JPH01228926A - Production of p-tert-butylbenzyl chloride - Google Patents
Production of p-tert-butylbenzyl chlorideInfo
- Publication number
- JPH01228926A JPH01228926A JP5540688A JP5540688A JPH01228926A JP H01228926 A JPH01228926 A JP H01228926A JP 5540688 A JP5540688 A JP 5540688A JP 5540688 A JP5540688 A JP 5540688A JP H01228926 A JPH01228926 A JP H01228926A
- Authority
- JP
- Japan
- Prior art keywords
- tert
- butyltoluene
- chlorine
- forming agent
- raw material
- 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
- WAXIFMGAKWIFDQ-UHFFFAOYSA-N 1-tert-butyl-4-(chloromethyl)benzene Chemical compound CC(C)(C)C1=CC=C(CCl)C=C1 WAXIFMGAKWIFDQ-UHFFFAOYSA-N 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000460 chlorine Substances 0.000 claims abstract description 18
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 18
- QCWXDVFBZVHKLV-UHFFFAOYSA-N 1-tert-butyl-4-methylbenzene Chemical compound CC1=CC=C(C(C)(C)C)C=C1 QCWXDVFBZVHKLV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- CWQDDKWOLSHALN-UHFFFAOYSA-N (1-chloro-2,2-dimethylpropyl)benzene Chemical compound CC(C)(C)C(Cl)C1=CC=CC=C1 CWQDDKWOLSHALN-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract 4
- 239000003905 agrochemical Substances 0.000 abstract 1
- 239000002304 perfume Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 23
- MNGDHYSFNGVSIA-UHFFFAOYSA-N 2-tert-butyl-4-chloro-1-methylbenzene Chemical compound CC1=CC=C(Cl)C=C1C(C)(C)C MNGDHYSFNGVSIA-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- -1 azobispropane Chemical compound 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JTIAYWZZZOZUTK-UHFFFAOYSA-N 1-tert-butyl-3-methylbenzene Chemical compound CC1=CC=CC(C(C)(C)C)=C1 JTIAYWZZZOZUTK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- QZWCABOLGIVZCP-UHFFFAOYSA-N 1-tert-butyl-3-(chloromethyl)benzene Chemical group CC(C)(C)C1=CC=CC(CCl)=C1 QZWCABOLGIVZCP-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction 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、農薬原料および香料原料として有用なｐ−ｔ
ｅｒｔ−ブチルベンジルクロライドの製造方法に関する
。Detailed Description of the Invention [Industrial Field of Application] The present invention provides pt.
The present invention relates to a method for producing ert-butylbenzyl chloride.
ｐ −ｔｅｒｔ−ブチルトルエンを塩素でクロル化して
、ｐ−ｔｅｒｔ−ブチルベンジルクロライドを合成する
場合、無触媒では核クロル化物が副生成物として生成す
ることは公知である。従来これら核クロル化物の生成を
押えるために触媒としてラジカル形成剤を存在させるか
、または光反応が提案されている。It is known that when p-tert-butyl toluene is chlorinated with chlorine to synthesize p-tert-butylbenzyl chloride, a nuclear chloride is produced as a by-product in the absence of a catalyst. Conventionally, in order to suppress the formation of these nuclear chlorides, it has been proposed to use a radical forming agent as a catalyst or to use a photoreaction.
しかしながらこれらラジカル形成剤存在下のクロル化、
または光反応でのクロル化においても、選択的にｐ−ｔ
ｅｒｔ−ブチルベンジルクロライドを製造することは困
廻であった。即ち、ｐ−ｔｅｒｔ−ブチルトルエンのメ
チル基のクロル化と同時にｔｅｒｔ−ブチル基のクロル
化もがなり起こるからである。この副生するｐ−クロル
−ｔｅｒｔ−ブチルトルエンとｐ−ｔｅｒｔ−ブチルベ
ンジルクロライドとは、沸点差がほとんどないため通常
の蒸留等で分離することは殆ど不可能である。However, chlorination in the presence of these radical formers,
Alternatively, in photoreaction chlorination, selective p-t
It has been difficult to produce ert-butylbenzyl chloride. That is, chlorination of the tert-butyl group occurs simultaneously with the chlorination of the methyl group of p-tert-butyltoluene. Since the by-produced p-chloro-tert-butyltoluene and p-tert-butylbenzyl chloride have almost no difference in boiling point, it is almost impossible to separate them by ordinary distillation or the like.
特開昭５９−８０６２４号ではｐ−ｔｅｒｔ−ブチルベ
ンジルクロライドを選択的に製造するために、高エネル
ギー輻射線の作用下および／又はラジカル形成剤の存在
下、約−１０〜＋１０℃の温度でｐ −ｔｅｒｔ−ブチ
ルトルエンと塩素を反応させる方法が提案されている。In JP-A-59-80624, p-tert-butylbenzyl chloride is selectively produced at temperatures of about -10 to +10°C under the action of high-energy radiation and/or in the presence of radical formers. A method has been proposed in which p-tert-butyltoluene and chlorine are reacted.
しかし、一般には約−１０〜＋１０℃の温度範囲では熱
分解によるラジカル形成剤の活性はほとんど認められな
い、それゆえ前記特許の方法を実行しようとすれば、高
エネルギー輻射線の作用下での反応となる。このような
高エネルギー輻射線の作用下（通常、中圧、または高圧
水銀灯などのＵＶ−照明器による照射下）での反応は石
英ガラス製などの特殊な反応装置が必要となり、更に一
１０〜＋ｌＯ℃という温度も工業的に有利な方法とは言
い難い。However, in general, the activity of radical forming agents due to thermal decomposition is hardly observed in the temperature range of about -10 to +10°C, therefore, if the method of the said patent is to be carried out, it is difficult to carry out the process under the action of high-energy radiation. It becomes a reaction. Reactions under the action of such high-energy radiation (usually under irradiation by UV illuminators such as medium-pressure or high-pressure mercury lamps) require special reaction equipment, such as those made of quartz glass, and require A temperature of +10° C. is also hardly an industrially advantageous method.
本発明者らは工業的に不利な上記の製法に代わる選択性
が良く、しかも特殊な反応装置を必要としないｐ−ｔｅ
ｒｔ−ブチルベンジルクロライドの製造方法を確立すべ
く、鋭意検討した結果、工業的に通常使用されている８
０℃以下のきわめて温和な条件下でｐ−ｔｅｒｔ−ブチ
ルベンジルクロライドが効率的に製造できることを見出
し、本発明に至った。The present inventors have developed a p-te method which has good selectivity and does not require special reaction equipment, as an alternative to the industrially disadvantageous above-mentioned production method.
As a result of intensive studies to establish a method for producing rt-butylbenzyl chloride, we found that 8
It was discovered that p-tert-butylbenzyl chloride can be efficiently produced under extremely mild conditions of 0° C. or lower, leading to the present invention.
即ち、本発明は、６０〜８０℃の温度でｐ−ｔｅｒｔ−
ブチルトルエンと塩素を反応させてｐ−ｔｅｒｔ−ブチ
ルベンジルクロライドを製造するに当たり、ラジカル形
成剤として、ｐ−ｔｅｒｔ−ブチルトルエンに対し２．
５ｗｔ％以下のアゾビス化合物を使用し、かつｐ−ｔｅ
ｒｔ−ブチルトルエン１モル当たりの塩素の供給速度を
１モル／ｈｒ以下にすることを特徴とする。That is, the present invention provides p-tert-
In producing p-tert-butylbenzyl chloride by reacting butyltoluene with chlorine, 2.
Using an azobis compound of 5 wt% or less, and p-te
It is characterized in that the feed rate of chlorine per mole of rt-butyltoluene is 1 mole/hr or less.
本発明の方法によれば核クロル化物は殆ど副生ぜず、ｐ
−ｔｅｒｔ−ブチルトルエンのメチル基を選択的にクロ
ル化することができる。According to the method of the present invention, almost no nuclear chloride is produced as a by-product, and p
The methyl group of -tert-butyltoluene can be selectively chlorinated.
反応は６０〜８０℃、特に好ましくは６５〜７５℃で行
なわれる。６０℃以下ではラジカル形成剤であるアゾビ
ス化合物が有効に働かず、８０℃以上では選択性が失わ
れる。The reaction is carried out at 60-80°C, particularly preferably at 65-75°C. At temperatures below 60°C, the azobis compound, which is a radical forming agent, does not work effectively, and at temperatures above 80°C, selectivity is lost.
本発明の反応は常圧下、又は加圧下、特に水柱６０〜３
００醜程度に加圧された条件下で行なうことができる。The reaction of the present invention is carried out under normal pressure or under pressure, especially 60 to 3 water columns.
It can be carried out under pressurized conditions to the extent of 0.00 Ugly.
本発明の方法において、塩素は、ガス状でｐ−ｔｅｒｔ
−ブチルトルエンに好適に導入することができ、その供
給速度は、１時間当たり、出発物質であるｐ−ｔｅｒｔ
−ブチルトルエンと当モル以下、特に好ましくは０．０
５〜０．２５モルにする必要がある。塩素の供給が早過
ぎるとｔｅｒｔ−ブチル基のクロル化物が増加し、逆に
遅過ぎると反応時間が長くなり工業的に不利となる。ま
た導入される塩素ガスは窒素のような不活性ガスで希釈
して使用することができる。In the method of the invention, chlorine is used in gaseous form as p-tert.
-butyltoluene, the feed rate of which is the starting material p-tert per hour.
-Equimolar or less than butyltoluene, particularly preferably 0.0
It is necessary to make it 5 to 0.25 mol. If chlorine is supplied too quickly, the amount of chloride of the tert-butyl group will increase; if it is supplied too slowly, the reaction time will be prolonged, which is industrially disadvantageous. Further, the introduced chlorine gas can be diluted with an inert gas such as nitrogen before use.
本発明において使用できるアゾビス化合物としてはアゾ
ビスイソブチロニトリル、アゾビスプロパン、アゾビス
シクロヘキサンカルボニトリル、アゾビスイソ酪酸エス
テル、アゾビス（２゜４−ジメチル）バレロニトリル等
が挙げられ、特に好ましいのはアゾビスイソブチロニト
リルである。Examples of the azobis compounds that can be used in the present invention include azobisisobutyronitrile, azobispropane, azobiscyclohexanecarbonitrile, azobisisobutyric acid ester, azobis(2゜4-dimethyl)valeronitrile, etc., and particularly preferred is It is bisisobutyronitrile.
本発明の方法において使用するラジカル形成剤であるア
ゾビス化合物の使用量は出発物質であるｐ−ｔｅｒｔ−
ブチルトルエンに対して２．５ｗｔ％以下、特に１％以
下、さらに好ましくはＯ，ＯＳ〜０．５％の間で使用す
るのが良い、アゾビス化合物が存在しないと反応が進行
しにくく、かつ進行しても様々な反応が起こり多くの副
生物が生成する。逆にラジカル形成剤が多くなると塩素
分子の原子への解離が激しくなりやはり副生成物が多く
なる。更にラジカル形成剤が少ないということはラジカ
ル形成剤自身の分解生成物の混入が少ないという利点を
有する０本発明の方法にしたがって反応を行なうと供給
される塩素とラジカルの形成とは好適に釣り合って、系
外に塩素が逸脱しない、塩素の供給量はｐ−ｔｅｒｔ−
ブチルトルエンに対して理論的にはモル比で１＝１であ
り、０．４〜１．５の間で必要に応じて変えることがで
きるが、実用的には、二基素化生成物等の生成をできる
だけ避けるために、０．６〜１．１が好ましい、この場
合未反応ｐ−ｔｅｒｔ−ブチルトルエンは蒸留によって
回収することができ、回収したｐ−ｔｅｒｔ−ブチルト
ルエンは次回の反応に使用できる。また本反応によって
えられたｐ−ｔｅｒｔ−ブチルベンジルクロライドは蒸
留によって好適に精製することができ、該留分は少なく
とも９５％以上の純度を有している。The amount of the azobis compound, which is a radical forming agent used in the method of the present invention, is determined based on the starting material p-tert-
It is preferable to use 2.5 wt% or less, especially 1% or less, more preferably between O,OS and 0.5% based on butyltoluene.If the azobis compound is not present, the reaction will be difficult to proceed, and However, various reactions occur and many by-products are generated. Conversely, when the amount of radical forming agents increases, the dissociation of chlorine molecules into atoms becomes more intense, resulting in an increase in by-products. Furthermore, the presence of less radical forming agent has the advantage that there is less contamination by decomposition products of the radical forming agent itself.When the reaction is carried out according to the method of the present invention, the chlorine supplied and the formation of radicals are well balanced. , chlorine does not escape outside the system, the amount of chlorine supplied is p-tert-
Theoretically, the molar ratio is 1=1 with respect to butyltoluene, and it can be changed as necessary between 0.4 and 1.5, but in practical terms, In order to avoid the formation of p-tert-butyltoluene as much as possible, a value of 0.6 to 1.1 is preferred. In this case, unreacted p-tert-butyltoluene can be recovered by distillation, and the recovered p-tert-butyltoluene can be used in the next reaction. Can be used. Further, the p-tert-butylbenzyl chloride obtained by this reaction can be suitably purified by distillation, and the fraction has a purity of at least 95%.
以下に実施例を示し、本発明を更に詳細に説明するが、
本発明はその要旨を越えないかぎり以下の実施例に限定
されるものではない。The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to the following examples unless it exceeds the gist thereof.
実施例−１
温度計、撹拌機、塩素導入管、還流冷却器を備えた丸底
フラスコに、水を満たした塩化水素吸収装置を接続した
。このフラスコにｐ−ｔｅｒｔ−ブチルトルエン１００
ｇ （０，６７６モル）とアゾビスイソブチロニトリ
ル０．１ｇを入れた。系内を窒素で置換した後、６８〜
７２℃に昇温し、塩素ガス導入管を通じて塩素ガス５１
ｇ （０，７１８モル）を６時間かけて供給した。この
時の塩素ガスの供給速度は、ｐ−ｔｅｒｔ−ブチルトル
エン１モル当たり０．１８モル／ｈｒであった０反応で
生成する塩化水素ガスは吸収装置中で水に吸収させた。Example-1 A hydrogen chloride absorber filled with water was connected to a round bottom flask equipped with a thermometer, a stirrer, a chlorine inlet tube, and a reflux condenser. Add 100 p-tert-butyltoluene to this flask.
g (0,676 mol) and 0.1 g of azobisisobutyronitrile were added. After replacing the system with nitrogen, 68~
The temperature was raised to 72℃, and 51% of chlorine gas was introduced through the chlorine gas introduction pipe.
g (0,718 mol) was fed over 6 hours. The supply rate of chlorine gas at this time was 0.18 mol/hr per mol of p-tert-butyltoluene. Hydrogen chloride gas generated in the reaction was absorbed into water in an absorption device.
反応終了液に窒素ガスを通じて残存塩化水素ガスを除去
した後、理論段数約２０段のガラス製分留塔を用いて蒸
留を行なった。After removing residual hydrogen chloride gas by passing nitrogen gas through the reaction-completed liquid, distillation was performed using a glass fractionator having about 20 theoretical plates.
ｐ−ｔｅｒｔ−ブチルトルエン１４ｇを回収し、純度９
７％のｐ−ｔｅｒｔ−ブチルベンジルクロライド留分７
５ｇを得た０分析は２５ｍのＰＥＧ−２０Ｍキャピラリ
ーカラムを装備したＧＣで行なった。14 g of p-tert-butyltoluene was recovered and the purity was 9.
7% p-tert-butylbenzyl chloride fraction 7
The analysis yielding 5 g was performed on a GC equipped with a 25 m PEG-20M capillary column.
また生成物の確認はＮＭＲとＧＣマススペクトル分析で
行なった０反応でのｐ−クロル−ｔｅｒｔ−ブチルトル
エンとｐ−ｔｅｒｔ−ブチルベンジルクロライドとの生
成比は、１／４０．７であり、留分中の不純物としては
、主としてｐ−クロル−ｔｅｒｔ−ブチルトルエンと市
販品位のＰ−ｔｅｒｔ−ブチルトルエン中には既に２〜
５％存在しているｍ −ｔｅｒｔ−ブチルトルエンから
生成するｍ−ｔｅｒｔ−ブチルベンジルクロライドであ
る。In addition, the product was confirmed by NMR and GC mass spectrometry, and the production ratio of p-chloro-tert-butyltoluene and p-tert-butylbenzyl chloride in the 0 reaction was 1/40.7. The impurities in the solution are mainly p-chloro-tert-butyltoluene and commercially available P-tert-butyltoluene.
It is m-tert-butylbenzyl chloride produced from m-tert-butyltoluene present at 5%.
実施例−２
塩素ガスの供給量を、３５．５ｇ （０，５モル）とし
、４時間１０分掛けて反応した以外は実施例＝１と同様
の操作を行ない、ｐ−ｔｅｒｔ−ブチルトルエン３５ｇ
を回収し、９５％のｐ−ｔｅｒｔ−ブチルベンジルクロ
ライド留分６８ｇを得た。Example 2 The same operation as in Example 1 was carried out except that the amount of chlorine gas supplied was 35.5 g (0.5 mol) and the reaction took 4 hours and 10 minutes, and 35 g of p-tert-butyltoluene was
was collected to obtain 68 g of a 95% p-tert-butylbenzyl chloride fraction.
反応でのｐ−クロル−ｔｅｒｔ−ブチルトルエンとｐ−
ｔｅｒｔ−ブチルベンジルクロライドとの生成比は、１
７２６であった。p-chloro-tert-butyltoluene and p-chloro-tert-butyltoluene in the reaction
The production ratio with tert-butylbenzyl chloride is 1
It was 726.
比較例−１
反応温度を５０℃で行なった以外は実施例−１と同様に
反応したが、転化率が５０％以下であり、かつｐ−クロ
ル−ｔｅｒｔ−ブチルトルエンとｐ−ｔｅｒｔ−ブチル
ベンジルクロライドとの生成比は、１／２．４であった
。Comparative Example-1 The reaction was carried out in the same manner as in Example-1 except that the reaction temperature was 50°C, but the conversion rate was 50% or less, and p-chloro-tert-butyltoluene and p-tert-butylbenzyl The production ratio with chloride was 1/2.4.
比較例−２
反応温度を９０℃で行なった以外は実施例−１と同様に
反応を行なったが、ｐ−クロル−ｔｅｒｔ−ブチルトル
エンとｐ−ｔｅｒｔ−ブチルベンジルクロライドとの生
成比は、１１５．９であり、かつ高沸物が多くなった。Comparative Example-2 The reaction was carried out in the same manner as in Example-1 except that the reaction temperature was 90°C, but the production ratio of p-chloro-tert-butyltoluene and p-tert-butylbenzyl chloride was 115 .9, and the number of high-boiling substances increased.
比較例−３
塩素の供給速度をｐ−ｔｅｒｔ−ブチルトルエン１モル
当たり１．３３モル／ｈｒにした以外は実施例−１の方
法と同様に反応を行なったが、ｐ−クロル−ｔｅｒｔ−
ブチルトルエンとＰ−ｔｅｒｔ−ブチルベンジルクロラ
イドとの生成比は、１／９であった。Comparative Example 3 The reaction was carried out in the same manner as in Example 1 except that the chlorine supply rate was 1.33 mol/hr per mol of p-tert-butyltoluene, but p-chloro-tert-
The production ratio of butyltoluene and P-tert-butylbenzyl chloride was 1/9.
比較例−４
ラジカル形成剤であるアゾビスイソブチロニトリルの添
加量を５ｗｔ％にした以外は実施例−１と同様に反応を
行なった。Ｐ−クロル−ｔｅｒｔ−ブチルトルエンとｐ
−ｔｅｒｔ−ブチルベンジルクロライドとの生成比は、
１／９．５であった。Comparative Example-4 The reaction was carried out in the same manner as in Example-1 except that the amount of azobisisobutyronitrile, a radical forming agent, added was 5 wt%. P-chloro-tert-butyltoluene and p
The production ratio with -tert-butylbenzyl chloride is
It was 1/9.5.
通常のラジカル形成剤であるアゾビス化合物を使用して
、６０〜８０℃という工業的に有利な温度範囲において
高選択率、高収率でｐ−ｔｅｒｔ−ブチルベンジルクロ
ライドを製造できるという利点を有している。更に従来
は光反応を行なうため、石英ガラス製の特殊な製造装置
を必要としていたが、本発明の方法では、通常の反応装
置が使用できるという利点がある。It has the advantage that p-tert-butylbenzyl chloride can be produced with high selectivity and high yield in an industrially advantageous temperature range of 60 to 80°C using an azobis compound, which is a common radical forming agent. ing. Furthermore, while conventionally a special manufacturing device made of quartz glass was required to carry out the photoreaction, the method of the present invention has the advantage that a normal reaction device can be used.
Claims (1)
ンと塩素を反応させてｐ−ｔｅｒｔ−ブチルベンジルク
ロライドを製造するに当たり、ラジカル形成剤として、
ｐ−ｔｅｒｔ−ブチルトルエンに対し２．５ｗｔ％以下
のアゾビス化合物を使用し、かつｐ−ｔｅｒｔ−ブチル
トルエン１モル当たりの塩素の供給量を１モル／ｈｒ以
下にすることを特徴とするｐ−ｔｅｒｔ−ブチルベンジ
ルクロライドの製造方法。1. In producing p-tert-butylbenzyl chloride by reacting p-tert-butyltoluene and chlorine at a temperature of 60 to 80°C, as a radical forming agent,
p-, characterized in that 2.5 wt% or less of the azobis compound is used with respect to p-tert-butyltoluene, and the amount of chlorine supplied per mol of p-tert-butyltoluene is 1 mol/hr or less. A method for producing tert-butylbenzyl chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5540688A JPH01228926A (en) | 1988-03-09 | 1988-03-09 | Production of p-tert-butylbenzyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5540688A JPH01228926A (en) | 1988-03-09 | 1988-03-09 | Production of p-tert-butylbenzyl chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01228926A true JPH01228926A (en) | 1989-09-12 |
Family
ID=12997661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5540688A Pending JPH01228926A (en) | 1988-03-09 | 1988-03-09 | Production of p-tert-butylbenzyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01228926A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721466A (en) * | 2019-01-22 | 2019-05-07 | 江苏佳麦化工有限公司 | A kind of synthetic method of benzyl chloride |
-
1988
- 1988-03-09 JP JP5540688A patent/JPH01228926A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721466A (en) * | 2019-01-22 | 2019-05-07 | 江苏佳麦化工有限公司 | A kind of synthetic method of benzyl chloride |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU613296B2 (en) | Hydrodehalogenation of cf3 chc1f in the presence of supported pd | |
| HUP9901285A2 (en) | Process for the production of difluoromethane | |
| JPH06256235A (en) | Preparation of 1,1,1,3,3,-pentafluoropropane | |
| JPWO2009122940A1 (en) | Method for purifying pyridine and method for producing chlorinated pyridine | |
| JP3495541B2 (en) | Preparation of alkyl chloride | |
| RU2054407C1 (en) | Method for production of 1,1-dichlor-1-fluoroethane | |
| JP3502523B2 (en) | Continuous production of alkyl halides. | |
| JPH07196577A (en) | Preparation of aliphatic omega-difluorocarboxyl compound | |
| JPH01228926A (en) | Production of p-tert-butylbenzyl chloride | |
| JPH0349609B2 (en) | ||
| US5241113A (en) | Process for producing trifluoroacetyl chloride | |
| JP2797626B2 (en) | Method for producing perfluoroalkyl bromide | |
| KR830002449B1 (en) | Process for preparation of 4-trichloromethoxy-benzoyl chloride | |
| JPS62129236A (en) | Manufacture of methylisopropylketone and diethylketone | |
| US2399361A (en) | Manufacture of cyanogen | |
| US3760015A (en) | Production of vinylidene chloride and methyl chloroform | |
| KR860001889B1 (en) | Process for preparation of 2,3-dichloropropionitril | |
| JP3164284B2 (en) | Method for producing 2-chloro-4-trifluoromethylbenzal chloride | |
| JPS6357592A (en) | Production of tert-butyldimethylchlorosilane | |
| US5126497A (en) | Catalyst and process for the preparation of trifluoromethyltoluenes | |
| JPS58213724A (en) | Preparation of alpha-ketoamide | |
| JPS6312862B2 (en) | ||
| JP4029447B2 (en) | Method for producing 2-chloro-1,4-bistrichloromethylbenzene | |
| EP1119534B1 (en) | Method for the preparation of 3-bromo-1,1,1-trifluoropropane | |
| JPS62181234A (en) | Production of isophthaloyl dichloride |