JP2009196917A - Method for producing 1,3-dioxane - Google Patents
Method for producing 1,3-dioxane Download PDFInfo
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- JP2009196917A JP2009196917A JP2008038964A JP2008038964A JP2009196917A JP 2009196917 A JP2009196917 A JP 2009196917A JP 2008038964 A JP2008038964 A JP 2008038964A JP 2008038964 A JP2008038964 A JP 2008038964A JP 2009196917 A JP2009196917 A JP 2009196917A
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- dioxane
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- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- -1 aldehyde compound Chemical class 0.000 claims abstract description 56
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003377 acid catalyst Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 8
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000002250 absorbent Substances 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 9
- 230000018044 dehydration Effects 0.000 abstract description 7
- 238000010992 reflux Methods 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003205 fragrance Substances 0.000 description 16
- FTZILAQGHINQQR-UHFFFAOYSA-N 2-Methylpentanal Chemical compound CCCC(C)C=O FTZILAQGHINQQR-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 239000002453 shampoo Substances 0.000 description 4
- DASQRZJTRKBKPP-UHFFFAOYSA-N 5-butan-2-yl-2-(2,4-dimethylcyclohex-3-en-1-yl)-5-methyl-1,3-dioxane Chemical compound O1CC(C(C)CC)(C)COC1C1C(C)C=C(C)CC1 DASQRZJTRKBKPP-UHFFFAOYSA-N 0.000 description 3
- LODLFUCEWWWXPR-UHFFFAOYSA-N 5-methyl-2-pentan-2-yl-5-propyl-1,3-dioxane Chemical compound CCCC(C)C1OCC(C)(CCC)CO1 LODLFUCEWWWXPR-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006359 acetalization reaction Methods 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000000093 1,3-dioxanes Chemical class 0.000 description 2
- JVZZUPJFERSVRN-UHFFFAOYSA-N 2-methyl-2-propylpropane-1,3-diol Chemical compound CCCC(C)(CO)CO JVZZUPJFERSVRN-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000003287 bathing Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000007921 spray Substances 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
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- MSRXHJALEMAKGB-UHFFFAOYSA-N 2-butan-2-yl-2-methylpropane-1,3-diol Chemical compound CCC(C)C(C)(CO)CO MSRXHJALEMAKGB-UHFFFAOYSA-N 0.000 description 1
- NOJNKSAQZMVMFF-UHFFFAOYSA-N 3,4-dimethylcyclohex-3-ene-1-carbaldehyde Chemical compound CC1=C(C)CC(C=O)CC1 NOJNKSAQZMVMFF-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 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
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
Abstract
Description
本発明は調合香料原料として有用な１,３−ジオキサンの製造方法に関する。 The present invention relates to a method for producing 1,3-dioxane useful as a raw material for blended fragrances.
５, ５−ジアルキル置換１,３−ジオキサンは、調合香料原料として有用なことが知られている。例えば、非特許文献１には、５−メチル-５−プロピル−２−（１−メチルブチル）−１，３−ジオキサンがリグスター、カシュー様香気を有し、２−（２,４−ジメチル−３−シクロヘキセニル）−５−メチル−５−（１−メチルプロピル）−１，３−ジオキサンがパワフルで拡散性のあるドライ、ウッディアンバー香気を有していることが記載されている。これらの１,３−ジオキサンはアルデヒド化合物と１,３−ジオール化合物との脱水反応により製造することができるが、この反応は平衡反応であるため、高収率で脱水反応を行うためには脱水剤を添加したり、溶媒を用いた共沸脱水を行うことにより、反応により生成する水を反応系外に取り除くことが一般的であることが、非特許文献２に記載されている。また、例えば、特許文献１には２−メチルペンタナールと１,３−アルカンジオールとの反応で５−メチル−５−プロピル−２−（１−メチルブチル）−１，３−ジオキサンを製造する際に、脱水剤としてオルト蟻酸トリエチルエステルを使用する方法が開示されている。また、特許文献２には、２−（２,４−ジメチル−３−シクロヘキセニル）−５−メチル−５−（１−メチルプロピル）−１，３−ジオキサンをシクロヘキサンの共沸脱水により製造する方法が開示されている。 5,5-dialkyl-substituted 1,3-dioxane is known to be useful as a raw material for blended fragrances. For example, in Non-Patent Document 1, 5-methyl-5-propyl-2- (1-methylbutyl) -1,3-dioxane has a ligster and cashew-like odor, and 2- (2,4-dimethyl-3 -Cyclohexenyl) -5-methyl-5- (1-methylpropyl) -1,3-dioxane is described as having a powerful, diffusible dry, woody bar aroma. These 1,3-dioxanes can be produced by a dehydration reaction between an aldehyde compound and a 1,3-diol compound. However, since this reaction is an equilibrium reaction, dehydration is required to perform a dehydration reaction at a high yield. Non-Patent Document 2 describes that it is common to remove water generated by the reaction from the reaction system by adding an agent or performing azeotropic dehydration using a solvent. For example, Patent Document 1 discloses that when 5-methyl-5-propyl-2- (1-methylbutyl) -1,3-dioxane is produced by a reaction between 2-methylpentanal and 1,3-alkanediol. Discloses a method of using ortho formic acid triethyl ester as a dehydrating agent. In Patent Document 2, 2- (2,4-dimethyl-3-cyclohexenyl) -5-methyl-5- (1-methylpropyl) -1,3-dioxane is produced by azeotropic dehydration of cyclohexane. A method is disclosed.
本発明においては、アルデヒド化合物とジオール化合物とを反応させてアセタール化反応を行う際に、実質的にアルデヒド化合物、ジオール化合物及び酸触媒からなる混合物を反応させる。従って、脱水剤、溶媒等を実質的に使用しないため、反応槽内の容積を有効に利用して高い生産性で製造を行うことができる。また、アセタール化反応で一般に使用される還流や共沸脱水のための設備を用いることなく製造することができる。
すなわち、本発明は、一般に使用される溶媒や、還流、共沸脱水のための設備を用いることなく、高い生産性で効率的に、かつ高収率で１,３−ジオキサンを製造することができる、１,３−ジオキサンの製造方法を提供することを目的とする。
In the present invention, when an acetalization reaction is performed by reacting an aldehyde compound and a diol compound, a mixture substantially consisting of an aldehyde compound, a diol compound and an acid catalyst is reacted. Therefore, since a dehydrating agent, a solvent, and the like are not substantially used, the volume in the reaction tank can be effectively used to perform production with high productivity. Moreover, it can manufacture, without using the equipment for the recirculation | reflux and azeotropic dehydration generally used by acetalization reaction.
That is, the present invention can produce 1,3-dioxane with high productivity and high yield without using a commonly used solvent and equipment for refluxing and azeotropic dehydration. An object of the present invention is to provide a process for producing 1,3-dioxane.
実質的に、酸触媒、一般式（１） Substantially an acid catalyst, general formula (1)
で表されるアルデヒド化合物、及び一般式（２）
And an aldehyde compound represented by the general formula (2)
で表される１，３−ジオール化合物、からなる混合物を、反応中に生成する水を実質除去することなく反応させる、一般式(３)
A mixture comprising a 1,3-diol compound represented by general formula (3) is reacted without substantially removing water produced during the reaction:
で表される１,３−ジオキサンの製造方法、を提供するものである。
The manufacturing method of 1, 3- dioxane represented by these is provided.
本発明の製造方法によれば、上記一般式(１)で表されるアルデヒド化合物と、上記一般式(２)で表されるジオール化合物とを、酸触媒の存在下混合して、反応中に発生する水を実質除去することなく反応させることができる。従って、脱水剤も溶媒も実質的に使用しないために反応槽内の容積を有効に利用して高い生産性で製造を行うことができる。また、アセタール化反応で一般に使用される還流や共沸脱水のための設備も用いることなく、高い生産性で効率的に、かつ高収率で１,３−ジオキサンを製造することができる。 According to the production method of the present invention, the aldehyde compound represented by the general formula (1) and the diol compound represented by the general formula (2) are mixed in the presence of an acid catalyst, The reaction can be carried out without substantially removing the generated water. Therefore, since neither a dehydrating agent nor a solvent is used substantially, the volume in the reaction vessel can be effectively utilized to produce with high productivity. Further, 1,3-dioxane can be produced efficiently with high productivity and high yield without using the equipment for reflux and azeotropic dehydration generally used in the acetalization reaction.
本発明においては、実質的に、酸触媒、上記一般式（１）で表されるアルデヒド化合物、及び一般式（２）で表される１，３−ジオール化合物からなる混合物を、反応中に生成する水を実質除去することなく反応させることで上記式（３）で表わされる１,３−ジオキサンを製造することができる。 In the present invention, a mixture substantially comprising an acid catalyst, an aldehyde compound represented by the above general formula (1), and a 1,3-diol compound represented by the general formula (2) is generated during the reaction. The 1,3-dioxane represented by the above formula (3) can be produced by reacting water without substantially removing water.
上記一般式（１）で表されるアルデヒド化合物において、Ｒ1はメチル基または、Ｒ2と結合して６員環を形成しうる炭化水素基を表わす。Ｒ1がＲ2と結合して形成する６員環としては、例えば、シクロヘキサン、シクロヘキセン等が挙げられるが、得られる生成物の調香原料としての有用性の観点から、シクロヘキセンが好ましい。形成されるシクロヘキサンやシクロヘキセンなどの６員環は、無置換であっても良いし、合計炭素数１〜３の炭化水素基を置換基として有していてもよい。上記６員環を形成するＲ1で表わされる炭化水素基としては、例えば、ＣＨ2、ＣＨ3ＣＨ、ＣＨ3ＣＨ2ＣＨ、（ＣＨ3）2Ｃ等が挙げられるが、例えばＣＨ2である場合あるいは炭素数２以上の炭化水素基のうち１の炭素原子のみが６員環を構成する場合は、Ｒ1は別の１の炭素原子を介してＲ2と結合して６員環を形成することができる。本発明においては、反応性ならびに得られる生成物の調香原料としての有用性の観点から、Ｒ1としてはメチル基、または別の１の炭素原子を介してＲ2と結合して６員環を形成しうる炭化水素基の場合はＣＨ2またはＣＨ3ＣＨが好ましく、メチル基が特に好ましい。 In the aldehyde compound represented by the general formula (1), R 1 represents a methyl group or a hydrocarbon group capable of forming a 6-membered ring by bonding with R 2 . Examples of the 6-membered ring formed by combining R 1 with R 2 include cyclohexane and cyclohexene, and cyclohexene is preferred from the viewpoint of the usefulness of the resulting product as an aromatic material. The formed 6-membered ring such as cyclohexane or cyclohexene may be unsubstituted or may have a hydrocarbon group having 1 to 3 carbon atoms in total as a substituent. Examples of the hydrocarbon group represented by R 1 forming the 6-membered ring include CH 2 , CH 3 CH, CH 3 CH 2 CH, (CH 3 ) 2 C, and the like, for example, CH 2 . Or when only one carbon atom of a hydrocarbon group having 2 or more carbon atoms forms a 6-membered ring, R 1 is bonded to R 2 via another 1 carbon atom to form a 6-membered ring. can do. In the present invention, from the viewpoint of reactivity and usefulness of the resulting product as a fragrance raw material, R 1 is a methyl group or a 6-membered ring bonded to R 2 via another carbon atom. In the case of a hydrocarbon group capable of forming, CH 2 or CH 3 CH is preferred, and a methyl group is particularly preferred.
一般式（１）において、Ｒ2はメチル基またはＲ1と結合して６員環を形成しうる炭化水素基を示す。６員環を形成するＲ2で表わされる炭化水素基としては、例えば、ＣＨ2、ＣＨ、ＣＨ3ＣＨ、ＣＨ3Ｃ、ＣＨ3ＣＨ2ＣＨ、（ＣＨ3）2Ｃ等が挙げられる。本発明においては、反応性ならびに得られる生成物の調香原料としての有用性の観点から、Ｒ2としてはメチル基またはＲ1と結合して６員環を形成しうるＣＨまたはＣＨ3Ｃが好ましく、メチル基が特に好ましい。
また、Ｒ3としては水素原子またはメチル基が挙げられるが、反応性の観点から、水素原子が好ましい。
本発明において、一般式（１）で表されるアルデヒド化合物としては、Ｒ1とＲ2がメチル基でかつＲ3が水素原子である化合物、またはＲ1とＲ2が結合して炭化水素の６員環を形成しかつＲ3が水素原子である化合物が好ましく、反応性ならびに得られる１，３−ジオキサンの調香原料としての有用性の観点から、２−メチルペンタナールが特に好ましい。
In the general formula (1), R 2 represents a methyl group or a hydrocarbon group that can be bonded to R 1 to form a 6-membered ring. Examples of the hydrocarbon group represented by R 2 forming a 6-membered ring include CH 2 , CH, CH 3 CH, CH 3 C, CH 3 CH 2 CH, (CH 3 ) 2 C, and the like. In the present invention, from the viewpoint of reactivity and usefulness of the resulting product as a fragrance raw material, R 2 is CH or CH 3 C capable of forming a 6-membered ring by binding to a methyl group or R 1. A methyl group is preferred and a methyl group is particularly preferred.
R 3 includes a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint of reactivity.
In the present invention, as the aldehyde compound represented by the general formula (1), a compound in which R 1 and R 2 are methyl groups and R 3 is a hydrogen atom, or R 1 and R 2 are bonded to form a hydrocarbon. A compound in which a 6-membered ring is formed and R 3 is a hydrogen atom is preferred, and 2-methylpentanal is particularly preferred from the viewpoints of reactivity and usefulness as a perfuming raw material of 1,3-dioxane to be obtained.
一般式（２）で表わされる１，３−ジオール化合物において、Ｒ4はメチル基またはエチル基を示し、Ｒ5はメチル基、エチル基、プロピル基、イソプロピル基、ブチル基またはｓｅｃ−ブチル基を示す。反応性ならびに得られる１，３−ジオキサンの調香原料としての有用性の観点からは、Ｒ4としてはメチル基が好ましく、また、同様の観点から、Ｒ5としてはプロピル基、ｓｅｃ−ブチル基が好ましく、より好ましくは、プロピル基である。本発明においては、一般式（２）で表わされる１，３−ジオール化合物としては、調香原料としての有用性の観点から、Ｒ4がメチル基で、Ｒ5がプロピル基、イソプロピル基、ブチル基またはｓｅｃ−ブチル基である化合物が好ましく、Ｒ4がメチル基でＲ5がプロピル基またはｓｅｃ−ブチル基である化合物がより好ましく、Ｒ4がメチル基でＲ5がプロピル基である化合物が更に好ましい。 In the 1,3-diol compound represented by the general formula (2), R 4 represents a methyl group or an ethyl group, and R 5 represents a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a sec-butyl group. Show. From the viewpoint of reactivity and usefulness of the resulting 1,3-dioxane as a perfuming raw material, R 4 is preferably a methyl group, and from the same viewpoint, R 5 is a propyl group or sec-butyl group. Is more preferable, and a propyl group is more preferable. In the present invention, as the 1,3-diol compound represented by the general formula (2), R 4 is a methyl group, R 5 is a propyl group, isopropyl group, butyl, from the viewpoint of usefulness as a perfuming raw material. A compound in which R 4 is a methyl group and R 5 is a propyl group or a sec-butyl group, and a compound in which R 4 is a methyl group and R 5 is a propyl group. Further preferred.
本発明においては、１，３−ジオキサンは、実質的に、酸触媒、上記一般式（１）で表されるアルデヒド化合物、及び一般式（２）で表される１，３−ジオール化合物からなる混合物を反応させて得ることができる。すなわち、当該混合物は、実質的に、酸触媒、一般式（１）で表されるアルデヒド化合物、及び一般式（２）で表される１，３−ジオール化合物以外の物質、特に溶媒、水吸収剤などを実質含まないものである。本発明において「実質的に、酸触媒、上記一般式（１）で表されるアルデヒド化合物、及び一般式（２）で表される１，３−ジオール化合物からなる混合物」とは、該混合物が、「酸触媒、上記一般式（１）で表されるアルデヒド化合物、及び一般式（２）で表される１，３−ジオール化合物のみからなる混合物」はもちろん、「本質的に酸触媒、一般式（１）で表されるアルデヒド化合物、及び一般式（２）で表される１，３−ジオール化合物のみからなるが、これら以外の物質を、本発明の効果に実質的に影響を与えない範囲において含む混合物」も包含することを意味する。 In the present invention, 1,3-dioxane substantially comprises an acid catalyst, an aldehyde compound represented by the above general formula (1), and a 1,3-diol compound represented by the general formula (2). It can be obtained by reacting the mixture. That is, the mixture is substantially a substance other than the acid catalyst, the aldehyde compound represented by the general formula (1), and the 1,3-diol compound represented by the general formula (2), particularly a solvent, water absorption. It does not contain any agents. In the present invention, “substantially a mixture comprising an acid catalyst, an aldehyde compound represented by the above general formula (1), and a 1,3-diol compound represented by the general formula (2)” means that the mixture is , “An acid catalyst, an aldehyde compound represented by the above general formula (1), and a mixture consisting only of a 1,3-diol compound represented by the general formula (2)”, as well as “essentially an acid catalyst, Although it consists only of the aldehyde compound represented by Formula (1) and the 1,3-diol compound represented by General Formula (2), substances other than these do not substantially affect the effects of the present invention. It is meant to also include “a mixture comprising in scope”.
上記「本発明の効果に実質的に影響を与えない範囲」とは、本発明の効果、すなわち、高い生産性で効率的に、かつ高収率で１,３−ジオキサンを製造することができる点について明らかな影響を与えない範囲を意味する。従って、上記混合物は、例えば、溶媒、水吸収剤等についても、上記範囲内でこれらを含むことができる。
すなわち、本発明において「酸触媒、上記一般式（１）で表されるアルデヒド化合物、及び一般式（２）で表される１，３−ジオール化合物」の合計質量に対して、溶媒、水吸収剤などの合計含有量は５０質量％以下であることが好ましく、１０質量％以下であることがより好ましく、１質量％以下であることがさらに好ましい。
The above “range that does not substantially affect the effect of the present invention” means that the effect of the present invention, that is, 1,3-dioxane can be produced efficiently with high productivity and in high yield. It means a range that does not clearly affect the point. Therefore, the said mixture can contain these in the said range also about a solvent, a water absorber, etc., for example.
That is, in the present invention, with respect to the total mass of the “acid catalyst, the aldehyde compound represented by the general formula (1) and the 1,3-diol compound represented by the general formula (2)”, the solvent and water absorption The total content of the agent and the like is preferably 50% by mass or less, more preferably 10% by mass or less, and further preferably 1% by mass or less.
なお、上記溶媒としては、ヘキサン、シクロヘキサン、ヘプタン、ベンゼン、トルエン、キシレン、ジエチルエーテル、テトラヒドロフラン、ジメチルスルホキシド、塩化メチレン等を挙げることができ、水吸収剤としては、モレキュラーシーブスなどのゼオライト、硫酸ナトリウム、硫酸カルシウム、硫酸マグネシウムなどの金属塩、Ｎ，Ｎ’−ジシクロヘキシルカルボジイミドなどのカルボジイミド系化合物、オルソギ酸メチル、オルソギ酸エチルなどのオルソエステル等を挙げることができる。 Examples of the solvent include hexane, cyclohexane, heptane, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dimethyl sulfoxide, and methylene chloride. Examples of the water absorbent include zeolites such as molecular sieves, sodium sulfate, and the like. And metal salts such as calcium sulfate and magnesium sulfate, carbodiimide compounds such as N, N′-dicyclohexylcarbodiimide, and orthoesters such as methyl orthoformate and ethyl orthoformate.
本発明においては、反応に用いるアルデヒド化合物と１，３−ジオール化合物の混合比率は特に限定されないが、生産性の観点からアルデヒド化合物と１，３−ジオール化合物のモル比（アルデヒド化合物のモル数：１，３−ジオール化合物のモル数）で１：５〜５：１が好ましく、１：２〜２：１がより好ましく、１：１．５〜１．５：１が更に好ましい。
反応は、アルデヒド化合物と１，３−ジオール化合物を一括で混合して行うこともできるが、反応速度を制御するために、アルデヒド化合物中に１，３−ジオール化合物を添加しながら行うこともでき、また、１，３−ジオール化合物中にアルデヒド化合物を添加しながら行うこともできる。
In the present invention, the mixing ratio of the aldehyde compound and the 1,3-diol compound used in the reaction is not particularly limited, but from the viewpoint of productivity, the molar ratio of the aldehyde compound to the 1,3-diol compound (number of moles of aldehyde compound: The molar ratio of 1,3-diol compound is preferably 1: 5 to 5: 1, more preferably 1: 2 to 2: 1, and still more preferably 1: 1.5 to 1.5: 1.
The reaction can be carried out by mixing the aldehyde compound and the 1,3-diol compound at one time, but can also be carried out while adding the 1,3-diol compound to the aldehyde compound in order to control the reaction rate. Moreover, it can also carry out, adding an aldehyde compound in a 1, 3-diol compound.
反応に用いる酸触媒は特に限定されず、リン酸、硫酸、硝酸、塩酸、メタンスルホン酸、パラトルエンスルホン酸、リン酸二水素ナトリウム、リン酸カリウム、リン酸二水素カリウム、硫酸水素カリウム、硫酸水素ナトリウム、硫酸銅、硫酸鉄、塩化銅、塩化鉄、塩化アルミニウム、塩化スズ、塩化チタン、硝酸鉄、三フッ化ホウ素、アルミナなどをいずれも用いることができるが、反応活性の観点からは、リン酸、硫酸、メタンスルホン酸、パラトルエンスルホン酸が好ましい。用いる酸触媒の量は、特に限定されないが、同様の観点から、用いるアルデヒド化合物に対して０．０１〜２０質量％が好ましく、０．０５〜１０質量％がより好ましく、０．１〜５質量％がさらに好ましい。
反応温度は特に限定されないが、０〜１２０℃が好ましく、３０〜１００℃がさらに好ましい。
The acid catalyst used for the reaction is not particularly limited, and phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, methanesulfonic acid, paratoluenesulfonic acid, sodium dihydrogen phosphate, potassium phosphate, potassium dihydrogen phosphate, potassium hydrogen sulfate, sulfuric acid Sodium hydrogen, copper sulfate, iron sulfate, copper chloride, iron chloride, aluminum chloride, tin chloride, titanium chloride, iron nitrate, boron trifluoride, alumina, etc. can be used, but from the viewpoint of reaction activity, Phosphoric acid, sulfuric acid, methanesulfonic acid, and paratoluenesulfonic acid are preferred. The amount of the acid catalyst to be used is not particularly limited, but from the same viewpoint, 0.01 to 20% by mass is preferable, 0.05 to 10% by mass is more preferable, and 0.1 to 5% by mass with respect to the aldehyde compound to be used. % Is more preferable.
Although reaction temperature is not specifically limited, 0-120 degreeC is preferable and 30-100 degreeC is more preferable.
アルデヒド化合物と１，３−ジオール化合物との反応には、上記溶媒、水吸収剤と同様、本発明の効果に実質的に影響を与えない範囲において、フェノール系酸化防止剤、リン酸系酸化防止剤等の酸化防止剤を使用することができる。フェノール系酸化防止剤としては、モノフェノール系酸化防止剤、ビスフェノール系酸化防止剤、高分子型フェノール系酸化防止剤等が挙げられる。 In the reaction between the aldehyde compound and the 1,3-diol compound, as in the case of the above solvent and water absorbent, a phenolic antioxidant and a phosphoric acid antioxidant are used as long as the effects of the present invention are not substantially affected. An antioxidant such as an agent can be used. Examples of the phenolic antioxidant include a monophenolic antioxidant, a bisphenolic antioxidant, and a polymer type phenolic antioxidant.
上記の実質的に、酸触媒、一般式（１）で表されるアルデヒド化合物、及び一般式（２）で表される１，３−ジオール化合物からなる混合物を反応させて得られる前記式（３）で表わされる１,３−ジオキサンにおいて、Ｒ1〜Ｒ5の各々は前記一般式（１）及び一般式（２）について述べたＲ1〜Ｒ5の各々と同じである。本発明においては、式（３）で表わされる１,３−ジオキサンとして、調香原料としての有用性の観点から、Ｒ1、Ｒ2及びＲ4がいずれもメチル基であり、Ｒ3が水素原子であり、かつＲ5がプロピル基であるもの、またはＲ1とＲ2が結合して炭化水素の６員環を形成しかつＲ3が水素原子でありＲ4がメチル基でＲ5がプロピル基またはｓｅｃ−ブチル基であるものが好ましく、Ｒ1、Ｒ2及びＲ4がいずれもメチル基であり、Ｒ3が水素原子であり、かつＲ5がプロピル基であるものがより好ましい。 The above-mentioned formula (3) obtained by reacting a mixture of the acid catalyst, the aldehyde compound represented by the general formula (1), and the 1,3-diol compound represented by the general formula (2). in 1,3-dioxane represented by), each of R 1 to R 5 are the same as each of R 1 to R 5 described for the general formula (1) and the general formula (2). In the present invention, as 1,3-dioxane represented by the formula (3), R 1 , R 2 and R 4 are all methyl groups and R 3 is hydrogen from the viewpoint of usefulness as a perfuming raw material. An atom and R 5 is a propyl group, or R 1 and R 2 combine to form a hydrocarbon 6-membered ring, R 3 is a hydrogen atom, R 4 is a methyl group, and R 5 is A propyl group or a sec-butyl group is preferred, and R 1 , R 2, and R 4 are all methyl groups, R 3 is a hydrogen atom, and R 5 is a propyl group.
本発明の製造方法においては、実質的に、酸触媒、一般式（１）で表されるアルデヒド化合物、及び一般式（２）で表される１，３−ジオール化合物からなる混合物を、反応中に生成する水を実質除去することなく反応させる。従来、このような反応においては、収率等の観点から、反応中に生成する水を、水吸収剤の使用、あるいは溶媒存在下での共沸蒸留等の方法により除去しながら反応を行い、１,３−ジオキサンを製造することが通常であったが、本発明においては、そのような水の除去を行うことなく反応を行うことにより、高収率で１,３−ジオキサンを製造することができる。なお、本発明において、「実質除去することなく」とは、全く水を除去しない場合はもちろん、本発明の効果に実質的に影響を与えない範囲において、水の除去操作を行う場合を包含する趣旨である。 In the production method of the present invention, a mixture comprising an acid catalyst, an aldehyde compound represented by the general formula (1), and a 1,3-diol compound represented by the general formula (2) is substantially reacted. The reaction is carried out without substantially removing the water produced. Conventionally, in such a reaction, from the viewpoint of yield and the like, the reaction is performed while removing water generated during the reaction by using a water absorbent or by a method such as azeotropic distillation in the presence of a solvent, Although it was usual to produce 1,3-dioxane, in the present invention, 1,3-dioxane is produced in a high yield by carrying out the reaction without removing such water. Can do. In the present invention, “without substantially removing” includes not only removing water but also performing a water removing operation within a range that does not substantially affect the effect of the present invention. It is the purpose.
本発明の製造方法により得られた一般式（３）で表される１,３−ジオキサンは、単独で又は他の成分と組合せて、香水、石鹸、シャンプー、リンス、ボディーシャンプー、洗剤、化粧品、スプレー製品、芳香剤、入浴剤等の賦香成分として使用することができる。
すなわち、上記１,３−ジオキサンは、これを単独で又は２種以上を組み合わせて、通常用いられる他の香料成分や、所望組成の調合香料に配合して香料組成物を得ることができる。１,３−ジオキサンの配合量は、調合香料の種類、目的とする香気の種類及び香気の強さ等により異なるが、調合香料中に０．１〜９０質量％が好ましく、１〜４０質量％がより好ましい。
１,３−ジオキサンと組み合わせて用いることができる香料成分としては、炭化水素類、アルコール類、フェノール類、エステル類、カーボネート類、アルデヒド類、ケトン類、アセタール類（ただし、一般式（３）で表される１,３−ジオキサンを除く）、エーテル類、ニトリル類、カルボン酸類、ラクトン類等の天然精油や天然抽出物、合成香料を挙げることができる。
The 1,3-dioxane represented by the general formula (3) obtained by the production method of the present invention is a perfume, soap, shampoo, rinse, body shampoo, detergent, cosmetic, alone or in combination with other ingredients. It can be used as a fragrance component for spray products, fragrances, bathing agents and the like.
That is, the above 1,3-dioxane can be used alone or in combination of two or more, and blended with other commonly used fragrance components or blended fragrances having a desired composition to obtain a fragrance composition. The blending amount of 1,3-dioxane varies depending on the kind of the blended fragrance, the type of the target fragrance, the strength of the fragrance, and the like, but is preferably 0.1 to 90% by weight, and 1 to 40% by weight in the blended fragrance. Is more preferable.
Perfume ingredients that can be used in combination with 1,3-dioxane include hydrocarbons, alcohols, phenols, esters, carbonates, aldehydes, ketones, acetals (however, in general formula (3) And natural essential oils such as ethers, nitriles, carboxylic acids, and lactones, natural extracts, and synthetic fragrances.
以下に実施例等により、本発明を更に具体的に説明する。
実施例１
フラスコに２−メチル−２−プロピル−１，３−プロパンジオール１８５ｇ（１．４モル）と硫酸１ｇを入れて攪拌しながら加熱した。２−メチルペンタナール １８４ｇ（１．８モル）を滴下して、８０から９０℃で５.５時間反応を行った。得られた反応混合物中の５−メチル−５−プロピル−２−（１−メチルブチル）−１，３−ジオキサンの収率をガスクロマトグラフィーで分析した結果９９％であり、高い収率で目的物が得られた。
Hereinafter, the present invention will be described more specifically with reference to examples and the like.
Example 1
A flask was charged with 185 g (1.4 mol) of 2-methyl-2-propyl-1,3-propanediol and 1 g of sulfuric acid and heated with stirring. 184 g (1.8 mol) of 2-methylpentanal was added dropwise and reacted at 80 to 90 ° C. for 5.5 hours. The yield of 5-methyl-5-propyl-2- (1-methylbutyl) -1,3-dioxane in the obtained reaction mixture was analyzed by gas chromatography. was gotten.
実施例２
２−メチル−２−プロピル−１，３−プロパンジオール１８５ｇの代わりに２−ｓｅｃ−ブチル−２−メチル−１，３−プロパンジオール２０５ｇを、２−メチルペンタナール１８４ｇの代わりに２，４−ジメチル−３−シクロヘキセンカルバルデヒド２４９ｇを使用する以外は実施例１と同様に反応を行うことにより、５−ｓｅｃ−ブチル−２−（２，４−ジメチル−３−シクロヘキセニル）−５−メチル−１，３−ジオキサンが得られる。
Example 2
In place of 185 g of 2-methyl-2-propyl-1,3-propanediol, 205 g of 2-sec-butyl-2-methyl-1,3-propanediol was used, and in place of 184 g of 2-methylpentanal, 2,4- The reaction was conducted in the same manner as in Example 1 except that 249 g of dimethyl-3-cyclohexenecarbaldehyde was used, whereby 5-sec-butyl-2- (2,4-dimethyl-3-cyclohexenyl) -5-methyl- 1,3-dioxane is obtained.
本発明の製造方法により得られる１,３−ジオキサンは、香水、石鹸、シャンプー、リンス、ボディーシャンプー、洗剤、化粧品、スプレー製品、芳香剤、入浴剤等の賦香成分として好適に使用できる。 1,3-dioxane obtained by the production method of the present invention can be suitably used as a perfuming component for perfumes, soaps, shampoos, rinses, body shampoos, detergents, cosmetics, spray products, fragrances, bathing agents and the like.
Claims (6)
で表されるアルデヒド化合物、及び一般式（２）
で表される１，３−ジオール化合物、からなる混合物を、反応中に生成する水を実質除去することなく反応させる、一般式(３)
で表される１,３−ジオキサンの製造方法。 Substantially an acid catalyst, general formula (1)
And an aldehyde compound represented by the general formula (2)
A mixture comprising a 1,3-diol compound represented by general formula (3) is reacted without substantially removing water produced during the reaction:
The manufacturing method of 1, 3- dioxane represented by these.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140081034A1 (en) * | 2012-09-17 | 2014-03-20 | International Flavors & Fragrances Inc. | 5-sec-butyl-2-(2,4-dimethyl-cyclohex-3-enyl)-5-methyl-[1,3]dioxane and process for making the same |
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| JP2002234885A (en) * | 2000-12-04 | 2002-08-23 | Kao Corp | Method for producing acetal |
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| JPS56167614A (en) * | 1980-04-25 | 1981-12-23 | Henkel Kgaa | Use of substituted 2-(1-methylbutyl)-1,3-dioxane as perfume and perfume composition containing it |
| JP2002234886A (en) * | 2000-12-04 | 2002-08-23 | Kao Corp | Method for producing acetal |
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| JPN6012063853; ＭＡＺＥＴ，Ｍ．: 'Ｔｒａｎｓｐｏｓｉｔｉｏｎ ｎｅｏｐｅｎｔｙｌｉｑｕｅ ｄｅｓ ｐｒｏｐａｎｅｄｉｏｌｓ-１，３ ｄｉｓｕｂｓｔｉｔｕｅｓ ｅｎ ２， ｅｎ ｍｉｌｉｅｕ ａｃｉｄｅ，' Ｂｕｌｌｅｔｉｎ ｄｅ ｌａ Ｓｏｃｉｅｔｅ Ｃｈｉｍｉｑｕｅ ｄｅ Ｆｒａｎｃｅ Ｎｏ．１２, 1969, ｐ．４３０９-４３２１ * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140081034A1 (en) * | 2012-09-17 | 2014-03-20 | International Flavors & Fragrances Inc. | 5-sec-butyl-2-(2,4-dimethyl-cyclohex-3-enyl)-5-methyl-[1,3]dioxane and process for making the same |
| US9029576B2 (en) * | 2012-09-17 | 2015-05-12 | International Flavors & Fragrances Inc. | 5-sec-butyl-2-(2-4-dimethyl-cyclohex-3-enyl)-5-methyl-[1,3]dioxane and process for making the same |
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