JPH0459741A - Production of hydroxymethylbenzaldehyde - Google Patents
Production of hydroxymethylbenzaldehydeInfo
- Publication number
- JPH0459741A JPH0459741A JP2168373A JP16837390A JPH0459741A JP H0459741 A JPH0459741 A JP H0459741A JP 2168373 A JP2168373 A JP 2168373A JP 16837390 A JP16837390 A JP 16837390A JP H0459741 A JPH0459741 A JP H0459741A
- Authority
- JP
- Japan
- Prior art keywords
- alpha
- xylene
- trichloroxylene
- raw material
- reaction
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- XVHIUKSUZLPFCP-UHFFFAOYSA-N 2-(hydroxymethyl)benzaldehyde Chemical compound OCC1=CC=CC=C1C=O XVHIUKSUZLPFCP-UHFFFAOYSA-N 0.000 title claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 10
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 9
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229920001002 functional polymer Polymers 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- NRFOWKFRVQFTGC-UHFFFAOYSA-N 1-(chloromethyl)-2-(dichloromethyl)benzene Chemical group ClCC1=CC=CC=C1C(Cl)Cl NRFOWKFRVQFTGC-UHFFFAOYSA-N 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract 1
- 229940078552 o-xylene Drugs 0.000 abstract 1
- 229940044170 formate Drugs 0.000 description 9
- 239000008096 xylene Substances 0.000 description 8
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 150000004675 formic acid derivatives Chemical class 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- VMMUHZZNIYRBPI-UHFFFAOYSA-N 1,3,4-trichloro-2,5-dimethylbenzene Chemical group CC1=CC(Cl)=C(C)C(Cl)=C1Cl VMMUHZZNIYRBPI-UHFFFAOYSA-N 0.000 description 1
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical group ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000000998 batch distillation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229940044172 calcium formate Drugs 0.000 description 1
- 235000019255 calcium formate Nutrition 0.000 description 1
- 239000004281 calcium formate Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はヒドロキシメチルベンズアルデヒドの製法に関
する。さらに詳しくはα、α、α°−トリクロルキシレ
ンを加水分解する事を特徴とするヒドロキシメチルベン
ズアルデヒドの製法である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing hydroxymethylbenzaldehyde. More specifically, it is a method for producing hydroxymethylbenzaldehyde, which is characterized by hydrolyzing α, α, α°-trichloroxylene.
ヒドロキシメチルベンズアルデヒドは農薬、医薬品等の
有機合成薬品の中間体、機能性ポリマーのモノマーとし
て非常に有用である。Hydroxymethylbenzaldehyde is very useful as an intermediate for organic synthetic chemicals such as agricultural chemicals and pharmaceuticals, and as a monomer for functional polymers.
従来より、ヒドロキシメチルベンズアルデヒドの製法に
関して検討されているが必ずしも充分とは言えない０例
えば、ＣＡＳ登録番号ＣＡｌｌ０−１７２８７４には１
．パラジウム触媒の存在下、テレフタルアルデヒドの水
素添加法によるヒドロキシメチルベンズアルデヒドの製
法の記載があるが、高価な触媒、および原料を使用して
おり工業的方法とは言えない。このように未だ工業的に
有効なヒドロキシメチルベンズアルデヒドの製法がない
のが現状である。Conventionally, studies have been made regarding the production method of hydroxymethylbenzaldehyde, but it cannot be said that it is necessarily sufficient.For example, CAS registration number CAll0-172874 has 1
．． Although there is a description of a method for producing hydroxymethylbenzaldehyde by hydrogenating terephthalaldehyde in the presence of a palladium catalyst, it cannot be called an industrial method because it uses expensive catalysts and raw materials. As described above, there is currently no industrially effective method for producing hydroxymethylbenzaldehyde.
本発明の目的は、α、α、α゛−トリクロルキシレンか
らヒドロキシメチルベンズアルデヒドの製法を提供する
事にある。An object of the present invention is to provide a method for producing hydroxymethylbenzaldehyde from α,α,α゛-trichloroxylene.
本発明者らは上記目的を達成する為、鋭意検討し遂に本
発明に至った。In order to achieve the above object, the present inventors conducted extensive studies and finally arrived at the present invention.
即ち本発明はα、α、α゛−トリクロルキシレンを加水
分解する事を特徴とするヒドロキシメチルベンズアルデ
ヒドの製法である。That is, the present invention is a method for producing hydroxymethylbenzaldehyde, which is characterized by hydrolyzing α,α,α゛-trichloroxylene.
以下本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明に用いるα、α、α”−トリクロルキシレントハ
α、α、α”−トリクロル−０−キシレン、α、α、α
゛−トリクロルーｍ−キシレン、α、α、α −トリク
ロル−ｐ−キシレンである。α,α,α”-trichloroxylene used in the present invention α,α,α”-trichlor-0-xylene, α,α,α
゛-Trichlor-m-xylene, α, α, α-trichlor-p-xylene.
α、α１α゛〜トリクロルキシレンは０−キシレンまた
は画一キシレンまたはｐ−キシレンの塩素化反応によっ
て製造される。例えば、０−キシレンまたは画一キシレ
ンまたはｐ−キシレンに、分子状の塩素を光の存在下ま
たは過酸化物系ラジカル開始剤またはアブ系ラジカル開
始剤の存在下、作用させる事によって製造できる。キシ
レンの塩素化反応は逐次反応であり、塩素とキシレンの
モル比によって生成物の制御ができる事は一般的によく
知られている。α、α、α゛−トリクロルキシレンは塩
素とキシレンのモル比が約３で、反応マス中に最も多量
に含まれるが、α、α、αトリクロルキシレンの収率を
上げる為に、モル比を３以下に抑え低沸成分をリサイク
ルする事がよく行われる。この様な塩素化反応マスの他
、中間体として非常に有用なα、α゛−ジクロルキシレ
ンの製造の際、蒸留後の釜残に多量に残存するαα、α
゛−トリクロルキシレンでも、以下に述べる方法で精製
する事により、本発明に使用可能である。塩素化反応マ
スまたはα、α゛−ジクロルキシレンの蒸留釜残からα
、α、α゛−トリクロルキシレンを取り出すには、蒸留
法が最も適当である。晶析法の場合はα、α、α゛−ト
リクロルキシレンとα α゛−ジクロルキシレン共晶化
合物を形成する為、好ましくない。α,α1α゛~Trichloroxylene is produced by the chlorination reaction of 0-xylene, uniform xylene or p-xylene. For example, it can be produced by allowing molecular chlorine to act on 0-xylene, uniform xylene, or p-xylene in the presence of light or in the presence of a peroxide-based radical initiator or an ab-based radical initiator. It is generally well known that the chlorination reaction of xylene is a sequential reaction, and that the product can be controlled by controlling the molar ratio of chlorine and xylene. α,α,α゛-Trichloroxylene has a molar ratio of chlorine to xylene of approximately 3, and is contained in the largest amount in the reaction mass.However, in order to increase the yield of α,α,αtrichloroxylene, the molar ratio is changed. It is common practice to reduce the boiling point to 3 or less and recycle low-boiling components. In addition to such chlorination reaction mass, in the production of α, α゛-dichloroxylene, which is very useful as an intermediate, large amounts of αα, α remain in the residue after distillation.
゛-Trichloroxylene can also be used in the present invention by purifying it by the method described below. α from the chlorination reaction mass or α, α゛-dichloroxylene distillation still residue
, α, α゛-Trichloroxylene is most suitable to be extracted by distillation. The crystallization method is not preferred because it forms a eutectic compound of α, α, α゛-trichloroxylene and αα゛-dichloroxylene.
本発明に用いるアルカリ金属またはアルカリ土類金属の
炭酸塩、またはギ酸塩の代表的な例としては、炭酸ナト
リウム、炭酸カリウム、炭酸カルシウム、炭酸マグネシ
ウム、ギ酸ナトリウム、ギ酸カリウム、ギ酸リチウム、
ギ酸カルシウム、ギ酸カリウムが挙げられる。これらの
アルカリ金属またはアルカリ土類金属の炭酸塩、または
ギ酸塩は、単独で使用しても良いが、２種類以上を併用
することもできる。Representative examples of alkali metal or alkaline earth metal carbonates or formates used in the present invention include sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium formate, potassium formate, lithium formate,
Examples include calcium formate and potassium formate. These alkali metal or alkaline earth metal carbonates or formates may be used alone, but two or more types can also be used in combination.
本発明の製法はα、α、α１−トリクロルキシレンをア
ルカリ金属またはアルカリ土類金属の炭酸塩、またはギ
酸塩の存在下に加水分解させることが好ましい。通常の
加水分解反応によく用いられ強塩基、例えば水酸化ナト
リウム、水酸化カリウムではオリゴマー等の副生物が多
量副生する為、好ましくない。In the production method of the present invention, α,α,α1-trichloroxylene is preferably hydrolyzed in the presence of an alkali metal or alkaline earth metal carbonate or formate. Strong bases often used in ordinary hydrolysis reactions, such as sodium hydroxide and potassium hydroxide, are not preferred because they produce large amounts of by-products such as oligomers.
炭酸塩またはギ酸塩がアルカリ金属との塩の場合は、炭
酸塩またはギ酸塩の添加量は、α、α。If the carbonate or formate is a salt with an alkali metal, the amount of carbonate or formate added is α, α.
α゛−トリクロルキシレン２〜４モル倍が望ましく、更
に望ましくは、２〜２．５モル倍である。The amount of α-trichloroxylene is preferably 2 to 4 times the amount by mole, and more preferably 2 to 2.5 times the amount by mole.
炭酸塩またはギ酸塩がアルカリ土類金属との塩の場合は
、「、α、α′−トリクロルキシレンの１〜２モル倍が
望ましく、更に望ましくは、１〜１．５モル倍である。When the carbonate or formate is a salt with an alkaline earth metal, the amount is preferably 1 to 2 moles, more preferably 1 to 1.5 times that of α,α'-trichloroxylene.
炭酸塩またはギ酸塩の添加量が上述の最小値よりも少な
い場合は、α、α、α゛−トリクロルキシレンの加水分
解速度が小さくなり、反応を完結させる事が困難になる
。また上述の最大値を超えても効果は変わらないばかり
ではなく、反応液からヒドロキシメチルベンズアルデヒ
ドを精製する場合、除去すべき炭酸塩またはギ酸塩の量
が多（なり好ましくない。If the amount of carbonate or formate added is less than the above-mentioned minimum value, the rate of hydrolysis of α,α,α゛-trichloroxylene will be low and it will be difficult to complete the reaction. Moreover, even if the above-mentioned maximum value is exceeded, not only the effect remains unchanged, but also the amount of carbonate or formate to be removed is large (which is not preferable) when hydroxymethylbenzaldehyde is purified from the reaction solution.
本発明の加水分解に用いる水は、特に限定を受けず、水
道水、イオン交換水、水蕉気の凝縮水、本発明のヒドロ
キジメチルヘンズアルデヒド製造装置に於ける、粗製の
含水ヒドロキシメチルベンズアルデヒドを濃縮、脱水す
る際に回収される凝縮水等を任意に使用する事ができる
。The water used for the hydrolysis of the present invention is not particularly limited, and may include tap water, ion-exchanged water, water condensed water, and crude hydrous hydroxymethylbenzaldehyde in the hydroxydimethylhenzaldehyde production apparatus of the present invention. Condensed water etc. recovered during concentration and dehydration can be used as desired.
水の使用量は、α、α、α゛−トリクロルキシレンの３
〜４００モル倍が望ましく、更に望ましくは、５〜３０
０モル倍である。水の使用量が３モル倍未満の場合は、
α、α、α”−トリクロルキンレンの加水分解が充分行
われない為好ましくない。The amount of water used is α, α, α゛-trichloroxylene.
~400 times by mole is desirable, more preferably 5 to 30 times
It is 0 mole times. If the amount of water used is less than 3 moles,
This is not preferred because the hydrolysis of α,α,α”-trichlorokylene is not sufficiently carried out.
また、４００モル倍を趙えても効果は変わらないばかり
ではなく、反応器の容量が必要以上に大きくなると共に
、反応後、反応液から留去しなければならない水量が増
加し好ましくない。Further, even if the amount is increased by 400 moles, not only the effect remains the same, but also the capacity of the reactor becomes larger than necessary, and the amount of water that must be distilled off from the reaction solution after the reaction increases, which is not preferable.
本発明における反応温度は、炭酸塩またはギ酸塩の種類
や使用量、水使用量、反応圧力によって異なり、−律に
規定する事はできないが７０〜２５０°Ｃが望ましく、
更に望ましくは、８０〜１７５°Ｃである。７０″Ｃ未
満の場合は、α、α、α′−トリクロルキシレンの加水
分解速度が小さくなり、反応を完結させる為には長時間
反応させる必要が生し好ましくない。また２５０℃を超
える場合は、炭酸塩またはギ酸塩が分解し好ましくない
。The reaction temperature in the present invention varies depending on the type and amount of carbonate or formate used, the amount of water used, and the reaction pressure, and is preferably 70 to 250°C, although it cannot be strictly specified.
More preferably, the temperature is 80 to 175°C. If the temperature is less than 70"C, the rate of hydrolysis of α,α,α'-trichloroxylene will be low, and it will be necessary to react for a long time to complete the reaction, which is undesirable. If the temperature exceeds 250°C, , carbonate or formate are decomposed and undesirable.
反応圧力は、常圧、加圧いずれでもよい。The reaction pressure may be either normal pressure or increased pressure.
反応器の型式は、攪拌型反応器、管型反応器等を任意に
しようする事ができる。Any type of reactor can be used, such as a stirred reactor or a tubular reactor.
本発明の製法においては、必要に応じて種々の添加物が
使用可能である。例えば、α、α、α゛−トリクロルキ
シレンをよく溶解する有機溶媒を添加し反応を効率よく
進める事も可能であり、また炭酸塩またはギ酸塩の他に
、水酸化ナトリウム、水酸化カリウム等の塩酸中和剤を
添加してもよい。In the production method of the present invention, various additives can be used as necessary. For example, it is possible to efficiently proceed with the reaction by adding an organic solvent that dissolves α, α, α゛-trichloroxylene well, and in addition to carbonates or formates, sodium hydroxide, potassium hydroxide, etc. A hydrochloric acid neutralizer may be added.
加水分解反応後、反応生成物中に存在する水と、残存炭
酸塩またはギ酸塩及び、副生物である塩化物を溶剤抽出
法や、濃縮濾過法等の任意の方法によって除去し、目的
物であるヒドロキシメチルヘンズアルデヒドを、晶析法
、蒸留法、アダクト形成法、溶剤抽出法等の既知の方法
によって精製する事により、高純度の製品を得る事がで
きる。After the hydrolysis reaction, water present in the reaction product, residual carbonate or formate, and by-product chloride are removed by any method such as solvent extraction or concentration filtration, and the desired product is removed. A highly pure product can be obtained by purifying certain hydroxymethyl henzaldehyde using known methods such as crystallization, distillation, adduct formation, and solvent extraction.
以下α、α、α″−トリクロルキシレン製造例、実施例
、比較例、精製例で本発明を更に詳細に説明する。The present invention will be explained in more detail below with reference to α, α, α″-trichloroxylene production examples, examples, comparative examples, and purification examples.
α、α、α゛−トリクロルキシレン製造例ジャケット、
還流冷却器、攪拌機、塩素ガス吹き込み口を備えた容積
１１のガラス製の、内部照射型１００−水銀ランプ付光
反応器に、ｐ−キシレンを２００ｇ、溶剤として四塩化
炭素を３００ｇ仕込んだ後、攪拌しながら、１０ｇ１分
の速度で塩素を４００ｇ吹き込んだ０反応温度はジャケ
ットに冷水を送り７０℃に調節した０反応マスの各種塩
素化物の分析゛をガスクロマトグラフィーにより行った
結果、α、α。α, α, α゛-Trichloroxylene production example jacket,
After charging 200 g of p-xylene and 300 g of carbon tetrachloride as a solvent into a 11-volume glass photoreactor equipped with a reflux condenser, a stirrer, and a chlorine gas inlet, and equipped with an internally illuminated 100-mercury lamp, While stirring, 400g of chlorine was blown in at a rate of 10g/min.The reaction temperature was adjusted to 70℃ by sending cold water to the jacket.As a result of analyzing various chlorides in the reaction mass by gas chromatography, α, α .
α°−トリクロルーｐ−キシレン４８ｍｔＸ、α、α、
−ジクロルーｐ−キシレン２０ｗｔχ、α、α、α゛、
α゛−テトラクロル−ｐ−キシレン２３ｗｔχ、その他
９−ｔ！であった。また反応器がら排出されるガス中に
は、塩素はほとんど認められなかった。α°-Trichloro-p-xylene 48mtX, α, α,
-dichloro-p-xylene 20wtχ, α, α, α゛,
α゛-Tetrachloro-p-xylene 23wtχ, others 9-t! Met. In addition, almost no chlorine was detected in the gas discharged from the reactor.
以上の反応液を３００ｇ取り出し、１０段のオールダシ
ヨー型蒸留器（ガラス製、欄段弐）にて、バッチ蒸留を
行った。還流比３で塔頂真空を１０ｍｄｇに設定し、塔
頂温度１３５℃までの留分１．１５５°Ｃまでの留分２
を分取し、ガスクロマトグラフィーにて組成分析を行っ
た。その結果、留分１は？３．で、その組成はα、αゝ
−ジクロルーｐ−キシレン７２ｗｔχ、α、α、α”−
トリクロル−ｐ−キシレン１４ｗｔχ、その他１４ｗｔ
χであった。また留分２は１３８ｇで、その組成はα、
α°−ジクロルーｐ−キシレン５ｗｔχ、α。300 g of the above reaction solution was taken out and subjected to batch distillation in a 10-stage old-shot distiller (made of glass, column 2). With a reflux ratio of 3 and a column top vacuum of 10 mdg, the fraction with a column top temperature of up to 135°C is 1, and the fraction with a temperature of up to 155°C is 2.
was fractionated and subjected to compositional analysis using gas chromatography. As a result, what is fraction 1? 3. Its composition is α, αゝ-dichloro-p-xylene 72wtχ, α, α, α”-
Trichlor-p-xylene 14wtχ, other 14wt
It was χ. In addition, fraction 2 weighs 138 g, and its composition is α,
α°-dichloro-p-xylene 5wtχ, α.
α、α°−トリクロルーｐ−キシレン９０ｗ ｔχ、α
、α。α, α°-Trichloro-p-xylene 90w tχ, α
, α.
α′、αゝ−テトラクロルーｐ−キシレン３ｗｔχ、そ
の他２ｗｔＸであった。α', αゝ-tetrachloro-p-xylene was 3wtχ, and the others were 2wtX.
留分１はα、α′−ジクロルーｐ−キシレンが多量に含
まれている為、再度反応に供与できる。また留分２にお
いて、純度９ｏχのα、α、α°−トリクロルーｐ−キ
シレンが得られた。Since fraction 1 contains a large amount of α,α'-dichloro-p-xylene, it can be used again for the reaction. Further, in fraction 2, α, α, α°-trichloro-p-xylene with a purity of 9oχ was obtained.
実施例１
還流冷却器、保温した滴下ロート、温度計及び攪拌機付
の４つロフラスコに、炭酸ナトリウムを１６．７０ｇ、
蒸留水を１２０ｇを入れ、窒素置換後、１００℃に調節
し、製造例で得たα、α、α゛−トリクロルーｐ−キシ
レン１０ｇを１０分間で滴下させた。熟成反応を１０時
間行った後、反応液の分析をガスクロマトグラフィーで
行った。その結果、ｐ−ヒドロキシベンズアルデヒドの
選択率は９５χであった。また未反応の塩素化物は検出
されなかった。結果を第１表に示す。Example 1 In a four-loaf flask equipped with a reflux condenser, a heated dropping funnel, a thermometer, and a stirrer, 16.70 g of sodium carbonate was added.
120 g of distilled water was added, the temperature was adjusted to 100° C. after purging with nitrogen, and 10 g of α,α,α゛-trichloro-p-xylene obtained in the production example was added dropwise over 10 minutes. After the aging reaction was carried out for 10 hours, the reaction solution was analyzed by gas chromatography. As a result, the selectivity of p-hydroxybenzaldehyde was 95χ. Further, no unreacted chlorinated substances were detected. The results are shown in Table 1.
実施例２〜１０、比較例１ 実施例１と同様にして、第１表に示す条件で反応した。Examples 2 to 10, Comparative Example 1 The reaction was carried out in the same manner as in Example 1 under the conditions shown in Table 1.
結果を第１表にまとめて示す。The results are summarized in Table 1.
実施例１１ ２ＱＯＷ！高圧オートクレーブ中に、α、α、α。Example 11 2QOW! During high-pressure autoclaving, α, α, α.
トリクロル−ｐ−キシレン１０ｇ、水１２０ｇ、炭酸ナ
トリウム１６．７．を仕込み、１２０℃で２時間反応さ
せた。その結果、α、α、α°−トリクロルーｐ−キシ
レンの転化率は１００Ｘ、 ｐ−ヒドロキシベンズアル
デヒドの選択率は９５χであった。10 g of trichloro-p-xylene, 120 g of water, 16.7. was charged and reacted at 120°C for 2 hours. As a result, the conversion rate of α, α, α°-trichloro-p-xylene was 100X, and the selectivity of p-hydroxybenzaldehyde was 95χ.
［発明の効果〕
本発明の製法によれば、分子内にアルデヒド基とヒドロ
キシメチル基を有する特徴ある化合物を、高収率で得る
事ができ、産業上非常に有用である。[Effects of the Invention] According to the production method of the present invention, a characteristic compound having an aldehyde group and a hydroxymethyl group in the molecule can be obtained in high yield, and is very useful industrially.
特許出願人 三井東圧化学株式会社Patent applicant Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
事を特徴とするヒドロキシメチルベンズアルデヒドの製
法。 ２、アルカリ金属またはアルカリ土類金属の炭酸塩、ま
たはギ酸塩の存在下にα，α，α′−トリクロルキシレ
ンを加水分解する事を特徴とする請求項１記載のヒドロ
キシメチルベンズアルデヒドの製法。[Claims] 1. A method for producing hydroxymethylbenzaldehyde, which comprises hydrolyzing α,α,α'-trichloroxylene. 2. The method for producing hydroxymethylbenzaldehyde according to claim 1, characterized in that α,α,α'-trichloroxylene is hydrolyzed in the presence of an alkali metal or alkaline earth metal carbonate or formate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2168373A JPH0768159B2 (en) | 1990-06-28 | 1990-06-28 | Method for producing hydroxymethylbenzaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2168373A JPH0768159B2 (en) | 1990-06-28 | 1990-06-28 | Method for producing hydroxymethylbenzaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0459741A true JPH0459741A (en) | 1992-02-26 |
| JPH0768159B2 JPH0768159B2 (en) | 1995-07-26 |
Family
ID=15866895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2168373A Expired - Lifetime JPH0768159B2 (en) | 1990-06-28 | 1990-06-28 | Method for producing hydroxymethylbenzaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0768159B2 (en) |
-
1990
- 1990-06-28 JP JP2168373A patent/JPH0768159B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0768159B2 (en) | 1995-07-26 |
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