JPS6267057A - Production of chlorophenylhydrazine compound - Google Patents
Production of chlorophenylhydrazine compoundInfo
- Publication number
- JPS6267057A JPS6267057A JP20784685A JP20784685A JPS6267057A JP S6267057 A JPS6267057 A JP S6267057A JP 20784685 A JP20784685 A JP 20784685A JP 20784685 A JP20784685 A JP 20784685A JP S6267057 A JPS6267057 A JP S6267057A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- phenyl nucleus
- atom
- sulfuryl chloride
- 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
- -1 chlorophenylhydrazine compound Chemical class 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- 125000001424 substituent group Chemical group 0.000 claims abstract 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 abstract description 10
- 238000005660 chlorination reaction Methods 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000004009 herbicide Substances 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- SNRGCDPTDOAQEQ-UHFFFAOYSA-N 3-anilino-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound O=C1CSC(=S)N1NC1=CC=CC=C1 SNRGCDPTDOAQEQ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000002363 herbicidal effect Effects 0.000 abstract description 2
- 239000002917 insecticide Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- MULHANRBCQBHII-UHFFFAOYSA-N (2,4,6-trichlorophenyl)hydrazine Chemical compound NNC1=C(Cl)C=C(Cl)C=C1Cl MULHANRBCQBHII-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 125000003545 alkoxy group Chemical group 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 125000001309 chloro group Chemical group Cl* 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- UMKLWBFJFMDZAH-UHFFFAOYSA-N 1-chloro-1-phenylhydrazine Chemical class NN(Cl)C1=CC=CC=C1 UMKLWBFJFMDZAH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012320 chlorinating reagent Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical group NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 3
- 229940067157 phenylhydrazine Drugs 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- SVVSNFUAOGDDMG-UHFFFAOYSA-N 3-anilinoimidazolidine-2,4-dione Chemical compound O=C1CNC(=O)N1NC1=CC=CC=C1 SVVSNFUAOGDDMG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 150000004031 phenylhydrazines Chemical class 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241001125046 Sardina pilchardus Species 0.000 description 1
- 102100025342 Voltage-dependent N-type calcium channel subunit alpha-1B Human genes 0.000 description 1
- 101710088658 Voltage-dependent N-type calcium channel subunit alpha-1B Proteins 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 235000019512 sardine Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はり［Ｉルフ工ニルヒドラジン系化合物を製造す
る方法に関し、更に詳しくは除草剤、殺虫剤、写真用カ
プラーのＢＩＩＩとして有用なりＯルフェニルヒドラジ
ン系化合物を高収率に製造する方法に関するものである
。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a method for producing a fluorinyl hydrazine compound, and more specifically to a method for producing a compound useful as a herbicide, an insecticide, or a BIII of a photographic coupler. The present invention relates to a method for producing phenylhydrazine compounds in high yield.
［発明の背景］
除草剤［例えばプロピオニルクロライド（２゜４．６−
ドリクロルフエニル）ヒドラゾン、イソブヂリル（２，
４−ジクロルフェニルヒドラゾン）］、π真用ピラゾＯ
ン型マゼンタカプラー笠の中固体として、フェニル核に
クロル原子を有ηるフェニルヒドラジン系化合物（例え
ば２，４゜６−ドリクロルヒドラジン）が用いられてい
る。[Background of the invention] Herbicides [e.g. propionyl chloride (2°4.6-
Dolichlorphenyl) hydrazone, isobutyryl (2,
4-dichlorophenylhydrazone)], π-pyrazo O
A phenylhydrazine compound having a chloro atom in the phenyl nucleus (for example, 2,4°6-dolychlorhydrazine) is used as the solid medium in the 2-type magenta coupler shade.
従来、フェニルヒドラジン系化合物を出発原料として用
いてクロルフェニルヒドラジン系化合物ヲ￥Ｊ Ｎ ｔ
６１Ｃハ、例エバＪ 、 Ｈｕｍｐｈｒｉｅｓ、 Ｈ
。Conventionally, phenylhydrazine compounds were used as starting materials to produce chlorphenylhydrazine compounds.
61C, e.g. Eva J., Humphries, H.
.
ト１ ｕｌｂｌｅ Ｒ，Ｅｖａｎｓ、 Ｊ
、 Ｃｈｅｗ 、 Ｓ ｏｃ、 １２
７．１３０４〜１３０７頁（１９２５）に記載されてい
るように、フェニルヒドラジン系化合物とアルフ゛ヒト
；したはケ［・ンの反応生成物であるじドラシン化合物
のフェニル核の少なくとｂｌつの水素原子をクロル化し
、次いで亜鉛等を用いて還元を行なっていた。1 ulble R, Evans, J
, Chew , S oc , 12
7. As described on pages 1304 to 1307 (1925), at least one hydrogen atom of the phenyl nucleus of a didracine compound, which is a reaction product of a phenylhydrazine compound and an alpha or chemical compound, is chlorinated. and then reduction using zinc or the like.
しかしながら、この方法は還元の際に用いられる亜鉛に
通常不純物としてカドミウムを含むためその反応残漬物
の処理が分書上問題となり、処理コストが高くつくとい
う欠点があった。また、フェニルヒドラジン系化合物の
β位の窒素原子の保護基として用いられるアルデヒドや
ケトン類は還元により！’１１１２された際に、β位の
窒素原子との結合部分がメチル基またはメチレン基とな
った化合物としてｌ！１１脱するものと考えられ、これ
をｅｉ！ＩＩとして再使用することは困難であり、コス
ト高を沼く欠点があった。However, this method has the disadvantage that since the zinc used in the reduction usually contains cadmium as an impurity, the disposal of the reaction residue poses a problem in terms of separation, and the processing cost is high. In addition, aldehydes and ketones used as protective groups for the nitrogen atom at the β position of phenylhydrazine compounds are reduced! '1112 as a compound in which the bonding moiety with the nitrogen atom at the β position becomes a methyl group or a methylene group. It is thought that it will escape from 11, and this is ei! It is difficult to reuse it as II, and it has the disadvantage of increasing costs.
［発明の目的１
本発明は上記事情に鑑みてなされたものでその目的とす
るところは、下記一般式［Ｉ］で示される化合物のＮ−
アニリドのフェニル核の水素原子の少なくとｂｌつをク
ロル化し、次いで加水分解することにより高収率にしか
も安価にクロルフェニルヒドラジン系化合物を製造する
方法を提供することにある。[Objective of the Invention 1 The present invention has been made in view of the above circumstances, and its object is to reduce the N-
The object of the present invention is to provide a method for producing chlorphenylhydrazine compounds in high yield and at low cost by chlorinating at least one hydrogen atom of the phenyl nucleus of anilide and then hydrolyzing it.
一般式［Ｉ１
式中、Ｒは直換Ｕを表わし、ｎはＯ〜４の整数、Ｘ及び
Ｙは酸素又はＦｉＡ黄原子を示し、同一でも異なってい
てもよい、Ｚｌ：ｉ環を形成するための少なくと、６１
つのへテロ原子を含む原子群を示１゜また、本発明の他
の目的は、フェニルヒドラジン系化合物のβ位の窒素原
子の保護基を公害上の問題もなく、しかも極めて温和な
条件で離脱せしめることもできるクロルフェニルヒドラ
ジン系化合物の製造方法を提供することにある。General formula [I1 In the formula, R represents a direct U, n is an integer of O to 4, X and Y represent oxygen or FiA yellow atoms, and may be the same or different, forming a Zl:i ring at least 61 for
Another object of the present invention is to remove the protecting group of the nitrogen atom at the β position of phenylhydrazine compounds without causing any pollution problems and under extremely mild conditions. It is an object of the present invention to provide a method for producing a chlorphenylhydrazine compound that can also be used as a chlorphenylhydrazine compound.
［発明の構成］
本発明の上記目的は、上記、一般式［Ｔ］で示される化
合物のフェニル桟の水素原子の少なくと一般式［ＩＪに
おいて、２により完成される環としては５〜６ 、；、
ｉ ｎが好ましく、又、２により形成される環は置Ｌ％
ｕ（例えばアルキル基、アリール基、ハロゲン原子）を
有していてもよい。又、２が含有するヘテロ原子として
好ましいものとしては、酸素原子、窒素原子、硫黄原子
が挙げられる。[Structure of the Invention] The above-mentioned object of the present invention is to provide at least one hydrogen atom of the phenyl chain of the compound represented by the general formula [T] in the general formula [IJ], where the ring completed by 2 is 5 to 6, ;,
i n is preferred, and the ring formed by 2 is
u (for example, an alkyl group, an aryl group, a halogen atom). Further, preferable examples of the hetero atom contained in 2 include an oxygen atom, a nitrogen atom, and a sulfur atom.
本発明で用いられる、一般式［］で示される化合物のへ
テロ環部分を、以下に例示するが、本発明はこれらに限
定されない。The heterocyclic moiety of the compound represented by the general formula [] used in the present invention is illustrated below, but the present invention is not limited thereto.
以下余白
次に一般式［ＩＪにより表わされる化合物の具体例を示
すが、本発明はこれらに限定される乙のではない。In the following margin, specific examples of compounds represented by the general formula [IJ] will be shown, but the present invention is not limited thereto.
本発明で用いられる、一般式［Ｉ］で示される化合物は
既知の合成方法により容易に合成することができる。例
えば、次のような文献が挙げられる。The compound represented by the general formula [I] used in the present invention can be easily synthesized by known synthesis methods. For example, the following documents can be cited.
１−１ｏｍ１−１ｏ ：Ｊ、 ｐｒ、 ［２１８１
４５６Ｓｃｈｌｏｅｇｌ ：Ｍ、８９ ［Ｉ９５８
］ Ｇ１−７１これらの化合物は、反応系から分１ｄ
れ又は分離されることなく次の反応１稈に使用される。1-1om1-1o :J, pr, [2181
456 Schloegl: M, 89 [I958
] G1-71 These compounds are removed from the reaction system for 1 d.
It is used for the next reaction without being separated or separated.
本発明において前記一般式［ＩＪで示される化合物のク
ロル化に用いられるクロル化剤は一般に用いられるもの
であれば特にｉｔ、ＩＪ Ｉｉはないが、例えばＪ！！
素ガス、スルフリルクロライド、次亜塩素ニ又はその塩
（例えばナトリウム塩、カルシウム塩等）等を挙げるこ
とができ、またサラシ粉（次亜塩素酸カルシウムを含む
混合物）でもＪ、い。In the present invention, the chlorinating agent used in the chlorination of the compound represented by the general formula [IJ] is not particularly limited to it, IJ Ii, as long as it is commonly used, but for example, J! !
Examples include raw gas, sulfuryl chloride, hypochlorite or its salts (eg, sodium salt, calcium salt, etc.), and also sardine powder (a mixture containing calcium hypochlorite).
このスルフリルクロライドは溶媒としても用いることが
できる。This sulfuryl chloride can also be used as a solvent.
反応Ｈａとしては、スルフリルクロライドの他、クロロ
ホルム、四塩化炭素、ベンゼン、酢酸等を好ましいもの
としてｑげることがでさ・る。As the reaction Ha, in addition to sulfuryl chloride, chloroform, carbon tetrachloride, benzene, acetic acid, etc. can be preferably used.
クロル化剤は、一般式［Ｉ］で示される化合物に導入さ
れるクロル原子の数によって異なるが、通常は導入する
りＯル原子１個当り１〜１．１モルである。ここに一般
式［Ｉ］で示される化合物に導入されるクロル原子の数
とは、該化合物のフェニル核に限らず、フェニル核以外
の部分（例えばヘテロ環部分）に導入されるクロル原子
の数の総］をいい、フェニル核および他の部分の両方が
クロル化される場合も本発明に包含される。しかし、ク
ロル化剤として、例えばスルフリルクロライドを用いた
場合には、溶媒どしての役割を果たすので場合によって
は大過剰のＲ１例えば６モル程度の団を用いることもあ
る。この場合であっても反応温度を調節することによっ
て尋人されるりＯル原子の数を制御することは可能であ
る。例えば、溶媒を兼ねて６モルのスルフリルクロライ
ドを用いた場合であっても、反応温度を約１０℃以下で
クロル化を行なえば前記化合物のフェニル核の２位と４
位にクロル原子が尋人される。また反応温度を約１０℃
以下ヒてクロル化を行なえば、前記化合物の２．４及び
６位にクロル原子が導入される。The amount of the chlorinating agent used varies depending on the number of chlorine atoms introduced into the compound represented by the general formula [I], but is usually 1 to 1.1 mol per O atom introduced. The number of chlorine atoms introduced into the compound represented by the general formula [I] is not limited to the phenyl nucleus of the compound, but also refers to the number of chlorine atoms introduced into parts other than the phenyl nucleus (e.g., heterocyclic part). ], and cases where both the phenyl nucleus and other moieties are chlorinated are also included in the present invention. However, when, for example, sulfuryl chloride is used as the chlorinating agent, since it acts as a solvent, a large excess of R1, for example, about 6 moles, may be used in some cases. Even in this case, it is possible to control the number of O atoms by adjusting the reaction temperature. For example, even if 6 moles of sulfuryl chloride is used as a solvent, if the chlorination is carried out at a reaction temperature of about 10°C or lower, the 2- and 4-positions of the phenyl nucleus of the compound
The chlorine atom is placed in the position. Also, the reaction temperature was set to about 10℃.
By carrying out chlorination, chlorine atoms are introduced into the 2.4 and 6 positions of the compound.
本発明の一般式［Ｉ］で示される化合物のクロル化反応
の温度は、用いる化合物の種類によっても異なるが、概
ねＯ℃〜１００℃の範囲である。また反応時間について
も同様であり、概ね３１［間程で充分である。The temperature of the chlorination reaction of the compound represented by the general formula [I] of the present invention varies depending on the type of compound used, but is generally in the range of 0°C to 100°C. The same applies to the reaction time, and approximately 31 hours is sufficient.
クロル化によって得られる化合物は、原料のフェニル核
が未置換である場合についていえば、クロル原子が好ま
しくはフェニル基の２位、４位及び６位の少なくとも１
つに導入されたものであり、より好ましくは２位および
４位に、更に好ましくは２位、４位および６位にクロル
原子が導入されたものである。In the case where the phenyl nucleus of the raw material is unsubstituted, the compound obtained by chlorination preferably has a chlorine atom in at least one of the 2-, 4-, and 6-positions of the phenyl group.
Chlor atoms are preferably introduced at the 2- and 4-positions, and even more preferably at the 2-, 4-, and 6-positions.
本発明の方法は）Ｉニル核の２位及び６位の両方にクロ
ル原子を導入する場合に特に有効である。The method of the present invention is particularly effective when introducing chlorine atoms into both the 2- and 6-positions of the I-nyl nucleus.
本発明の方法によって（りられるクロル化された化合物
は、これを反応系から分離してもよく又はそのまま次の
加水分解反応に使用することがでさる。The chlorinated compound obtained by the method of the present invention may be separated from the reaction system or used as it is in the next hydrolysis reaction.
この加水分解は溶媒として、例えば水及び水温相性有機
溶媒（例えばメタノール、エタノール）を用い、Ｍ（例
えば塩酸、＠酸等）又はアルカリ剤（例えば水酸化ナト
リウム、水酸化カリウム等）の試薬の存在下で行なわれ
る。加水分解反応は５０℃〜１２０℃の範囲で行なわれ
るのが好ましく、加水分解に要する時間は使用ブる原料
や反応温度によって異なるが３〜２０時間が好ましい。This hydrolysis is carried out using water and water-temperature compatible organic solvents (e.g. methanol, ethanol) as solvents, and in the presence of reagents such as M (e.g. hydrochloric acid, @acid, etc.) or alkaline agents (e.g. sodium hydroxide, potassium hydroxide, etc.). It takes place below. The hydrolysis reaction is preferably carried out at a temperature of 50°C to 120°C, and the time required for hydrolysis varies depending on the raw materials used and the reaction temperature, but is preferably 3 to 20 hours.
前記試薬の使用母はクロル化された化合物１モル当り、
好ましくは１モル以上、より好ましくは２モル以上であ
り、１０Ｅル程度で充分といえる。又、加圧、分解が好
ましいこともある。The used base of the reagent is per mole of chlorinated compound,
Preferably it is 1 mol or more, more preferably 2 mol or more, and about 10El is sufficient. Moreover, pressurization and decomposition may be preferable.
［発明の効果］
本発明の方法によれば、除ｖ剤、写真用カプラー等の中
間体として有用なりロルフェニルヒドラジン系化合物が
安価に、かつ高収率で得られｏ０又、本発明の方法によ
れば、フェニル核の２位及び６位の両方にクロル原子を
有するクロルフェニルヒドラジン系化合物（例えば２．
４．６−）リクＯルフェニルヒドラジン）をも、収率よ
く、安価に１迄することもできる。[Effects of the Invention] According to the method of the present invention, lorphenylhydrazine compounds that are useful as intermediates for UV removers, photographic couplers, etc. can be obtained at low cost and in high yield. According to chlorphenylhydrazine compounds having chloro atoms at both the 2- and 6-positions of the phenyl nucleus (for example, 2.
4.6-) Liquor phenylhydrazine) can also be produced up to 1 in good yield and at low cost.
［実施例１］
１〜リクロルフエニルヒドラジンの製造方法Ｆ、Ｃ，Ｂ
ｒｏｗｎ： Ｊ、Ｏ，Ｃ，２４，１０６０（１９５９）
の方法によって合成した３−７ニリノローダニン１９．
２ｇｒを塩化スルフリル８１ ｇｒ中へ撹はんしながら
、水冷却下、徐々に加えると激しく反応し、塩酸及び亜
＠駁ガスを発生しながら溶解した。更に２５±５℃で１
時間撹はんを続けた。次いで、過（りで残留している塩
化スルフリルを常圧魚雷り、て回収し、最後に減圧乾固
すると褐色のアメ状物が残留した。得られた組成物はそ
のまま加水分解した。[Example 1] 1-Method for producing lychlorphenylhydrazine F, C, B
row: J, O, C, 24, 1060 (1959)
3-7 nylinorhodanine synthesized by the method of 19.
When 2 gr of sulfuryl chloride was gradually added to 81 gr of sulfuryl chloride while stirring and cooling with water, it reacted violently and dissolved while generating hydrochloric acid and submersible gas. Furthermore, 1 at 25±5℃
Stirring was continued for an hour. Next, the sulfuryl chloride remaining in the filtrate was collected using an atmospheric pressure torpedo, and finally dried under reduced pressure to leave a brown candy-like substance.The resulting composition was hydrolyzed as it was.
即ち、これをエタノール２００１１２、苛性カリ１０１
１１ｒの溶液にとかし煮沸逼流撹はんを５時間行なった
。That is, ethanol 200112, caustic potassium 101
The mixture was dissolved in a 11r solution and boiled and stirred for 5 hours.
寂Ｊ！１ｌｊ１１７ｔｅで中和したのちアルコールを減
圧回収した。残った褐色ｎ末を水中にＱｌ）し、よく水
洗してからろ集し、乾燥してから、アルコールより再結
し、白色粉末（１点１４０℃−１４１℃）として２．４
．６−トリクミルフェニルヒドラジン１９！フｒｆ得た
。Jaku J! After neutralizing with 1lj117te, the alcohol was recovered under reduced pressure. The remaining brown powder was dissolved in water, washed thoroughly with water, collected by filtration, dried, and reconsolidated with alcohol to give a white powder (1 point 140°C-141°C) with a yield of 2.4
．． 6-Tricumylphenylhydrazine 19! I got a full RF.
［実施例２］
実施例１の３−アニリノローダニン１９．２Ｑｒの代わ
りにＨ，Ｂａｙａｒｄ Ｍｉｌｎｅ、 Ｄｕａｎｅ
Ｗ、 ＦｉｓｈＪ、 Ｏ，Ｃ，、２７３１７７−３１８
２（１９６２） （＋）方法によって合成した３−アニ
リノヒダントイン１９． Ｉｇｒを出発物質にして、実
施例１と同様にしてクロル化を行なった後、アルカリで
加水分解をした。ついで塩酸酸性にして、ろ過水洗後、
湿ったままアルコール２００顧、塩Ｍ１５ｄの溶液で４
１Ｉ８間煮沸遠流した。アルカリで中和後減圧でアルコ
ールを追出して残さをよく水洗して乾燥した。アルコー
ルより再結晶して２．４．６−ドリクロルフエニルヒド
ラジンの純品１５ｏｒを得た。[Example 2] H, Bayard Milne, Duane instead of 19.2 Qr of 3-anilinorhodanine in Example 1
W, FishJ, O,C,, 273177-318
2 (1962) (+) 3-anilinohydantoin synthesized by method 19. Using Igr as a starting material, chlorination was carried out in the same manner as in Example 1, followed by hydrolysis with an alkali. Then acidified with hydrochloric acid, filtered and washed with water,
While still wet, add 200 g of alcohol and a solution of M15 d of salt.
The mixture was boiled and centrifuged for 1 to 8 hours. After neutralizing with alkali, the alcohol was removed under reduced pressure, and the residue was thoroughly washed with water and dried. Recrystallization from alcohol gave 15or of pure 2.4.6-dolychlorophenylhydrazine.
［実施例３］
実施例２の３−アニリノヒダントイン１９、Ｉｇｒの代
わりにに、 Ｓｃｈｌｏｅｇｌ ； Ｍｏｎａｔｓｈ
、 、 ８９ ｅｌ−７３（１９５８）の方法によっ
て合成した３−アニリノ、 −６メヂルージヒドロビ
リミジンー２．４−ジオン２１．９ｇｒを出発物質にし
て、実施例２と同様にして、りＯル化、加水分解を順次
行って、２，４゜６トリクロルフエニルヒドラジンを得
た。アルコール再結後の収足は１７９ｒであった。[Example 3] In place of 3-anilinohydantoin 19 and Igr in Example 2, Schloegl; Monatsh
, , 89 el-73 (1958) using 21.9 gr of 3-anilino, -6 medyludihydrobyrimidine-2,4-dione as a starting material and in the same manner as in Example 2. 2,4°6-trichlorophenylhydrazine was obtained by sequentially carrying out oxidation and hydrolysis. The yield after alcohol reconstitution was 179r.
Claims (1)
フェニル核の水素原子の少なくとも１つをクロル化し、
次いで加水分解することによりクロルフェニルヒドラジ
ン系化合物を製造する方法。 一般式［ I ］ ▲数式、化学式、表等があります▼ 式中、Ｒは置換基を表わし、ｎは０〜４の整数であり、
Ｘ及びＹは酸素又は硫黄原子を示し、同一でも異なって
いてもよい。Ｚは環を形成するための少なくとも１つの
ヘテロ原子を含む原子群である。[Claims] At least one hydrogen atom of the phenyl nucleus of the N-anilide of the compound represented by the following general formula [I] is chlorinated,
A method for producing a chlorphenylhydrazine compound by subsequent hydrolysis. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R represents a substituent, n is an integer from 0 to 4,
X and Y represent oxygen or sulfur atoms, and may be the same or different. Z is an atomic group containing at least one heteroatom to form a ring.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20784685A JPS6267057A (en) | 1985-09-20 | 1985-09-20 | Production of chlorophenylhydrazine compound |
| DE8686304961T DE3662394D1 (en) | 1985-06-27 | 1986-06-26 | Process for producing chlorophenylhydrazine compounds |
| EP86304961A EP0208477B1 (en) | 1985-06-27 | 1986-06-26 | Process for producing chlorophenylhydrazine compounds |
| US06/878,690 US5041667A (en) | 1985-06-27 | 1986-06-26 | Process for producing chlorophenylhydrazine compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20784685A JPS6267057A (en) | 1985-09-20 | 1985-09-20 | Production of chlorophenylhydrazine compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6267057A true JPS6267057A (en) | 1987-03-26 |
Family
ID=16546493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20784685A Pending JPS6267057A (en) | 1985-06-27 | 1985-09-20 | Production of chlorophenylhydrazine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6267057A (en) |
-
1985
- 1985-09-20 JP JP20784685A patent/JPS6267057A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| J.CHEM.SOC=1925 * |
| J.CHEM.SOC=1957 * |
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