JPS6234748B2 - - Google Patents
Info
- Publication number
- JPS6234748B2 JPS6234748B2 JP54123960A JP12396079A JPS6234748B2 JP S6234748 B2 JPS6234748 B2 JP S6234748B2 JP 54123960 A JP54123960 A JP 54123960A JP 12396079 A JP12396079 A JP 12396079A JP S6234748 B2 JPS6234748 B2 JP S6234748B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- anhydride
- saturated fatty
- cupric
- cyclic terpene
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 19
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 14
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 9
- 235000007586 terpenes Nutrition 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- -1 cyclic terpene ester Chemical class 0.000 claims description 8
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 6
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 6
- 239000005749 Copper compound Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 150000001880 copper compounds Chemical class 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 229940112669 cuprous oxide Drugs 0.000 claims description 4
- 238000006317 isomerization reaction Methods 0.000 claims description 4
- NDTYTMIUWGWIMO-UHFFFAOYSA-N perillyl alcohol Chemical compound CC(=C)C1CCC(CO)=CC1 NDTYTMIUWGWIMO-UHFFFAOYSA-N 0.000 claims description 4
- LCYXQUJDODZYIJ-UHFFFAOYSA-N pinocarveol Chemical compound C1C2C(C)(C)C1CC(O)C2=C LCYXQUJDODZYIJ-UHFFFAOYSA-N 0.000 claims description 4
- 229930006721 pinocarveol Natural products 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 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 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 229940076286 cupric acetate Drugs 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BKATZVAUANSCKN-GHMZBOCLSA-N [(1r,5s)-6,6-dimethyl-4-bicyclo[3.1.1]hept-3-enyl]methyl acetate Chemical compound C1[C@]2([H])C(COC(C)=O)=CC[C@@]1([H])C2(C)C BKATZVAUANSCKN-GHMZBOCLSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- BKATZVAUANSCKN-UHFFFAOYSA-N myrtenyl acetate Natural products CC(=O)OCC1=CCC2C(C)(C)C1C2 BKATZVAUANSCKN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 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
本発明は環状テルペンエステル、更に詳細には
エキソ二重結合を有する環状テルペンアルコール
より香料もしくは香料合成中間体として有用な環
状テルペンエステルを製造する方法に関する。
鎖状脂肪族アリルアルコールを、金属化合物の
存在下、有機酸中でエステル化と同時に異性化す
ることは公知（特開昭52−17410号）であり、ま
た第三級ビニルカルビノールを強酸の存在下、低
級アルカン酸及びその酸無水物との混合物中で室
温以下で反応させ、アリルエステルを製造する方
法（特公昭54−4928）も公知である。しかしなが
ら、下記反応式に示すように、エキソ二重結合を
有する環状テルペンアリルアルコールをエステル
化と同時に異性化することは、本発明者等の提案
（特開昭54−59254号）があるのである。
（式中、Ｒは水素または炭素数１〜４個のアルキ
ル基を表わす。）
しかしながら、上記提案の方法も反応収率、副
生成物の生成等で幾分の改良の余地を残してい
た。
本発明の目的は高反応収率にて副生成物の生成
を最少限として環状テルペンエステルを製造する
方法を提供することにある。
本発明によれば、銅化合物、白金塩素化物、及
び強酸からなる群より選択した触媒並びに低級飽
和脂肪酸無水物の存在下にエキソ二重結合を有す
る環状テルペンアルコールを低級飽和脂肪酸と加
熱反応させ、エステル化と異性化とを同時に行な
うことを特徴とする環状テルペンエステルの製造
方法が提供される。
本発明者等は提案の製造方法（特開昭54−
59254号）を改善すべく鋭意検討した結果、使用
する低級飽和脂肪酸に酸無水物を添加して反応を
行なう事により、その欠点が改良されることを見
出した。更に詳しくは、前記反応式に示した通
り、反応で生成する水分が原料の環状テルペンア
ルコールの脱水反応を促進させて、炭化水素類を
副生し、更に増加した水分が脂肪酸の濃度を希釈
させ、エステル化−異性化の速度を低下させるこ
とが反応経路（反応機構）の反応生成物の追跡調
査の結果明らかとなつた。故に、酸無水物を添加
して、反応で生成する水分と結合させる事によ
り、反応液を常に無水状態に保ち、上記欠点を改
善することが出来ることを見出したのである。
本発明の環状テルペンエステル類の製造に供さ
れる出発物質であるエキソ二重結合を有する環状
テルペンアルコール類としては、たとえばピノカ
ルベオール（式−）及びイソ−カルベオール
（式−）をあげることができる。
本発明にて使用する低級飽和脂肪酸無水物とし
ては無水酢酸、無水プロピオン酸、ｎ−または
iso−酪酸が好ましい。また、低級飽和脂肪酸と
しては酢酸、プロピオン酸、ｎ−またはiso酪酸
を用いることができる。低級飽和脂肪酸と無水物
とは必らずしも同一のものを用いねばならないわ
けではないが、たとえば無水酢酸を用いた場合に
は酢酸を用いる方が後処理の際都合がよいので好
ましい。
低級飽和脂肪酸及び低級飽和脂肪酸無水物の使
用量は原料の環状テルペンアルコールに対して飽
和脂肪酸が３〜10倍モル、酸無水物が２〜５倍モ
ル量が好ましい。また反応温度としては使用され
る低級飽和脂肪酸の沸点附近115゜〜165℃の範囲
で行なうのが好適である。
本件で使用する触媒は、銅化合物、白金塩素化
物及び強酸である。そして具体的に銅化合物とし
ては、例えば酸化第一銅、酸化第二銅、塩化第一
銅、塩化第二銅、硫酸第二銅、硫酸第二銅、酢酸
第一銅、酢酸第二銅等であり、また白金塩素化物
としては、例えば塩化白金酸、塩化第一白金、塩
化白金酸ソーダ、塩化白金酸カリウム等であり、
また強酸としてはイオン定数が１×10-4以上の強
酸、例えば硫酸、燐酸、メタンスルホン酸、ｐ−
トルエンスルホン酸等である。触媒の使用量とし
ては１〜５重量％の量にて添加するのが好まし
い。
次に本発明を以下の実施例について説明する。
実施例 １
撹拌機、還流冷却管、及び温度計を備えた容量
１の四つ口フラスコにピノカルベオール76ｇ
（0.5モル）、酢酸300ｇ（5.0モル）、無水酢酸127.5
ｇ（1.25モル）及び酸化第一銅3.8ｇを仕込ん
だ。撹拌しながら120〜125℃で５時間反応させ
た。反応終了後、反応液は先づ減圧下に酢酸−無
水酢酸を留去し、次で析出する触媒をロ別した。
残渣を蒸留して沸点72〜75℃／２mmHgのミルテ
ニルアセテートの留分68ｇを得た。
比較例 １
実施例１と同一の装置にピノカルベオール76ｇ
（0.5モル）、酢酸300ｇ（5.0モル）、及び酸化第一
銅3.8ｇを仕込んだ。撹拌しながら120〜125℃で
５時間反応させた。反応液の後処理は実施例１に
準じて処理し、残渣を蒸留して沸点72〜75℃／２
mmHgのミルテニルアセテートの留分48ｇを得
た。
実施例 ２〜９
実施例１と同様の手法により種々の環状テルペ
ンエステルを調製した。反応条件及び結果は表
に示す。
The present invention relates to a cyclic terpene ester, and more particularly to a method for producing a cyclic terpene ester useful as a fragrance or a fragrance synthesis intermediate from a cyclic terpene alcohol having an exo double bond. It is known that chain aliphatic allyl alcohol is esterified and simultaneously isomerized in an organic acid in the presence of a metal compound (Japanese Patent Application Laid-Open No. 17410/1983). A method (Japanese Patent Publication No. 54-4928) of producing allyl esters by reacting them at room temperature or below in a mixture with a lower alkanoic acid and its acid anhydride is also known. However, as shown in the reaction formula below, isomerization of a cyclic terpene allyl alcohol having an exo double bond at the same time as esterification has been proposed by the present inventors (Japanese Patent Laid-Open No. 54-59254). . (In the formula, R represents hydrogen or an alkyl group having 1 to 4 carbon atoms.) However, the above proposed method also leaves room for some improvement in terms of reaction yield, production of by-products, etc. An object of the present invention is to provide a method for producing cyclic terpene esters with a high reaction yield and with minimal production of by-products. According to the present invention, a cyclic terpene alcohol having an exo double bond is thermally reacted with a lower saturated fatty acid in the presence of a catalyst selected from the group consisting of a copper compound, a platinum chloride, and a strong acid and a lower saturated fatty acid anhydride, Provided is a method for producing a cyclic terpene ester, characterized in that esterification and isomerization are carried out simultaneously. The present inventors have proposed a manufacturing method (Unexamined Japanese Patent Publication No.
No. 59254), and as a result of intensive studies, it was discovered that the drawbacks could be improved by adding an acid anhydride to the lower saturated fatty acids used and carrying out the reaction. More specifically, as shown in the reaction formula above, the water produced in the reaction accelerates the dehydration reaction of the cyclic terpene alcohol as a raw material, producing hydrocarbons as a by-product, and the increased water dilutes the concentration of fatty acids. As a result of a follow-up investigation of reaction products in the reaction route (reaction mechanism), it was revealed that the rate of esterification-isomerization was reduced. Therefore, the inventors have discovered that by adding an acid anhydride and binding it to the water produced in the reaction, the reaction solution can always be maintained in an anhydrous state and the above-mentioned drawbacks can be improved. Examples of the cyclic terpene alcohols having an exo double bond that are used as starting materials for producing the cyclic terpene esters of the present invention include pinocarveol (formula-) and iso-carveol (formula-). can. The lower saturated fatty acid anhydrides used in the present invention include acetic anhydride, propionic anhydride, n- or
Iso-butyric acid is preferred. Further, as the lower saturated fatty acid, acetic acid, propionic acid, n- or isobutyric acid can be used. Although the lower saturated fatty acid and the anhydride do not necessarily have to be the same, for example, when acetic anhydride is used, it is preferable to use acetic acid because it is more convenient for post-treatment. The amount of the lower saturated fatty acid and lower saturated fatty acid anhydride used is preferably 3 to 10 times the saturated fatty acid and 2 to 5 times the acid anhydride by mole relative to the cyclic terpene alcohol as the raw material. The reaction temperature is preferably within the range of 115° to 165°C, which is around the boiling point of the lower saturated fatty acid used. The catalysts used in this case are copper compounds, platinum chlorides and strong acids. Specific examples of copper compounds include cuprous oxide, cupric oxide, cuprous chloride, cupric chloride, cupric sulfate, cupric sulfate, cuprous acetate, cupric acetate, etc. Examples of platinum chlorides include chloroplatinic acid, platinum chloride, sodium chloroplatinate, potassium chloroplatinate, etc.
Examples of strong acids include strong acids with an ionic constant of 1 x 10 -4 or more, such as sulfuric acid, phosphoric acid, methanesulfonic acid, p-
Toluenesulfonic acid, etc. The amount of catalyst used is preferably 1 to 5% by weight. Next, the present invention will be explained with reference to the following examples. Example 1 76 g of pinocarveol in a 4-neck flask with a capacity of 1 equipped with a stirrer, reflux condenser, and thermometer.
(0.5 mol), acetic acid 300g (5.0 mol), acetic anhydride 127.5
(1.25 mol) and 3.8 g of cuprous oxide were charged. The reaction was carried out at 120 to 125°C for 5 hours while stirring. After the reaction was completed, acetic acid and acetic anhydride were first distilled off from the reaction solution under reduced pressure, and then the precipitated catalyst was filtered out.
The residue was distilled to obtain 68 g of myrtenyl acetate fraction with a boiling point of 72-75°C/2 mmHg. Comparative Example 1 76 g of pinocarveol was added to the same device as in Example 1.
(0.5 mol), 300 g (5.0 mol) of acetic acid, and 3.8 g of cuprous oxide were charged. The reaction was carried out at 120 to 125°C for 5 hours while stirring. The reaction solution was post-treated according to Example 1, and the residue was distilled to a boiling point of 72-75℃/2
48 g of myrtenyl acetate fraction of mmHg was obtained. Examples 2 to 9 Various cyclic terpene esters were prepared in the same manner as in Example 1. Reaction conditions and results are shown in the table.
【表】【table】
Claims (1)
群より選択した触媒並びに低級飽和脂肪酸無水物
の存在下にエキソ二重結合を有する環状テルペン
アルコールを低級飽和脂肪酸と加熱反応させ、エ
ステル化と異性化とを同時に行なうことを特徴と
する環状テルペンエステルの製造方法。 ２ エキソ二重結合を有する前記環状テルペンア
ルコールがピノカルベオール及びイソ−カルベオ
ールであることを特徴とする特許請求の範囲第１
項に記載の方法。 ３ 前記銅化合物を酸化第一銅、酸化第二銅、塩
化第一銅、塩化第二銅、硫酸第二銅、硝酸第二
銅、酢酸第一銅及び酢酸第二銅からなる群から選
択することを特徴とする特許請求の範囲第１項ま
たは第２項に記載の方法。 ４ 前記白金塩素化物を塩化白金酸、塩化第一白
金、塩化白金酸ソーダ及び塩化白金酸カリウムか
らなる群から選択することを特徴とする特許請求
の範囲第１項または第２項に記載の方法。 ５ 前記強酸を硫酸、リン酸、メタンスルホン酸
及びｐ−トルエンスルホン酸からなる群から選択
することを特徴とする特許請求の範囲第１項また
は第２項に記載の方法。 ６ 前記低級飽和脂肪酸とその酸無水物が酢酸−
無水酢酸、プロピオン酸−無水プロピオン酸、ｎ
−またはiso−酪酸−無水酪酸であり、その使用
量が原料環状テルペンアルコールに対し飽和脂肪
酸が３〜10倍モル、その酸無水物が２〜５倍モル
量で、反応温度が115〜165℃で反応を行なうこと
を特徴とする特許請求の範囲第１項に記載の方
法。[Claims] 1. A cyclic terpene alcohol having an exo double bond is heated to react with a lower saturated fatty acid in the presence of a catalyst selected from the group consisting of a copper compound, a platinum chloride, and a strong acid and a lower saturated fatty acid anhydride. , a method for producing a cyclic terpene ester, characterized by carrying out esterification and isomerization simultaneously. 2. Claim 1, wherein the cyclic terpene alcohol having an exo double bond is pinocarveol and iso-carveol.
The method described in section. 3. The copper compound is selected from the group consisting of cuprous oxide, cupric oxide, cuprous chloride, cupric chloride, cupric sulfate, cupric nitrate, cuprous acetate, and cupric acetate. A method according to claim 1 or 2, characterized in that: 4. The method according to claim 1 or 2, characterized in that the platinum chloride is selected from the group consisting of chloroplatinic acid, platinum chloride, sodium chloroplatinate, and potassium chloroplatinate. . 5. A method according to claim 1 or 2, characterized in that the strong acid is selected from the group consisting of sulfuric acid, phosphoric acid, methanesulfonic acid and p-toluenesulfonic acid. 6 The lower saturated fatty acid and its acid anhydride are acetic acid-
Acetic anhydride, propionic acid-propionic anhydride, n
- or iso-butyric acid - butyric anhydride, the amount of saturated fatty acid used is 3 to 10 times the molar amount of the raw material cyclic terpene alcohol, the acid anhydride is 2 to 5 times the molar amount, and the reaction temperature is 115 to 165 ° C. 2. A method according to claim 1, characterized in that the reaction is carried out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12396079A JPS5649339A (en) | 1979-09-28 | 1979-09-28 | Prepartion of cyclic terpene ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12396079A JPS5649339A (en) | 1979-09-28 | 1979-09-28 | Prepartion of cyclic terpene ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5649339A JPS5649339A (en) | 1981-05-02 |
| JPS6234748B2 true JPS6234748B2 (en) | 1987-07-28 |
Family
ID=14873589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12396079A Granted JPS5649339A (en) | 1979-09-28 | 1979-09-28 | Prepartion of cyclic terpene ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5649339A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10308278B4 (en) * | 2003-02-26 | 2007-07-05 | Dr. André Rieks, Labor für Enzymtechnologie GmbH | Antimicrobial agents against bacteria, yeasts and molds |
-
1979
- 1979-09-28 JP JP12396079A patent/JPS5649339A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5649339A (en) | 1981-05-02 |
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