ
ｒ、ＣＦ3ＣＦ2ＣＨ2Ｉ、Ｆ（ＣＦ2）3ＣＨ2Ｃｌ、Ｆ
（ＣＦ2） 4ＣＨ2Ｃｌ、Ｆ（ＣＦ2）5ＣＨ2Ｃｌ、Ｆ（Ｃ
Ｆ2）6ＣＨ2Ｃｌ、Ｆ（ＣＦ2）7ＣＨ2Ｃｌ、Ｆ（Ｃ
Ｆ2）8ＣＨ2Ｃｌ。[0008] CFThreeCHTwoCl, CFThreeCHTwoBr, CFThree
CHTwoI, CFThreeCFTwoCHTwoCl, CFThreeCFTwoCHTwoB
r, CFThreeCFTwoCHTwoI, F (CFTwo)ThreeCHTwoCl, F
(CFTwo) FourCHTwoCl, F (CFTwo)FiveCHTwoCl, F (C
FTwo)6CHTwoCl, F (CFTwo)7CHTwoCl, F (C
FTwo)8CHTwoCl.
【０００９】ＣＦ3（ＣＨ2）2Ｃｌ、ＣＦ3（ＣＨ2）2Ｂ
ｒ、ＣＦ3（ＣＨ2）2Ｉ、ＣＦ3ＣＦ 2（ＣＨ2）2Ｃｌ、
ＣＦ3ＣＦ2（ＣＨ2）2Ｂｒ、ＣＦ3ＣＦ2（ＣＨ2）2Ｉ、
Ｆ（ＣＦ2）3（ＣＨ2）2Ｃｌ、Ｆ（ＣＦ2）4（ＣＨ2）2
Ｃｌ、Ｆ（ＣＦ2）5（ＣＨ2）2Ｃｌ、Ｆ（ＣＦ2）6（Ｃ
Ｈ2）2Ｃｌ、Ｆ（ＣＦ2）7（ＣＨ2）2Ｃｌ、Ｆ（Ｃ
Ｆ2）8（ＣＨ2）2Ｃｌ。[0009] CFThree(CHTwo)TwoCl, CFThree(CHTwo)TwoB
r, CFThree(CHTwo)TwoI, CFThreeCF Two(CHTwo)TwoCl,
CFThreeCFTwo(CHTwo)TwoBr, CFThreeCFTwo(CHTwo)TwoI,
F (CFTwo)Three(CHTwo)TwoCl, F (CFTwo)Four(CHTwo)Two
Cl, F (CFTwo)Five(CHTwo)TwoCl, F (CFTwo)6(C
HTwo)TwoCl, F (CFTwo)7(CHTwo)TwoCl, F (C
FTwo)8(CHTwo)TwoCl.
【００１０】ＣＦ3（ＣＨ2）3Ｃｌ、ＣＦ3（ＣＨ2）3Ｂ
ｒ、ＣＦ3（ＣＨ2）3Ｉ、ＣＦ3ＣＦ 2（ＣＨ2）3Ｃｌ、
ＣＦ3ＣＦ2（ＣＨ2）3Ｂｒ、ＣＦ3ＣＦ2（ＣＨ2）3Ｉ、
Ｆ（ＣＦ2）4（ＣＨ2）3Ｃｌ、Ｆ（ＣＦ2）4（ＣＨ2）3
Ｃｌ、Ｆ（ＣＦ2）5（ＣＨ2）3Ｃｌ、 Ｆ（ＣＦ2）
6（ＣＨ2）3Ｃｌ、Ｆ（ＣＦ2）7（ＣＨ2）3Ｃｌ、Ｆ
（ＣＦ2）8（ＣＨ2）3Ｃｌ。[0010] CFThree(CHTwo)ThreeCl, CFThree(CHTwo)ThreeB
r, CFThree(CHTwo)ThreeI, CFThreeCF Two(CHTwo)ThreeCl,
CFThreeCFTwo(CHTwo)ThreeBr, CFThreeCFTwo(CHTwo)ThreeI,
F (CFTwo)Four(CHTwo)ThreeCl, F (CFTwo)Four(CHTwo)Three
Cl, F (CFTwo)Five(CHTwo)ThreeCl, F (CFTwo)
6(CHTwo)ThreeCl, F (CFTwo)7(CHTwo)ThreeCl, F
(CFTwo)8(CHTwo)ThreeCl.
【００１１】本発明においてはＦ（ＣＦ2）n（ＣＨ2）m
ＸとＮＨ3とを反応させる際に、Ｆ（ＣＦ2）n（ＣＨ2）
mＸに対して４倍モル以上のＮＨ3を用いる点が特徴の一
つである。ただし、該反応におけるＮＨ3の量が多くな
りすぎると、反応圧力が高くなる、未反応のＮＨ3が残
存する、操作性および経済性が低下する等の問題が起こ
るおそれがある。よってＮＨ3の量は、Ｆ（ＣＦ2）
n（ＣＨ2）mＸに対して４〜１０倍モルが好ましく、特
に４〜６倍モルが好ましい。In the present invention, F (CF 2 ) n (CH 2 ) m
When reacting X with NH 3 , F (CF 2 ) n (CH 2 )
One of the features is that NH 3 is used at least 4 times the molar amount of m X. However, if the amount of NH 3 in the reaction is too large, problems such as an increase in reaction pressure, remaining unreacted NH 3 , and deterioration in operability and economy may occur. Therefore, the amount of NH 3 is F (CF 2 )
n (CH 2) m 4~10 moles are preferred with respect to X, especially 4-6 moles are preferred.
【００１２】Ｆ（ＣＦ2）n（ＣＨ2）mＸとＮＨ3との反
応では副生成物（ＨＸ）が生成する。このＨＸはさらに
ＮＨ3と反応してＮＨ4Ｘを生成させるが、ＮＨ3の量が
少ない場合にはＨＸはＦ（ＣＦ2）n（ＣＨ2）mＮＨ2と
も反応してＦ（ＣＦ2）n（ＣＨ2）mＮＨ2・ＨＸを生成
させる。しかし本発明においては、ＮＨ3の量を特定量
以上にすることでＦ（ＣＦ2）n（ＣＨ2）mＮＨ2・ＨＸ
の生成量は顕著に少なくなる。さらに、過剰に存在する
ＮＨ3は、後述する第二アミン化合物や第三アミン化合
物が生成する副反応を抑制する作用も有すると考えられ
る。また、過剰に存在するＮＨ3は、フッ化アルキルア
ミン化合物とＨＸとの反応で生成するＦ（ＣＦ2）n（Ｃ
Ｈ2）mＮＨ2・ＨＸをＦ（ＣＦ2）n（ＣＨ2）mＮＨ2に変
換する作用も有すると考えられる。In the reaction between F (CF 2 ) n (CH 2 ) m X and NH 3 , a by-product (HX) is produced. This HX further reacts with NH 3 to form NH 4 X, but when the amount of NH 3 is small, HX also reacts with F (CF 2 ) n (CH 2 ) m NH 2 to form F (CF 2 ) N (CH 2 ) m NH 2 · HX is produced. However, in the present invention, F (CF 2) by the amount of NH 3 more than the specific amount n (CH 2) m NH 2 · HX
Is significantly reduced. Further, it is considered that NH 3 present in excess has an effect of suppressing a side reaction generated by a secondary amine compound or a tertiary amine compound described later. In addition, NH 3 present in excess is formed by F (CF 2 ) n (C
It is considered that H 2 ) m NH 2 · HX also has an action of converting F (CF 2 ) n (CH 2 ) m NH 2 .
【００１３】さらに、本発明においては、Ｆ（ＣＦ2）n
（ＣＨ2）mＸとＮＨ3との反応を有機溶媒を必須成分と
する反応溶媒の存在下で行う。反応溶媒としては、実質
的に有機溶剤のみ、または、有機溶剤および水、からな
るのが好ましく、実質的に有機溶剤のみからなるのが特
に好ましい。反応溶媒が、有機溶剤および水からなる場
合には、有機溶剤の量を水に対して１質量％以上にする
のが好ましく、１０質量％以上にするのが特に好まし
い。Further, in the present invention, F (CF 2 ) n
The reaction between (CH 2 ) m X and NH 3 is carried out in the presence of a reaction solvent containing an organic solvent as an essential component. The reaction solvent is preferably substantially composed of only an organic solvent or an organic solvent and water, and particularly preferably composed of substantially only an organic solvent. When the reaction solvent is composed of an organic solvent and water, the amount of the organic solvent is preferably at least 1% by mass, particularly preferably at least 10% by mass, based on water.
【００１４】反応溶媒中に含まれる有機溶剤は、Ｆ（Ｃ
Ｆ2）n（ＣＨ2）mＸの溶解度と、ＮＨ3とＦ（ＣＦ2）n
（ＣＨ2）mＸとの反応性を上げる作用を有するものと考
えられる。反応溶媒中の有機溶剤量を多くするとフッ化
アルキルアミン化合物の収率が顕著に高くなる効果があ
る。また、有機溶剤を用いることにより、反応器の腐食
が防止される効果もある。The organic solvent contained in the reaction solvent is F (C
F 2 ) n (CH 2 ) mx solubility of NH 3 and F (CF 2 ) n
It is considered to have the effect of increasing the reactivity with (CH 2 ) m X. Increasing the amount of the organic solvent in the reaction solvent has the effect of significantly increasing the yield of the fluorinated alkylamine compound. The use of an organic solvent also has the effect of preventing corrosion of the reactor.
【００１５】有機溶媒としては、反応条件で液体であっ
て、沸点が１００℃以上であるものが好ましく、特に１
５０℃以上であるものが好ましい。また、有機溶媒とし
ては、ＮＨ3の溶解量が２５℃、０．１ＭＰａ（絶対
圧）において、０．００１ｇ／ｍｌ以上であるものが好
ましく、０．０１ｇ／ｍｌ以上であるものが好ましい。As the organic solvent, those which are liquid under the reaction conditions and have a boiling point of 100 ° C. or higher are preferable,
Those having a temperature of 50 ° C. or higher are preferred. The organic solvent preferably has a solubility of NH 3 of not less than 0.001 g / ml and not less than 0.01 g / ml at 25 ° C. and 0.1 MPa (absolute pressure).
【００１６】有機溶媒の具体例としては、Ｎ−メチルピ
ロリドン（ＮＭＰ）、エチレングリコール、プロピレン
グリコール（ＰＧ）等の多価アルコール類、ジグライ
ム、トリグライム等のグライム類、スルホラン、Ｎ，Ｎ
−ジメチルホルムアミド、１，３−ジメチル−２−イミ
ダゾリジノン、ジメチルスルホキシド等が好ましく、本
発明の反応を促進しうる点からＮＭＰまたはＰＧが特に
好ましい。Specific examples of the organic solvent include polyhydric alcohols such as N-methylpyrrolidone (NMP), ethylene glycol and propylene glycol (PG), glymes such as diglyme and triglyme, sulfolane, N, N
-Dimethylformamide, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide and the like are preferred, and NMP or PG is particularly preferred in that it can accelerate the reaction of the present invention.
【００１７】反応溶媒の量は、多すぎると反応容器の容
積効率が悪くなり生産性が低下する欠点がある。一方、
反応溶媒の量が少なすぎると反応溶媒中にＮＨ3とＦ
（ＣＦ2）n（ＣＨ2）mＸとが充分に溶解しないおそれが
あり、これにより反応圧力が高くなりすぎ、反応活性も
低下するおそれがある。よって、Ｆ（ＣＦ2）n（Ｃ
Ｈ2）mＸに対する反応溶媒の量は０．５〜５０倍質量が
好ましく、１〜２０倍質量が特に好ましい。If the amount of the reaction solvent is too large, there is a drawback that the volumetric efficiency of the reaction vessel deteriorates and the productivity decreases. on the other hand,
If the amount of the reaction solvent is too small, NH 3 and F
(CF 2 ) n (CH 2 ) m X may not be sufficiently dissolved, which may cause the reaction pressure to become too high and the reaction activity to be reduced. Therefore, F (CF 2 ) n (C
H 2) The amount of the reaction solvent to m X is preferably 0.5 to 50 times by mass, 1 to 20 times by mass is particularly preferable.
【００１８】本発明の反応の反応温度は３０〜２５０℃
が好ましく、１５０〜２５０℃が特に好ましく、１７０
〜２１０℃がとりわけ好ましい。反応温度は一定である
必要はなく、必要に応じて変更するのが好ましい。The reaction temperature of the reaction of the present invention is 30 to 250 ° C.
Is preferable, and 150 to 250 ° C. is particularly preferable.
~ 210 ° C is particularly preferred. The reaction temperature does not need to be constant, but is preferably changed as necessary.
【００１９】また、反応圧力は反応溶媒とＦ（ＣＦ2）n
（ＣＨ2）mＸの供給比により、適宜変更するのが好まし
い。通常の反応圧力は、０．５〜１０ＭＰａ（ゲージ
圧。以下特に記載しない場合には、ゲージ圧を示す。）
が好ましく、１〜５ＭＰａが特に好ましい。反応溶媒が
多いと反応圧力が低下し、少ないと反応圧力が上昇す
る。また、反応圧力が高すぎると、操作性や設備投資の
点で不利であり、低すぎると充分な反応速度が得られな
いおそれがある。The reaction pressure is set between the reaction solvent and F (CF 2 ) n
It is preferable to appropriately change the ratio depending on the supply ratio of (CH 2 ) m X. The usual reaction pressure is 0.5 to 10 MPa (gauge pressure. The gauge pressure is indicated unless otherwise specified).
Is preferable, and 1 to 5 MPa is particularly preferable. When the amount of the reaction solvent is large, the reaction pressure decreases, and when the amount is small, the reaction pressure increases. On the other hand, if the reaction pressure is too high, it is disadvantageous in terms of operability and equipment investment, and if it is too low, a sufficient reaction rate may not be obtained.
【００２０】本発明の反応ではＦ（ＣＦ2）n（ＣＨ2）m
ＮＨ2で表されるフッ化アルキルアミン化合物が生成す
る。該化合物中のｎおよびｍは、原料におけるｎおよび
ｍと同一である。フッ化アルキルアミン化合物の具体例
としては、つぎの化合物が挙げられる。In the reaction of the present invention, F (CF 2 ) n (CH 2 ) m
A fluorinated alkylamine compound represented by NH 2 is produced. N and m in the compound are the same as n and m in the raw material. Specific examples of the fluorinated alkylamine compound include the following compounds.
【００２１】ＣＦ3ＣＨ2ＮＨ2、ＣＦ3ＣＦ2ＣＨ2Ｎ
Ｈ2、Ｆ（ＣＦ2）3ＣＨ2ＮＨ2、Ｆ（ＣＦ2）4ＣＨ2ＮＨ
2、Ｆ（ＣＦ2）5ＣＨ2ＮＨ2、 Ｆ（ＣＦ2）6ＣＨ2Ｎ
Ｈ2、Ｆ（ＣＦ2）7ＣＨ2ＮＨ2、Ｆ（ＣＦ2）8ＣＨ2ＮＨ
2。CF 3 CH 2 NH 2 , CF 3 CF 2 CH 2 N
H 2 , F (CF 2 ) 3 CH 2 NH 2 , F (CF 2 ) 4 CH 2 NH
2 , F (CF 2 ) 5 CH 2 NH 2 , F (CF 2 ) 6 CH 2 N
H 2 , F (CF 2 ) 7 CH 2 NH 2 , F (CF 2 ) 8 CH 2 NH
2 .
【００２２】ＣＦ3（ＣＨ2）2ＮＨ2、ＣＦ3ＣＦ2（ＣＨ
2）2ＮＨ2、Ｆ（ＣＦ2）3（ＣＨ2） 2ＮＨ2、Ｆ（Ｃ
Ｆ2）4（ＣＨ2）2ＮＨ2、Ｆ（ＣＦ2）5（ＣＨ2）2Ｎ
Ｈ2、Ｆ（ＣＦ2）6（ＣＨ2）2ＮＨ2、Ｆ（ＣＦ2）7（Ｃ
Ｈ2）2ＮＨ2、Ｆ（ＣＦ2）8（ＣＨ2）2ＮＨ2。CFThree(CHTwo)TwoNHTwo, CFThreeCFTwo(CH
Two)TwoNHTwo, F (CFTwo)Three(CHTwo) TwoNHTwo, F (C
FTwo)Four(CHTwo)TwoNHTwo, F (CFTwo)Five(CHTwo)TwoN
HTwo, F (CFTwo)6(CHTwo)TwoNHTwo, F (CFTwo)7(C
HTwo)TwoNHTwo, F (CFTwo)8(CHTwo)TwoNHTwo.
【００２３】ＣＦ3（ＣＨ2）3ＮＨ2、ＣＦ3ＣＦ2（ＣＨ
2）3ＮＨ2、Ｆ（ＣＦ2）3（ＣＨ2） 3ＮＨ2、Ｆ（Ｃ
Ｆ2）4（ＣＨ2）3ＮＨ2、Ｆ（ＣＦ2）5（ＣＨ2）3Ｎ
Ｈ2、Ｆ（ＣＦ2）6（ＣＨ2）3ＮＨ2、Ｆ（ＣＦ2）7（Ｃ
Ｈ2）3ＮＨ2、Ｆ（ＣＦ2）8（ＣＨ2）3ＮＨ2。[0023] CFThree(CHTwo)ThreeNHTwo, CFThreeCFTwo(CH
Two)ThreeNHTwo, F (CFTwo)Three(CHTwo) ThreeNHTwo, F (C
FTwo)Four(CHTwo)ThreeNHTwo, F (CFTwo)Five(CHTwo)ThreeN
HTwo, F (CFTwo)6(CHTwo)ThreeNHTwo, F (CFTwo)7(C
HTwo)ThreeNHTwo, F (CFTwo)8(CHTwo)ThreeNHTwo.
【００２４】生成するフッ化アルキルアミン化合物は、
Ｆ（ＣＦ2）n（ＣＨ2）mＸと反応して第二アミン化合物
や第三アミン化合物を生成させるおそれがあるが、本発
明においては特定量以上のＮＨ3を用いることにより、
Ｆ（ＣＦ2）n（ＣＨ2）mＸはＮＨ3と優先的に反応し、
副反応が抑制されうる。The resulting fluorinated alkylamine compound is
There is a possibility that the compound reacts with F (CF 2 ) n (CH 2 ) m X to form a secondary amine compound or a tertiary amine compound. However, in the present invention, by using a specific amount or more of NH 3 ,
F (CF 2 ) n (CH 2 ) m X reacts preferentially with NH 3 ,
Side reactions can be suppressed.
【００２５】本発明の反応は、反応溶媒、Ｆ（ＣＦ2）n
（ＣＨ2）mＸ、およびＮＨ3を、バッチ方式または連続
方式で反応容器内に導入し、反応系中の化合物を反応溶
媒中に溶解させて行うのが好ましい。ＮＨ3を導入する
時期については特に限定されず、反応前にあらかじめ全
量を一括で仕込む方法、反応中に連続的に供給する方
法、反応中に分割して供給する方法等が挙げられる。ま
た、反応の開始段階には少量のＮＨ3量で反応を行い、
反応の最終段階でＮＨ3を多く供給して反応を行っても
よい。反応の開始段階で用いるＮＨ3量が少ないと（Ｃ
Ｆ2）n（ＣＨ2）mＮＨ2・ＨＸが生成しうるが、その場
合にも反応の最終段階においてＮＨ3を大量に供給する
ことにより、Ｆ（ＣＦ2）n（ＣＨ2）mＮＨ2・ＨＸの量
を減少させ、目的化合物の収率を多くできる。In the reaction of the present invention, a reaction solvent, F (CF 2 ) n
Preferably, (CH 2 ) m X and NH 3 are introduced into the reaction vessel in a batch or continuous manner, and the compound in the reaction system is dissolved in a reaction solvent. The timing of introducing NH 3 is not particularly limited, and examples include a method in which the whole amount is previously charged at once before the reaction, a method in which the solution is continuously supplied during the reaction, and a method in which the solution is dividedly supplied during the reaction. Also, at the beginning of the reaction, the reaction is carried out with a small amount of NH 3 ,
The reaction may be performed by supplying a large amount of NH 3 at the final stage of the reaction. If the amount of NH 3 used at the start of the reaction is small, (C
F 2 ) n (CH 2 ) m NH 2 .HX can be produced, but also in this case by supplying a large amount of NH 3 at the final stage of the reaction, F (CF 2 ) n (CH 2 ) m NH 2. The amount of HX can be reduced and the yield of the target compound can be increased.
【００２６】本発明の反応は、反応率および選択率が高
いことから、反応により得られるフッ化アルキルアミン
化合物を含む反応粗生成物は、簡単な精製操作で高純度
のフッ化アルキルアミン化合物とすることができる。た
とえば、反応粗生成物をそのまま蒸留精製することで、
高純度のＦ（ＣＦ2）n（ＣＨ2）mＮＨ2が回収できる。
蒸留する際には、Ｆ（ＣＦ2）n（ＣＨ2）mＮＨ2がＮＨ3
に同伴して排出されることによって回収率が低下するの
を防ぐため、コンデンサの温度をＦ（ＣＦ2）n（Ｃ
Ｈ2）mＮＨ2の沸点より１０℃以上低く保つのが好まし
い。また、蒸留時の圧力は、０．１ＭＰａ（絶対圧）以
上とするのが好ましい。Since the reaction of the present invention has a high reaction rate and selectivity, the crude reaction product containing the fluorinated alkylamine compound obtained by the reaction can be converted into a high-purity fluorinated alkylamine compound by a simple purification operation. can do. For example, by distilling and purifying the crude reaction product as it is,
High-purity F (CF 2 ) n (CH 2 ) m NH 2 can be recovered.
During the distillation, F (CF 2 ) n (CH 2 ) m NH 2 is converted to NH 3
In order to prevent the recovery rate from being lowered by being discharged together with the temperature of the condenser, the temperature of the condenser is set to F (CF 2 ) n (C
It is preferred to keep the boiling point of H 2 ) m NH 2 lower by at least 10 ° C. Further, the pressure at the time of distillation is preferably 0.1 MPa (absolute pressure) or more.
【００２７】フッ化アルキルアミン化合物は、各種有機
化合物の合成原料として有用な化合物である。たとえ
ば、ＣＦ3ＣＨ2ＮＨ2は、骨粗鬆症や癌等の治療薬の合
成中間体として、また農薬の合成中間体等として有用な
化合物である。Fluorinated alkylamine compounds are compounds useful as raw materials for synthesizing various organic compounds. For example, CF 3 CH 2 NH 2 is a compound useful as a synthetic intermediate for a therapeutic agent for osteoporosis and cancer, as a synthetic intermediate for agrochemicals, and the like.
【００２８】[0028]
【実施例】以下に本発明の具体的態様を実施例（例１〜
３）および比較例（例４）により具体的に説明するが、
本発明はこれらに限定されない。また、生成物の分析は
ガスクロマトグラフィ（ＧＣ）および19Ｆ−ＮＭＲによ
り行い、表１中の成分比はモル％への換算値である。ま
た、表１中のその他の成分の成分比は、ＣＦ3ＣＨ2Ｃｌ
のモルファクターを用いて算出した。EXAMPLES Hereinafter, specific embodiments of the present invention will be described with reference to Examples (Examples 1 to 4).
3) and a comparative example (Example 4),
The present invention is not limited to these. The product was analyzed by gas chromatography (GC) and 19 F-NMR, and the component ratios in Table 1 are values converted to mol%. The component ratio of other components in Table 1 is CF 3 CH 2 Cl
Calculated using the molar factor of
【００２９】［例１］容量が２００ｍｌであるステンレ
ス鋼製の加圧撹拌式オートクレーブ中に、ＣＦ3ＣＨ2Ｃ
ｌを０．１５ｍｏｌ、無水のアンモニアを０．６ｍｏｌ
（ＣＦ3ＣＨ2Ｃｌに対して４倍モル）、ＮＭＰを０．８
ｍｏｌ（ＣＦ3ＣＨ2Ｃｌに対して５．３倍モル）供給
し、２００℃で４８時間撹拌して反応を行った。オート
クレーブ内の圧力は初期には２．５ＭＰａであったが、
終了時には２．０ＭＰａまで低下した。反応終了後にオ
ートクレーブを１２０℃まで冷却し、コンデンサを通し
てオートクレーブ内のガス分をパージし、ＣＦ3ＣＨ2Ｎ
Ｈ2を含むガス分を冷却トラップにより捕集した。一
方、オートクレーブ内に水を１００ｇ添加して残留物を
溶解させ、溶解物を19Ｆ−ＮＭＲで測定したところ、ピ
ークは検出されなかった。冷却トラップによる捕集物を
分析した結果を表１に示す。反応後に反応容器の腐食は
ほとんど認められなかった。[Example 1] CF 3 CH 2 C was placed in a pressure-stirred autoclave made of stainless steel having a capacity of 200 ml.
l 0.15 mol, anhydrous ammonia 0.6 mol
(4 times mol with respect to CF 3 CH 2 Cl), NMP was 0.8
mol (5.3 times mol with respect to CF 3 CH 2 Cl), and the mixture was stirred at 200 ° C. for 48 hours to carry out a reaction. The pressure inside the autoclave was initially 2.5 MPa,
At the end of the test, the pressure dropped to 2.0 MPa. After the reaction was completed, the autoclave was cooled to 120 ° C., the gas content in the autoclave was purged through a condenser, and CF 3 CH 2 N
A gas containing H 2 was collected by a cooling trap. On the other hand, 100 g of water was added to the autoclave to dissolve the residue, and the dissolved substance was measured by 19 F-NMR. As a result, no peak was detected. Table 1 shows the result of analyzing the collected matter by the cooling trap. After the reaction, almost no corrosion of the reaction vessel was observed.
【００３０】［例２］例１におけるＮＭＰ０．８ｍｏｌ
の代わりにＰＧを１．２ｍｏｌ（ＣＦ3ＣＨ2Ｃｌに対し
て８．０倍モル）用いて同様に反応を行った。圧力は反
応初期には２．２ＭＰａであったが、反応終了時には
１．７ＭＰａまで低下した。生成物を分析した結果を表
１に示す。反応後に反応容器の腐食はほとんど認められ
なかった。Example 2 0.8 mol of NMP in Example 1
Was replaced with 1.2 mol (8.0-fold mol of CF 3 CH 2 Cl) of PG. The pressure was 2.2 MPa at the beginning of the reaction, but dropped to 1.7 MPa at the end of the reaction. The results of analyzing the products are shown in Table 1. After the reaction, almost no corrosion of the reaction vessel was observed.
【００３１】［例３］容量が２０００ｍｌであるステン
レス鋼製の加圧撹拌式オートクレーブ中に、ＣＦ3ＣＨ2
Ｃｌを１．５ｍｏｌ、無水のアンモニアを６ｍｏｌ（Ｃ
Ｆ3ＣＨ2Ｃｌに対して４倍モル）、ＰＧを１２ｍｏｌ
（ＣＦ3ＣＨ2Ｃｌに対して８．０倍モル）供給し、２０
０℃で４８時間撹拌して反応を行った。反応圧力は初期
には２．２ＭＰａであったが、終了時には１．７ＭＰａ
まで低下した。反応終了後にオートクレーブを１０℃ま
で冷却した。オートクレーブから回収した反応粗生成物
を分析した結果、転化率は９７．５％、ＣＦ3ＣＨ2ＮＨ
2の選択率は９７．８％であった。さらに反応粗生成物
を、常圧下に、−２０℃（コンデンサ温度）で蒸留精製
を行って留分を得た。留分の分析結果を表１に示す。反
応後に反応容器の腐食はほとんど認められなかった。Example 3 CF 3 CH 2 was placed in a pressure-stirred autoclave made of stainless steel having a capacity of 2000 ml.
1.5 mol of Cl and 6 mol of anhydrous ammonia (C
4 times the molar amount of F 3 CH 2 Cl), 12 mol of PG
(8.0 times mol with respect to CF 3 CH 2 Cl).
The reaction was carried out by stirring at 0 ° C. for 48 hours. The reaction pressure was 2.2 MPa at the beginning, but 1.7 MPa at the end.
Down to After the completion of the reaction, the autoclave was cooled to 10 ° C. As a result of analyzing the reaction crude product recovered from the autoclave, the conversion was 97.5%, and CF 3 CH 2 NH
The selectivity of 2 was 97.8%. Further, the reaction crude product was purified by distillation at -20 ° C (condenser temperature) under normal pressure to obtain a fraction. Table 1 shows the analysis results of the fractions. After the reaction, almost no corrosion of the reaction vessel was observed.
【００３２】［例４］例１における無水アンモニア量を
０．３ｍｏｌ（ＣＦ3ＣＨ2Ｃｌに対して２倍モル）とす
ること以外は、同様に反応を行った。反応圧力は初期に
は２．０ＭＰａであったが、終了時には１．５ＭＰａま
で低下した。生成物を分析した結果を表１に示す。Example 4 A reaction was carried out in the same manner as in Example 1, except that the amount of anhydrous ammonia was changed to 0.3 mol (twice the mol of CF 3 CH 2 Cl). The reaction pressure was 2.0 MPa at the beginning, but dropped to 1.5 MPa at the end. The results of analyzing the products are shown in Table 1.
【００３３】[0033]
【表１】 [Table 1]
【００３４】[0034]
【発明の効果】本発明によれば、反応に用いるＮＨ3量
を特定量以上とし、かつ、有機溶剤を必須とする反応溶
媒を用いることにより、生成物中の副生成物量を少なく
し、かつ、反応器の腐食を防止しつつ、高い収率で目的
とするフッ化アルキルアミン化合物を製造できる。According to the present invention, the amount of by-products in the product is reduced by making the amount of NH 3 used in the reaction a specific amount or more and using a reaction solvent in which an organic solvent is essential. In addition, the desired fluorinated alkylamine compound can be produced at a high yield while preventing corrosion of the reactor.
Claims (8)
は、塩素原子、臭素原子またはヨウ素原子を示し、ｎお
よびｍは、それぞれ独立して１以上の整数を示す。）で
表される化合物とＮＨ3とを反応させてＦ（ＣＦ2）
n（ＣＨ2）mＮＨ2（ｎおよびｍは、前記と同じ意味を示
す。）で表される化合物を製造する方法において、Ｆ
（ＣＦ 2）n（ＣＨ2）mＸに対して４倍モル以上のＮＨ3
を用いて、有機溶媒を必須成分とする反応溶媒の存在下
に反応を行うことを特徴とするフッ化アルキルアミン化
合物の製造方法。(1) F (CFTwo)n(CHTwo)mX (however, X
Represents a chlorine atom, a bromine atom or an iodine atom, and n and
And m each independently represent an integer of 1 or more. )so
Compound represented and NHThreeAnd react with F (CFTwo)
n(CHTwo)mNHTwo(N and m have the same meaning as above.
You. In the method for producing a compound represented by the formula
(CF Two)n(CHTwo)mNH at least 4 times the mole of XThree
In the presence of a reaction solvent containing an organic solvent as an essential component
Fluorinated alkylamination characterized by reacting to
Manufacturing method of compound.
造方法。3. The method according to claim 1, wherein m is 1.
に記載の製造方法。4. The method according to claim 1, wherein X is a chlorine atom.
The production method described in 1.
を４〜１０倍モル用いる請求項１〜４のいずれかに記載
の製造方法。5. F (CF 2 ) n (CH 2 ) m X with NH 3
The method according to any one of claims 1 to 4, wherein 4 to 10 times the molar amount is used.
る請求項１〜５のいずれかに記載の製造方法。6. The method according to claim 1, wherein the reaction solvent consists essentially of an organic solvent.
多価アルコールである請求項１〜６のいずれかに記載の
製造方法。7. The method according to claim 1, wherein the organic solvent is N-methylpyrrolidone or a polyhydric alcohol.
ることにより精製されたフッ化アルキルアミン化合物を
得る請求項１〜７のいずれかに記載の製造方法。8. The process according to claim 1, wherein a purified fluorinated alkylamine compound is obtained by distilling a crude reaction product produced by the reaction.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11-357781 | 1999-12-16 | ||
| JP35778199 | 1999-12-16 | ||
| JP2000357871A JP4665306B2 (en) | 1999-12-16 | 2000-11-24 | Method for producing fluorinated alkylamine compound |
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|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2007026513A1 (en) * | 2005-08-30 | 2009-03-05 | ユニマテック株式会社 | Fluoroether having terminal alkylamino group and process for producing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2348321A (en) * | 1941-12-13 | 1944-05-09 | Kinetic Chemicals Inc | Fluorine compounds |
| JPS323369B1 (en) * | 1954-10-18 | 1957-06-06 | ||
| US4618718A (en) * | 1985-06-14 | 1986-10-21 | Halocarbon Products Corporation | Preparation of trifluoroethylamine |
-
2000
- 2000-11-24 JP JP2000357871A patent/JP4665306B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2348321A (en) * | 1941-12-13 | 1944-05-09 | Kinetic Chemicals Inc | Fluorine compounds |
| JPS323369B1 (en) * | 1954-10-18 | 1957-06-06 | ||
| US4618718A (en) * | 1985-06-14 | 1986-10-21 | Halocarbon Products Corporation | Preparation of trifluoroethylamine |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2007026513A1 (en) * | 2005-08-30 | 2009-03-05 | ユニマテック株式会社 | Fluoroether having terminal alkylamino group and process for producing the same |
| JP4798133B2 (en) * | 2005-08-30 | 2011-10-19 | ユニマテック株式会社 | Fluoroether having terminal alkylamino group and process for producing the same |
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