JP4336135B2 - Halogenated difluoroalkyl polycyclic compounds - Google Patents

Description

【００１２】
（式中、ｎは０〜５の整数、ｍは０または１、ｐは０〜３の整数、Xは塩素原子、臭素原子またはヨウ素原子を表し、R₁〜R₁₄は、それぞれ独立に水素原子、炭素数１〜１０の直鎖または分岐のアルキル基、ハロゲン原子、含酸素置換基または含窒素置換基からなる群から選ばれる置換基を表す。）
で示されるハロゲン化ジフルオロアルキル多環式化合物。
【００１３】
（２） 前記一般式（１）においてｍ＝１であるハロゲン化ジフルオロアルキル多環式化合物を製造する方法であって、
一般式（２）
【００１４】
【化５】

【００１５】
（式中、ｎは０〜５の整数、ｐは０〜３の整数を表し、R₁〜R₁₄は、それぞれ独立に水素原子、炭素数１〜１０の直鎖または分岐のアルキル基、ハロゲン原子、含酸素置換基または含窒素置換基からなる群から選ばれる置換基を表す。）
で表されるカルボニル基含有多環式化合物と一般式（３）
ＣＦ₂ＹＺ （３）
（式中、ＹおよびＺは、それぞれ独立に、フッ素原子、塩素原子、臭素原子またはヨウ素原子を表す）
で表されるジハロジフルオロメタンを反応させ、一般式（４）
【００１６】
【化６】

【００１７】
（式中、ｎ、ｐ及びR₁〜R₁₄は、前記定義に同じ）
で表されるジフルオロオレフィン基含有多環式化合物を得た後、前記一般式（４）で表されるジフルオロオレフィン基含有多環式化合物とハロゲン化水素を反応させることを特徴とする前記一般式（１）においてｍ＝１であるハロゲン化ジフルオロアルキル多環式化合物の製造方法。
【００１８】
【発明の実施の形態】
以下に、さらに詳細に本発明を説明する。
【００１９】
前記一般式（１）において、ｎは０〜５の整数、ｍは０または１、ｐは０〜３の整数である。ｎ、ｍおよびｐがこの範囲において、有機化合物との相溶性に優れる等の多環式構造の特性が十分に発揮される。
【００２０】
Ｘは塩素原子、臭素原子またはヨウ素原子である。これらのうち、ジフルオロアルキルカルボン酸やジフルオロアルキルスルホン酸等への変換が容易であることから、臭素原子またはヨウ素原子が好ましい。
【００２１】
置換基R₁〜R₁₄は、水素原子、炭素数１〜１０の直鎖または分岐のアルキル基、ハロゲン原子、含酸素置換基または含窒素置換基である。置換基R₁〜R₁₄は同一または異なっていてもよい。これら炭素数1〜１０の直鎖または分岐のアルキル基としては、例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ−ブチル基、１−メチルプロピル基、２−メチルプロピル基、ペンチル基、１，１−ジメチルプロピル基、１，２−ジメチルプロピル基、２，２−ジメチルプロピル基、１−メチルブチル基、２−メチルブチル基、３−メチルブチル基、シクロプロピル基、シクロブチル基、ジメチルシクロプロピル基、メチルシクロブチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、３−メチルシクロヘキシル基、４−メチルシクロヘキシル基、ヘプチル基、オクチル基、シクロオクチル基、ノニル基、デシル基等が挙げられる。
【００２２】
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
【００２３】
含酸素置換基としては、メトキシ基、エトキシ基、プロポキシ基等のアルコキシ基、ヒドロキシル基、アセチル基、ベンゾイル基等のアシル基、蟻酸基、酢酸基の有機酸基等を挙げることができる。
【００２４】
含窒素置換基としては、アミノ基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基等のアミノ基、シアノ基、ニトロ基等を挙げることができる。
【００２５】
次に、本発明のハロゲン化ジフルオロアルキル多環式化合物の製造方法について説明する。
【００２６】
前記一般式（１）においてｍ＝１のハロゲン化ジフルオロアルキル多環式化合物は、前記一般式（２）で表されるカルボニル基含有多環式化合物と前記一般式（３）で表されるジハロジフルオロメタンを反応させ、前記一般式（４）で表されるジフルオロオレフィン基含有多環式化合物を得た後、ハロゲン化水素を反応させることにより得られる。
【００２７】
前記一般式（２）の化合物は、例えば、米国特許４２２９６００公報等に示されるように、カルボニル基含有オレフィン化合物とシクロペンタジエン構造含有化合物を反応させた後、炭素−炭素二重結合部位を水素化還元する方法等により得ることができる。
【００２８】
前記一般式（２）の化合物と前記一般式（３）の化合物の反応は、Ｗｉｔｔｉｇ反応として知られる反応を利用するものであり、通常、リン化合物、金属、溶媒等の存在下にて行われる。リン化合物としては、トリフェニルホスフィン、トリ−ｏ−トリルホスフィン、トリメシチルホスフィン、トリ（ｍ−クロロフェニル）ホスフィン、トリ（ｐ−メトキシフェニル）ホスフィン等のアリールホスフィン類、トリメチルホスフィン、トリエチルホスフィン、トリ−ｎ−ブチルホスフィン、トリ−ｔ−ブチルホスフィン、トリオクチルホスフィン、トリシクロヘキシルホスフィン等のアルキルホスフィン類、トリメチルホスファイト、トリエチルホスファイト、トリブチルホスファイト、トリオクチルホスファイト、トリフェニルホスファイト等のホスファイト類等を用いることができる。また金属としては、Ｌｉ、Ｎａ、Ｋ等のＩａ族金属、Ｍｇ、Ｃａ等のIIａ族金属、Ｂ、Ａｌ、Ｇａ等のIIIａ族金属、Ｃｕ、Ａｇ等のＩｂ族金属、Ｚｎ、Ｃｄ、Ｈｇ等のIIｂ族金属、またはこれらの塩を用いることができる。
【００２９】
溶媒としては、ペンタン、ヘキサン、シクロヘキサン、ヘプタン、オクタンなどの脂肪族炭化水素類、ベンゼン、トルエン、キシレンなどの芳香族炭化水素類、ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン、ジオキサンなどのエーテル類、メタノール、エタノール、イソプロパノール、ｔ−ブタノールなどのアルコール類、酢酸エチル、酢酸イソプロピル、酢酸アミル、酢酸ブチル、プロピオン酸メチル、プロピオン酸エチルなどのエステル類、ジクロロメタン、クロロホルム、四塩化炭素などのハロゲン化炭化水素類、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン類、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン、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、アセトニトリル、リン酸ヘキサメチルトリアミドなどの極性溶媒をあげることができる。
【００３０】
前記一般式（２）の化合物に対し、前記一般式（３）の化合物はモル比０．１〜１０、好ましくは０．５〜２の範囲で用いられる。前記一般式の（３）の化合物が、０．１未満の場合は、収率の点で、１０を超える場合は副反応を生じる場合があり好ましくない。
【００３１】
リン化合物は、前記一般式（２）の化合物に対し、モル比０．１〜１０の範囲で用いられる。金属を用いる場合、前記一般式（２）の化合物に対し、モル比０．１〜１０の範囲で用いられる。また、溶媒を用いる場合、前記一般式（２）の化合物に対し、重量比で０．１〜１００の範囲で用いられる。また、反応温度は、通常、０〜１５０℃である。
【００３２】
生成した前記一般式（４）の化合物は、反応液から直接蒸留分離したり、水および有機溶媒を加え、抽出分離することにより、反応液から分離することができる。また、反応液から分離することなく、次の反応に使用することもできる。
【００３３】
前記一般式（４）の化合物をハロゲン化水素と反応させることにより、前記一般式（１）においてｍ＝１の化合物を合成することができる。ハロゲン化水素としては、例えば塩化水素、臭化水素またはヨウ化水素が挙げられる。これらハロゲン化水素は、ガス状、または、水溶液、有機溶媒溶液等いずれを用いてもよい。また、ハロゲン含有化合物とプロトン性化合物を添加して、反応時に発生させてもよい。ハロゲン含有化合物としては、ハロゲン化金属化合物、ハロゲン化珪素化合物、ハロゲン化燐化合物等を挙げることができる。プロトン性化合物としては、水、アルコール類、有機カルボン酸類、燐酸、硫酸等の鉱酸類を挙げることができる。ハロゲン化水素は、前記一般式（４）の化合物に対し、モル比０．１〜１０の範囲で用いられる。また、反応温度は、通常、０〜１５０℃である。
【００３４】
生成した前記一般式（１）においてｍ＝１の化合物は、反応液から直接蒸留分離したり、水および有機溶媒を加え、抽出分離することにより、反応液から分離することができる。
【００３５】
なお、前記一般式（１）においてｍ＝０の化合物は、例えば、ハロジフルオロメチル基含有オレフィン化合物とシクロペンタジエン構造含有化合物を反応させた後、炭素−炭素二重結合部位を水素化還元する方法等により得ることができる。
【００３６】
【実施例】
以下に実施例を用いて本発明を詳細に説明するが、本発明はこの実施例によって限定されるものではない。
【００３７】
実施例１
２０L四つ口フラスコに攪拌機、温度計、還流冷却管を取り付け、N-メチルピロリドン ９．４L、トリフェニルホスフィン ３３７９ｇ、ジフルオロジブロモメタン １７５１ｇ、２−ホルミル−ビシクロ[２．２．１]ヘプタン １００１ｇ、を入れた。次に、亜鉛 ８４３ｇを徐々に添加した。この間、反応温度は２５℃から６５℃に上昇した。反応後、還流冷却管の代わりに、リービッヒ冷却管を取り付け、１０〜１５ｋPａに減圧し、７０〜１２５℃の留分を分取した。留出物を再度減圧蒸留し、６．８ｋPａの圧力で６５〜６６℃の留分を分取し、純度９９％の２−（２，２−ジフルオロエテニル）−ビシクロ[２．２．１]ヘプタン ９１９ｇを得た（収率 ７４．５％）
ＧＣ−ＭＳ（ＥＩ）ｍ／ｚ：２８，３９，５１，６７，７９，９０，１１６，１２９，１５８
【００３８】
実施例２
１Ｌ四つ口フラスコに温度計、ガス吹き込み管を取り付け、ヘキサン５００Ｌ、２−（２，２−ジフルオロエテニル）−ビシクロ[２．２．１]ヘプタン ５０．０ｇを入れた。ガス吹き込み管から乾燥臭化水素ガスを吹き込みながら８０℃にて９時間反応させた。反応液に飽和炭酸水素ナトリウム水溶液を加えて中和し、有機層を減圧濃縮し、蒸留精製した。１ｋPａの圧力で、６６〜６７℃の留分を分取し、２−（２−ブロモ−２，２−ジフルオロエチル）−ビシクロ[２．２．１]ヘプタン １２ｇを得た（収率１６％）。
¹Ｈ−ＮＭＲ（２００ＭＨｚ，ＣＤＣｌ₃，δ，ｐｐｍ）：（図１参照）
¹⁹Ｆ−ＮＭＲ（９０ＭＨｚ，ＣＤＣｌ₃，δ，ｐｐｍ）：（図２参照）
ＧＣ−ＭＳ（ＥＩ）ｍ／ｚ：２７，３９，８４，６７，７７，９５，１０９，１２９，１５９，２３８，２４０
【００３９】
実施例３
２０Ｌ四つ口フラスコに温度計、滴下漏斗、還流冷却管を取り付け、アセトニトリル ８．２Ｌ、ヨウ化ナトリウム １６１４ｇを入れ、溶解させた。次に滴下漏斗から、クロロトリメチルシラン １１７０ｇを滴下し、続いて、水 ９７ｇ、２−（２，２−ジフルオロエテニル）−ビシクロ[２．２．１]ヘプタン ８５０ｇを滴下した。滴下後、４０℃にて１５時間反応を継続させた。冷却後、水１０Ｌを加え、下層を分取した。これを蒸留精製し、０．３〜０．６ｋPａの圧力で、７６〜８１℃の留分を分取し、２−（２−ヨード−２，２−ジフルオロエチル）−ビシクロ[２．２．１]ヘプタン １３７４ｇを得た（収率 ８９％）。
¹Ｈ−ＮＭＲ（２００ＭＨｚ，ＣＤＣｌ₃，δ，ｐｐｍ）：（図３参照）
¹⁹Ｆ−ＮＭＲ（９０ＭＨｚ，ＣＤＣｌ₃，δ，ｐｐｍ）：（図４参照）
ＧＣ−ＭＳ（ＥＩ）ｍ／ｚ：２７，４１，５５，６７，９５，１２７，１５９
【００４０】
実施例４
１３５ｍｌオートクレーブに３−ブロモ−３，３−ジフルオロプロペン １６ｇ、ジシクロペンタジエン ６．６ｇを入れ、１７０℃で１２時間反応させた。次に、反応液に５％Ｐｄ／Ｃ １．０ｇを加え、大気圧下で水素を１２時間吹き込んだ。
反応混合物をろ過し、触媒を除去後、カラムクロマトグラフィにて精製し、２−ブロモジフルオロメチルビシクロ[２．２．１]ヘプタン ４．３ｇを得た（収率１９％）。
ＧＣ−ＭＳ（ＥＩ）ｍ／ｚ：６７，７７，１２５，１４５
¹⁹Ｆ−ＮＭＲ（９０ＭＨｚ，ＣＤＣｌ₃，δ，ｐｐｍ）
主異性体
-43.009 ( dd, J=153.8, 17.1 )、-49.177 ( dd, J=153.8, 17.1 )
副生異性体
-46.150 ( dd, J=151.4, 12.2 )、-52.070 ( dd, J=151.4, 19.5 )
【００４１】
【発明の効果】
本発明によれば、有機化合物との相溶性に優れ、合成の容易なビシクロ[２．２．１]ヘプタン構造を有し、かつ、ジフルロアルキルカルボン酸やジフルオロアルキルスルホン酸等への変換可能なハロゲン化ジフルオロアルキル基を有する多環式化合物およびその製造方法を提供できる。
【図面の簡単な説明】
【図１】 実施例２で得た２−（２−ブロモ−２，２−ジフルオロエチル）−ビシクロ[２．２．１]ヘプタンの¹Ｈ−ＮＭＲ測定チャート
【図２】 実施例２で得た２−（２−ブロモ−２，２−ジフルオロエチル）−ビシクロ[２．２．１]ヘプタンの¹⁹Ｆ−ＮＭＲ測定チャート
【図３】 実施例３で得た２−（２−ヨード−２，２−ジフルオロエチル）−ビシクロ[２．２．１]ヘプタンの¹Ｈ−ＮＭＲ測定チャート
【図４】 実施例３で得た２−（２−ヨード−２，２−ジフルオロエチル）−ビシクロ[２．２．１]ヘプタンの¹⁹Ｆ−ＮＭＲ測定チャート[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a halogenated difluoroalkyl polycyclic compound. More specifically, the present invention relates to a halogenated difluoroalkyl polycyclic compound useful as a raw material for surfactants, coating agents, electronic materials, organic synthesis catalysts, and the like, and a method for producing the same.
[0002]
[Prior art]
[Non-Patent Document 1]
Environmental Science Society 2002 Annual Meeting Abstract p228
Perfluoroalkyl halides such as perfluorooctyl iodide and perfluorohexyl iodide can convert halogen atoms into carboxylic acid groups, sulfinic acid groups, sulfonic acid groups, sulfonic acid derivatives, etc., and are raw materials of organic acids having strong acidity It becomes. These are widely used in applications such as surfactants, coating agents, electronic materials, and organic synthesis catalysts.
[0003]
However, these perfluoroalkyl sulfonic acids and perfluoroalkyl carboxylic acids are extremely difficult to decompose due to the strong covalent bond of carbon-fluorine, and they are problematic because of their accumulation in the living body (non-patent literature). 1).
[0004]
On the other hand, trifluoromethanesulfonic acid having a low fluorine content, for example, has not been pointed out an accumulation problem, but has volatility, and therefore has problems such as limited use conditions and corrosion of the apparatus.
[0005]
Further, these perfluoroalkyl compounds may not have sufficient compatibility with organic compounds not containing fluorine, and there is a problem that performance is not sufficiently exhibited.
[0006]
For this reason, as a fluorine-containing alkyl halide compound that substitutes for these, a fluorine-containing alkyl having a carbon number equal to or greater than that of perfluorooctyl halide and having the minimum fluorine necessary for expressing appropriate acidity Halide was desired.
[0007]
On the other hand, a polycyclic compound containing a bicyclo [2.2.1] heptane structure has excellent compatibility with an organic compound and also easily synthesizes a ring skeleton from a cyclopentadiene as a raw material by a Diels-Alder reaction. It is a widely used compound that has characteristics that can be achieved. However, a bicyclo [2.2.1] heptane compound having a halogenated difluoroalkyl group that can be converted into difluoroalkylcarboxylic acid, difluoroalkylsulfonic acid or the like has not been known so far.
[0008]
[Problems to be solved by the invention]
The present invention has been made in view of these problems. That is, difluoroalkyl halides that have a bicyclo [2.2.1] heptane structure that is excellent in compatibility with organic compounds and that can be easily synthesized, and that can be converted into difluoroalkylcarboxylic acids, difluoroalkylsulfonic acids, and the like. It aims at providing the polycyclic compound which has group, and its manufacturing method.
[0009]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found various halogenated difluoroalkyl polycyclic compounds and production methods thereof, and have completed the present invention.
[0010]
That is, the present invention relates to the following gist.
(1) The following general formula (1)
[0011]
[Formula 4]

[0012]
(In the formula, n is an integer of 0 to 5, m is 0 or 1, p is an integer of 0 to 3, X represents a chlorine atom, a bromine atom or an iodine atom, and R _{1 to} R ₁₄ are each independently hydrogen. This represents a substituent selected from the group consisting of an atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, an oxygen-containing substituent or a nitrogen-containing substituent.
A difluoroalkyl polycyclic compound represented by the formula:
[0013]
(2) A method for producing a halogenated difluoroalkyl polycyclic compound in which m = 1 in the general formula (1),
General formula (2)
[0014]
[Chemical formula 5]

[0015]
(Wherein n represents an integer of 0 to 5, p represents an integer of 0 to 3, R _{1 to} R ₁₄ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, halogen, Represents a substituent selected from the group consisting of an atom, an oxygen-containing substituent or a nitrogen-containing substituent.)
A carbonyl group-containing polycyclic compound represented by the general formula (3)
CF ₂ YZ (3)
(In the formula, Y and Z each independently represent a fluorine atom, a chlorine atom, a bromine atom or an iodine atom)
Is reacted with a dihalodifluoromethane represented by the general formula (4)
[0016]
[Chemical 6]

[0017]
(Wherein n, p and R _{1 to} R ₁₄ are the same as defined above)
After obtaining the difluoroolefin group-containing polycyclic compound represented by formula (4), the difluoroolefin group-containing polycyclic compound represented by formula (4) is reacted with a hydrogen halide. A method for producing a halogenated difluoroalkyl polycyclic compound in which m = 1 in (1).
[0018]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in further detail below.
[0019]
In the general formula (1), n is an integer of 0 to 5, m is 0 or 1, and p is an integer of 0 to 3. When n, m and p are in this range, the characteristics of the polycyclic structure such as excellent compatibility with organic compounds are sufficiently exhibited.
[0020]
X is a chlorine atom, a bromine atom or an iodine atom. Of these, a bromine atom or an iodine atom is preferable because it can be easily converted into difluoroalkylcarboxylic acid, difluoroalkylsulfonic acid, or the like.
[0021]
The substituents R _{1 to} R ₁₄ are a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, an oxygen-containing substituent, or a nitrogen-containing substituent. The substituents R _{1 to} R ₁₄ may be the same or different. Examples of these linear or branched alkyl groups having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a 1-methylpropyl group, a 2-methylpropyl group, Pentyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, cyclopropyl group, cyclobutyl group, dimethyl Examples include cyclopropyl group, methylcyclobutyl group, cyclopentyl group, hexyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, heptyl group, octyl group, cyclooctyl group, nonyl group, decyl group and the like.
[0022]
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
[0023]
Examples of the oxygen-containing substituent include alkoxy groups such as methoxy group, ethoxy group and propoxy group, acyl groups such as hydroxyl group, acetyl group and benzoyl group, organic acid groups such as formic acid group and acetic acid group.
[0024]
Examples of the nitrogen-containing substituent include amino groups such as amino group, methylamino group, dimethylamino group, and diethylamino group, cyano group, and nitro group.
[0025]
Next, the manufacturing method of the halogenated difluoroalkyl polycyclic compound of this invention is demonstrated.
[0026]
In the general formula (1), the halogenated difluoroalkyl polycyclic compound with m = 1 is a carbonyl group-containing polycyclic compound represented by the general formula (2) and a divalent compound represented by the general formula (3). It can be obtained by reacting halodifluoromethane to obtain a difluoroolefin group-containing polycyclic compound represented by the general formula (4) and then reacting with hydrogen halide.
[0027]
The compound of the general formula (2) is obtained by reacting a carbonyl group-containing olefin compound and a cyclopentadiene structure-containing compound, as shown in, for example, US Pat. No. 4,229,600, and then hydrogenating a carbon-carbon double bond site. It can be obtained by a reduction method or the like.
[0028]
The reaction of the compound of the general formula (2) and the compound of the general formula (3) utilizes a reaction known as Wittig reaction, and is usually performed in the presence of a phosphorus compound, a metal, a solvent, or the like. . Examples of phosphorus compounds include triphenylphosphine, tri-o-tolylphosphine, trimesitylphosphine, tri (m-chlorophenyl) phosphine, tri (p-methoxyphenyl) phosphine, and other arylphosphines, trimethylphosphine, triethylphosphine, tri- Alkylphosphines such as n-butylphosphine, tri-t-butylphosphine, trioctylphosphine, tricyclohexylphosphine, phosphites such as trimethylphosphite, triethylphosphite, tributylphosphite, trioctylphosphite, triphenylphosphite Etc. can be used. Examples of the metal include a group Ia metal such as Li, Na and K, a group IIa metal such as Mg and Ca, a group IIIa metal such as B, Al and Ga, a group Ib metal such as Cu and Ag, Zn, Cd and Hg. Group IIb metals such as these, or salts thereof can be used.
[0029]
Solvents include aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane and octane, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane, methanol, Alcohols such as ethanol, isopropanol and t-butanol, esters such as ethyl acetate, isopropyl acetate, amyl acetate, butyl acetate, methyl propionate and ethyl propionate, and halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride , Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-di Chill-2-imidazolidinone, dimethyl sulfoxide, acetonitrile, can be mentioned polar solvents such as phosphoric acid hexamethyltriamide.
[0030]
The compound of the general formula (3) is used in a molar ratio of 0.1 to 10, preferably 0.5 to 2, with respect to the compound of the general formula (2). When the compound of the general formula (3) is less than 0.1, it is not preferable because the side reaction may occur when it exceeds 10 in terms of yield.
[0031]
The phosphorus compound is used in a molar ratio of 0.1 to 10 with respect to the compound of the general formula (2). When using a metal, it is used in a molar ratio of 0.1 to 10 with respect to the compound of the general formula (2). Moreover, when using a solvent, it is used in the range of 0.1-100 by weight ratio with respect to the compound of the said General formula (2). Moreover, reaction temperature is 0-150 degreeC normally.
[0032]
The generated compound of the general formula (4) can be separated from the reaction solution by direct distillation separation from the reaction solution, or by adding water and an organic solvent to extract and separate. Moreover, it can also be used for next reaction, without isolate | separating from a reaction liquid.
[0033]
By reacting the compound of the general formula (4) with hydrogen halide, a compound of m = 1 in the general formula (1) can be synthesized. Examples of the hydrogen halide include hydrogen chloride, hydrogen bromide, and hydrogen iodide. These hydrogen halides may be used in the form of a gas or an aqueous solution or an organic solvent solution. Alternatively, a halogen-containing compound and a protic compound may be added and generated during the reaction. Examples of the halogen-containing compound include metal halide compounds, silicon halide compounds, and halogenated phosphorus compounds. Examples of protic compounds include mineral acids such as water, alcohols, organic carboxylic acids, phosphoric acid and sulfuric acid. The hydrogen halide is used in a molar ratio of 0.1 to 10 with respect to the compound of the general formula (4). Moreover, reaction temperature is 0-150 degreeC normally.
[0034]
The compound of m = 1 in the generated general formula (1) can be separated from the reaction solution by direct distillation separation from the reaction solution, or by adding water and an organic solvent to extract and separate.
[0035]
In addition, the compound of m = 0 in the said General formula (1) is the method of hydrogenating and reducing a carbon-carbon double bond part, for example after making a halo difluoromethyl group containing olefin compound and a cyclopentadiene structure containing compound react. Etc. can be obtained.
[0036]
【Example】
Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the examples.
[0037]
Example 1
A 20 L four-necked flask was equipped with a stirrer, thermometer, reflux condenser, N-methylpyrrolidone 9.4 L, triphenylphosphine 3379 g, difluorodibromomethane 1751 g, 2-formyl-bicyclo [2.2.1] heptane 1001 g, Put. Next, 843 g of zinc was gradually added. During this time, the reaction temperature rose from 25 ° C to 65 ° C. After the reaction, a Liebig condenser was attached instead of the reflux condenser, and the pressure was reduced to 10 to 15 kPa, and a fraction at 70 to 125 ° C. was fractionated. The distillate was distilled again under reduced pressure, and a fraction at 65 to 66 ° C. was separated at a pressure of 6.8 kPa, and 2- (2,2-difluoroethenyl) -bicyclo [2.2.1] having a purity of 99%. ] 919 g of heptane was obtained (yield 74.5%)
GC-MS (EI) m / z: 28, 39, 51, 67, 79, 90, 116, 129, 158
[0038]
Example 2
A 1 L four-necked flask was equipped with a thermometer and a gas blowing tube, and 500 L of hexane and 50.0 g of 2- (2,2-difluoroethenyl) -bicyclo [2.2.1] heptane were added. The reaction was carried out at 80 ° C. for 9 hours while blowing dry hydrogen bromide gas from the gas blowing tube. The reaction solution was neutralized with a saturated aqueous sodium hydrogen carbonate solution, and the organic layer was concentrated under reduced pressure and purified by distillation. A fraction at 66 to 67 ° C. was collected at a pressure of 1 kPa to obtain 12 g of 2- (2-bromo-2,2-difluoroethyl) -bicyclo [2.2.1] heptane (yield 16%). ).
¹ H-NMR (200 MHz, CDCl ₃ , δ, ppm): (see FIG. 1)
¹⁹ F-NMR (90 MHz, CDCl ₃ , δ, ppm): (see FIG. 2)
GC-MS (EI) m / z: 27, 39, 84, 67, 77, 95, 109, 129, 159, 238, 240
[0039]
Example 3
A thermometer, a dropping funnel and a reflux condenser were attached to a 20 L four-necked flask, and 8.2 L of acetonitrile and 1614 g of sodium iodide were added and dissolved. Next, 1170 g of chlorotrimethylsilane was dropped from the dropping funnel, and subsequently, 97 g of water and 850 g of 2- (2,2-difluoroethenyl) -bicyclo [2.2.1] heptane were dropped. After dropping, the reaction was continued at 40 ° C. for 15 hours. After cooling, 10 L of water was added, and the lower layer was separated. This was purified by distillation, and a fraction at 76 to 81 ° C. was collected at a pressure of 0.3 to 0.6 kPa, and 2- (2-iodo-2,2-difluoroethyl) -bicyclo [2.2. 1] 1374 g of heptane was obtained (yield 89%).
¹ H-NMR (200 MHz, CDCl ₃ , δ, ppm): (see FIG. 3)
¹⁹ F-NMR (90 MHz, CDCl ₃ , δ, ppm): (see FIG. 4)
GC-MS (EI) m / z: 27, 41, 55, 67, 95, 127, 159
[0040]
Example 4
In a 135 ml autoclave, 16 g of 3-bromo-3,3-difluoropropene and 6.6 g of dicyclopentadiene were added and reacted at 170 ° C. for 12 hours. Next, 1.0 g of 5% Pd / C was added to the reaction solution, and hydrogen was blown under atmospheric pressure for 12 hours.
The reaction mixture was filtered to remove the catalyst, and then purified by column chromatography to obtain 4.3 g of 2-bromodifluoromethylbicyclo [2.2.1] heptane (yield 19%).
GC-MS (EI) m / z: 67, 77, 125, 145
¹⁹ F-NMR (90 MHz, CDCl ₃ , δ, ppm)
Main isomer
-43.009 (dd, J = 153.8, 17.1), -49.177 (dd, J = 153.8, 17.1)
By-product isomers
-46.150 (dd, J = 151.4, 12.2), -52.070 (dd, J = 151.4, 19.5)
[0041]
【The invention's effect】
According to the present invention, it has a bicyclo [2.2.1] heptane structure that is excellent in compatibility with organic compounds and can be easily synthesized, and can be converted into difluoroalkylcarboxylic acid, difluoroalkylsulfonic acid, and the like. A polycyclic compound having a halogenated difluoroalkyl group and a method for producing the same can be provided.
[Brief description of the drawings]
1 is a ¹ H-NMR measurement chart of 2- (2-bromo-2,2-difluoroethyl) -bicyclo [2.2.1] heptane obtained in Example 2. FIG. 2 is obtained in Example 2. ¹⁹ F-NMR measurement chart of 2- (2-bromo-2,2-difluoroethyl) -bicyclo [2.2.1] heptane [FIG. 3] 2- (2-iodo-2 obtained in Example 3 , 2-Difluoroethyl) -bicyclo [2.2.1] heptane ¹ H-NMR measurement chart FIG. 4 shows 2- (2-iodo-2,2-difluoroethyl) -bicyclo [ 2.2.1] ¹⁹ F-NMR measurement chart of heptane

Claims (2)

The following general formula (1)

(In the formula, p is an integer of 0 to 3, R _{4 to} R ₁₄ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, an oxygen-containing substituent, or a nitrogen-containing substituent. Represents a substituent selected from the group consisting of groups.)
A difluoroalkyl polycyclic compound represented by the formula: A method for producing a halogenated difluoroalkyl polycyclic compound represented by the general formula (1) , comprising:
General formula (2)

(In the formula, p is an integer of 0 to 3, R _{4 to} R ₁₄ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, an oxygen-containing substituent, or Represents a substituent selected from the group consisting of nitrogen-containing substituents.)
A carbonyl group-containing polycyclic compound represented by the general formula (3)
CF ₂ YZ (3)
(In the formula, Y and Z each independently represent a fluorine atom, a chlorine atom, a bromine atom or an iodine atom)
Is reacted with a dihalodifluoromethane represented by the general formula (4)

( Wherein p and R _{4 to} R ₁₄ are the same as defined above)
After obtaining the difluoroolefin group-containing polycyclic compound represented by formula (4), the difluoroolefin group-containing polycyclic compound represented by formula (4) is reacted with hydrogen iodide. A method for producing the halogenated difluoroalkyl polycyclic compound represented by (1).

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