JPS6251256B2 - - Google Patents
Info
- Publication number
- JPS6251256B2 JPS6251256B2 JP54103406A JP10340679A JPS6251256B2 JP S6251256 B2 JPS6251256 B2 JP S6251256B2 JP 54103406 A JP54103406 A JP 54103406A JP 10340679 A JP10340679 A JP 10340679A JP S6251256 B2 JPS6251256 B2 JP S6251256B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- trimethoxybenzoic acid
- acid
- trimethoxybenzoic
- solvent
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 230000018044 dehydration Effects 0.000 claims description 15
- 238000006297 dehydration reaction Methods 0.000 claims description 15
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 14
- -1 trimethoxybenzoic acid halide Chemical class 0.000 claims description 14
- HZNQSWJZTWOTKM-UHFFFAOYSA-N 2,3,4-trimethoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C(OC)=C1OC HZNQSWJZTWOTKM-UHFFFAOYSA-N 0.000 claims description 11
- 238000005658 halogenation reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 230000026030 halogenation Effects 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000002140 halogenating effect Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000008282 halocarbons Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- SJSOFNCYXJUNBT-UHFFFAOYSA-N Eudesmic acid Natural products COC1=CC(C(O)=O)=CC(OC)=C1OC SJSOFNCYXJUNBT-UHFFFAOYSA-N 0.000 description 20
- IWPZKOJSYQZABD-UHFFFAOYSA-N 3,4,5-trimethoxybenzoic acid Natural products COC1=CC(OC)=CC(C(O)=O)=C1 IWPZKOJSYQZABD-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- RSRWINFPRJPFMA-UHFFFAOYSA-N (2,3,4-trimethoxybenzoyl) 2,3,4-trimethoxybenzoate Chemical compound COC1=C(OC)C(OC)=CC=C1C(=O)OC(=O)C1=CC=C(OC)C(OC)=C1OC RSRWINFPRJPFMA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- HFRXJVQOXRXOPP-UHFFFAOYSA-N thionyl bromide Chemical compound BrS(Br)=O HFRXJVQOXRXOPP-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000010977 unit operation Methods 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)
Description
【発明の詳細な説明】
本発明は、トリメトキシ安息香酸ハライドの製
造法に関する。さらにくわしくは、トリメトキシ
安息香酸を50〜200℃の沸点を有し、水と共沸混
合物を形成し、かつ水への溶解度が１％以下でか
つ水の溶解度が１％以下である芳香族炭化水素、
脂肪族炭化水素、ハロゲン化炭化水素から選ばれ
た１種の溶媒中で加熱蒸留する工程（脱水工程と
略称）と、ひきつづき、当該溶媒中でＮ，Ｎ―ジ
メチルホルムアミド、Ｎ，Ｎ―ジメチルアセトア
ミド、ピリジン、ルイス酸類から選ばれた少なく
とも１種の触媒の共存下にハロゲン化チオニール
によつて酸クロル化するハロゲン化工程とからな
ることを特徴とするトリメトキシ安息香酸ハライ
ドの製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing trimethoxybenzoic acid halide. More specifically, trimethoxybenzoic acid has a boiling point of 50 to 200°C, forms an azeotrope with water, has a solubility in water of 1% or less, and has a solubility in water of 1% or less. hydrogen,
A step of heating and distilling in one type of solvent selected from aliphatic hydrocarbons and halogenated hydrocarbons (abbreviated as a dehydration step), followed by a step of distilling N,N-dimethylformamide and N,N-dimethylacetamide in the solvent. The present invention relates to a method for producing trimethoxybenzoic acid halide, which comprises a halogenation step of acid chlorination with thionyl halide in the coexistence of at least one catalyst selected from , pyridine, and Lewis acids. .
トリメトキシ安息香酸ハライド、就中、３，
４，５―トリメトキシ安息香酸ハライドは、医薬
および農薬中間体やその他の有機合成薬品の中間
体として有用な化合物である。本発明は本化合物
の工業的に有利なる製造方法に関する。 Trimethoxybenzoic acid halide, especially 3,
4,5-trimethoxybenzoic acid halide is a compound useful as a pharmaceutical and agricultural intermediate and as an intermediate for other organic synthetic drugs. The present invention relates to an industrially advantageous method for producing the present compound.
従来、含水芳香族カルボン酸をこれと不活性な
水と共沸系を形成する溶媒を用いて加熱蒸留し、
当該カルボン酸中の水分を系外に留去して乾燥す
る方法は公知である。また、当該溶媒、就中、ハ
ロゲン化チオニールならびに酸ハライドと不活性
な溶媒中で、Ｎ，Ｎ―ジメチルホルムアミドのよ
うな電子供与体を触媒として、カルボン酸をハロ
ゲン化して酸ハライドを製造する方法も公知であ
る。 Conventionally, hydrous aromatic carboxylic acid is heated and distilled using a solvent that forms an azeotrope with inert water.
A method of drying the carboxylic acid by distilling water out of the system is known. Also, a method for producing an acid halide by halogenating a carboxylic acid in the solvent, especially a thionyl halide and an acid halide, and an inert solvent using an electron donor such as N,N-dimethylformamide as a catalyst. is also publicly known.
本発明における原料となるトリメトキシ安息香
酸は、通常、没食子酸等から合成し、単離する場
合、水―アルコール系または水から再結晶したも
のとして入手されるため、これをハロゲン化チオ
ニール等のハロゲン化剤を用いてハロゲン化し、
酸ハライドを製造する場合、乾燥、脱水する必要
があることも常識であり、当工程での原料中の水
分管理は、塩素化剤の原単位の低減、製品の品質
の向上、収率の向上等に関与し、重要である。 Trimethoxybenzoic acid, which is a raw material in the present invention, is usually synthesized from gallic acid, etc., and when isolated, it is obtained as a water-alcohol system or recrystallized from water. Halogenate using a halogenating agent,
It is common knowledge that drying and dehydration are necessary when producing acid halides, and controlling the moisture in the raw materials in this process is important in reducing the unit consumption of chlorinating agents, improving product quality, and improving yield. etc., and is important.
本発明者等は、上記乾燥工程の簡易化、酸ハラ
イドの品質、収率の向上等について鋭意検討を加
え、従来の単位操作を組合わせることにより、工
程の簡素化、品質、収率の向上等、相乗効果をみ
とめ、本発明に到達した。 The inventors of the present invention have made extensive studies to simplify the drying process and improve the quality and yield of acid halides, and have combined conventional unit operations to simplify the process, improve quality, and yield. The present invention was achieved by observing synergistic effects such as these.
すなわち、本発明者の要旨は、トリメトキシ安
息香酸、就中、医薬農薬中間体としても最も有用
な３，４，５―トリメトキシ安息香酸を、このも
のに不活性であり、ハロゲン化チオニールおよび
製品である３，４，５―トリメトキシ安息香酸ハ
ライドに不活性な、沸点範囲50〜200℃の水と共
沸系を形成し、水への溶解度が１％以内であり、
かつ水の溶解度が１％以内である芳香族炭化水
素、脂肪族炭化水素、ハロゲン化炭化水素から選
ばれた１種の溶媒中で、加熱蒸留するいわゆる脱
水工程と、当該工程にひきつづき同溶媒中で触媒
の共存下にハロゲン化チオニールと反応させるこ
とを特徴とする３，４，５―トリメトキシ安息香
酸ハライドの工業的に有利な製造方法である。 That is, the inventor's gist is that trimethoxybenzoic acid, especially 3,4,5-trimethoxybenzoic acid, which is most useful as a pharmaceutical and agricultural intermediate, is inert to thionyl halides and products. It is inert to certain 3,4,5-trimethoxybenzoic acid halide, forms an azeotropic system with water with a boiling point range of 50 to 200°C, and has a solubility in water of 1% or less,
and a so-called dehydration step of heating and distilling in one type of solvent selected from aromatic hydrocarbons, aliphatic hydrocarbons, and halogenated hydrocarbons in which the solubility of water is within 1%, and subsequent to the dehydration step in the same solvent. This is an industrially advantageous method for producing 3,4,5-trimethoxybenzoic acid halide, which is characterized in that it is reacted with thionyl halide in the presence of a catalyst.
本発明を実施する場合、前述の脱水工程にひき
つづき、ハロゲン化工程を実施しなければならな
いことは必須条件であり、脱水工程は前述溶媒と
３，４，５―トリメトキシ安息香酸の混合物を還
流冷却器および分留器を付設した撹拌機付の加熱
設備を常備した反応器に添加し、加熱、蒸留す
る。留去した水―溶媒混合物は、そのまま系外に
取除いてもよいが、別に留分を層分離器に導き、
水相を系外に除去、溶媒はもとの反応器に還流し
てもよい、系外に取出された水分を計量すること
により原料、３，４，５―トリメトキシ安息香酸
の含水率を掌握することができる。かくのごとく
して脱水を終えた系を所定の温度に設定した後、
所定のハロゲン化チオニールおよび触媒を添加
し、副生するハロゲン化水素ガスおよび亜硫酸ガ
スは還流冷却器を経由して除去する。 When carrying out the present invention, it is an essential condition that a halogenation step must be carried out following the above-mentioned dehydration step, and the dehydration step involves cooling the mixture of the above-mentioned solvent and 3,4,5-trimethoxybenzoic acid under reflux. The mixture is added to a reactor equipped with heating equipment equipped with a stirrer and a fractionator, and heated and distilled. The distilled water-solvent mixture may be removed from the system as it is, but the distillate may be separately led to a layer separator.
The aqueous phase is removed from the system, and the solvent may be returned to the original reactor. The water content of the raw material, 3,4,5-trimethoxybenzoic acid, can be determined by measuring the water taken out of the system. can do. After the system has been dehydrated in this way and is set at a predetermined temperature,
A predetermined thionyl halide and a catalyst are added, and by-product hydrogen halide gas and sulfur dioxide gas are removed via a reflux condenser.
かくのごとくしてハロゲン化工程を終えた反応
物は、蒸留または晶析によつて、目的物である
３，４，５―トリメトキシ安息香酸ハライドを取
得することができる。 The reaction product that has undergone the halogenation step in this manner can be subjected to distillation or crystallization to obtain the target product, 3,4,5-trimethoxybenzoic acid halide.
本発明を実施するにあたつて用いられる触媒は
Ｎ，Ｎ―ジメチルホルムアミド、Ｎ，Ｎ―ジメチ
ルアセトアミド、ピリジンの他に、塩化アルミニ
ウム、塩化錫、塩化第二鉄、硫酸等のルイス酸か
らえらばれた少くとも１種である。 Catalysts used in carrying out the present invention are selected from N,N-dimethylformamide, N,N-dimethylacetamide, pyridine, and Lewis acids such as aluminum chloride, tin chloride, ferric chloride, and sulfuric acid. At least one species has been discovered.
本発明を実施するにあたつて、原料の３，４，
５―トリメトキシ安息香酸の含水率は、その由来
する工程によつて異るが、その量に制限は全くな
い。強いていえば、１％〜150％対乾燥原料でよ
い。 In carrying out the present invention, the raw materials 3, 4,
The moisture content of 5-trimethoxybenzoic acid varies depending on the process from which it is derived, but there is no limit to its amount. Strictly speaking, 1% to 150% dry raw material is sufficient.
また、使用する溶媒は前述の条件を満足するも
の、すなわち、沸点が50℃〜200℃の範囲内にあ
り、水と共沸混合物を形成し、かつ水への溶解度
が１％以内で、水の溶解度が１％以下のものであ
ればよいが、沸点がこの範囲にないものは取扱い
に困難で特殊な装置を必要とし、また水に対する
溶解性がこの範囲を外れるものは共沸留出に時間
がかかり工業的に有利でない。工業的に有利な溶
媒としては、ベンゼン、トルエン、キシレン、ク
メンなどの芳香族炭化水素溶媒、１，２―ジクロ
ロエタンのごときハロゲン化炭化水素溶媒、ｎ―
ヘキサン、ｎ―ヘプタンなどの脂肪族炭化水素溶
媒が好適である。 In addition, the solvent used should satisfy the above conditions, that is, it should have a boiling point in the range of 50℃ to 200℃, form an azeotrope with water, and have a solubility in water of 1% or less. It is sufficient that the solubility in water is 1% or less, but those with a boiling point outside this range are difficult to handle and require special equipment, and those with a solubility in water outside this range cannot be azeotropically distilled. It takes time and is not industrially advantageous. Industrially advantageous solvents include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and cumene, halogenated hydrocarbon solvents such as 1,2-dichloroethane, and n-
Aliphatic hydrocarbon solvents such as hexane and n-heptane are preferred.
脱水条件は常圧下に、単蒸留で実施できその目
的とするところは、３，４，５―トリメトキシ安
息香酸中の水分を0.001％〜２％に、好ましくは
0.01％〜0.05％にすることにある。脱水率は、溶
媒量のたき上げ量と、溶媒を前述のごとく系内に
還流させる場合は分液器の容積を小さくするほど
良好で、反応器の内容積の1/2以下が望ましい。
もちろん、減圧、精留塔をつけても実施可能であ
るが、不経済である。 The dehydration conditions can be carried out by simple distillation under normal pressure, and the purpose is to reduce the water content in 3,4,5-trimethoxybenzoic acid to 0.001% to 2%, preferably
The goal is to make it 0.01% to 0.05%. The dehydration rate is better as the volume of the separator is made smaller as the amount of the solvent is raised and when the solvent is refluxed into the system as described above, preferably 1/2 or less of the internal volume of the reactor.
Of course, it is possible to reduce the pressure and add a rectification column, but this is uneconomical.
当脱水工程をへて得た３，４，５―トリメトキ
シ安息香酸を含む溶液をそのまま、次工程のハロ
ゲン化反応に供することができ、脱水工程酸の効
果は、脱水、乾燥の合理化と相俟つて、当該ハロ
ゲン化工程における酸ハライドの収率向上、酸無
水物等の副生成物の低減をもたらす効果がある。 The solution containing 3,4,5-trimethoxybenzoic acid obtained through this dehydration step can be directly subjected to the halogenation reaction in the next step, and the effect of the acid in the dehydration step is combined with the rationalization of dehydration and drying. This has the effect of improving the yield of acid halides and reducing by-products such as acid anhydrides in the halogenation step.
本発明で用いる酸ハロゲン化剤として通常、塩
化チオニールおよび臭化チオニール等が適当であ
るが、就中、塩化チオニールが経済的に有利であ
る。塩化チオニールは３，４，５―トリメトキシ
安息香酸のモル数に対して1.0〜2.0、好ましくは
1.01〜1.5が適当であり、大過剰の当該ハロゲン
化剤の使用は反応に影響をあたえることはない
が、あと処理等が繁雑となるため経済的でない。
ハロゲン化反応を実施するにあたつての温度は通
常50〜100℃、好ましくは60〜80℃である。 Generally, thionyl chloride and thionyl bromide are suitable as the acid halogenating agent used in the present invention, and thionyl chloride is especially economically advantageous. Thionyl chloride is 1.0 to 2.0, preferably 1.0 to 2.0, based on the number of moles of 3,4,5-trimethoxybenzoic acid.
A value of 1.01 to 1.5 is appropriate, and using a large excess of the halogenating agent does not affect the reaction, but it is not economical because post-treatment etc. become complicated.
The temperature for carrying out the halogenation reaction is usually 50 to 100°C, preferably 60 to 80°C.
本発明の効果は、(1)原料の乾燥にいわゆる乾燥
器と呼ばれる通常の機器を必要とせず、ハロゲン
化槽が兼用でき、工業的に工程が簡素化された。
(2)したがつて、粉体の移送等がはぶける。(3)原料
中の水分の管理が容易となる。また、(4)原料中の
微量の水分等の除去が可能となり、収率向上がみ
とめられ品質も向上し、製品品質が安定した。等
であり、工業的に有利になつた。 The effects of the present invention are as follows: (1) No ordinary equipment called a so-called dryer is required for drying raw materials, and a halogenation tank can also be used, which simplifies the process industrially.
(2) Therefore, the transfer of powder, etc. is interrupted. (3) Moisture in raw materials can be easily controlled. In addition, (4) it became possible to remove trace amounts of water, etc. from the raw materials, resulting in an improvement in yield and quality, resulting in stable product quality. etc., making it industrially advantageous.
以下、実施例により具体的な実施の概要を示す
が、これによつて本発明の権利の範囲に制限を受
けるものではない。 Hereinafter, an outline of specific implementation will be shown using Examples, but the scope of the rights of the present invention is not limited thereby.
実施例 １
水溶媒を用いて再結晶した３，４，５―トリメ
トキシ安息香酸、湿ケーキ300g（1.17mol）にキ
シレン1400gを添加し、常圧蒸留を行なつた。
500ml留去させ、水分を除去したのち、無水塩化
アルミニウム1.5g（0.01mol）を添加し、温度を
80℃に保ち、塩化チオニール166.4g（1.40ml）を
３時間にわたつて滴下した。滴下終了後、温度を
85℃に上げ、２時間熟成した。収率は97.9モル％
であり、未反応のトリメトキシ安息香酸は1.1％
で、副生成物のトリメトキシ安息香酸無水物は
0.28％であつた。反応液は微黄色で、タール状物
質は全く含まれていなかつた。Example 1 1400 g of xylene was added to 300 g (1.17 mol) of a wet cake of 3,4,5-trimethoxybenzoic acid recrystallized using an aqueous solvent, and distillation was carried out at atmospheric pressure.
After 500ml was distilled off to remove water, 1.5g (0.01mol) of anhydrous aluminum chloride was added and the temperature was lowered.
The temperature was maintained at 80°C, and 166.4 g (1.40 ml) of thionyl chloride was added dropwise over 3 hours. After dropping, lower the temperature.
The temperature was raised to 85°C and aged for 2 hours. Yield is 97.9 mol%
and unreacted trimethoxybenzoic acid is 1.1%
The by-product trimethoxybenzoic anhydride is
It was 0.28%. The reaction solution was slightly yellow in color and did not contain any tar-like substances.
比較例 １
脱水工程を実施せず、無水塩化アルミニウムの
代りに、Ｎ，Ｎ―ジメチルホルムアミド2gを添
加した以外は実施例―１と同様に操作した。収率
は95.0モル％で、未反応のトリメトキシ安息香酸
は1.2％で、副生成物のトリメトキシ安息香酸無
水物は3.3％であつた。また反応液は褐色で、フ
ラスコの底にタール状物質が２〜3g付着してい
た。Comparative Example 1 The same procedure as in Example 1 was carried out except that the dehydration step was not performed and 2 g of N,N-dimethylformamide was added instead of anhydrous aluminum chloride. The yield was 95.0 mol%, with 1.2% of unreacted trimethoxybenzoic acid and 3.3% of trimethoxybenzoic anhydride as a by-product. Moreover, the reaction liquid was brown, and 2 to 3 g of tar-like substance was attached to the bottom of the flask.
実施例 ２
水溶媒を用いて再結晶した３，４，５―トリメ
トキシ安息香酸湿ケーキ350g（1.20モル）にトル
エン2000gを添加し、常圧蒸留を行なつた。水分
を1000g留去させた後、無水塩化亜鉛1.36g（0.01
モル）を添加、温度を79〜81℃に保ちながら、塩
化チオニール171.4g（1.44モル）を３時間にわた
つて滴下した。同温度で更に４時間熟成を行ない
塩化チオニールを留去したのち、塩化亜鉛を過
により取り除いた。反応収率は97.4モル％であ
り、未反応のトリメトキシ安息香酸は1.2％、副
生成した酸無水物は0.36％であつた。Example 2 To 350 g (1.20 mol) of 3,4,5-trimethoxybenzoic acid wet cake recrystallized using an aqueous solvent, 2000 g of toluene was added and distilled at atmospheric pressure. After distilling off 1000g of water, 1.36g of anhydrous zinc chloride (0.01
171.4 g (1.44 mol) of thionyl chloride was added dropwise over 3 hours while maintaining the temperature at 79-81°C. After further aging at the same temperature for 4 hours to distill off thionyl chloride, zinc chloride was removed by filtration. The reaction yield was 97.4 mol%, with 1.2% of unreacted trimethoxybenzoic acid and 0.36% of acid anhydride as a by-product.
また、反応液は微黄色でタール状物質は全く生
成していなかつた。 Further, the reaction solution was slightly yellow in color and no tar-like substance was produced at all.
実施例 ３
実施例１のキシレンに代えてｎ―ヘプタン
1400gを添加した以外は実施例１と同様、の操作
を行なつた。その結果、収率は97.0モル％であ
り、未反応のトリメトキシ安息香酸は2.0％で、
副生成物のトリメトキシ安息香酸無水物は0.5％
であつた。反応液中にタール状物質は全く含まれ
ていなかつた。Example 3 n-heptane instead of xylene in Example 1
The same operation as in Example 1 was performed except that 1400 g was added. As a result, the yield was 97.0 mol%, and unreacted trimethoxybenzoic acid was 2.0%.
By-product trimethoxybenzoic anhydride is 0.5%
It was hot. The reaction solution contained no tar-like substances at all.
Claims (1)
の範囲内であり、水と共沸混合物を形成し、かつ
水への溶解度が１％以内で、水の溶解度が１％以
下である芳香族炭化水素、脂肪族炭化水素、ハロ
ゲン化炭化水素から選ばれた１種の溶媒と加熱蒸
留する脱水工程と、当該溶媒中で当該トリメトキ
シ安息香酸をＮ，Ｎ―ジメチルホルムアミド、
Ｎ，Ｎ―ジメチルアセトアミド、ピリジン、ルイ
ス酸類から選ばれた少なくとも１種の触媒の存在
化にハロゲン化チオニールでハロゲン化する工程
とからなることを特徴とするトリメトキシ安息香
酸ハライドの製造方法。 ２ トリメトキシ安息香酸が３，４，５―トリメ
トキシ体である特許請求の範囲１項記載の方法。 ３ 脱水工程並びにハロゲン化工程で使用する溶
媒がトルエンである特許請求の範囲１項記載の方
法。 ４ 脱水工程並びにハロゲン化工程で使用する溶
媒がキシレンである特許請求の範囲１項記載の方
法。 ５ ハロゲン化工程で用いるハロゲン化剤が塩化
チオニールである特許請求の範囲１項記載の方
法。[Claims] 1 Trimethoxybenzoic acid with a boiling point of 50°C to 200°C
From aromatic hydrocarbons, aliphatic hydrocarbons, and halogenated hydrocarbons that form an azeotrope with water and have a solubility in water of 1% or less, and have a solubility in water of 1% or less. A dehydration step of heating and distilling the trimethoxybenzoic acid with one selected solvent, and converting the trimethoxybenzoic acid into N,N-dimethylformamide,
A method for producing trimethoxybenzoic acid halide, which comprises the steps of halogenating with thionyl halide in the presence of at least one catalyst selected from N,N-dimethylacetamide, pyridine, and Lewis acids. 2. The method according to claim 1, wherein the trimethoxybenzoic acid is a 3,4,5-trimethoxy form. 3. The method according to claim 1, wherein the solvent used in the dehydration step and the halogenation step is toluene. 4. The method according to claim 1, wherein the solvent used in the dehydration step and the halogenation step is xylene. 5. The method according to claim 1, wherein the halogenating agent used in the halogenation step is thionyl chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10340679A JPS5626841A (en) | 1979-08-13 | 1979-08-13 | Preparation of trimethoxybenzoic acid halide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10340679A JPS5626841A (en) | 1979-08-13 | 1979-08-13 | Preparation of trimethoxybenzoic acid halide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5626841A JPS5626841A (en) | 1981-03-16 |
| JPS6251256B2 true JPS6251256B2 (en) | 1987-10-29 |
Family
ID=14353160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10340679A Granted JPS5626841A (en) | 1979-08-13 | 1979-08-13 | Preparation of trimethoxybenzoic acid halide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5626841A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0213857A (en) * | 1988-06-30 | 1990-01-18 | Shimadzu Corp | Spectrum analyser |
| JPH0455541U (en) * | 1990-09-20 | 1992-05-13 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0199107A (en) * | 1987-10-12 | 1989-04-18 | Ishikawajima Harima Heavy Ind Co Ltd | Electrohydraulic servo control device |
-
1979
- 1979-08-13 JP JP10340679A patent/JPS5626841A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0213857A (en) * | 1988-06-30 | 1990-01-18 | Shimadzu Corp | Spectrum analyser |
| JPH0455541U (en) * | 1990-09-20 | 1992-05-13 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5626841A (en) | 1981-03-16 |
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