JPS625426B2 - - Google Patents
Info
- Publication number
- JPS625426B2 JPS625426B2 JP11960579A JP11960579A JPS625426B2 JP S625426 B2 JPS625426 B2 JP S625426B2 JP 11960579 A JP11960579 A JP 11960579A JP 11960579 A JP11960579 A JP 11960579A JP S625426 B2 JPS625426 B2 JP S625426B2
- Authority
- JP
- Japan
- Prior art keywords
- chloro
- pyridine
- dichloromethyl
- trichloromethyl
- chloromethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- DCUJJWWUNKIJPH-UHFFFAOYSA-N nitrapyrin Chemical compound ClC1=CC=CC(C(Cl)(Cl)Cl)=N1 DCUJJWWUNKIJPH-UHFFFAOYSA-N 0.000 claims description 14
- VHKDPJQJCMVQFZ-UHFFFAOYSA-N 2-chloro-6-(chloromethyl)pyridine Chemical class ClCC1=CC=CC(Cl)=N1 VHKDPJQJCMVQFZ-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- FOXDMOFYUBDIFD-UHFFFAOYSA-N 2-(dichloromethyl)pyridine Chemical compound ClC(Cl)C1=CC=CC=N1 FOXDMOFYUBDIFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 23
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 19
- OBMOIJAXNPCIDU-UHFFFAOYSA-N 2-chloro-6-(dichloromethyl)pyridine Chemical compound ClC(Cl)C1=CC=CC(Cl)=N1 OBMOIJAXNPCIDU-UHFFFAOYSA-N 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000007327 hydrogenolysis reaction Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- GXZDYRYYNXYPMQ-UHFFFAOYSA-N 2-chloro-6-methylpyridine Chemical compound CC1=CC=CC(Cl)=N1 GXZDYRYYNXYPMQ-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- -1 6-chloro-2-(chloromethyl)pyridine 6-chloro-2-(dichloromethyl)pyridine Chemical compound 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- KAQJMEHRXVENSF-UHFFFAOYSA-N 2-(trichloromethyl)pyridine Chemical compound ClC(Cl)(Cl)C1=CC=CC=N1 KAQJMEHRXVENSF-UHFFFAOYSA-N 0.000 description 1
- XAYLRCRXDBZOBH-UHFFFAOYSA-N 3-chloro-2-(trichloromethyl)pyridine Chemical compound ClC1=CC=CN=C1C(Cl)(Cl)Cl XAYLRCRXDBZOBH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
Description
【発明の詳細な説明】
本発明は下記の化学式で表わされる新規物質６
−クロロ−２−（クロロメチル）ピリジン，およ
び６−クロロ−２−（ジクロロメチル）ピリジ
ン，ならびにそれらの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel substance 6 represented by the following chemical formula.
-Chloro-2-(chloromethyl)pyridine and 6-chloro-2-(dichloromethyl)pyridine, and methods for producing them.
６−クロロ−２−（クロロメチル）ピリジン
６−クロロ−２−（ジクロロメチル）ピリジン
従来、６−クロロ−２−（クロロメチル）ピリ
ジン類としては、６−クロロ−２−（トリクロロ
メチル）ピリジンが知られているが、本発明の物
質である６−クロロ−２−（クロロメチル）ピリ
ジンと６−クロロ−２−（ジクロロメチル）ピリ
ジンに関しては過去の文献にその製造例および物
理的性状等の記載がなく新規化合物である。 6-chloro-2-(chloromethyl)pyridine 6-chloro-2-(dichloromethyl)pyridine Conventionally, 6-chloro-2-(trichloromethyl)pyridine is known as 6-chloro-2-(chloromethyl)pyridine, but the substance of the present invention Regarding 6-chloro-2-(chloromethyl)pyridine and 6-chloro-2-(dichloromethyl)pyridine, there is no description of their production examples or physical properties in past literature, and they are new compounds.
本発明者らは６−クロロ−２−（クロロメチ
ル）ピリジンおよび６−クロロ−２−（ジクロロ
メチル）ピリジンが６−クロロ−２−（トリクロ
ロメチル）ピリジンの還元、特に選定された金属
および酸の存在における選択的液相水素添加分解
により容易に製造し得ることを見出し本発明に到
つた。 The present inventors have demonstrated that 6-chloro-2-(chloromethyl)pyridine and 6-chloro-2-(dichloromethyl)pyridine can be used for the reduction of 6-chloro-2-(trichloromethyl)pyridine, particularly with selected metals and acids. The present inventors have discovered that it can be easily produced by selective liquid phase hydrogenolysis in the presence of .
さらに本発明者らは６−クロロ−２−（トリク
ロロメチル）ピリジンの還元方法について検討を
加えた結果、上記方法以外に、液相中においてパ
ラジウム，白金およびニツケルから成る群から選
定される触媒の存在で分子状水素と反応させるこ
とを特徴とする方法，リチウムアルミニウムハイ
ドライドおよびソジウムボロハイドライド等の金
属水素化物を用いることを特徴とする方法および
電解還元等があり、いずれも実施可能であるが、
上記の液相中における酸と金属による水素添加分
解方法が工業上の実施にあたり経済的にも最も有
利であることがわかつた。 Furthermore, the present inventors investigated methods for reducing 6-chloro-2-(trichloromethyl)pyridine, and found that, in addition to the above method, a catalyst selected from the group consisting of palladium, platinum, and nickel was used in the liquid phase. There are methods characterized by reacting with molecular hydrogen in the presence of hydrogen, methods characterized by using metal hydrides such as lithium aluminum hydride and sodium borohydride, and electrolytic reduction, all of which are possible. ,
It has been found that the above-mentioned hydrogenolysis method using an acid and a metal in a liquid phase is the most economically advantageous for industrial implementation.
本発明において反応に使用される選定された金
属とは、一般に選定された酸と反応して水素を生
成し、且つ、また触媒としても作用する任意の金
属である。 The selected metal used in the reaction in this invention is generally any metal that reacts with the selected acid to produce hydrogen and also acts as a catalyst.
このタイプの金属としては、亜鉛，鉄，スズ，
コバルト，ニツケルおよびアルミニウムのごとき
水素より起電力の大きい金属が適当であるが、中
でも亜鉛および鉄はこの反応に好ましい金属であ
り、特に亜鉛が最も好ましい結果を与える。 Metals of this type include zinc, iron, tin,
Metals having a higher electromotive force than hydrogen such as cobalt, nickel and aluminum are suitable, but zinc and iron are the preferred metals for this reaction, with zinc in particular giving the most favorable results.
金属を微粉末または粉じんのような微粉砕され
た金属の形態で使用するのが好ましい。 Preferably, the metal is used in the form of a finely divided metal, such as a fine powder or dust.
本発明において使用される酸は、選定された金
属と反応して、水素を発生する任意の酸であり、
無機酸としては、塩酸，硫酸およびリン酸，有機
酸としては酢酸が好ましく、就中経済的、且つ工
業的理由から特に塩酸が好ましい。 The acid used in the present invention is any acid that reacts with the selected metal to generate hydrogen,
Preferred inorganic acids are hydrochloric acid, sulfuric acid and phosphoric acid, and preferred organic acids are acetic acid, with hydrochloric acid being particularly preferred for economical and industrial reasons.
必要な量の水素を発生するのに十分な量の選定
された金属を使用して反応を行うことが肝要で、
この必要な水素の量は、理論的には６−クロロ−
２−（トリクロロメチル）ピリジン１モル当り、
６−クロロ−２−（クロロメチル）ピリジン製造
の場合は２モル必要であり、６−クロロ−２−
（ジクロロメチル）ピリジン製造の場合には１モ
ル必要であるが、理論値の0.6〜1.5倍程度でもよ
い場合もある。 It is important to carry out the reaction using sufficient amounts of the selected metal to generate the required amount of hydrogen;
The amount of hydrogen required is theoretically 6-chloro-
per mole of 2-(trichloromethyl)pyridine,
In the case of 6-chloro-2-(chloromethyl)pyridine production, 2 moles are required, and 6-chloro-2-
In the case of producing (dichloromethyl)pyridine, 1 mol is required, but in some cases it may be about 0.6 to 1.5 times the theoretical value.
また本発明の反応は逐次反応であるので、６−
クロロ−２−（ジクロロメチル）ピリジンより６
−クロロ−２−（クロロメチル）ピリジンを製造
することができ、この場合にも等モルの水素を必
要とするので前記と同様である。 Furthermore, since the reaction of the present invention is a sequential reaction, 6-
6 from chloro-2-(dichloromethyl)pyridine
-Chloro-2-(chloromethyl)pyridine can be produced, and in this case as well, equimolar hydrogen is required, so it is the same as above.
製造目的によつては、理論値より少なくして、
６−クロロ−２−（クロロメチル）ピリジンまた
は６−クロロ−２−（ジクロロメチル）ピリジン
の生成量を抑制した状態で反応液の後処理をし、
高次塩素化物を回収し、再び水素添加分解反応に
使用することができる。 Depending on the manufacturing purpose, it may be less than the theoretical value.
After-treating the reaction solution while suppressing the amount of 6-chloro-2-(chloromethyl)pyridine or 6-chloro-2-(dichloromethyl)pyridine,
The higher chlorinated products can be recovered and used again in the hydrogenolysis reaction.
反応触媒として６−クロロ−２−（トリクロロ
メチル）ピリジンを溶解し、且つ酸とも溶解する
有機溶剤，特に低級アルコールを使用すると反応
速度が増大すると共に副生物の生成量が減少する
ので収率が高くなり、工業的に特に有利である。 If an organic solvent, especially a lower alcohol, which dissolves 6-chloro-2-(trichloromethyl)pyridine and acid is used as a reaction catalyst, the reaction rate will increase and the amount of by-products produced will decrease, resulting in a lower yield. It is particularly advantageous industrially.
低級アルコールとしては、メタノール，エタノ
ール等も実施可能であるが、イソプロパノールが
最も好ましい結果を与える。 Although methanol, ethanol, etc. can be used as the lower alcohol, isopropanol gives the most favorable results.
反応温度は−20℃から混合物の沸点まで使用す
ることができるが、20〜40℃の範囲が好ましい。 The reaction temperature can be from -20°C to the boiling point of the mixture, but is preferably in the range of 20 to 40°C.
反応は、６−クロロ−２−（トリクロロメチ
ル）ピリジン，金属粉末と低級アルコールの混合
物を適度に撹拌しつつ、酸を徐々に滴下すること
により円滑に進行する。 The reaction proceeds smoothly by gradually adding the acid dropwise to the mixture of 6-chloro-2-(trichloromethyl)pyridine, metal powder, and lower alcohol while stirring the mixture moderately.
本発明の新規物質である６−クロロ−２−（ク
ロロメチル）ピリジンおよび６−クロロ−２−
（ジクロロメチル）ピリジンは農薬の中間原料と
して重要なことがわかり、その製造方法は工業的
に有効であることから、本発明の工業的価値は極
めて高い。 6-chloro-2-(chloromethyl)pyridine and 6-chloro-2- which are new substances of the present invention
(Dichloromethyl)pyridine has been found to be important as an intermediate raw material for agricultural chemicals, and the method for producing it is industrially effective, so the industrial value of the present invention is extremely high.
以上本化合物の製法および用途等について一般
的に述べたが、さらに元素分析値、マススペクト
ル，赤外吸収スペクトル，NMRスペクトル，物
理的性状を掲げると共に製法について実施例をも
つて具体的に説明する。 The manufacturing method and uses of this compound have been generally described above, but the elemental analysis values, mass spectra, infrared absorption spectra, NMR spectra, and physical properties are also listed, and the manufacturing method will be specifically explained with examples. .
実施例 １
反応フラスコに６−クロロ−２−（トリクロロ
メチル）ピリジン50ｇ，亜鉛粉末28.3ｇ，および
イソプロパノール200ｇを仕込み、適度に撹拌し
た。Example 1 A reaction flask was charged with 50 g of 6-chloro-2-(trichloromethyl)pyridine, 28.3 g of zinc powder, and 200 g of isopropanol and stirred appropriately.
約30℃に反応温度を保ちながら、20％塩酸
118.5ｇを徐々に滴下し、水素添加分解反応を行
なつた。 20% hydrochloric acid while keeping the reaction temperature at approximately 30°C.
118.5 g was gradually added dropwise to carry out a hydrogenolysis reaction.
反応液をガスクロマトグラフ法によつて分析す
ると、６−クロロ−２−メチルピリジン9.6％、
６−クロロ−２−（クロロメチル）ピリジン64.1
％、６−クロロ−２−（ジクロロメチル）ピリジ
ン20.5％および未反応原料６−クロロ−２−（ト
リクロロメチル）ピリジン1.1％であつた。 Analysis of the reaction solution by gas chromatography revealed that 6-chloro-2-methylpyridine was 9.6%;
6-chloro-2-(chloromethyl)pyridine 64.1
%, 20.5% of 6-chloro-2-(dichloromethyl)pyridine and 1.1% of unreacted raw material 6-chloro-2-(trichloromethyl)pyridine.
反応液を四塩化炭素で抽出後、20％硫酸で洗浄
すると塩基性の強い低次塩素化物−６−クロロ−
２−メチルピリジンの大部分が除かれた。 After extracting the reaction solution with carbon tetrachloride and washing with 20% sulfuric acid, a strongly basic lower chloride -6-chloro-
Most of the 2-methylpyridine was removed.
次に四塩化炭素層を50％硫酸で抽出すると、塩
基性の弱い高次塩素化物６−クロロ−２−（ジク
ロロメチル）ピリジンと６−クロロ−２−（トリ
クロロメチル）ピリジンの大部分が四塩化炭素層
中に未抽出で残つた。 Next, when the carbon tetrachloride layer was extracted with 50% sulfuric acid, most of the weakly basic higher chlorides 6-chloro-2-(dichloromethyl)pyridine and 6-chloro-2-(trichloromethyl)pyridine were extracted with tetrachloride. It remained unextracted in the carbon chloride layer.
水層を炭酸ナトリウムで中和後、四塩化炭素で
抽出し、減圧蒸留すると純度99％以上の６−クロ
ロ−２−（クロロメチル）ピリジン8.4ｇが98〜
100℃／10mmHgの留分として得られた。 After neutralizing the aqueous layer with sodium carbonate, extraction with carbon tetrachloride and distillation under reduced pressure yielded 8.4 g of 6-chloro-2-(chloromethyl)pyridine with a purity of 99% or more.
Obtained as a fraction at 100°C/10mmHg.
この化合物の分析値および物性は次の通りであ
つた。 The analytical values and physical properties of this compound were as follows.
元素分析結果
C6H5NCl2としての計算値
C44.48％，H3.11％，N8.65％，
Cl43.76％
分析値
C44.63％，H3.19％，N8.52％，
Cl43.25％
マススペクトル
ｍ／e161
赤外吸収スペクトル
1580（ｍ），1560（ｍ），1440（ｍ），1410
（Ｓ），1170（ｍ），1130（ｍ），1080（Ｓ），990
（ｍ），800（Ｓ），740（ｍ），710（Ｓ），680
（ｍ），680（Ｓ）
NMRスペクトル
7.75〜7.1（ｍ），3H，4.55（Ｓ）2H
融点は44〜45℃で、白色結晶である。Elemental analysis results Calculated values as C 6 H 5 NCl 2 C44.48%, H3.11%, N8.65%, Cl43.76% Analysis values C44.63%, H3.19%, N8.52%, Cl43 .25% Mass spectrum m/e161 Infrared absorption spectrum 1580 (m), 1560 (m), 1440 (m), 1410
(S), 1170 (m), 1130 (m), 1080 (S), 990
(m), 800 (S), 740 (m), 710 (S), 680
(m), 680 (S) NMR spectrum 7.75-7.1 (m), 3H, 4.55 (S) 2H Melting point is 44-45°C, white crystal.
四塩化炭素，アセトン，エタノール，エーテル
等の有機溶剤に溶けやすく、水には殆んど溶解し
ない。 Easily soluble in organic solvents such as carbon tetrachloride, acetone, ethanol, and ether, and almost insoluble in water.
実施例 ２
反応フラスコに６−クロロ−２−（トリクロロ
メチル）ピリジン50ｇ，亜鉛粉末17.0ｇおよびイ
ソプロパノール200ｇを仕込み、適度に撹拌し
た。Example 2 A reaction flask was charged with 50 g of 6-chloro-2-(trichloromethyl)pyridine, 17.0 g of zinc powder, and 200 g of isopropanol, followed by moderate stirring.
約30℃に反応温度を保ちながら、20％塩酸71.1
ｇを徐々に滴下しながら水素添加分解反応を行な
つた。 20% hydrochloric acid 71.1 while keeping the reaction temperature at approximately 30°C.
The hydrogenolysis reaction was carried out while gradually adding g.
反応液をガスクロマトグラフ法によつて分析す
ると６−クロロ−２−メチルピリジン4.6％，６
−クロロ−２−（クロロメチル）ピリジン17.8
％，６−クロロ−２−（ジクロロメチル）ピリジ
ン66.6％，６−クロロ−２−（トリクロロメチ
ル）ピリジン7.6％であつた。 Analysis of the reaction solution by gas chromatography revealed that 6-chloro-2-methylpyridine was 4.6%.
-chloro-2-(chloromethyl)pyridine 17.8
%, 6-chloro-2-(dichloromethyl)pyridine 66.6%, and 6-chloro-2-(trichloromethyl)pyridine 7.6%.
反応後四塩化炭素で抽出後、50％硫酸で洗浄す
ると低次塩素化物６−クロロ−２−メチルピリジ
ンと６−クロロ−２−（クロロメチル）ピリジン
の大部分が除かれた。 After the reaction, most of the lower chlorinated compounds 6-chloro-2-methylpyridine and 6-chloro-2-(chloromethyl)pyridine were removed by extraction with carbon tetrachloride and washing with 50% sulfuric acid.
次に四塩化炭素層を70％硫酸で摘出すると６−
クロロ−２−（トリクロロメチル）ピリジンの大
部分が四塩化炭素中に未抽出で残つた。 Next, when the carbon tetrachloride layer is extracted with 70% sulfuric acid, 6-
Most of the chloro-2-(trichloromethyl)pyridine remained unextracted in the carbon tetrachloride.
水層を炭酸ナトリウム中和後、四塩化炭素で抽
出し、減圧蒸留すると純度99％以上の６−クロロ
−２−（ジクロロメチル）ピリジン10.7ｇが114〜
116℃／10mmHgの留分として得られた。 After neutralizing the aqueous layer with sodium carbonate, extraction with carbon tetrachloride and distillation under reduced pressure yielded 10.7 g of 6-chloro-2-(dichloromethyl)pyridine with a purity of 99% or more.
Obtained as a fraction at 116°C/10mmHg.
この化合物の分析値および物性は次の通りであ
つた。 The analytical values and physical properties of this compound were as follows.
元素分析結果
C6H4NCl3としての計算値
C36.6％，H2.05％，N7.13％，
Cl54.1％
分析値
C36.83％，H2.11％，N7.44％，
Cl53.50％
マススペクトル
ｍ／e195
赤外吸収スペクトル
1590（Ｓ），1580（ｍ），1560（ｍ），1444
（ｍ），1410（ｍ），1250（Ｓ），1220（ｍ），
1150（Ｓ），1130（Ｓ），1080（Ｓ），990
（ｍ），900（ｍ），810（Ｓ），730（ｍ），710
（ｍ），700（ｍ），600（ｍ）
NMRスペクトル
8.0〜7.1（ｍ）3H，6.6（Ｓ）1H
無色透明の液体である。Elemental analysis results Calculated values as C 6 H 4 NCl 3 C36.6%, H2.05%, N7.13%, Cl54.1% Analysis values C36.83%, H2.11%, N7.44%, Cl53 .50% Mass spectrum m/e195 Infrared absorption spectrum 1590 (S), 1580 (m), 1560 (m), 1444
(m), 1410 (m), 1250 (S), 1220 (m),
1150(S), 1130(S), 1080(S), 990
(m), 900 (m), 810 (S), 730 (m), 710
(m), 700 (m), 600 (m) NMR spectrum 8.0-7.1 (m) 3H, 6.6 (S) 1H It is a colorless and transparent liquid.
四塩化炭素，アセトン，エタノール，エーテル
等の有機溶剤に溶けやすく、水には殆んど溶解し
ない。 Easily soluble in organic solvents such as carbon tetrachloride, acetone, ethanol, and ether, and almost insoluble in water.
実施例 ３
反応フラスコに６−クロロ−２−（トリクロロ
メチル）ピリジン50ｇ，鉄粉末24.6ｇおよびイソ
プロパノール200ｇを仕込み、適度に撹拌した。Example 3 A reaction flask was charged with 50 g of 6-chloro-2-(trichloromethyl)pyridine, 24.6 g of iron powder, and 200 g of isopropanol, followed by moderate stirring.
約30℃に反応温度を保ちながら、酢酸39.1ｇを
徐々に滴下しながら水素添加分解を行なつた。 Hydrogenolysis was carried out by gradually dropping 39.1 g of acetic acid while maintaining the reaction temperature at about 30°C.
反応液をガスクロマトグラフ法により分析する
と６−クロロ−２−メチルピリジン17.1％，６−
クロロ−２−（クロロメチル）ピリジン51.7％，
６−クロロ−２−（ジクロロメチル）ピリジン
28.2％，６−クロロ−２−（トリクロロメチル）
ピリジン0.5％であつた。 Analysis of the reaction solution by gas chromatography revealed that 6-chloro-2-methylpyridine was 17.1%, 6-
Chloro-2-(chloromethyl)pyridine 51.7%,
6-chloro-2-(dichloromethyl)pyridine
28.2%, 6-chloro-2-(trichloromethyl)
It was 0.5% pyridine.
実施例 ４
反応フラスコに６−クロロ−２−（ジクロロメ
チル）ピリジン５ｇ，亜鉛粉末1.7ｇおよびイソ
プロパノール20ｇを仕込み適度に撹拌した。Example 4 A reaction flask was charged with 5 g of 6-chloro-2-(dichloromethyl)pyridine, 1.7 g of zinc powder, and 20 g of isopropanol and stirred moderately.
約30℃に反応温度を保ちながら、20％塩酸7.1
ｇを徐々に滴下しながら水素添加分解反応を行な
つた。 20% hydrochloric acid 7.1 while keeping the reaction temperature at approximately 30°C.
The hydrogenolysis reaction was carried out while gradually dropping 1.
反応液をガスクロマトグラフ法によつて分析す
ると、６−クロロ−２−（ジクロロメチル）ピリ
ジン9.6％，６−クロロ−２−（クロロメチル）ピ
リジン80.3％，６−クロロ−２−メチルピリジン
8.1％であつた。 Analysis of the reaction solution by gas chromatography revealed 9.6% of 6-chloro-2-(dichloromethyl)pyridine, 80.3% of 6-chloro-2-(chloromethyl)pyridine, and 6-chloro-2-methylpyridine.
It was 8.1%.
Claims (1)
ロロメチル）ピリジン類。 ２ ６−クロロ−２−（トリクロロメチル）ピリ
ジンを還元することを特徴とする６−クロロ−２
−（ジクロロメチル）ピリジンの製造方法。 ３ ６−クロロ−２−（トリクロロメチル）ピリ
ジンまたは６−クロロ−２−（ジクロロメチル）
ピリジンを還元することを特徴とする６−クロロ
−２−（クロロメチル）ピリジンの製造方法。 ４ 無機酸および有機酸より成る群から選定され
た酸の存在下に、液相中において、亜鉛，スズ，
コバルト，ニツケルおよびアルミニウムより成る
群から選定された金属と６−クロロ−２−（トリ
クロロメチル）ピリジン，または６−クロロ−２
−（ジクロロメチル）ピリジンを反応させること
を特徴とする特許請求の範囲第２項または第３項
記載の方法。 ５ 金属が亜鉛であり、且つ酸が塩酸である特許
請求の範囲第４項記載の方法。 ６ 低級アルコールを溶剤として使用する特許請
求の範囲第４項または第５項記載の方法。[Claims] 1. 6-chloro-2-(chloromethyl)pyridines represented by the general formula [Formula] (where n = 1 or 2). 2 6-chloro-2 characterized by reducing 6-chloro-2-(trichloromethyl)pyridine
- A method for producing (dichloromethyl)pyridine. 3 6-chloro-2-(trichloromethyl)pyridine or 6-chloro-2-(dichloromethyl)
A method for producing 6-chloro-2-(chloromethyl)pyridine, which comprises reducing pyridine. 4 Zinc, tin,
A metal selected from the group consisting of cobalt, nickel and aluminum and 6-chloro-2-(trichloromethyl)pyridine or 6-chloro-2
The method according to claim 2 or 3, characterized in that -(dichloromethyl)pyridine is reacted. 5. The method according to claim 4, wherein the metal is zinc and the acid is hydrochloric acid. 6. The method according to claim 4 or 5, wherein a lower alcohol is used as a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11960579A JPS5643268A (en) | 1979-09-17 | 1979-09-17 | 6-chloro-2-(chloromethyl)pyridine and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11960579A JPS5643268A (en) | 1979-09-17 | 1979-09-17 | 6-chloro-2-(chloromethyl)pyridine and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5643268A JPS5643268A (en) | 1981-04-21 |
| JPS625426B2 true JPS625426B2 (en) | 1987-02-04 |
Family
ID=14765527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11960579A Granted JPS5643268A (en) | 1979-09-17 | 1979-09-17 | 6-chloro-2-(chloromethyl)pyridine and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5643268A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0512436A1 (en) * | 1991-05-02 | 1992-11-11 | Ishihara Sangyo Kaisha, Ltd. | Method for producing substituted pyridine derivatives |
| CN104130184B (en) | 2010-03-12 | 2016-06-15 | 日本曹达株式会社 | The manufacture method of the compound that contains pyridine ring and halogenated methyl pyridine derivate and tetrazole radical 9 oxime derivate |
-
1979
- 1979-09-17 JP JP11960579A patent/JPS5643268A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5643268A (en) | 1981-04-21 |
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