JPS6114144B2 - - Google Patents
Info
- Publication number
- JPS6114144B2 JPS6114144B2 JP51104319A JP10431976A JPS6114144B2 JP S6114144 B2 JPS6114144 B2 JP S6114144B2 JP 51104319 A JP51104319 A JP 51104319A JP 10431976 A JP10431976 A JP 10431976A JP S6114144 B2 JPS6114144 B2 JP S6114144B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- coo
- benzyl benzoate
- producing
- ch3coo
- 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
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 16
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 15
- 229960002903 benzyl benzoate Drugs 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 8
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 8
- 229940095102 methyl benzoate Drugs 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 4
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 2
- -1 NaCH3COO Substances 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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)
Description
【発明の詳細な説明】
本発明は、安息香酸メチルとベンジルアルコー
ルからベンジルベンゾエートを製造する方法に関
する。ベンジルベンゾエート（以下BZBと略称す
る）は、香料、医薬の原料及びその他工業用に使
用される重要な化合物である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing benzyl benzoate from methyl benzoate and benzyl alcohol. Benzyl benzoate (hereinafter abbreviated as BZB) is an important compound used as a raw material for fragrances, medicines, and other industrial applications.
BZBは、従来安息香酸とベンジルアルコールと
のエステル化反応により製造されていたが、本発
明者らは、BZBの新規な合成法について鋭意検討
し、本発明に到達した。 BZB has conventionally been produced by an esterification reaction between benzoic acid and benzyl alcohol, but the present inventors have intensively studied a new method for synthesizing BZB and have arrived at the present invention.
即ち、本発明は、安息香酸メチルとベンジルア
ルコールとを触媒の存在下、高められた温度で反
応せしめるベンジルベンゾエートの製造法であ
る。本発明法によれば、安息香酸メチルとベンジ
ルアルコールとの反応により高収率で高品位の
BZBの製造が可能となる。特に本発明法はビツテ
ンハーキユレス（Witten−Hercules）法により
ジメチルテレフタレートを製造するに際し系より
抜き出された、安息香酸メチル（以下MBと略称
する）を多量に含有する低沸点混合物から、MB
をBZBとして分離するのに有効である。 That is, the present invention is a method for producing benzyl benzoate by reacting methyl benzoate and benzyl alcohol at an elevated temperature in the presence of a catalyst. According to the method of the present invention, a high-yield, high-grade product is produced by the reaction of methyl benzoate with benzyl alcohol.
It becomes possible to manufacture BZB. In particular, the method of the present invention uses a low boiling point mixture containing a large amount of methyl benzoate (hereinafter abbreviated as MB) extracted from the system during the production of dimethyl terephthalate by the Witten-Hercules method. M.B.
It is effective to separate BZB as BZB.
次に本発明方法について詳述する。 Next, the method of the present invention will be explained in detail.
本発明方法の原料であるMBは、従来公知のい
かなる方法で製造されたものでもよい。特に前記
ビツテン・ハーキユレス法ジメチルテレフタレー
ト製造における低沸点混合物（以下、単に低沸点
混合物と略称する）に起因するMBが好ましく、
それら低沸点混合物は、そのままベンジルアルコ
ール（以下、BOHと略称する）との反応に供し
てもよく、又一旦低沸点混合物からMBを分離し
た後、使用することもできる。 MB, which is a raw material for the method of the present invention, may be produced by any conventionally known method. Particularly preferred is MB resulting from the low boiling point mixture (hereinafter simply referred to as low boiling point mixture) in the production of dimethyl terephthalate by the Bitten Hercules method,
These low-boiling point mixtures may be directly subjected to the reaction with benzyl alcohol (hereinafter abbreviated as BOH), or may be used after MB is once separated from the low-boiling point mixture.
本発明方法におけるもう一方の原料BOHは、
従来公知のいかなる方法により製造されたもので
も使用しうる。 The other raw material BOH in the method of the present invention is
Any material manufactured by any conventionally known method may be used.
本発明を実施する温度は、150〜300℃であり、
好ましくは170〜250℃である。150℃未満では、
反応に長時間を要する為不経済であるだけでな
く、好ましからざる副生成物を生じる。一方300
℃を越えると、反応生成物が着色するのみなら
ず、原料であるBOHの分解がおこり、結果的に
反応収率が低下するのみならず、得られるBZBの
品質も低下するので、前記温度範囲で実施するの
が好ましい。 The temperature at which the present invention is carried out is 150-300°C,
Preferably it is 170-250°C. Below 150℃,
Not only is it uneconomical because the reaction takes a long time, but it also produces undesirable by-products. while 300
If the temperature exceeds ℃, not only will the reaction product be colored, but the raw material BOH will be decomposed, resulting in not only a decrease in reaction yield but also a decrease in the quality of the BZB obtained. It is preferable to carry out.
本発明方法実施に際して使用される触媒（以下
触媒と略称する）は、MBとBOHとのエステル交
換を達成せしめるものであればいかなるものでも
よいが、例えばSb（OCH3）3、Pb（CH3COO）2・
3H2O、Mn（CH3COO）2・4H2O、Ti（OCH3）4、
Fe（）−acety−lacetonate、Zn（CH3COO）2・
2H2O、CO（CH3COO）2、Cd（CH3COO）2、
GeO2、Cu（）−acetylaceto−nate、Li
（CH3COO）・2H2O、NaCH3COO、Mg
（CH3COO）2・4H2O、Ca（CH3COO）2・H2O、
H3BO2、Ni（CH3COO）2・4H2O等が好んで用い
られる。 The catalyst used in carrying out the method of the present invention (hereinafter abbreviated as catalyst) may be any catalyst as long as it achieves the transesterification of MB and BOH, such as Sb(OCH 3 ) 3 , Pb(CH 3 COO) 2・
3H 2 O, Mn (CH 3 COO) 2・4H 2 O, Ti (OCH 3 ) 4 ,
Fe()−acety−lacetonate, Zn( CH3COO ) 2・
2H2O , CO( CH3COO ) 2 , Cd( CH3COO ) 2 ,
GeO 2 , Cu()−acetylaceto−nate, Li
( CH3COO )・2H2O , NaCH3COO , Mg
(CH 3 COO) 2・4H 2 O, Ca (CH 3 COO) 2・H 2 O,
H 3 BO 2 , Ni(CH 3 COO) 2.4H 2 O, etc. are preferably used.
反応を実施する際の上記の触媒とMBとの割合
は0.01〜30mol％、好ましくは0.05〜10mol％であ
る。又、本発明方法のMBとBOHの仕込み割合は
通常量論量で充分であるが、BOHをMB1molに対
して0.5〜50mol加えることができ、特に1.1〜
10mol加えた場合に良い結果を与えることが多
い。 The ratio of the above catalyst to MB when carrying out the reaction is 0.01 to 30 mol%, preferably 0.05 to 10 mol%. In addition, the charging ratio of MB and BOH in the method of the present invention is usually sufficient in stoichiometric amounts, but BOH can be added in an amount of 0.5 to 50 mol per 1 mol of MB, especially 1.1 to 50 mol.
Adding 10 mol often gives good results.
本発明方法の反応を実施する時間は５分〜10時
間であるが、通常10分〜５時間である。 The reaction time of the method of the present invention is 5 minutes to 10 hours, and usually 10 minutes to 5 hours.
本発明方法において、MBとBOHとの反応は反
応溶媒の存在、非存在いづれでも行ないうる。溶
媒を使用する場合は、反応に不活性なものであれ
ばいかなるものでもよい。例えば水、芳香族及び
脂肪族炭化水素類が好んで用いられる。特に前記
低沸点混合物を用いる場合は、溶媒を必要としな
いので有利である。 In the method of the present invention, the reaction between MB and BOH can be carried out in the presence or absence of a reaction solvent. When a solvent is used, any solvent may be used as long as it is inert to the reaction. For example, water, aromatic and aliphatic hydrocarbons are preferably used. Particularly advantageous is the use of the aforementioned low-boiling mixtures, since no solvent is required.
本発明方法を実施する際、MB、BOH、及び触
媒の混合物を前記反応温度まで10分〜３時間、好
ましくは20分〜２時間かけて昇温するのが好まし
い。昇温の方法は温度を時間の関数と考えた時、
直線的に及び／又は段階状に及び／又は曲線状に
昇温することができる。反応液を反応温度まで10
分末満の時間で急激に昇温すると反応収率が充分
でなく、著るしく収率が低い結果を与えることが
あるので上記範囲で実施するのが好ましい。 When carrying out the method of the present invention, it is preferred to heat the mixture of MB, BOH and catalyst to the reaction temperature over a period of 10 minutes to 3 hours, preferably 20 minutes to 2 hours. The heating method is based on considering temperature as a function of time.
The temperature can be increased linearly and/or stepwise and/or curved. Bring the reaction solution up to the reaction temperature for 10 minutes.
If the temperature is raised rapidly before the end of the reaction, the reaction yield may not be sufficient and the yield may be significantly low, so it is preferable to carry out the reaction within the above range.
本発明方法は回分、連続いづれでも実施でき系
内の気相部は不活性ガス、例えば窒素、アルゴ
ン、ヘリウムで置換するのが好ましい。 The method of the present invention can be carried out either batchwise or continuously, and the gas phase in the system is preferably replaced with an inert gas, such as nitrogen, argon, or helium.
かくして、MBとBOHからメタノール留去せし
めることにより、BZBの含有物がえられ、従来公
知の蒸留、抽出等により高品位のBZBが高収率で
得られる。 Thus, by distilling off methanol from MB and BOH, a substance containing BZB can be obtained, and high-grade BZB can be obtained in high yield by conventionally known distillation, extraction, etc.
次に実施例を示すが、本発明方法は何らこれに
限定されるものではない。実施例中「部」、「％」
は「重量部」、「重量％」を意味する。 Examples will be shown next, but the method of the present invention is not limited thereto. "Part", "%" in Examples
means "part by weight" or "% by weight".
実施例
ビツテン・ハーキユレス法によるジメチルテレ
フタレート製造プロセスより抜き出された、メチ
ルベンゾエート50部、パラトルアルデヒド20部、
パラメチルベンジルメチルエーテル30部からなる
混合物100部とベンジルアルコール150部、Zn
（CH3COO）2・2H2O 0.8部を単蒸留型式の留出管
付のフラスコに仕込み、撹拌しながら30分間N2
ガスを吹き込み、反応系中の分子状酸素をN2で
置換する。次に100℃で30分加熱し、さらに150℃
で30分加熱した後190℃で２時間加熱することに
より、エステル交換反応を行なわしめベンジルベ
ンゾエートを合成する。このような操作によつて
反応液240部、留出物11部が得られ、反応液中に
はベンジルベンゾエート72部、パラトルアルデヒ
ド17部、パラメチルベンジルメチルエーテル29部
が含まれていた。この反応液240部を用いて通常
の蒸留操作を行ない、ベンジルベンゾエートの留
分として、純度98％のものが70部得られた。Example: 50 parts of methyl benzoate, 20 parts of paratoaldehyde, extracted from the dimethyl terephthalate production process by the bitten-Hercules method.
100 parts of a mixture of 30 parts of paramethylbenzyl methyl ether and 150 parts of benzyl alcohol, Zn
(CH 3 COO) 0.8 part of 2・2H 2 O was placed in a simple distillation type flask equipped with a distillation tube, and N 2 was added for 30 minutes while stirring.
Gas is blown into the reaction system to replace molecular oxygen in the reaction system with N 2 . Next, heat at 100℃ for 30 minutes, then further heat to 150℃.
After heating for 30 minutes at 190°C for 2 hours, a transesterification reaction is carried out to synthesize benzyl benzoate. Through such operations, 240 parts of a reaction solution and 11 parts of a distillate were obtained, and the reaction solution contained 72 parts of benzyl benzoate, 17 parts of p-tolualdehyde, and 29 parts of para-methylbenzyl methyl ether. A normal distillation operation was performed using 240 parts of this reaction solution to obtain 70 parts of a benzyl benzoate fraction with a purity of 98%.
Claims (1)
エステル交換触媒の存在下、高められた温度で反
応せしめることを特徴とするベンジルベンゾエー
トの製造法。 ２ 安息香酸メチル1molに対するベンジルアル
コールの仕込割合が0.5〜50mol、好ましくは1.1
〜10molである特許請求の範囲第１項記載のベン
ジルベンゾエートの製造法。 ３ 触媒がSb（OCH3）3、Pb（CH3COO）2・
3H2O、Mn（CH3COO）2・4H2O、Ti（OCH3）4、
Fe（）−acetylacetonate、Zn（CH3COO）2・
2H2O、Co（CH3COO）2、Cd（CH3COO）2、
GeO2、Cu（）−acetylacetonate、Li
（CH3COO）・2H2O、NaCH3COO、Mg
（CH3COO）2・4H2O、Ca（CH3COO）2・H2O、
H3BO2、Ni（CH3COO）2・4H2Oから選ばれた少
くとも１種である所の特許請求の範囲第１項記載
のベンジルベンゾエートの製造法。 ４ 反応を150〜300℃、好ましくは170〜250℃の
温度において行なう特許請求の範囲第１項記載の
ベンジルベンゾエートの製造法。 ５ 反応温度迄の昇温をゆるやかに及び／又は段
階的に行なう特許請求の範囲第１項記載のベンジ
ルベンゾエートの製造法。 ６ 安息香酸メチルがビツテン・ハーキユレス法
によるジメチルテレフタレート製造プロセスの副
生成物である特許請求の範囲第１項記載のベンジ
ルベンゾエートの製造法。[Claims] 1. Methyl benzoate and benzyl alcohol,
1. A method for producing benzyl benzoate, which comprises reacting at elevated temperature in the presence of a transesterification catalyst. 2 The charging ratio of benzyl alcohol to 1 mol of methyl benzoate is 0.5 to 50 mol, preferably 1.1
The method for producing benzyl benzoate according to claim 1, wherein the amount is 10 mol. 3 The catalyst is Sb(OCH 3 ) 3 , Pb(CH 3 COO) 2 .
3H 2 O, Mn (CH 3 COO) 2・4H 2 O, Ti (OCH 3 ) 4 ,
Fe()−acetylacetonate, Zn( CH3COO ) 2・
2H2O , Co( CH3COO ) 2 , Cd( CH3COO ) 2 ,
GeO 2 , Cu()−acetylacetonate, Li
( CH3COO )・2H2O , NaCH3COO , Mg
(CH 3 COO) 2・4H 2 O, Ca (CH 3 COO) 2・H 2 O,
The method for producing benzyl benzoate according to claim 1, wherein the benzyl benzoate is at least one selected from H 3 BO 2 and Ni(CH 3 COO) 2.4H 2 O. 4. The method for producing benzyl benzoate according to claim 1, wherein the reaction is carried out at a temperature of 150 to 300°C, preferably 170 to 250°C. 5. The method for producing benzyl benzoate according to claim 1, wherein the temperature is raised to the reaction temperature slowly and/or stepwise. 6. The method for producing benzyl benzoate according to claim 1, wherein methyl benzoate is a by-product of a process for producing dimethyl terephthalate by the bitten-Hercules method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10431976A JPS5331639A (en) | 1976-09-02 | 1976-09-02 | Preparation of benzyl benzoate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10431976A JPS5331639A (en) | 1976-09-02 | 1976-09-02 | Preparation of benzyl benzoate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5331639A JPS5331639A (en) | 1978-03-25 |
| JPS6114144B2 true JPS6114144B2 (en) | 1986-04-17 |
Family
ID=14377605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10431976A Granted JPS5331639A (en) | 1976-09-02 | 1976-09-02 | Preparation of benzyl benzoate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5331639A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0114932Y2 (en) * | 1980-03-19 | 1989-05-02 | ||
| JPH0124629Y2 (en) * | 1980-09-24 | 1989-07-25 | ||
| DE3128930A1 (en) * | 1981-07-22 | 1983-02-10 | Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe | Sample bottle changer |
| JPS6113160A (en) * | 1984-06-28 | 1986-01-21 | Konishiroku Photo Ind Co Ltd | Biochemical analyser |
| JPH06725B2 (en) * | 1985-01-29 | 1994-01-05 | ダイセル化学工業株式会社 | Method for producing diphenyl carbonate |
| JPS63150250A (en) * | 1986-12-12 | 1988-06-22 | Toray Ind Inc | Production of dibenzyl phthalates |
| WO1992018459A1 (en) * | 1991-04-18 | 1992-10-29 | Yoshitomi Pharmaceutical Industries, Ltd. | Benzoic ester compound and production thereof |
| JP2001226323A (en) | 2000-02-17 | 2001-08-21 | Nippon Steel Chem Co Ltd | Method for recovering benzyl benzoate |
-
1976
- 1976-09-02 JP JP10431976A patent/JPS5331639A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5331639A (en) | 1978-03-25 |
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