JPH07116104B2 - Method for producing a good tetrakis [3- (3,5-di-t- butyl-4-hydroxyphenyl) propionyloxymethyl] methane powder characteristics - Google Patents

Method for producing a good tetrakis [3- (3,5-di-t- butyl-4-hydroxyphenyl) propionyloxymethyl] methane powder characteristics

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Publication number
JPH07116104B2
JPH07116104B2 JP22399788A JP22399788A JPH07116104B2 JP H07116104 B2 JPH07116104 B2 JP H07116104B2 JP 22399788 A JP22399788 A JP 22399788A JP 22399788 A JP22399788 A JP 22399788A JP H07116104 B2 JPH07116104 B2 JP H07116104B2
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Prior art keywords
hydroxyphenyl
butyl
di
propionyloxymethyl
methane
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Expired - Lifetime
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JP22399788A
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Japanese (ja)
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JPH0272139A (en
Inventor
孝則 三浦
正則 古原
邦英 岡
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吉富製薬株式会社
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Priority to JP22399788A priority Critical patent/JPH07116104B2/en
Priority claimed from EP19890116354 external-priority patent/EP0358157B1/en
Priority claimed from AT89116354T external-priority patent/AT98625T/en
Publication of JPH0272139A publication Critical patent/JPH0272139A/en
Publication of JPH07116104B2 publication Critical patent/JPH07116104B2/en
Anticipated expiration legal-status Critical
Application status is Expired - Lifetime legal-status Critical

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Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、ポリオレフィンなどの酸化防止剤として広く使用されているテトラキス〔3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオニルオキシメチル〕メタン(以下、化合物(A)という)の改良された製造方法に関するものである。 DETAILED DESCRIPTION OF THE INVENTION The present invention [relates] is tetrakis widely used as an antioxidant, such as polyolefin [3- (3,5-di -t- butyl-4-hydroxyphenyl) propionyloxymethyl] methane (hereinafter compound (a) hereinafter) to an improved method for manufacturing.

〔従来の技術〕 [Prior art]

現在市販されている化合物(A)の製品は微粉末であるため、流動性が悪く、また取り扱い時に飛散しやすく、 For products of the compounds which are currently commercially available (A) is a fine powder, poor fluidity, also tends to scatter at the time of handling,
作業性および環境衛生上に重要な問題を有し、その改良が望まれている。 Have important problems in workability and environmental health, its improvement is desired. これらの改良方法として、特公昭60-1 As these of the improved method, JP-B-60-1
3017号、同60-13018号および特開昭62-258343号などが知られている。 No. 3017, such as the 60-13018 and No. JP-A-62-258343 is known.

〔発明が解決しようとする課題〕 [Problems that the Invention is to Solve]

従来の方法は、粉体特性の良好な化合物(A)を得るために、工程数を増やしたりまた不純物を多量に存在させるなど必ずしも経済的製造法とはいえない。 Conventional methods, in order to obtain compound having good powder properties the (A), not always economical production methods, such as is present in a large amount or also impurities increasing the number of steps. すなわち、 That is,
特公昭60-13017号および同60-13018号の方法ではエステル交換反応の際に式(III)で示されている特定のジカルボン酸エステルの添加が必要であること、および化合物(A)とイソプロパノールとの分子付加物の単離が必要であるため、工程数が増え経済的方法とは言えない。 He in JP-B 60-13017 and No. same 60-13018 Patent methods requires the addition of a specific dicarboxylic acid ester shown by the formula (III) during the transesterification reaction, and compound (A) and isopropanol isolation is required molecular adducts with for, not be economical method the number of steps is increased.
また、特開昭62-258343号の方法では、再結晶精製の前に原料である化合物(1)および反応未了中間体であるトリス置換体を多量に含有させる必要があるため(同明細書にも書かれている様に反応終了時に目的とする化合物(A)の含量が高くなりすぎた場合は、わざわざ化合物(1)またはトリス置換体を混合しなければならない)、得られる製品の純度が低くなりやすく、同時に再結晶歩留りも悪くなり経済的方法とは言えない。 In the method of JP 62-258343, recrystallization is a starting material compound before purification (1) and the reaction incomplete for the tris-substituted product which is an intermediate is necessary in a large amount is contained (the specification and an object also at the end of the reaction as written if the content of the compound (a) becomes too high, must be mixed bother compound (1) or tris substitutions), the resulting product purity is likely to be low, it can not be said that economic way become worse recrystallization yield at the same time.

本発明は、粉体特性の良好な化合物(A)を簡便な操作で経済的に製造する方法を提供することを目的とする。 The present invention aims at providing an economical process for preparing compound having good powder characteristics (A) by a simple operation.

〔課題を解決するための手段〕 [Means for Solving the Problems]

上記に鑑み、本発明者らは再結晶用溶媒に着目して鋭意検討を重ねたところ、驚くべきことに炭素数8〜10の脂肪族飽和炭化水素を用いて化合物(A)を再結晶すると、所期の目的を達成することを見出し、本発明を完成させるに至った。 In view of the above, the present inventors have revealed that intensive studies focusing on the recrystallization solvent, surprisingly re crystallization of the compound (A) with aliphatic saturated hydrocarbon having 8 to 10 carbon atoms in the found that to achieve the intended purpose, and completed the present invention. 本発明は、3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオン酸エステルとペンタエリスリトールからエステル交換反応により得られるテトラキス〔3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオニルオキシメチル〕メタンを再結晶溶媒として、炭素数8〜10の脂肪族飽和炭化水素を単独またはその混合溶媒により再結晶をすることを特徴とする粉体特性の良好なテトラキス〔3−(3,5− The present invention is 3- (3,5-di -t- butyl-4-hydroxyphenyl) tetrakis obtained by transesterification from propionate and pentaerythritol [3- (3,5-di -t- butyl - as the recrystallization solvent 4-hydroxyphenyl) propionyloxymethyl] methane, good tetrakis powder properties, characterized in that the recrystallization of an aliphatic saturated hydrocarbon having 8 to 10 carbon atoms by a single or a mixed solvent [3- (3,5
ジ−t−ブチル−4−ヒドロキシフェニル)プロピオニルオキシメチル〕メタンの製造方法に関する。 The method for producing a di -t- butyl-4-hydroxyphenyl) propionyloxymethyl] methane.

本発明に使用される炭素数8〜10の脂肪族炭化水素の具体的例としては、アイソパー(エクソン化学商品名)、 Specific examples of the aliphatic hydrocarbon having 8 to 10 carbon atoms used in the present invention, Isopar (Exxon Chemical trade name),
シェルゾール(シェル化学商品名)、IPソルベント(出光石油化学商品名)などで単独または混合して使用することができる。 Shellsol (Shell Chemical trade name), IP Solvent (manufactured by Idemitsu Petrochemical product name) may be used alone or in combination with like. 化合物(I)としてはメチルエステル、 Methyl ester as compound (I),
エチルエステルが用いられる。 Ethyl ester. エステル交換反応はよく知られた条件下に行なわれる。 Transesterification reaction is carried out in well-known conditions.

〔作用〕 [Action]

本発明の方法は、化合物(I)とペンタエリスリトールとをエステル交換させ、得られる反応物に対して本発明に用いられる溶媒を0.25〜2.0倍重量比を用いて再結晶するという極めて簡単な方法により行なうことができる。 The method of the present invention, an extremely simple method of compound (I) and the pentaerythritol is transesterified recrystallized using a solvent of 0.25 to 2.0 times the weight ratios used in the present invention to the reaction product obtained it can be carried out by. 本発明では、反応時に第三物質の添加や反応物の組成を限定する必要もなく、通常のエステル交換反応で得られる組成物(化合物(A)の含量が80〜98%)をそのまま再結晶すればよく、またイソプロパノールで分子付加物を作り、単離後再結晶する等の煩雑な操作の必要もない。 In the present invention, there is no need to limit the composition of the additive and the reaction product of the third material upon reaction, the resulting composition in the usual transesterification (compound content 80-98% of (A)) as it is recrystallized it is sufficient, also isopropanol make molecular adduct, there is no need of complicated operations such as isolating after recrystallization.

本発明により得られる化合物(A)は粉体特性として具体的には流動性に優れ、また、粒度分布が均一でその幅が狭く、嵩比重が大きいなどの特徴を有すると同時に再結晶前の反応物中の化合物(A)の含量が90%までの場合、再結晶して得られる製品は、主としてβ晶の結晶構造を有し、91%以上では主としてα晶の結晶構造を有する製品が得られる。 Compounds obtained by the present invention (A) is excellent particularly in flowability as a powder characteristics, its width is narrow and uniform particle size distribution, bulk density is large, such as before recrystallization simultaneously having the characteristics of If the content of the compound in the reaction product in (a) is up to 90%, the product obtained was recrystallized mainly has the crystal structure of β crystal, the products having a predominantly crystalline structure of α crystals in 91% or more can get. 驚くべきことには、従来α晶は微粉末としてしか得られず、そのために濾過性が非常に悪く、実質的に再結晶法による精製は不可能であったが、 Surprisingly, not only is obtained as a conventional α crystals are fine powder, very poor filtration properties to them, was the purification by substantially recrystallization impossible,
本方法ではβ晶と変わらない品質の化合物(A)を得ることができる。 In this way it is possible to obtain compounds of the quality unchanged and β crystal of (A).

〔実施例〕 〔Example〕

以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, a detailed explanation of the present invention through examples, but the invention is not limited thereto.

実施例 攪拌機、還流冷却器、温度計を備えた500mlの4口フラスコに3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオン酸メチル245.6g、ペンタエリスリトール27.2g、リチウムアミド0.2gおよびテトラリン8gを加え、130〜140℃/2〜3Torrで4時間攪拌し、生成するメタノールを留去した。 Example agitator, reflux condenser, 4-necked flask 500ml equipped with a thermometer 3- (3,5-di -t- butyl-4-hydroxyphenyl) propionate 245.6G, pentaerythritol 27.2 g, lithium amide added 0.2g and tetralin 8 g, was stirred for 4 hours at 130~140 ℃ / 2~3Torr, and removing the generated methanol. その後、さらに150〜160℃/2〜 After that, further 150~160 ℃ / 2~
3Torrの減圧下に10時間保持して少量のメタノールとテトラリンを留去し、反応を完結した。 It was distilled off a small amount of methanol and tetralin and held for 10 hours under a reduced pressure of 3 Torr, to complete the reaction. 反応物を120℃まで冷却し、窒素で大気圧に戻した後、氷酢酸で中和した。 The reaction was cooled to 120 ° C., after returning to atmospheric pressure with nitrogen and neutralized with glacial acetic acid. 得られた反応物をHPLC分析したところ、目的物である化合物(A)を82%含有していた。 The resulting reaction product obtained was analyzed by HPLC and contained the intended compound of (A) 82%. この反応物にアイソパーE(エクソン化学の商品名で炭素数8〜10の脂肪族炭化水素)250gを加えて100℃に加温溶解し、不溶物を濾過して除いた後、攪拌下100〜50℃まで30分で冷却し少量のβ晶の結晶を添加後、引続き35〜50℃で4時間、さらに35〜25℃で4時間攪拌して晶出させた。 The reaction was added to 250 g (aliphatic hydrocarbon having 8 to 10 carbon atoms in the trade name of Exxon Chemical) Isopar E were dissolved by heating to 100 ° C., after it was filtered off the insoluble matter, stirring 100 after addition of a small amount of β crystal was cooled in 30 minutes to 50 ° C. crystals, subsequently 4 hours at 35 to 50 ° C., was further crystallized by stirring for 4 hours at 35-25 ° C.. 結晶を濾別し冷アイソパーE100mlで洗浄後、乾燥して化合物(A)188.5gを得た。 After washing with the crystals were filtered off cold Isopar E100ml, and dried to give Compound (A) 188.5 g. これはペンタエリスリトールから This is from pentaerythritol
80%の収率であり、また反応で生成した化合物(A)から95%の晶出歩留り(HPLC定量)である。 Is 80% yield, also a compound produced by the reaction of 95% crystallized yield from (A) (HPLC quantification).

このようにして得た化合物(A)の外観、融点、結晶構造、嵩比重、安息角、オリフィス径および粒度分布を測定し、第1表にまとめた。 Appearance of the compound thus obtained (A), melting point, crystal structure, bulk density, angle of repose, and measuring the orifice diameter and particle size distribution are summarized in Table 1. さらに、同様にして得た化合物(A)について、種々の溶媒を用いて再結晶し、その結晶の性質を測定し、市販品と対比して第1表にまとめた。 Furthermore, the compounds obtained in the same manner for (A), and recrystallized using various solvents, to measure the properties of the crystals are summarized in Table 1 in comparison with a commercial product.

〔発明の効果〕 上記明細書、特に第1表の記載から明らかなように、本発明方法により粉体特性の改良されたテトラキス〔3− The specification [Effect of the Invention, in particular is apparent from the description of Table 1, improved tetrakis powder properties by the method of the invention [3-
(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオニルオキシメチル〕メタンが簡単かつ経済的に製造される。 (3,5-di -t- butyl-4-hydroxyphenyl) propionyloxymethyl] methane is produced simply and economically.

Claims (1)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオン酸エステルとペンタエリスリトールからエステル交換反応により得られるテトラキス〔3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオニルオキシメチル〕メタンを再結晶溶媒として、炭素数8〜10の脂肪族飽和炭化水素を単独またはその混合溶媒により再結晶をすることを特徴とする粉体特性の良好なテトラキス〔3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオニルオキシメチル〕メタンの製造方法。 1. A 3- (3,5-di -t- butyl-4-hydroxyphenyl) tetrakis [3- (3,5-di -t- butyl obtainable by transesterification from propionate and pentaerythritol as the recrystallization solvent-4-hydroxyphenyl) propionyloxymethyl] methane, good powder properties, characterized in that the recrystallization sole or mixed solvent of an aliphatic saturated hydrocarbon having 8 to 10 carbon atoms method for producing tetrakis [3- (3,5-di -t- butyl-4-hydroxyphenyl) propionyloxymethyl] methane.
JP22399788A 1988-09-07 1988-09-07 Method for producing a good tetrakis [3- (3,5-di-t- butyl-4-hydroxyphenyl) propionyloxymethyl] methane powder characteristics Expired - Lifetime JPH07116104B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP22399788A JPH07116104B2 (en) 1988-09-07 1988-09-07 Method for producing a good tetrakis [3- (3,5-di-t- butyl-4-hydroxyphenyl) propionyloxymethyl] methane powder characteristics

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP22399788A JPH07116104B2 (en) 1988-09-07 1988-09-07 Method for producing a good tetrakis [3- (3,5-di-t- butyl-4-hydroxyphenyl) propionyloxymethyl] methane powder characteristics
EP19890116354 EP0358157B1 (en) 1988-09-07 1989-09-05 Individual alpha-form particle crystals of tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-oxymethyl]methane and process for its production
AT89116354T AT98625T (en) 1988-09-07 1989-09-05 Individual particulate crystals in the form of alpha-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy> methane and process for its preparation.
DE1989611436 DE68911436D1 (en) 1988-09-07 1989-09-05 Individual particles crystals in the form of alpha-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] methane and process for its preparation.
DE1989611436 DE68911436T2 (en) 1988-09-07 1989-09-05 Individual particles crystals in the form of alpha-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] methane and process for its preparation.
KR8912906A KR920000911B1 (en) 1988-09-07 1989-09-06 Individual alpha-form particle crystals of tetrakis 3-(3.5-dit-butyl-4-hydro phenyl) propionyl-oxymethyl methane and process for its production
US07/403,492 US5089655A (en) 1988-09-07 1989-09-06 Individual α-form particle crystals of tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethyl]methane and process for its production

Publications (2)

Publication Number Publication Date
JPH0272139A JPH0272139A (en) 1990-03-12
JPH07116104B2 true JPH07116104B2 (en) 1995-12-13

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8834354B2 (en) 2000-04-03 2014-09-16 Intuitive Surgical Operations, Inc. Steerable endoscope and improved method of insertion
US8845524B2 (en) 2000-04-03 2014-09-30 Intuitive Surgical Operations, Inc. Steerable segmented endoscope and method of insertion
US8882657B2 (en) 2003-03-07 2014-11-11 Intuitive Surgical Operations, Inc. Instrument having radio frequency identification systems and methods for use
US8888688B2 (en) 2000-04-03 2014-11-18 Intuitive Surgical Operations, Inc. Connector device for a controllable instrument

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07116105B2 (en) * 1989-03-08 1995-12-13 吉富製薬株式会社 Independent particulate α crystals tetrakis [3- (3,5-di -t- butyl-4-hydroxyphenyl) propionyloxymethyl] methane, and a manufacturing method thereof
JP4858364B2 (en) * 2007-09-06 2012-01-18 豊田合成株式会社 Vehicle interior lighting system
JP4853438B2 (en) * 2007-09-21 2012-01-11 豊田合成株式会社 Vehicle interior lighting device

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8834354B2 (en) 2000-04-03 2014-09-16 Intuitive Surgical Operations, Inc. Steerable endoscope and improved method of insertion
US8845524B2 (en) 2000-04-03 2014-09-30 Intuitive Surgical Operations, Inc. Steerable segmented endoscope and method of insertion
US8888688B2 (en) 2000-04-03 2014-11-18 Intuitive Surgical Operations, Inc. Connector device for a controllable instrument
US8882657B2 (en) 2003-03-07 2014-11-11 Intuitive Surgical Operations, Inc. Instrument having radio frequency identification systems and methods for use

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