JPS6314693B2 - - Google Patents
Info
- Publication number
- JPS6314693B2 JPS6314693B2 JP9436680A JP9436680A JPS6314693B2 JP S6314693 B2 JPS6314693 B2 JP S6314693B2 JP 9436680 A JP9436680 A JP 9436680A JP 9436680 A JP9436680 A JP 9436680A JP S6314693 B2 JPS6314693 B2 JP S6314693B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- toluene
- mol
- chlorine
- chlorination
- 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
- 239000000460 chlorine Substances 0.000 claims description 37
- 229910052801 chlorine Inorganic materials 0.000 claims description 37
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 24
- 229910017604 nitric acid Inorganic materials 0.000 claims description 24
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 81
- 239000000203 mixture Substances 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 39
- 235000017168 chlorine Nutrition 0.000 description 33
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 32
- 238000005660 chlorination reaction Methods 0.000 description 31
- 150000003613 toluenes Chemical class 0.000 description 31
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 28
- 238000000034 method Methods 0.000 description 23
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 14
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 13
- 150000003935 benzaldehydes Chemical class 0.000 description 12
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 12
- 229940073608 benzyl chloride Drugs 0.000 description 12
- 238000007664 blowing Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 5
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JQZAEUFPPSRDOP-UHFFFAOYSA-N 1-chloro-4-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1 JQZAEUFPPSRDOP-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 2
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 agriculture Substances 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BASMANVIUSSIIM-UHFFFAOYSA-N 1-chloro-2-(chloromethyl)benzene Chemical compound ClCC1=CC=CC=C1Cl BASMANVIUSSIIM-UHFFFAOYSA-N 0.000 description 1
- BXSVYGKOUULJCL-UHFFFAOYSA-N 1-chloro-2-(dichloromethyl)benzene Chemical compound ClC(Cl)C1=CC=CC=C1Cl BXSVYGKOUULJCL-UHFFFAOYSA-N 0.000 description 1
- MFHPYLFZSCSNST-UHFFFAOYSA-N 1-chloro-2-(trichloromethyl)benzene Chemical compound ClC1=CC=CC=C1C(Cl)(Cl)Cl MFHPYLFZSCSNST-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 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
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明はベンズアルデヒド類の製造方法に関す
る。更に詳しくは、一般式が
The present invention relates to a method for producing benzaldehydes. More specifically, the general formula is
【式】（たゞ
し、式中ＸはＨ、Cl、Br、CNまたはNO2をあら
わす）で示される化合物（以下これらをトルエン
類と記す）のメチル基を塩素化して、トルエン類
１分子に対して平均1.0〜2.0個の塩素原子を有す
る塩素化物（以下塩素化トルエン混合物と記す）
を製造する第１工程と、第１工程で得られた塩素
化トルエン混合物を硝酸と反応させて一般式が
[Formula] (wherein X represents H, Cl, Br, CN, or NO 2 ) The methyl group of the compound (hereinafter referred to as toluenes) is chlorinated to produce one molecule of toluenes. Chlorinated products having an average of 1.0 to 2.0 chlorine atoms (hereinafter referred to as chlorinated toluene mixture)
The first step is to produce the chlorinated toluene mixture obtained in the first step, and the general formula is
【式】（たゞし、式中ＸはＨ、Cl、Br、
CNまたはNO2をあらわす）で示される化合物
（以下これらをベンズアルデヒド類と記す）を製
造する第２工程とからなることを特徴とするベン
ズアルデヒド類の製造方法に関する発明である。
ベンズアルデヒド類は医薬、農業、染料、香
料、その他の有機合成原料として有用である。従
来、ベンズアルデヒド類の製造方法としては、多
くの方法が知られている。ベンズアルデヒド類の
製造方法をベンズアルデヒドを例にとつて示せば
次のようである。すなわち、ベンズアルデヒドの
主な製法としては、トルエンの直接酸化法、ベン
ザルクロライドの加水分解法があり、他にベンジ
ルクロライド、ベンジルアルコール、ベンゾイル
クロライドを原料とする方法等が知られている。
しかしながらこれらの方法は必ずしも好ましい方
法ではない。例えば、トルエンの直接酸化法につ
いては、反応条件、触媒等について多くの研究が
なされているが、未だベンズアルデヒドを選択的
に製造することが出来ないので、安息香酸または
ベンジルアルコール等が多量に副生するのが実情
である。
ベンザルクロライドを加水分解する方法につい
ても触媒や反応条件について多くの研究がされて
いる。この場合は、反応触媒、反応条件を選ぶこ
とによつて、比較的高収率でベンズアルデヒドを
製造することが出来る。しかしながら、この場合
にはベンザルクロライドを製造すること自体にか
なりの困難がある。すなわち、ベンザルクロライ
ドの製造は通常はトルエンの熱または光塩素化に
よつて行なわれるが、この塩素化においては、塩
素化度と生全物組成との間に、例えば参考図のよ
うな関係がある。すなわち、ベンザルクロライド
はベンジルクロライドおよびベンゾトリクロライ
ドとの混合物の形で得られ、ベンザルクロライド
を選択的に合成することが出来ない。したがつて
ベンザルクロライドを得るためには、蒸留等混合
物からの分離操作が必要となるばかりでなく、ト
ルエンに対する収率は低くなる等の欠点がある。
したがつて、ベンザルクロライドの加水分解によ
るベンズアルデヒドの製造方法もトルエンを出発
物質としてみた場合には、高収率とはいえない。
ベンジルクロライドを出発原料とする方法とし
ては古くから、希硝酸または硝酸鉛と反応させる
方法、ヘキサメチレンテトラミン溶液と反応させ
る方法、加水分解後重クロム酸ソーダで酸化する
方法等いくつかの方法が知られている。しかしな
がらこの場合もベンザルクロライドの場合と同様
に、ベンジルクロライドを製造することがかなり
困難である。すなわち、トルエンの塩素化による
ベンジルクロライドの合成においては、参考図に
示されるようにベンジルクロライドはベンザルク
ロライド等との混合物の形で得られ、ベンジルク
ロライドを選択的に合成することが出来ない。し
たがつて分離操作が必要となるばかりでなく、収
率も低くなることはベンザルクロライドの場合と
同様である。
本発明者らは、これらの欠点を改善すべく、ベ
ンズアルデヒドの新規な製造方法について鋭意研
究を行なつた結果、トルエンのメチル基の塩素の
数（以下、塩素化度と記す）が特定の数である塩
素化トルエン混合物または、核にハロゲン、−
CNまたは−NO2を有する塩素化トルエン混合物
を特定の条件下に硝酸と反応させることによつ
て、好収率でベンズアルデヒド類を製造すること
が出来ることを見出して、本発明方法を完成する
に至つた。
本発明方法は、第１工程の塩素化反応におい一
般式[Formula] (wherein X represents H, Cl, Br, CN or NO 2 ) A second step of producing a compound (hereinafter referred to as benzaldehydes) This invention relates to a method for producing benzaldehydes. Benzaldehydes are useful as raw materials for medicine, agriculture, dyes, fragrances, and other organic synthesis. Conventionally, many methods are known as methods for producing benzaldehydes. The method for producing benzaldehydes is as follows, taking benzaldehyde as an example. That is, the main methods for producing benzaldehyde include the direct oxidation method of toluene and the hydrolysis method of benzal chloride, and other known methods include methods using benzyl chloride, benzyl alcohol, and benzoyl chloride as raw materials.
However, these methods are not necessarily preferred methods. For example, regarding the direct oxidation method of toluene, a lot of research has been done on reaction conditions, catalysts, etc., but it is still not possible to selectively produce benzaldehyde, so benzoic acid or benzyl alcohol etc. are produced as by-products in large quantities. The reality is that. Much research has been conducted on catalysts and reaction conditions regarding methods for hydrolyzing benzal chloride. In this case, benzaldehyde can be produced in a relatively high yield by selecting the reaction catalyst and reaction conditions. However, in this case, there are considerable difficulties in producing benzal chloride itself. That is, the production of benzal chloride is usually carried out by thermal or photochlorination of toluene, but in this chlorination, there is a relationship between the degree of chlorination and the composition of the whole organism, as shown in the reference diagram. There is. That is, benzal chloride is obtained in the form of a mixture with benzyl chloride and benzotrichloride, and benzal chloride cannot be selectively synthesized. Therefore, in order to obtain benzal chloride, not only is separation operation such as distillation required from the mixture, but there are also drawbacks such as a low yield relative to toluene.
Therefore, the method for producing benzaldehyde by hydrolysis of benzal chloride cannot be said to have a high yield when using toluene as a starting material. Several methods have been known for a long time using benzyl chloride as a starting material, such as reacting it with dilute nitric acid or lead nitrate, reacting it with a hexamethylenetetramine solution, and oxidizing it with sodium dichromate after hydrolysis. It is being However, in this case as well, it is quite difficult to produce benzyl chloride. That is, in the synthesis of benzyl chloride by chlorination of toluene, benzyl chloride is obtained in the form of a mixture with benzal chloride and the like, as shown in the reference diagram, and benzyl chloride cannot be synthesized selectively. Therefore, not only is a separation operation required, but the yield is also low, as in the case of benzal chloride. In order to improve these drawbacks, the present inventors conducted intensive research on a new method for producing benzaldehyde, and found that the number of chlorine atoms in the methyl group of toluene (hereinafter referred to as the degree of chlorination) reached a certain number. chlorinated toluene mixture or halogen in the core, -
The present invention was completed by discovering that benzaldehydes can be produced in good yield by reacting a chlorinated toluene mixture containing CN or -NO 2 with nitric acid under specific conditions. I've reached it. In the method of the present invention, in the chlorination reaction of the first step, the general formula
【式】（式中ＸはＨ、Cl、Br、CNま
たはNO2をあらわす）で示されるトルエン類１
モルに対して１〜２モルの塩素を反応させて、そ
のメチル基に平均１〜２個の塩素が導入された塩
素化トルエン混合物を製造し、得られた塩素化ト
ルエン混合物をそのまゝ、あるいは簡単な蒸留を
行なつた後、第２工程において特定の条件下に硝
酸と反応させることによつて、高収率でベンズア
ルデヒド類を製造する方法に関するものである。
本発明方法によれば、ベンジルクロライド（ま
たはその核置換体）とベンザルクロライド（また
はその核置換体）を主成分とする塩素化トルエン
混合物を特定の条件下に硝酸と反応させることに
より、そのいずれをもベンズアルデヒド類とする
ことが可能である。そして、トルエン類の塩素化
度を特定の範囲に限定することによつて、塩素化
トルエン混合物をそのまゞ硝酸との酸化反応の原
料にすることが出来るので、従来のベンザルクロ
ライドやベンジルクロライドを原料とするベンズ
アルデヒドの製造方法におけ原料調達の困難性が
解決される。従つて有利にベンズアルデヒド類を
製造することが可能である。
本発明方法の第１工程のトルエン類の塩素化は
通常は紫外線含有光照射下において、液相で塩素
をバブリングする方法またはベンゾイルパーオキ
サイドまたはアゾビスイソブチロニトリル等のラ
ジカル発生剤を反応液に添加して、液相に塩素を
バブリングして反応を行なう方法等により行な
う。なおこの場合、必ずしも反応溶媒を使用する
必要はないが、塩素化炭化水素溶媒例えば四塩化
炭素等の溶媒を使用することは勿論可能である。
塩素化反応は通常50℃〜160℃の反応温度で行な
われるが、実際の反応温度は溶媒の有無、その種
類および塩素化しようとするトルエン類の種類等
によつて適宜選択される。また、塩素化反応の時
期は反応装置に応じた塩素ガスの吹き込み方法に
よつて適宜決められる。本発明方法の塩素化反応
においては好ましくない不純物の生成を抑制する
ために、必要に応じてアルキレンポリアミン、ベ
ンスアミド、トリアリルホスフエート等を添加し
て反応を行なうことも可能である。塩素化反応は
回分法、または連続法のいずれの方法でも実施す
ることが可能である。
上記塩素化反応において重要なのは反応させる
塩素とトルエン類のモル比であつて、トルエン類
１分子に対して、そのメチル基に平均１〜２個の
塩素原子を有する塩素化トルエン混合物を製造す
るためには、トルエン類１モルに対して１〜２モ
ルの塩素を反応させる必要がある。トルエン類と
塩素との反応はほとんど定量的に行なうことが出
来るので、塩素化トルエン混合物の目的とする平
均塩素化度に相当する量に実質的に等しい量の塩
素またはやゝ過剰の塩素をトルエン類と反応させ
ることによつて目的とする平均塩素化度を有する
塩素化トルエン混合物を得ることが出来る。
本発明方法の第２工程は、第１工程で製造され
た塩素化トルエン混合物と硝酸を混合し、反応さ
せる工程である。第２工程で使用する塩素化トル
エン混合物は普通は特別な精製や分離操作を必要
としないが、塩素化反応の際に生じたタールその
他の副生物が多い場合には、これらの副生物を除
くために蒸留等を行なうことは好ましいことであ
る。なお、硝酸と反応を行なう前に塩素化トルエ
ン混合物を加水分解し、次いで硝酸と反応させる
ことも可能である。
本発明方法の第２工程を実施する場合の硝酸の
濃度は、一般的には0.5〜12wt％、好ましくは２
〜8wt％である。硝酸の濃度が高い場合にはカル
ボン酸類の副生が多くなる傾向があるので好まし
くない。また硝酸の濃度が低い場合には反応効率
が悪く経済性がなくなるので好ましくない。
第２工程の反応温度は通常は常圧の場合70〜
105℃である。加圧の場合は圧力の大きさにもよ
るが100〜130℃である。好ましい反応温度は常圧
下で、原料である塩素化トルエン混合物と硝酸水
溶液とを混合した反応混合物を還流する際の還流
温度であり、通常は100℃付近またはそれより少
し高い温度である。しかし、これらの温度は、硝
酸の濃度や反応物の種類、または相対量によつて
若干変動する場合がある。
塩素化トルエン混合物に対する硝酸の使用量
は、塩素化トルエン混合物１モルに対して、一般
的には0.2〜10モルであり、好ましくは1.0〜6.0モ
ルである。硝酸の使用量は反応させる物質、その
組成または反応条件に応じて適宜決定されるが、
一般的には塩素化トルエン混合物の平均塩素化度
が低い場合には、硝酸の量を多くすることによつ
て好結果が得られ、平均塩素化度が高い場合に
は、硝酸量を少なくすることが可能である。
本発明方法の第２工程の実施に当つては、触媒
を用いなくてもよいが、触媒を用いることによつ
て反応が促進され、反応時間が短縮されるので、
触媒を用いることは好ましい態様である。この場
合の触媒としては五酸化バナジウム、メタバナジ
ン酸アンモニウム、メタバナジン酸ナトリウム、
塩化バナジウム、硫酸バナジル等のバナジウム化
合物が効果の点から望ましい。触媒の添加量は触
媒の種類や塩素化トルエン混合物の組成または硝
酸の濃度によつて異るが、通常は塩素化トルエン
混合物１重量部に対して0.001〜0.10重量部であ
る。
なお、塩酸や硫酸のような鉱酸もまた触媒とし
て使用することが可能である。この場合の触媒量
は塩素化トルエン混合物１重量部に対して0.01〜
1.5重量部である。
反応生成物から目的物を分離するには通常の分
離方法が行なわれる。すなわち、反応終了後の反
応混合物を冷却して、晶出する結晶を別する方
法、遊離する油状部を分離する方法、または反応
生成物に有機溶剤を加えて抽出する方法等によ
り、反応生成物からベンズアルデヒド類を分離す
ることが出来る。
このようにして分離されたベンズアルデヒド類
には、副生したカルボン酸化合物が含まれるが、
これらの酸性物質は希アルカリ性水溶液で洗浄す
ることによつて除くことが可能である。このよう
にして得られたベンズアルデヒド類は高純度であ
るから、そのまゝ使用することが出来るが、必要
に応じて更に蒸留または再結晶等の通常の精製法
によつて更に純度を高めることが出来る。また反
応生成物のアルカリ洗浄液からは遊離のカルボン
酸を回収することが可能である。
実施例 １
第１工程
温度計、撹拌機、塩素吹込管、排気兼用の還流
冷却器および高圧水銀灯による光照射装置を有す
る内容積が600mlの光反応器に、トルエン368ｇ
（4.0モル）を仕込み、内容物を95℃に加熱し、撹
拌しながら光照射下に塩素ガスを吹き込んだ。塩
素の吹き込み後間もなく、塩化水素の発生と共に
温度の上昇がみられた。反応温度を100℃に保持
し、光を照射しつつ、142ｇ／hr（2.0モル／hr）
の割合で塩素の導入を３時間続けた。排出される
ガス中には塩素はほとんど認められず、吹き込ん
だ塩素はほとんど完全に反応していた。
３時間の反応で、426ｇ（6.0モル）の塩素を吹
き込んだところで塩素の吹き込みを停止し、反応
液に乾燥窒素ガスを通じて系内の塩化水素および
塩素ガスを除いた。このようにして得られた反応
生成物は558ｇであつた。
反応生成物をガスクロマトグラフにより分析し
たところ、その組成はトルエン１モル％、ベンジ
ルクロライド48モル％、ベンザルクロライド46モ
ル％、ベンゾトリクロライド３モル％、その他１
モル％であつた。反応液の平均塩素化度は1.5で
あつた。
第２工程
温度計、撹拌機、還流冷却器を備えた２の三
つ口フラスコに第１工程で得られた塩素化トルエ
ン混合物49.3ｇ（平均塩素化度1.5として計算す
ると0.343モルに相当する）と3wt％の硝酸1440
ｇ、五酸化バナジウム1.5ｇを仕込み、この混合
物を撹拌下に加熱昇温し、還流状態で５時間反応
を行なつた。
反応混合物を冷却し、油状部を分離後、更に水
層に100mlのトルエンを加えて２回抽出を行なつ
た。油状部と抽出液を合せてトルエンを留去し、
残りの油状部を蒸留した。この方法により111〜
114℃／100mmHgの留分34.1ｇを得た。このもの
を赤外線吸収スペクトル分析したところ、ベンズ
アルデヒドであることが確認された。なお、ガス
クロマトグラフ分析による純度は99.4％であつ
た。
原料であるトルエンに対するベンズアルデヒド
収率は90.4％である。
実施例 ２
第１工程
実施例１の第１工程で用いたと同じ光反応装置
にトルエン368ｇ（4.0モル）をとり、実施例１の
第１工程の場合と同様に反応温度を100℃に保持
し、光照射下で塩素を吹き込んで塩素化反応を行
なつた。塩素の吹き込みは114ｇ／hr（1.6モル／
hr）の割合で行ない、３時間反応を続けた。341
ｇ（4.8モル）の塩素を吹き込んだところで、塩
素の吹き込みを停止し、乾燥窒素ガスを通じて系
内の塩化水素および塩素ガスを除いて523ｇの反
応液を得た。
このものをガスクロマトグラフ分析したとこ
ろ、ベンジルクロライド67モル％、ベンザルクロ
ライド27モル％、トルエン４モル％、その他２モ
ル％であつた。平均塩素化度は1.2であつた。
第２工程
実施例１の第２工程と同じ反応器に、第１工程
で得た塩素化トルエン混合物61.0ｇ（塩素化度
1.2として計算すると0.457モル相当）と4wt％の
硝酸1440ｇ、メタバナジン酸アンモニウム1.8ｇ
を仕込んだ。この混合物を撹拌しながら加熱昇温
し、還流状態で６時間反応を行なつた。反応終了
後、実施例１の第２工程と同様に処理し、蒸留に
よつてベンズアルデヒド留分43.6ｇを得た。ガス
クロマトグラフ分析の結果、純度は99.3％であつ
た。原料であるトルエンに対するベンズアルデヒ
ド収率は88.3％に相当する。
実施例 ３
第１工程
実施例１の第１工程で用いたと同じ光反応装置
に、トルエン368ｇ（4.0モル）をとり、実施例１
の第１工程と同様に反応温度を100℃に保持し、
光照射下に塩素を吹き込んで、塩素化反応を行な
つた。塩素の吹き込みは142ｇ／hr（2.0モル／hr）
の割合で行ない、3.6時間反応を続けた。7.2モル
の塩素を吹き込んだところで、塩素の吹き込みを
停止し、乾燥窒素ガスを通じて系内の塩化水素お
よび塩素ガスを除いて606ｇの反応液を得た。
このものをガスクロマトグラフ分析したとこ
ろ、組成はベンジルクロライド27モル％、ベンザ
ルクロライド66モル％、ベンゾトリクロライド
5.5モル％、その他1.5モル％で、平均塩素化度は
1.8であつた。
第２工程
実施例１の第２工程と同じ反応器に、第１工程
で得た塩素化トルエン混合物71ｇ（塩素化度1.8
として計算すると0.460モル相当）と4wt％の硝酸
1440ｇを仕込んだ。この混合物を撹拌しながら加
熱昇温し、還流状態で12時間反応を行なつた。反
応終了後、実施例１の第２工程と同様に処理し、
蒸留によつてベンズアルデヒド留分43.2ｇを得
た。原料であるトルエンに対するベンズアルデヒ
ドの収率は87％に相当する。
実施例 ４
第１工程
実施例１の第１工程で用いたと同じ光反応装置
に、ｐ−クロルトルエン380ｇ（3.0モル）をと
り、実施例１の第１工程と同様の方法で反応温度
を130℃に保持し、光照射下に塩素を吹き込んで
塩素化反応を行なつた。塩素の吹き込みは106
ｇ／hr（1.5モル／hr）の割合で行ない、3.0時間
反応を続けた。4.5モルの塩素を吹き込んだとこ
ろで、塩素の吹き込みを停止し、実施例１と同様
に処理して、527ｇの反応液を得た。
このものをガスクロマトグラフ分析したとこ
ろ、組成はｐ−クロルトルエン２モル％、４−ク
ロルベンジルクロライド48モル％、４−クロルベ
ンザルクロライド46モル％、その他４モル％で、
ｐ−クロルトルエンの平均塩素化度は1.5であつ
た。
第２工程
実施例１の第２工程と同じ反応器に、第１工程
で得たｐ−クロルトルエンの塩素化混合物81.3ｇ
（塩素化度1.5として計算すると0.456モル相当）
と5wt％の硝酸1440ｇ、五酸化バナジウム2.4ｇを
仕込み、この混合物を撹拌下に加熱昇温し、還流
状態で６時間反応を行なつた。
反応混合物を冷却し、晶出する結晶を別分離
後、液に100mlのトルエンを加えて２回抽出を
行なつた。結晶部と抽出液を合せてトルエンを留
出後、残渣を蒸留し、100〜102℃／20mmHgの留
分48ｇを得た。
このものを赤外線吸収スペクトル分析の結果、
ｐ−クロルベンズアルデヒドであることが確認さ
れた。
原料であるｐ−クロルトルエン基準のｐ−クロ
ルベンズアルデヒド収率は73.9％に相当する。
実施例 ５
第１工程
実施例１の第１工程で用いたと同じ光反応装置
にｏ−クロルトルエン380ｇ（3.0モル）をとり、
実施例１の第１工程と同様の方法で、反応温度を
130℃に保持し、光照射下に塩素を吹き込んで、
塩素化反応を行なつた。塩素の吹き込みは106
ｇ／hr（1.5モル／hr）の割合で行ない、3.6時間
反応を続けた。5.4モルの塩素を吹き込んだとこ
ろで、塩素の吹き込みを停止し、実施例１と同様
に処理して、558ｇの反応液を得た。
このものをガスクロマトグラフ分析したとこ
ろ、ｏ−クロルトルエン0.5モル％、ｏ−クロル
ベンジルクロライド28モル％、ｏ−クロルベンザ
ルクロライド67モル％、ｏ−クロルベンゾトリク
ロライド３モル％、その他1.5モル％で、ｏ−ク
ロルトルエンに対する平均塩素化度は1.8であつ
た。
第２工程
実施例１の第２工程と同じ反応器に、第１工程
で得たｏ−クロルトルエンの塩素化混合物64.7ｇ
（塩素化度1.8として計算すると0.343モル相当）
と3wt％の硝酸1440ｇ、五酸化バナジウム2.0ｇを
仕込み、この混合物を撹拌下に加熱昇温し、還流
状態で６時間反応を行なつた。
反応混合物を冷却し、これに200mlのトルエン
を加えて油相を分離し、水溶液部に100mlのトル
エンを加えて２回抽出操作を行なつた。最初の油
状部と抽出液を合せてトルエンを留去後、残つた
部分を蒸留し、107〜110℃／30mmHgの留分36ｇ
を得た。
このものを赤外線吸収スペクトル分析の結果、
ｏ−クロルベンズアルデヒドであることが確認さ
れた。
原料であるｏ−クロルトルエン基準のｏ−クロ
ルベンズアルデヒド収率は73.5％である。Toluenes 1 represented by [Formula] (wherein X represents H, Cl, Br, CN or NO 2 )
A chlorinated toluene mixture in which an average of 1 to 2 chlorines are introduced into the methyl group is produced by reacting 1 to 2 moles of chlorine per mole, and the resulting chlorinated toluene mixture is directly used as is. Alternatively, the present invention relates to a method for producing benzaldehydes in high yield by carrying out a simple distillation and then reacting with nitric acid under specific conditions in a second step. According to the method of the present invention, a chlorinated toluene mixture containing benzyl chloride (or its nuclear substituted product) and benzal chloride (or its nuclear substituted product) as main components is reacted with nitric acid under specific conditions. Any of them can be a benzaldehyde. By limiting the degree of chlorination of toluenes to a specific range, the chlorinated toluene mixture can be directly used as a raw material for the oxidation reaction with nitric acid. The difficulty in procuring raw materials is solved in the method for producing benzaldehyde using raw materials. It is therefore possible to advantageously produce benzaldehydes. The chlorination of toluenes in the first step of the method of the present invention is usually carried out by bubbling chlorine in the liquid phase under irradiation with ultraviolet light, or by adding a radical generator such as benzoyl peroxide or azobisisobutyronitrile to the reaction solution. The reaction is carried out by adding chlorine to the liquid phase and bubbling chlorine into the liquid phase to carry out the reaction. In this case, it is not always necessary to use a reaction solvent, but it is of course possible to use a chlorinated hydrocarbon solvent such as carbon tetrachloride.
The chlorination reaction is usually carried out at a reaction temperature of 50°C to 160°C, but the actual reaction temperature is appropriately selected depending on the presence or absence of a solvent, its type, and the type of toluene to be chlorinated. Further, the timing of the chlorination reaction is appropriately determined depending on the method of blowing chlorine gas depending on the reaction apparatus. In the chlorination reaction of the method of the present invention, alkylene polyamine, benzamide, triallyl phosphate, etc. may be added as necessary to suppress the formation of undesirable impurities. The chlorination reaction can be carried out either batchwise or continuously. What is important in the above chlorination reaction is the molar ratio of chlorine and toluene to be reacted, and this is because a chlorinated toluene mixture having an average of 1 to 2 chlorine atoms in the methyl group per molecule of toluene is produced. For this purpose, it is necessary to react 1 to 2 moles of chlorine per mole of toluene. Since the reaction between toluenes and chlorine can be carried out almost quantitatively, an amount of chlorine substantially equal to the amount corresponding to the desired average degree of chlorination of the chlorinated toluene mixture or a slight excess of chlorine is added to the toluene. A chlorinated toluene mixture having the desired average degree of chlorination can be obtained by reacting with chlorinated toluene. The second step of the method of the present invention is a step in which the chlorinated toluene mixture produced in the first step is mixed with nitric acid and reacted. The chlorinated toluene mixture used in the second step usually does not require any special purification or separation operations, but if there are many tars and other byproducts generated during the chlorination reaction, these byproducts may be removed. Therefore, it is preferable to perform distillation or the like. Note that it is also possible to hydrolyze the chlorinated toluene mixture before reacting with nitric acid, and then react with nitric acid. The concentration of nitric acid when carrying out the second step of the method of the present invention is generally 0.5 to 12 wt%, preferably 2
~8wt%. If the concentration of nitric acid is high, carboxylic acids tend to be produced as by-products, which is not preferable. Furthermore, when the concentration of nitric acid is low, the reaction efficiency is poor and economical efficiency is lost, which is not preferable. The reaction temperature in the second step is usually 70~70°C at normal pressure.
It is 105℃. In the case of pressurization, the temperature is 100 to 130°C, depending on the magnitude of the pressure. The preferred reaction temperature is the reflux temperature at which the reaction mixture of the raw materials chlorinated toluene mixture and nitric acid aqueous solution is refluxed under normal pressure, and is usually around 100°C or slightly higher. However, these temperatures may vary slightly depending on the concentration of nitric acid and the types or relative amounts of reactants. The amount of nitric acid used in the chlorinated toluene mixture is generally 0.2 to 10 mol, preferably 1.0 to 6.0 mol, per 1 mol of the chlorinated toluene mixture. The amount of nitric acid used is determined appropriately depending on the substance to be reacted, its composition, and reaction conditions.
Generally, when the average degree of chlorination of the chlorinated toluene mixture is low, good results can be obtained by increasing the amount of nitric acid, and when the average degree of chlorination is high, decreasing the amount of nitric acid can be obtained. Is possible. When carrying out the second step of the method of the present invention, it is not necessary to use a catalyst, but using a catalyst accelerates the reaction and shortens the reaction time.
Using a catalyst is a preferred embodiment. In this case, the catalysts include vanadium pentoxide, ammonium metavanadate, sodium metavanadate,
Vanadium compounds such as vanadium chloride and vanadyl sulfate are preferred from the viewpoint of effectiveness. The amount of catalyst added varies depending on the type of catalyst, the composition of the chlorinated toluene mixture, or the concentration of nitric acid, but is usually 0.001 to 0.10 parts by weight per 1 part by weight of the chlorinated toluene mixture. Note that mineral acids such as hydrochloric acid and sulfuric acid can also be used as catalysts. In this case, the amount of catalyst is 0.01 to 1 part by weight of the chlorinated toluene mixture.
It is 1.5 parts by weight. A conventional separation method is used to separate the target product from the reaction product. That is, the reaction product can be removed by cooling the reaction mixture after the completion of the reaction and separating the crystallized crystals, separating the liberated oil, or adding an organic solvent to the reaction product to extract it. Benzaldehydes can be separated from The benzaldehydes separated in this way include by-product carboxylic acid compounds, but
These acidic substances can be removed by washing with a dilute alkaline aqueous solution. Since the benzaldehydes obtained in this way are of high purity, they can be used as they are, but if necessary, the purity can be further increased by ordinary purification methods such as distillation or recrystallization. I can do it. Furthermore, free carboxylic acid can be recovered from the alkaline washing solution of the reaction product. Example 1 First step 368 g of toluene was placed in a photoreactor with an internal volume of 600 ml, which was equipped with a thermometer, a stirrer, a chlorine blowing pipe, a reflux condenser that also served as exhaust, and a light irradiation device using a high-pressure mercury lamp.
(4.0 mol) was charged, the contents were heated to 95°C, and chlorine gas was blown in while stirring and under light irradiation. Shortly after chlorine injection, a rise in temperature was observed along with the generation of hydrogen chloride. 142g/hr (2.0mol/hr) while maintaining the reaction temperature at 100℃ and irradiating with light.
The introduction of chlorine was continued for 3 hours at a rate of . Almost no chlorine was detected in the gas being discharged, and the chlorine injected had almost completely reacted. After 3 hours of reaction, chlorine injection was stopped after 426 g (6.0 mol) of chlorine had been blown into the reactor, and dry nitrogen gas was passed through the reaction solution to remove hydrogen chloride and chlorine gas from the system. The reaction product thus obtained was 558 g. When the reaction product was analyzed by gas chromatography, its composition was 1 mol% toluene, 48 mol% benzyl chloride, 46 mol% benzal chloride, 3 mol% benzotrichloride, and 1 mol% other.
It was in mol%. The average degree of chlorination of the reaction solution was 1.5. 2nd step: 49.3 g of the chlorinated toluene mixture obtained in the 1st step (corresponding to 0.343 mol when calculated as an average degree of chlorination of 1.5) into two three-necked flasks equipped with a thermometer, stirrer, and reflux condenser. and 3wt% nitric acid 1440
1.5 g of vanadium pentoxide were charged, and the mixture was heated to an elevated temperature while stirring, and the reaction was carried out under reflux for 5 hours. After the reaction mixture was cooled and the oily portion was separated, 100 ml of toluene was added to the aqueous layer for extraction twice. The oily part and the extract were combined and the toluene was distilled off.
The remaining oil was distilled. By this method 111~
34.1 g of a fraction at 114° C./100 mmHg was obtained. When this substance was analyzed by infrared absorption spectrum, it was confirmed that it was benzaldehyde. The purity as determined by gas chromatography was 99.4%. The yield of benzaldehyde based on the raw material toluene is 90.4%. Example 2 First step 368 g (4.0 mol) of toluene was placed in the same photoreaction device as used in the first step of Example 1, and the reaction temperature was maintained at 100°C as in the first step of Example 1. The chlorination reaction was carried out by blowing chlorine under light irradiation. Chlorine injection is 114g/hr (1.6mol/
hr), and the reaction was continued for 3 hours. 341
After blowing in chlorine (4.8 mol), the blowing of chlorine was stopped, and hydrogen chloride and chlorine gas in the system were removed by passing dry nitrogen gas to obtain 523 g of a reaction solution. Gas chromatographic analysis of this product revealed that it contained 67 mol% of benzyl chloride, 27 mol% of benzal chloride, 4 mol% of toluene, and 2 mol% of others. The average degree of chlorination was 1.2. 2nd step Into the same reactor as in the 2nd step of Example 1, 61.0 g of the chlorinated toluene mixture obtained in the 1st step (degree of chlorination
(equivalent to 0.457 moles when calculated as 1.2), 1440 g of 4wt% nitric acid, and 1.8 g of ammonium metavanadate.
I prepared it. This mixture was heated to an elevated temperature while stirring, and the reaction was carried out under reflux for 6 hours. After the reaction was completed, the same treatment as in the second step of Example 1 was carried out, and 43.6 g of benzaldehyde fraction was obtained by distillation. As a result of gas chromatography analysis, the purity was 99.3%. The yield of benzaldehyde based on toluene as a raw material is equivalent to 88.3%. Example 3 First step 368 g (4.0 mol) of toluene was placed in the same photoreactor as used in the first step of Example 1, and
As in the first step, the reaction temperature was maintained at 100 °C,
A chlorination reaction was carried out by blowing chlorine under light irradiation. Chlorine injection is 142g/hr (2.0mol/hr)
The reaction was continued for 3.6 hours. When 7.2 moles of chlorine had been blown into the system, the chlorine injection was stopped and dry nitrogen gas was passed through the system to remove hydrogen chloride and chlorine gas, yielding 606 g of a reaction solution. Gas chromatography analysis of this material revealed that the composition was 27 mol% benzyl chloride, 66 mol% benzyl chloride, and benzotrichloride.
5.5 mol%, other 1.5 mol%, the average degree of chlorination is
It was 1.8. 2nd step Into the same reactor as in the 2nd step of Example 1, 71 g of the chlorinated toluene mixture obtained in the 1st step (degree of chlorination: 1.8
(equivalent to 0.460 mol) and 4wt% nitric acid
I prepared 1440g. This mixture was heated to an elevated temperature while stirring, and the reaction was carried out under reflux for 12 hours. After the reaction was completed, the same treatment as in the second step of Example 1 was carried out,
43.2 g of benzaldehyde fraction was obtained by distillation. The yield of benzaldehyde based on toluene, the raw material, is equivalent to 87%. Example 4 First step 380 g (3.0 mol) of p-chlorotoluene was placed in the same photoreactor as used in the first step of Example 1, and the reaction temperature was raised to 130 mol in the same manner as in the first step of Example 1. The chlorination reaction was carried out by blowing chlorine into the solution while maintaining the temperature at 0.degree. C. and irradiating it with light. Chlorine blowing is 106
g/hr (1.5 mol/hr), and the reaction was continued for 3.0 hours. When 4.5 moles of chlorine had been blown into the reactor, the chlorine blowing was stopped, and the same procedure as in Example 1 was carried out to obtain 527 g of a reaction solution. Gas chromatography analysis of this material revealed that the composition was 2 mol% p-chlorotoluene, 48 mol% 4-chlorobenzyl chloride, 46 mol% 4-chlorobenzyl chloride, and 4 mol% others.
The average degree of chlorination of p-chlorotoluene was 1.5. Second step: Into the same reactor as in the second step of Example 1, add 81.3 g of the chlorinated mixture of p-chlorotoluene obtained in the first step.
(Equivalent to 0.456 moles when calculated as a degree of chlorination of 1.5)
1,440 g of 5 wt % nitric acid and 2.4 g of vanadium pentoxide were charged, and the mixture was heated to an elevated temperature with stirring, and the reaction was carried out under reflux for 6 hours. After cooling the reaction mixture and separating the crystals, 100 ml of toluene was added to the solution and extracted twice. The crystal part and the extract were combined and toluene was distilled off, and the residue was distilled to obtain 48 g of a fraction having a temperature of 100 to 102°C/20 mmHg. As a result of infrared absorption spectrum analysis,
It was confirmed that it was p-chlorobenzaldehyde. The yield of p-chlorobenzaldehyde based on the raw material p-chlorotoluene was equivalent to 73.9%. Example 5 First step 380 g (3.0 mol) of o-chlorotoluene was placed in the same photoreactor as used in the first step of Example 1.
The reaction temperature was adjusted in the same manner as in the first step of Example 1.
Maintained at 130℃ and blown chlorine under light irradiation,
A chlorination reaction was carried out. Chlorine blowing is 106
g/hr (1.5 mol/hr), and the reaction was continued for 3.6 hours. After blowing in 5.4 moles of chlorine, the blowing of chlorine was stopped, and the same treatment as in Example 1 was carried out to obtain 558 g of a reaction solution. Gas chromatographic analysis of this product revealed that o-chlorotoluene was 0.5 mol%, o-chlorobenzyl chloride was 28 mol%, o-chlorobenzal chloride was 67 mol%, o-chlorobenzotrichloride was 3 mol%, and others were 1.5 mol%. The average degree of chlorination with respect to o-chlorotoluene was 1.8. 2nd step In the same reactor as in the 2nd step of Example 1, 64.7 g of the chlorinated mixture of o-chlorotoluene obtained in the 1st step was added.
(Equivalent to 0.343 moles when calculated as a degree of chlorination of 1.8)
1,440 g of 3 wt % nitric acid and 2.0 g of vanadium pentoxide were charged, and the mixture was heated to an elevated temperature with stirring, and the reaction was carried out under reflux for 6 hours. The reaction mixture was cooled, 200 ml of toluene was added thereto to separate the oil phase, and 100 ml of toluene was added to the aqueous solution portion for two extraction operations. After combining the first oily part and the extract and distilling off the toluene, the remaining part was distilled, resulting in 36g of distillate at 107-110℃/30mmHg.
I got it. As a result of infrared absorption spectrum analysis,
It was confirmed to be o-chlorobenzaldehyde. The o-chlorobenzaldehyde yield based on the raw material o-chlorotoluene was 73.5%.
Claims (1)
れる化合物のメチル基を塩素化して、平均1.0〜
2.0個の塩素原子を有する塩素化物を製造する第
１工程と、第１工程で得られた塩素化物を硝酸と
反応させて一般式が【式】（たゞし、式中 ＸはＨ、Cl、Br、CNまたはNO2をあらわす）で
示される化合物を製造する第２工程とからなるこ
とを特徴とするベンズアルデヒド類の製造方法。[Claims] 1. By chlorinating the methyl group of a compound whose general formula is represented by [Formula] (wherein X represents H, Cl, Br, CN, or NO 2 ),
The first step is to produce a chlorinated product having 2.0 chlorine atoms, and the chlorinated product obtained in the first step is reacted with nitric acid to obtain the general formula [formula] (where X is H, Cl , Br, CN or NO 2 ).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9436680A JPS5718644A (en) | 1980-07-10 | 1980-07-10 | Preparatin of benzaldehydes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9436680A JPS5718644A (en) | 1980-07-10 | 1980-07-10 | Preparatin of benzaldehydes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5718644A JPS5718644A (en) | 1982-01-30 |
| JPS6314693B2 true JPS6314693B2 (en) | 1988-04-01 |
Family
ID=14108306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9436680A Granted JPS5718644A (en) | 1980-07-10 | 1980-07-10 | Preparatin of benzaldehydes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5718644A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274929B (en) * | 2013-04-09 | 2014-12-17 | 金凯(辽宁)化工有限公司 | Preparation method of 2-trifluoromethyl benzoic acid |
| CN104447250A (en) * | 2014-12-24 | 2015-03-25 | 常熟市新华化工有限公司 | Method for synthesizing p-chlorobenzaldehyde from p-chlorotoluene |
-
1980
- 1980-07-10 JP JP9436680A patent/JPS5718644A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5718644A (en) | 1982-01-30 |
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