JPH0576350B2 - - Google Patents
Info
- Publication number
- JPH0576350B2 JPH0576350B2 JP60227551A JP22755185A JPH0576350B2 JP H0576350 B2 JPH0576350 B2 JP H0576350B2 JP 60227551 A JP60227551 A JP 60227551A JP 22755185 A JP22755185 A JP 22755185A JP H0576350 B2 JPH0576350 B2 JP H0576350B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- distanoxane
- esterification
- esterification catalyst
- acid
- 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 - Lifetime
Links
- 238000005886 esterification reaction Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 11
- 230000032050 esterification Effects 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052799 carbon Chemical group 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- QCYYDSAKAHEUDF-UHFFFAOYSA-N 13-hexyl-oxacyclotridecan-2-one Chemical compound CCCCCCC1CCCCCCCCCCC(=O)O1 QCYYDSAKAHEUDF-UHFFFAOYSA-N 0.000 description 2
- BZUNJUAMQZRJIP-UHFFFAOYSA-N 15-hydroxypentadecanoic acid Chemical compound OCCCCCCCCCCCCCCC(O)=O BZUNJUAMQZRJIP-UHFFFAOYSA-N 0.000 description 2
- LOKPJYNMYCVCRM-UHFFFAOYSA-N 16-Hexadecanolide Chemical compound O=C1CCCCCCCCCCCCCCCO1 LOKPJYNMYCVCRM-UHFFFAOYSA-N 0.000 description 2
- UGAGPNKCDRTDHP-UHFFFAOYSA-N 16-hydroxyhexadecanoic acid Chemical compound OCCCCCCCCCCCCCCCC(O)=O UGAGPNKCDRTDHP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FKUPPRZPSYCDRS-UHFFFAOYSA-N Cyclopentadecanolide Chemical compound O=C1CCCCCCCCCCCCCCO1 FKUPPRZPSYCDRS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- -1 propionyloxy group Chemical group 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 125000004036 acetal group Chemical group 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- MILUHXCABWMFFL-UHFFFAOYSA-N methyl(stannyloxy)stannane Chemical compound C[SnH2]O[SnH3] MILUHXCABWMFFL-UHFFFAOYSA-N 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 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)
- Pyrane Compounds (AREA)
- Catalysts (AREA)
Description
〔産業上の利用分野〕
本発明はエステル化触媒に関し、さらに詳しく
は特定のジスタノキサン誘導体からなるエステル
化触媒に関する。
本発明により提供されるエステル化触媒はヒド
ロキシカルボン酸またはその反応性誘導体の分子
内エステル化反応ならびにアルコールまたはその
反応性誘導体とカルボン酸またはその反応性誘導
体との分子間エステル化反応を促進する。これら
の分子内または分子間でのエステル化反応により
香料、医薬品、高分子添加剤、液晶などとして有
用な種々のエステルが得られる。そのエステルの
代表例としてシクロベンタデカノリド、エチレン
ブラシレートなどの香料の香気成分が挙げられ
る。
〔従来の技術〕
従来、ヒドロキシカルボン酸またはその反応性
誘導体の分子内エステル化反応ならびにアルコー
ルまたはその反応性誘導体とカルボン酸またはそ
の反応性誘導体との分子間エステル化反応を促進
するエステル化触媒として、ｐ−トルエンスルホ
ン酸、硫酸などの酸またはナトリウムメトキシ
ド、カリウムｔ−ブトキシドなどの塩基が用いら
れ、また、これらの酸または塩基に替るものとし
てＮ，N′−ジシクロヘキシルカルボジイミド−
４−（Ｎ，Ｎ−ジメチルアミノ）ピリジン、トリ
フエニルホスフイン−２，2′−ジピリジルジスル
フイドなどの縮合剤が使用されている。
近年、ジブチルスタノキシド〔（C4H9）2SnO〕
などをエステル化触媒として用いることにより、
中性に近い条件下でエステル化反応が進行するこ
とが報告されている〔ジヤーナル・オブ・ジ・ア
メリカン・ケミカル・ソサエテイ（Journal of
the American Chemical Society）第102巻第
7578頁（1980年）参照〕。
〔発明が解決しようとする問題点〕
分子内にカルボニル基、アセタール基などの官
能基または炭素原子−炭素原子間二重結合を有す
るカルボン酸、アルコールまたはそれらの反応性
誘導体を酸または塩基の存在下でのエステル化反
応に付する場合には、酸または塩基の作用によつ
て前記の官能基の化学変化、二重結合の移動また
は二重結合に由来する幾何異性化などが生起する
ことがある。また、上記の縮合剤を用いるエステ
ル化反応では該縮合剤が原料のカルボン酸と等モ
ル量消費されるという欠点がある。エステル化触
媒として上記のジブチルスタノキシドを使用する
場合には、後述の参考例に示されるように、収率
よく目的とするエステルを得ることができない。
しかして、本発明の目的は、酸または塩基によ
つて影響を受け易い官能基または炭素原子−炭素
原子間二重結合を有するカルボン酸、アルコール
またはそれらの反応性誘導体を用いてエステル化
反応を行なうに際し、該官能基の化学変化、二重
結合の移動または二重結合に由来する幾何異性化
などを生ぜしめることがなく、好収率で目的とす
るエステルを与えるエステル化触媒を提供するこ
とにある。
〔問題点を解決するための手段〕
本発明によれば、上記の目的は、一般式
[Industrial Application Field] The present invention relates to an esterification catalyst, and more particularly to an esterification catalyst comprising a specific distanoxane derivative. The esterification catalyst provided by the present invention promotes the intramolecular esterification reaction of hydroxycarboxylic acids or reactive derivatives thereof as well as the intermolecular esterification reactions of alcohols or reactive derivatives thereof and carboxylic acids or reactive derivatives thereof. Through these intramolecular or intermolecular esterification reactions, various esters useful as perfumes, pharmaceuticals, polymer additives, liquid crystals, etc. can be obtained. Representative examples of such esters include aroma components of perfumes such as cyclobentadecanolide and ethylene brasileate. [Prior Art] Conventionally, esterification catalysts have been used to promote intramolecular esterification reactions of hydroxycarboxylic acids or their reactive derivatives and intermolecular esterification reactions between alcohols or their reactive derivatives and carboxylic acids or their reactive derivatives. , p-toluenesulfonic acid, sulfuric acid, or bases such as sodium methoxide and potassium t-butoxide.Also, as an alternative to these acids or bases, N,N'-dicyclohexylcarbodiimide-
Condensing agents such as 4-(N,N-dimethylamino)pyridine and triphenylphosphine-2,2'-dipyridyl disulfide are used. In recent years, dibutyl stanoxide [(C 4 H 9 ) 2 SnO]
By using etc. as an esterification catalyst,
It has been reported that the esterification reaction proceeds under conditions close to neutrality [Journal of the American Chemical Society].
the American Chemical Society) Volume 102, No.
See page 7578 (1980)]. [Problems to be solved by the invention] Carboxylic acids, alcohols, or their reactive derivatives having a functional group such as a carbonyl group or an acetal group or a carbon atom-to-carbon double bond in the molecule in the presence of an acid or base When subjected to the esterification reaction described below, chemical changes in the functional groups, migration of double bonds, or geometric isomerization derived from double bonds may occur due to the action of acids or bases. be. Furthermore, the esterification reaction using the above-mentioned condensing agent has the disadvantage that the condensing agent is consumed in an equimolar amount with the carboxylic acid as a raw material. When using the above-mentioned dibutyl stannoxide as an esterification catalyst, the desired ester cannot be obtained in good yield, as shown in the reference examples below. Therefore, the object of the present invention is to carry out an esterification reaction using a carboxylic acid, an alcohol, or a reactive derivative thereof having a functional group or a carbon atom-to-carbon double bond that is susceptible to acid or base. To provide an esterification catalyst that gives a desired ester in good yield without causing chemical change of the functional group, migration of double bonds, geometric isomerization derived from double bonds, etc. It is in. [Means for Solving the Problems] According to the present invention, the above object is achieved by solving the general formula
【化】
（式中、R1、R2、R3およびR4はそれぞれブチル
基を表わし、Ｘはヒドロキシル基、低級アルコキ
シル基、アリールオキシ基、アシルオキシ基また
はハロゲン原子を表わし、Ｙはハロゲン原子を表
わす。）
で示されるジスタノキサン誘導体からなるエステ
ル化触媒を提供することによつて達成される。
上記一般式（）におけるＸおよびＹを次に詳
しく説明する。Ｘはヒドロキシル基；メトキシ
基、エトキシ基、プロポキシ基、ブトキシ基、ペ
ンチルオキシ基、ヘキシルオキシ基などの低級ア
ルコキシル基；フエノキシ基、トリルオキシ基な
どのアリールオキシ基；アセトキシ基、プロピオ
ニルオキシ基、ブチロイルオキシ基、ベンゾイル
オキシ基などのアシルオキシ基；または塩素原
子、臭素原子、ヨウ素原子などのハロゲン原子を
表わす。また、Ｙは塩素原子、臭素原子、ヨウ素
原子などのハロゲン原子を表わす。
本発明のエステル化触媒は一般式（）で示さ
れるジスタノキサン誘導体のみからなるものであ
つてもよいし、通常使用される担体に一般式
（）で示されるジスタノキサン誘導体を常法に
より担持させたものであつてもよい。担体として
はシリカ、アルミナ、グラフアイト等が挙げら
れ、一般式（）で示されるジスタノキサン誘導
体はこれらの担体に対して１／1000〜１／５（重
量比）の割合で用いるのが適当である。
本発明のエステル化触媒は、例えば、一般式[Formula, R 1 , R 2 , R 3 and R 4 each represent a butyl group, X represents a hydroxyl group, lower alkoxyl group, aryloxy group, acyloxy group or halogen atom, and Y represents a halogen atom. This is achieved by providing an esterification catalyst consisting of a distanoxane derivative represented by X and Y in the above general formula () will be explained in detail below. X is a hydroxyl group; a lower alkoxyl group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, or a hexyloxy group; an aryloxy group such as a phenoxy group or a tolyloxy group; an acetoxy group, a propionyloxy group, or a butyroyloxy group , an acyloxy group such as a benzoyloxy group; or a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom. Further, Y represents a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom. The esterification catalyst of the present invention may consist only of the distanoxane derivative represented by the general formula (), or may be one in which the distanoxane derivative represented by the general formula () is supported on a commonly used carrier by a conventional method. It may be. Examples of the carrier include silica, alumina, graphite, etc., and it is appropriate to use the distanoxane derivative represented by the general formula () in a ratio of 1/1000 to 1/5 (weight ratio) to these carriers. . The esterification catalyst of the present invention has the general formula
以下、実施例により本発明を具体的に説明する
が、本発明はこれらの実施例により限定されるも
のではない。
実施例 １
12−ヒドロキシオクタデカン酸１ミリモル、１
−クロル−３−ヒドロキシテトラブチルジスタノ
キサン0.2ミリモルおよびデカン100mlの混合物を
24時間加熱還流した。反応混合物から減圧下にデ
カンを留去し、その残渣にヘキサンを加え、つい
でヘキサン溶液を重曹水で洗滌した。ヘキサン層
を無水硫酸マグネシウムで乾燥したのち低沸点物
を減圧下に留去し、得られた濃縮液をシリカゲル
カラムクロマトグラフイーで精製することによ
り、下記の物性を有する12−オクタデカノリドを
得た（収率90.4％）。
NMRスペクトル（60MHz）δTMS
CCl4
0.62〜1.90（ｍ、31H）、2.20（ｔ、Ｊ＝６Hz、
2H）、4.45〜4.95（ｍ、1H）
実施例 ２〜３
実施例１において12−ヒドロキシオクタデカン
酸１ミリモルの代りに15−ヒドロキシペンタデカ
ン酸または16−ヒドロキシヘキサデカン酸をそれ
ぞれ１ミリモル用いた以外は実施例１と同様にし
て反応および分離精製を行なうことにより、それ
ぞれ15−ペンタデカノリドまたは16−ヘキサデカ
ノリドを得た。それぞれのエステルの収率および
NMRスペクトルを第１表に示す。
EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. Example 1 1 mmol of 12-hydroxyoctadecanoic acid, 1
- a mixture of 0.2 mmol of chloro-3-hydroxytetrabutyl distanoxane and 100 ml of decane
The mixture was heated under reflux for 24 hours. Decane was distilled off from the reaction mixture under reduced pressure, hexane was added to the residue, and then the hexane solution was washed with aqueous sodium bicarbonate. After drying the hexane layer over anhydrous magnesium sulfate, low-boiling substances were distilled off under reduced pressure, and the resulting concentrated liquid was purified by silica gel column chromatography to obtain 12-octadecanolide having the following physical properties ( Yield 90.4%). NMR spectrum (60MHz) δTMS CCl 4 0.62-1.90 (m, 31H), 2.20 (t, J=6Hz,
2H), 4.45-4.95 (m, 1H) Examples 2-3 Same as Example 1 except that 1 mmol of 15-hydroxypentadecanoic acid or 16-hydroxyhexadecanoic acid was used instead of 1 mmol of 12-hydroxyoctadecanoic acid. By carrying out the reaction and separation and purification in the same manner as in Example 1, 15-pentadecanolide and 16-hexadecanolide were obtained, respectively. Yield of each ester and
The NMR spectra are shown in Table 1.
【表】
実施例４〜６および参考例１〜３
実施例１において１−クロル−３−ヒドロキシ
テトラブチルジスタノキサン0.2ミリモルの代り
に１，３−ジクロルテトラブチルジスタノキサン
（実施例４）、１−クロル−３−メトキシテトラブ
チルジスタノキサン（実施例５）、１−クロル−
３−フエノキシテトラブチルジスタノキサン（実
施例６）、１−ヒドロキシ−３−イソチオシアナ
ートテトラブチルジスタノキサン（参考例１）、
１−クロル−３−ヒドロキシテトラメチルジスタ
ノキサン（参考例２）または１，３−ジアセトキ
シテトラメチルジスタノキサン（参考例３）をそ
れぞれ0.2ミリモル用いた以外は実施例１と同様
にして反応および分離精製を行なうことにより、
12−オクタデカノリドを得た。それぞれの収率を
第２表に示す。[Table] Examples 4 to 6 and Reference Examples 1 to 3 1,3-dichlorotetrabutyl distanoxane (Example 4) was used instead of 0.2 mmol of 1-chloro-3-hydroxytetrabutyl distanoxane in Example 1. ), 1-chloro-3-methoxytetrabutyldistanoxane (Example 5), 1-chloro-
3-phenoxytetrabutyl distanoxane (Example 6), 1-hydroxy-3-isothiocyanatotetrabutyl distanoxane (Reference Example 1),
Reaction was carried out in the same manner as in Example 1, except that 0.2 mmol of each of 1-chloro-3-hydroxytetramethyldistanoxane (Reference Example 2) or 1,3-diacetoxytetramethyldistanoxane (Reference Example 3) was used. By performing separation and purification,
12-octadecanolide was obtained. The respective yields are shown in Table 2.
【表】
３ メチルジスタノキサン
[Table] 3 Methyldistannoxane
Claims (1)
基を表わし、Ｘはヒドロキシル基、低級アルコキ
シル基、アリールオキシ基、アシルオキシ基また
はハロゲン原子を表わし、Ｙはハロゲン原子を表
わす。） で示されるジスタノキサン誘導体からなるエステ
ル化触媒。[Claims] 1 General formula [Formula] (In the formula, R 1 , R 2 , R 3 and R 4 each represent a butyl group, and X represents a hydroxyl group, a lower alkoxyl group, an aryloxy group, an acyloxy group, or (Y represents a halogen atom.) An esterification catalyst comprising a distanoxane derivative represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60227551A JPS6287248A (en) | 1985-10-11 | 1985-10-11 | Esterification catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60227551A JPS6287248A (en) | 1985-10-11 | 1985-10-11 | Esterification catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6287248A JPS6287248A (en) | 1987-04-21 |
| JPH0576350B2 true JPH0576350B2 (en) | 1993-10-22 |
Family
ID=16862670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60227551A Granted JPS6287248A (en) | 1985-10-11 | 1985-10-11 | Esterification catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6287248A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5470969A (en) * | 1990-08-27 | 1995-11-28 | Mcneil-Ppc, Inc. | Catalyzed sucrose-6-ester process |
| ES2191745T3 (en) * | 1995-11-28 | 2003-09-16 | Mcneil Ppc Inc | SACAROSA 6-ESTER PREPARATION PROCEDURE. |
| DE69807394T2 (en) * | 1997-05-30 | 2003-03-20 | Mitsubishi Chem Corp | Process for the preparation of hydroxyalkyl monoacrylate |
| US7420020B2 (en) | 2004-05-14 | 2008-09-02 | Fuji Xerox Co., Ltd. | Resin particles and producing method thereof, toner for developing electrostatic latent image and producing method thereof, electrostatic latent image developer as well as image forming method |
| US7378210B2 (en) | 2004-05-14 | 2008-05-27 | Fuji Xerox Co., Ltd. | Electrophotographic toner and manufacturing method thereof, polyester resin for electrophotographic toner and manufacturing method thereof, electrophotographic developer and image forming method |
| JP2012020984A (en) * | 2010-07-16 | 2012-02-02 | Nippon Surfactant Kogyo Kk | Ester derivative and cosmetic containing the ester derivative, external preparation, coating material and ink composition |
| US9738587B2 (en) * | 2014-12-02 | 2017-08-22 | Shin-Etsu Chemical Co., Ltd. | Method for producing 2-isopropenyl-5-methyl-4-hexen-1-yl 3-methyl-2-butenoate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52153913A (en) * | 1976-06-18 | 1977-12-21 | Nitto Chem Ind Co Ltd | Preparation of dimethylaminoethylmethacrylate |
-
1985
- 1985-10-11 JP JP60227551A patent/JPS6287248A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52153913A (en) * | 1976-06-18 | 1977-12-21 | Nitto Chem Ind Co Ltd | Preparation of dimethylaminoethylmethacrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6287248A (en) | 1987-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0576350B2 (en) | ||
| US4424389A (en) | Synthesis of 6-hydroxychroman-2-methanol derivatives | |
| Tranel et al. | Claisen rearrangements based on vinyl fluorides | |
| WO2004046074A1 (en) | Method of preparing di(ketene acetals) | |
| US5286883A (en) | (3R,5S)-3,5,6-trihydroxyhexanoic acid derivative and production method thereof | |
| US5600029A (en) | Process for producing DL-tocopherols and intermediates therefor | |
| JPS6035347B2 (en) | Synthesis method of α-tocopherol | |
| US4958037A (en) | Precursors and synthesis of methyl-9-oxo-11α, 16-dihydroxy-16-vinyl-5-cis-13-trans-prostadienoates | |
| JP3756266B2 (en) | Method for producing optically active α-ionone | |
| JP3632135B2 (en) | Isocarbacycline derivative and method for producing the same | |
| JP7168161B2 (en) | Method for producing heterol multimer | |
| JPH07109235A (en) | Production of alcohols | |
| JP3471067B2 (en) | Method for producing optically active 6- (4-substituted inden-1-yl) -2-methyl-4-hepten-3-ols | |
| JP2958835B2 (en) | Method for producing 4- (1-carboxyalkyl) azetidin-2-one derivative | |
| JP4064645B2 (en) | New production method of polysubstituted cycloalkenes | |
| JP3795942B2 (en) | Method for producing 2-pyridinecarboxylic acid derivative | |
| JPH0131520B2 (en) | ||
| JPH04178350A (en) | Methyl ester which is synthetic intermediate for new sex pheromone of anomala rufocuprea, its production and production of sex pheromone of anomala rufocuprea using the same ester | |
| CN112638861A (en) | Process for preparing cis-alpha, beta-substituted cyclopentanones | |
| JP2652248B2 (en) | Process for producing alkoxynitrile compounds | |
| JPS6239134B2 (en) | ||
| JPS6046114B2 (en) | Production method of α-tocopherol | |
| Cai et al. | Novel stereoselective synthesis of (E)-cinnamonitriles via Heck arylation of acrylonitrile catalysed by a silica-supported bidentate arsine palladium (0) complex | |
| JPH03101674A (en) | Novel 4h pyran and its preparation | |
| JPS61227562A (en) | 3-oxo-2-azabicyclohexane derivative |