JPS6253499B2 - - Google Patents
Info
- Publication number
- JPS6253499B2 JPS6253499B2 JP17424780A JP17424780A JPS6253499B2 JP S6253499 B2 JPS6253499 B2 JP S6253499B2 JP 17424780 A JP17424780 A JP 17424780A JP 17424780 A JP17424780 A JP 17424780A JP S6253499 B2 JPS6253499 B2 JP S6253499B2
- Authority
- JP
- Japan
- Prior art keywords
- carboxylic acid
- acid ester
- decane
- tricyclo
- aqueous
- 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 13
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 150000008050 dialkyl sulfates Chemical class 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000003756 stirring Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 6
- 229940008406 diethyl sulfate Drugs 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- -1 alkali metal salt Chemical class 0.000 description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 3
- MGQPKOBPXHENPO-UHFFFAOYSA-N 80657-64-3 Chemical compound C1C2CCC1C1(C(=O)OCC)C2CCC1 MGQPKOBPXHENPO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- JYCKNDWZDXGNBW-UHFFFAOYSA-N dipropyl sulfate Chemical compound CCCOS(=O)(=O)OCCC JYCKNDWZDXGNBW-UHFFFAOYSA-N 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- ZWSMRUGTQTWTII-UHFFFAOYSA-N methyl 2-methyldecanoate Chemical compound CCCCCCCCC(C)C(=O)OC ZWSMRUGTQTWTII-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- SAOSCTYRONNFTC-UHFFFAOYSA-N 2-methyl-decanoic acid Chemical compound CCCCCCCCC(C)C(O)=O SAOSCTYRONNFTC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Natural products CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- KGKUZGKMSKOEOK-UHFFFAOYSA-N ethyl 2-methyldecanoate Chemical compound CCCCCCCCC(C)C(=O)OCC KGKUZGKMSKOEOK-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Description
【発明の詳細な説明】
本発明は三環式カルボン酸エステルの製造法に
関し、詳しくは式（）；
で表わされるトリシクロ〔５・１・１・０2、6〕
デカン−２−カルボン酸をアルカリ水溶液中で硫
酸ジアルキルでエステル化して式（）
（式中Ｒは炭素数１〜３のアルキル基である）で
表わされるトリシクロ〔５・２・１・０2、6〕デ
カン−２−カルボン酸エステルを製造する方法に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a tricyclic carboxylic acid ester, and more specifically, formula (); Tricyclo [5・1・1・0 2 , 6 ] represented by
Decane-2-carboxylic acid is esterified with dialkyl sulfate in an alkaline aqueous solution to give the formula () The present invention relates to a method for producing tricyclo[5.2.1.0 2 , 6 ]decane-2-carboxylic acid ester represented by the formula (wherein R is an alkyl group having 1 to 3 carbon atoms).
本発明の目的物たる三環式カルボン酸エステル
は優れた香気を有するものであり、すでに特許出
願した（特願昭55−32434（特公昭61−1014号）
及び同55−32435（特開昭56−128710号）。 The tricyclic carboxylic acid ester, which is the object of the present invention, has an excellent aroma, and a patent application has already been filed (Japanese Patent Application No. 32434/1983 (Japanese Patent Publication No. 1014/1983)).
and No. 55-32435 (Japanese Unexamined Patent Publication No. 56-128710).
式（）で表わされるカルボン酸は立体障害が
大きく、このカルボン酸と低級アルコールとの酸
触媒を用いる脱水エステル化反応によつては式
（）で表わされるカルボン酸エステルはほとん
ど得られない。 The carboxylic acid represented by the formula () is highly sterically hindered, and the carboxylic acid ester represented by the formula () is hardly obtained by the dehydration esterification reaction of this carboxylic acid and a lower alcohol using an acid catalyst.
このような立体障害の大きなカルボン酸のエス
テル化反応としては次のような方法が考えられ
る。 The following method can be considered as the esterification reaction of such a highly sterically hindered carboxylic acid.
(1) カルボン酸から酸ハライドに導き、さらにア
ルコールと反応させる。(1) Deriving acid halide from carboxylic acid and further reacting with alcohol.
(2) 強酸の存在下にエチレン等のオレフインと反
応させる。(2) React with olefin such as ethylene in the presence of a strong acid.
(3) カルボン酸のアルカリ金属塩とアルキルハラ
イドとを反応させる。(3) Reacting an alkali metal salt of a carboxylic acid with an alkyl halide.
(4) アセトン溶媒中でカルボン酸と硫酸ジアルキ
ルとを塩基の存在下に反応させる。(4) A carboxylic acid and a dialkyl sulfate are reacted in the presence of a base in an acetone solvent.
(1)の方法では、酸ハライドを合成するに当つて
塩化チオニル、三塩化リン、五塩化リン等の取り
扱いにくいハライドを用いなければならず、また
生成した酸ハライドも水分に極めて敏感であり取
扱いの上の問題が大きい。(2)の方法では低級アル
キルエステルを製造するにはエチレン等を高圧容
器中で反応させなければならず設備上問題があ
る。(3)の方法は一般的には極性の高い特殊な溶媒
（DMSO、DMF等）を用い、これも取扱いにくい
低級アルキルハライドを用いなければならず溶媒
の回収に問題が多い。(4)の方法はこれらのなかで
最も問題が少いように見えるが、一般には多量の
セトン溶媒を用いなければ生成してくるモノアル
キル硫酸アルカリ金属塩の析出が著るしく、撹拌
が困難となるといつた問題点がある。本発明者ら
はこの点を考慮して鋭意検討した結果、アセトン
等の溶媒を用いずにカルボン酸（）と硫酸ジア
ルキルとをアルカリ水溶液と接触させながら反応
させれば、反応中に系の撹拌が困難となることも
なく高収率でカルボン酸エステル（）が得ら
れ、しかも有機溶媒を使用していないので後処理
が容易であり、副反応生成物の量が極めて少いと
いうことを見出し本発明を完成した。 In method (1), halides that are difficult to handle such as thionyl chloride, phosphorus trichloride, and phosphorus pentachloride must be used to synthesize acid halides, and the produced acid halides are also extremely sensitive to moisture and cannot be handled easily. The above problem is a big one. In method (2), in order to produce lower alkyl esters, ethylene, etc. must be reacted in a high-pressure container, which poses problems in terms of equipment. Method (3) generally uses a special highly polar solvent (DMSO, DMF, etc.), which also requires the use of lower alkyl halides, which are difficult to handle, and there are many problems in recovering the solvent. Method (4) seems to have the least problems among these, but in general, unless a large amount of setone solvent is used, the precipitation of monoalkyl sulfate alkali metal salt is significant, making stirring difficult. Then, there is a problem. The inventors of the present invention have conducted extensive studies with this point in mind, and have found that if the carboxylic acid () and dialkyl sulfate are allowed to react while contacting with an aqueous alkali solution without using a solvent such as acetone, stirring of the system will occur during the reaction. It was discovered that the carboxylic acid ester (2) can be obtained in high yield without any difficulty, and since no organic solvent is used, post-treatment is easy, and the amount of side reaction products is extremely small. The invention has been completed.
本発明で使用される硫酸ジアルキルとしては、
炭素数１、２、３のアルキル基を有する硫酸ジア
ルキルである。具体的には、硫酸ジメチル、硫酸
ジエチル、硫酸ジｎ−プロピル、硫酸ジｉ−プロ
ピルが挙げられる。また本発明で使用されるアル
カリ水溶液としては、アルカリ金属水酸化物又は
アルカリ金属炭酸塩が挙げられ、アルカリ金属と
してはナトリウム、カリウムが最も適当である。
アルカリ水溶液はこれらのアルカリ物質の５〜50
％水溶液、好ましくは10〜30％水溶液とするのが
適当である。硫酸ジアルキルはカルボン酸（）
１モに対して1.0〜2.0モル、特に1.0〜1.4モル程
度使用し、またアルカリ物質はカルボン酸（）
１モルに対して約0.2〜３モル、常に0.4〜1.5モル
程度使用するのが適当である。 The dialkyl sulfate used in the present invention includes:
It is a dialkyl sulfate having an alkyl group having 1, 2, or 3 carbon atoms. Specific examples include dimethyl sulfate, diethyl sulfate, di-n-propyl sulfate, and di-i-propyl sulfate. Further, examples of the aqueous alkali solution used in the present invention include alkali metal hydroxides or alkali metal carbonates, and the most suitable alkali metals are sodium and potassium.
Alkaline aqueous solution contains 5 to 50 of these alkaline substances.
% aqueous solution, preferably 10-30% aqueous solution. Dialkyl sulfate is a carboxylic acid ()
Use 1.0 to 2.0 mol, especially 1.0 to 1.4 mol per mol, and the alkaline substance is carboxylic acid ()
It is appropriate to use about 0.2 to 3 moles per mole, always about 0.4 to 1.5 moles.
反応はカルボン（）と硫酸ジアルキルとの混
合溶液中にアルカリ水溶液を滴下するのが良い
が、このアルカリ水溶液を２回以上に分割して添
加し、１回滴下し適当時間反応させた後に水層を
抜き取る操作を繰り返すことによつてカルボン酸
エステルの収率を上げることができることがわか
つた。この理由は、反応系中の水はアルカリを溶
解させると共に生成するモノアルキル硫酸アルカ
リ金属塩を溶解する役割を果たしているが、同時
に反応剤たる硫酸ジアルキルを分解する役目も果
たして収率の向上を阻害しているが、これを適当
に反応系外へ抜き出してやれば硫酸ジアルキルの
分解が抑えられるためであろうと考えられる。ア
ルカリ水溶液は２回、３回、４回と分けて添加す
る回数を多くするほど収率は向上するがあまり回
数を多くすると操作が煩雑となるので10回程度ま
でが適切である。また回数を多くする代りに連続
的にアルカリ水溶液を滴下すると共に連続的に水
層のみを抜き出すこともできる。例えば下記の実
施例に示すように（カルボン酸（）１モルあた
り硫酸ジエチル1.1モル、苛性ソーダ1.1モルの条
件下でアルカリ水溶液を１回で添加した場合のカ
ルボン酸エチルエステルの単離収率（精製後）は
81％であるのに対し、２回に分けて添加した場合
の単離収率は90％、４回に分けて添加した場合の
単離収率は93％であつた。 The reaction is preferably carried out by dropping an alkaline aqueous solution into a mixed solution of carvone () and dialkyl sulfate, but this alkaline aqueous solution is added in two or more portions, and once dropped and reacted for an appropriate time, the aqueous layer is removed. It has been found that the yield of carboxylic acid ester can be increased by repeating the extraction operation. The reason for this is that water in the reaction system plays the role of dissolving the alkali and the alkali metal salt of monoalkyl sulfate that is produced, but at the same time it also plays the role of decomposing the dialkyl sulfate that is the reactant, inhibiting the improvement of the yield. However, this is thought to be because decomposition of dialkyl sulfate can be suppressed if this is properly extracted out of the reaction system. The yield improves as the number of times the aqueous alkali solution is added twice, three times, or four times is increased, but if the number of times is too large, the operation becomes complicated, so it is appropriate to add the aqueous solution up to about 10 times. Alternatively, instead of increasing the number of times, the alkaline aqueous solution can be dropped continuously and only the aqueous layer can be extracted continuously. For example, as shown in the example below, the isolated yield of carboxylic acid ethyl ester (purification After) is
The isolated yield was 81%, whereas the isolated yield when added in two portions was 90%, and the isolated yield when added in four portions was 93%.
本発明方法によれば(イ)反応を無溶媒で行うこと
ができるため、反応終了後に水層と有機層に分け
て有機層を蒸留するだけで純粋なカルボン酸エス
テル（）を得ることができ、後処理が極めて容
易になる、(ロ)反応中に不溶物が析出することがな
く円滑な撹拌を行うことができる、(ハ)単離収率で
80％以上、特に２回以上に分割してアルカリ水溶
液を滴下した場合には90％以上の商業的に実施し
得る高収率で目的物が得られる等の効果がある。 According to the method of the present invention, (a) since the reaction can be carried out without a solvent, pure carboxylic acid ester (2) can be obtained by simply separating the aqueous layer and the organic layer after the reaction and distilling the organic layer. , post-treatment becomes extremely easy, (b) smooth stirring can be performed without precipitation of insoluble matter during the reaction, and (c) isolated yield is high.
When the alkaline aqueous solution is added dropwise in two or more portions, the desired product can be obtained with a commercially viable yield of 80% or more, particularly 90% or more.
なお本発明の出発物質たるカルボン酸（）は
合成化学上興味あるものとして（H.Koch and
W.Haaf、Ann.638、111（1960））、また抗ウイル
ス剤製造の中間体として（特開昭53−82765）そ
れぞれ既知の化合物であり、これにはエンド及び
エキソの異性体があるが、その単独又は混合物の
いずれの場合でも本発明を適用することができ
る。以下に本発明を実施例を挙げて説明する。 The starting material of the present invention, carboxylic acid (), is considered to be of interest in terms of synthetic chemistry (H. Koch and
W. Haaf, Ann. 638 , 111 (1960)) and as an intermediate in the production of antiviral agents (Japanese Patent Application Laid-open No. 53-82765). It has endo and exo isomers. The present invention can be applied to either one or a mixture thereof. The present invention will be explained below by giving examples.
実施例 １
トリシクロ〔５・２・１・０2、6〕デカン−２
−カルボン酸（エンドとエキソの混合物）90.0ｇ
（0.5モル）と硫酸ジエチル84.8ｇ（0.55モル）の
混合物を50℃で撹拌しながら20％水酸化ナトリウ
ム水溶液110ｇ（0.55モル）を２時間かけて滴下
し、滴下後30分間その温度で撹拌を続けた。撹拌
終了後、室温でしばらく静置した後、分層し、蒸
留すれば、トリシクロ〔５・２・１・０2、6〕デ
カン−２−カルボン酸エチルの精製品84.2ｇ（収
率81％）が得られた。これらを分留すれば特願昭
55−32434の実施例７と同様にエキソ−トリシク
ロ〔５・２・１・０2、6〕デカン−エンド−２−
カルボン酸エチルとエンド−トリシクロ〔５・
２・１・０2、6〕デカン−エキソ−２−カルボン
酸エチルの混合物であつた。Example 1 Tricyclo[5.2.1.0 2 , 6 ]decane-2
-Carboxylic acid (mixture of endo and exo) 90.0g
(0.5 mol) and 84.8 g (0.55 mol) of diethyl sulfate were stirred at 50°C, and 110 g (0.55 mol) of a 20% aqueous sodium hydroxide solution was added dropwise over 2 hours. After the dropwise addition, stirring was continued at that temperature for 30 minutes. continued. After stirring, leave for a while at room temperature, separate the layers, and distill to obtain 84.2 g of purified ethyl tricyclo[5.2.1.0 2 , 6 ] decane-2-carboxylate (yield: 81%). )was gotten. If these are fractionated,
Similar to Example 7 of 55-32434, exo-tricyclo[5.2.1.0 2 , 6 ]decane-endo-2-
Ethyl carboxylate and endo-tricyclo[5.
2.1.0 2 , 6 ] was a mixture of ethyl decane-exo-2-carboxylate.
実施例 ２
トリシクロ〔５・２・１・０2、6〕デカン−２
−カルボン酸（エンドとエキソの混合物）90.0ｇ
（0.5モル）と硫酸ジエチル84.8ｇ（0.55モル）の
混合物を50℃で撹拌しながら20％水酸化ナトリウ
ム水溶液55.0ｇ（0.275モル）を１時間かけて滴
下し、滴下終了後30分間その温度で撹拌を続け
た。撹拌を止め、室温でしばらく静置した後、下
の水層を抜き取り、再び50℃に昇温して撹拌しな
がらさらに20％水酸化ナトリウム水溶液55.0ｇ
（0.275モル）を１時間かけて滴下し、滴下終了後
30分間その温度で撹拌した後、未反応の硫酸ジエ
チルを分解するため、20％水酸化ナトリウム水溶
液16.5ｇ（0.0825モル）を加え、100℃で45分間
撹拌する。放冷後分層して蒸留すればトリシクロ
〔５・２・１・０2、6〕デカン−２−カルボン酸
エチルの精製品93.6ｇ（収率90.0％）が得られ
た。Example 2 Tricyclo[5.2.1.0 2 , 6 ]decane-2
-Carboxylic acid (mixture of endo and exo) 90.0g
55.0 g (0.275 mol) of a 20% aqueous sodium hydroxide solution was added dropwise to a mixture of (0.5 mol) and 84.8 g (0.55 mol) of diethyl sulfate while stirring at 50°C over 1 hour. Stirring was continued. Stop stirring, let it stand for a while at room temperature, then remove the lower aqueous layer, raise the temperature to 50°C again, and add 55.0 g of 20% sodium hydroxide aqueous solution while stirring.
(0.275 mol) was added dropwise over 1 hour, and after the completion of dropping
After stirring at that temperature for 30 minutes, 16.5 g (0.0825 mol) of a 20% aqueous sodium hydroxide solution is added to decompose unreacted diethyl sulfate, and the mixture is stirred at 100° C. for 45 minutes. After cooling, the mixture was separated into layers and distilled to obtain 93.6 g (90.0% yield) of purified ethyl tricyclo[5.2.1.0 2 , 6 ]decane-2-carboxylate.
実施例 ３
実施例２で使用したカルボン酸90.0ｇ（0.5モ
ル）に対して20％水酸化ナトリウム水溶液110ｇ
（0.55モル）を４回に分けて実施例２と同様にし
て滴下し、処理すれば、トリシクロ〔５・２・
１・０2、6〕デカン−２−カルボン酸エチルの精
製品96.7ｇ（収率93％）が得られた。Example 3 110 g of 20% aqueous sodium hydroxide solution for 90.0 g (0.5 mol) of the carboxylic acid used in Example 2
(0.55 mol) was added dropwise in 4 portions in the same manner as in Example 2.
1.0 2 , 6 ] 96.7 g of purified ethyl decane-2-carboxylate (yield 93%) was obtained.
実施例 ４
実施例２の硫酸ジエチルの代りに硫酸ジメチル
0.55モルを用いて反応させ、トリシクロ〔５・
２・１・０2、6〕デカン−２−カルボン酸メチル
の精製品が91％の収率で得られた。Example 4 Dimethyl sulfate instead of diethyl sulfate in Example 2
The reaction was carried out using 0.55 mol of tricyclo[5.
2.1.0 2 , 6 ] A purified product of methyl decane-2-carboxylate was obtained in a yield of 91%.
実施例 ５
実施例３の硫酸ジエチルの代りに硫酸ジメチル
0.55モルを用いて反応させ、トリシクロ〔５・
２・１・０2、6〕デカン−２−カルボン酸メチル
の精製品が92.5％の収率で得られた。Example 5 Dimethyl sulfate instead of diethyl sulfate in Example 3
The reaction was carried out using 0.55 mol of tricyclo[5.
2.1.0 2 , 6 ] A purified product of methyl decane-2-carboxylate was obtained in a yield of 92.5%.
Claims (1)
カン−２−カルボン酸をエステル化して式
（）； （式中Ｒは炭素数１〜３のアルキル基を示す）で
示されるトリシクロ〔５・２・１・０2、6〕デカ
ン−２−カルボン酸エステルを製造するに当た
り、カルボン酸（）とアルキル基の炭素数が１
〜３の硫酸ジアルキルとをアルカリ水溶液に接触
させながら反応させることを特徴とする三環式カ
ルボン酸エステルの製造法。 ２ カルボン酸（）と硫酸ジアルキルとの混合
溶液中へ、アルカリ水溶液を２回以上に分けて滴
下し、１回ごとに水層を抜き取る特許請求の範囲
第１項記載の三環式カルボン酸エステルの製造
法。 ３ アルカリ水溶液がアルカリ金属水酸化物又は
アルカリ金属炭酸塩の水溶液である特許請求の範
囲第１項又は第２項記載の三環式カルボン酸エス
テルの製造法。[Claims] 1 Formula (); Tricyclo[5.1.1.0 2 , 6 ]decane-2-carboxylic acid represented by the formula () is esterified; In producing tricyclo[5.2.1.0 2 , 6 ]decane-2-carboxylic acid ester represented by the formula (R represents an alkyl group having 1 to 3 carbon atoms), carboxylic acid () and alkyl The number of carbon atoms in the group is 1
A method for producing a tricyclic carboxylic acid ester, which comprises reacting the dialkyl sulfate of 3 to 3 while bringing it into contact with an aqueous alkali solution. 2. The tricyclic carboxylic acid ester according to claim 1, wherein the aqueous alkali solution is dropped into a mixed solution of carboxylic acid () and dialkyl sulfate in two or more portions, and the aqueous layer is extracted each time. manufacturing method. 3. The method for producing a tricyclic carboxylic acid ester according to claim 1 or 2, wherein the aqueous alkali solution is an aqueous solution of an alkali metal hydroxide or an alkali metal carbonate.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17424780A JPS5798240A (en) | 1980-12-10 | 1980-12-10 | Preparation of tricyclic carboxylate |
| US06/239,896 US4411828A (en) | 1980-03-14 | 1981-03-03 | Fragrant tricyclic carboxylates |
| CH1521/81A CH652593A5 (en) | 1980-03-14 | 1981-03-06 | ESTERS OF TRICYCLE CARBOXYLIC ACID, PROCEDURE FOR THEIR PREPARATION AND USE IN PERFUME COMPOSITIONS. |
| CH1522/81A CH654204A5 (en) | 1980-03-14 | 1981-03-06 | PERFUME COMPOSITIONS AND PROCEDURE FOR THEIR PREPARATION. |
| US06/241,855 US4374052A (en) | 1980-03-14 | 1981-03-09 | Perfume composition |
| DE3108867A DE3108867C2 (en) | 1980-03-14 | 1981-03-09 | Perfume composition and process for making the same |
| DE3108868A DE3108868C2 (en) | 1980-03-14 | 1981-03-09 | Exo- and / or endo-tricyclo [5.2.1.0 → 2 → →, → → 6 →] decane-2-carboxylic acid esters, process for their preparation and perfume compositions containing them |
| FR8104884A FR2478084B1 (en) | 1980-03-14 | 1981-03-11 | NOVEL ESTERS OF TRICYCLO ACID (5.2.1.02,6) DECANE-2-CARBOXYLIC, PROCESSES FOR THEIR PREPARATION AND THEIR USE IN PERFUMERY |
| FR8104885A FR2477874B1 (en) | 1980-03-14 | 1981-03-11 | FRICTIONAL COMPOSITION BASED ON TRICYCLO (5.2.1.0.2,6) METHANE DECANE-2-CARBOXYLATE AND PROCESS FOR PREPARING THE SAME |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17424780A JPS5798240A (en) | 1980-12-10 | 1980-12-10 | Preparation of tricyclic carboxylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5798240A JPS5798240A (en) | 1982-06-18 |
| JPS6253499B2 true JPS6253499B2 (en) | 1987-11-10 |
Family
ID=15975284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17424780A Granted JPS5798240A (en) | 1980-03-14 | 1980-12-10 | Preparation of tricyclic carboxylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5798240A (en) |
-
1980
- 1980-12-10 JP JP17424780A patent/JPS5798240A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5798240A (en) | 1982-06-18 |
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