JP2010536802A - シクロプロパン化方法 - Google Patents
シクロプロパン化方法 Download PDFInfo
- Publication number
- JP2010536802A JP2010536802A JP2010521276A JP2010521276A JP2010536802A JP 2010536802 A JP2010536802 A JP 2010536802A JP 2010521276 A JP2010521276 A JP 2010521276A JP 2010521276 A JP2010521276 A JP 2010521276A JP 2010536802 A JP2010536802 A JP 2010536802A
- Authority
- JP
- Japan
- Prior art keywords
- mmol
- dibromomethane
- cyclopropanation
- tert
- reagent
- 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.)
- Granted
Links
- 238000005888 cyclopropanation reaction Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 136
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 26
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000004795 grignard reagents Chemical group 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 12
- 239000000796 flavoring agent Substances 0.000 claims abstract description 4
- 235000019634 flavors Nutrition 0.000 claims abstract description 4
- 239000003205 fragrance Substances 0.000 claims abstract description 4
- GUDMZGLFZNLYEY-UHFFFAOYSA-N cyclopropylmethanol Chemical class OCC1CC1 GUDMZGLFZNLYEY-UHFFFAOYSA-N 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 44
- CQRPUKWAZPZXTO-UHFFFAOYSA-M magnesium;2-methylpropane;chloride Chemical group [Mg+2].[Cl-].C[C-](C)C CQRPUKWAZPZXTO-UHFFFAOYSA-M 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 25
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical class OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 19
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 15
- -1 2,2,5a, 7a-tetramethyldecahydro-1H-dicyclopropa [b, d] naphthalen-6a-yl Chemical group 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 150000001721 carbon Chemical group 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 claims description 4
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 230000029936 alkylation Effects 0.000 claims description 3
- 238000005804 alkylation reaction Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- KJIOYTCLMVWFEZ-UHFFFAOYSA-N 1-(2,2-dimethyl-6-bicyclo[4.1.0]heptanyl)ethanol Chemical compound CC1(C)CCCC2(C(O)C)C1C2 KJIOYTCLMVWFEZ-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- FNORHVDKJWGANC-UHFFFAOYSA-N undecan-4-ol Chemical compound CCCCCCCC(O)CCC FNORHVDKJWGANC-UHFFFAOYSA-N 0.000 claims description 2
- JTWAPXXPIVWBGT-UHFFFAOYSA-N 1-(2-ethylcyclopropyl)propan-2-ol Chemical compound CCC1CC1CC(C)O JTWAPXXPIVWBGT-UHFFFAOYSA-N 0.000 claims 1
- VGNSBDAOHLYXFB-UHFFFAOYSA-N 1-ethyl-4,5-dimethylbicyclo[3.1.0]hexan-4-ol Chemical compound CC1(O)CCC2(CC)C1(C)C2 VGNSBDAOHLYXFB-UHFFFAOYSA-N 0.000 claims 1
- OAKFACUIGQLOCA-UHFFFAOYSA-N [1-methyl-2-[(1,2,2-trimethyl-3-bicyclo[3.1.0]hexanyl)methyl]cyclopropyl]methanol Chemical compound OCC1(C)CC1CC1C(C)(C)C2(C)CC2C1 OAKFACUIGQLOCA-UHFFFAOYSA-N 0.000 claims 1
- NWFDYJDCSIHFAB-UHFFFAOYSA-M [Cl-].CCC(C)(C)[Mg+] Chemical compound [Cl-].CCC(C)(C)[Mg+] NWFDYJDCSIHFAB-UHFFFAOYSA-M 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000004615 ingredient Substances 0.000 abstract 1
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- 239000012230 colorless oil Substances 0.000 description 23
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 238000011403 purification operation Methods 0.000 description 15
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 13
- 238000000746 purification Methods 0.000 description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 150000001299 aldehydes Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- YGJQBLWTTSNBMC-UHFFFAOYSA-N cyclopropane;methanol Chemical compound OC.C1CC1 YGJQBLWTTSNBMC-UHFFFAOYSA-N 0.000 description 7
- 150000002576 ketones Chemical class 0.000 description 7
- 125000001979 organolithium group Chemical group 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 description 5
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical group 0.000 description 4
- 238000003818 flash chromatography Methods 0.000 description 4
- 150000004820 halides Chemical group 0.000 description 4
- 125000002734 organomagnesium group Chemical group 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 150000001298 alcohols Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910000103 lithium hydride Inorganic materials 0.000 description 3
- CZZBXVONHOLICJ-UHFFFAOYSA-N lithium;prop-2-en-1-olate Chemical compound [Li]OCC=C CZZBXVONHOLICJ-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- KZUFTCBJDQXWOJ-PLNGDYQASA-N (2r,4z)-4-hepten-2-ol Chemical compound CC\C=C/CC(C)O KZUFTCBJDQXWOJ-PLNGDYQASA-N 0.000 description 2
- WSTQLNQRVZNEDV-CSKARUKUSA-N (e)-4-methyldec-3-en-5-ol Chemical compound CCCCCC(O)C(\C)=C\CC WSTQLNQRVZNEDV-CSKARUKUSA-N 0.000 description 2
- FVCDMHWSPLRYAB-UHFFFAOYSA-N 2-ethenyl-2-methyloxirane Chemical compound C=CC1(C)CO1 FVCDMHWSPLRYAB-UHFFFAOYSA-N 0.000 description 2
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 2
- OGHGFNURIXNXEM-UHFFFAOYSA-N 3-isopropylcyclopentenone Natural products CC(C)C1=CC(=O)CC1 OGHGFNURIXNXEM-UHFFFAOYSA-N 0.000 description 2
- WRYLYDPHFGVWKC-UHFFFAOYSA-N 4-terpineol Chemical compound CC(C)C1(O)CCC(C)=CC1 WRYLYDPHFGVWKC-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 2
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical class C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 2
- 239000005792 Geraniol Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KXSDPILWMGFJMM-UHFFFAOYSA-N Sabinene hydrate Chemical compound CC1(O)CCC2(C(C)C)C1C2 KXSDPILWMGFJMM-UHFFFAOYSA-N 0.000 description 2
- 150000004808 allyl alcohols Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000010523 cascade reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 2
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 2
- 229940113087 geraniol Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012552 review Methods 0.000 description 2
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- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- HEABYOIMZKYUDC-IAMFDIQRSA-N (1r,5s)-1-hexyl-2-methylbicyclo[3.1.0]hexan-2-ol Chemical compound C1CC(O)(C)[C@@]2(CCCCCC)[C@@H]1C2 HEABYOIMZKYUDC-IAMFDIQRSA-N 0.000 description 1
- KXSDPILWMGFJMM-SMILAEQMSA-N (1s,5r)-4-methyl-1-propan-2-ylbicyclo[3.1.0]hexan-4-ol Chemical compound CC1(O)CC[C@]2(C(C)C)[C@H]1C2 KXSDPILWMGFJMM-SMILAEQMSA-N 0.000 description 1
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- 238000001311 chemical methods and process Methods 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- KXSDPILWMGFJMM-GUBZILKMSA-N cis-sabinene hydrate Natural products C([C@@]1(O)C)C[C@]2(C(C)C)[C@H]1C2 KXSDPILWMGFJMM-GUBZILKMSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000005100 correlation spectroscopy Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical group 0.000 description 1
- 150000001925 cycloalkenes Chemical group 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 150000002170 ethers Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 108700039708 galantide Proteins 0.000 description 1
- 238000005570 heteronuclear single quantum coherence Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- GRYDGXUVWLGHPL-UHFFFAOYSA-M magnesium;heptane;bromide Chemical compound [Mg+2].[Br-].CCCCCC[CH2-] GRYDGXUVWLGHPL-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000001174 methyl (E)-non-2-enoate Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- KXGYGLSAOVEXPN-UHFFFAOYSA-N pentane;hydrobromide Chemical compound Br.CCCCC KXGYGLSAOVEXPN-UHFFFAOYSA-N 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
式II
(i)1〜6個の炭素原子、好ましくは1個の炭素原子を有し、該炭素原子はプロトン化されているかまたは置換されており、該置換基はCα、Cβ、Cγの置換基のいずれかから選択される、飽和または不飽和の炭素鎖;および
(ii)CαとCβとを結合させる1つの共有結合
から選択される部分を表す;
および;
(b)Cα、Cβ、CγおよびQの全体または一部は、一緒にシクロアルキルまたはシクロアルケニル環を形成する;
に従って選択され、および
(c)Mはアルカリ金属、アルカリ土類金属またはアルカリ土類金属一ハロゲン化物(monohalide)である、
前記方法を提供する。
・2〜5(特に≦3)当量のジブロモメタン中のアリルアルコールを、エーテル溶媒中の2〜5(特に≦3)当量の第三(α−三置換)グリニャール試薬R3CMgXを10〜20℃にて(X=Cl、Br)ゆっくりと加えることによりシクロプロパン化する;
・2〜5(特に≦3)当量のジブロモメタンおよび2〜5(特に≦3)当量の第三(α−三置換)グリニャール試薬R3CMgXを、エーテル溶媒中のアリルアルコールに、分割して、または連続的に、しかし別個に加える。
この連続的な反応を受ける共役エステルの例には、以下の変化におけるものが含まれる:
b)(E)−シトラール(4g、24mmol)およびテトラヒドロフラン中の3Mの塩化メチルマグネシウム(8ml、24mmol)。
c)酢酸4,8−ジメチルノナ−3,7−ジエン−2−イル(V. K. Agarwal, T. K. Thappa, S. Agarwal, M. S. Mehra, K. L. Dhar, C. K. Atal, Indian Perfumer 27, 112-118, 1983)(5g、24mmol)およびテトラヒドロフラン中の3Mのメチルマグネシウムクロリド(19ml、60mmol)。
d)4,8−ジメチルノナ−3,7−ジエン−2−イルエチルカルボナート(J.-P. Barras, B. Bourdin, F. Schroeder, Chimia 60, 574 - 579, 2006)(6g、24mmol)およびテトラヒドロフラン中の3Mの塩化メチルマグネシウム(25ml、60mmol)。
18時間後の25℃における精製操作およびバルブ・ツー・バルブ蒸留により、3.3g(83%)の無色油(シン/アンチ=82:18)が得られ、その分析データはこの化合物について文献(Charette, A. B.; Lebel, H. J. Org. Chem. 60, 2966 - 2967, 1995)に記載されているものと同一である。
Claims (9)
- 式I:
式II
(a)Cα、Cβ、Cγは、プロトン化されているか、または3個の炭素原子すべてについて合計5つまでの置換基で置換されていてもよい炭素原子を表し、該置換基はアルキル、アルケニル、シクロアルキルおよびシクロアルケニル基からなる群から選択され;
およびQは、
(i)1〜6個の炭素原子、好ましくは1個の炭素原子を有し、当該炭素原子がプロトン化されているかまたは置換されており、当該置換基がCα、Cβ、Cγの置換基のいずれかから選択される、飽和または不飽和の炭素鎖;および
(ii)CαとCβとを結合させる1つの共有結合
から選択される部分を表す;
および;
(b)Cα、Cβ、CγおよびQの全体または一部は、一緒にシクロアルキルまたはシクロアルケニル環を形成する;
に従って選択され、ならびに
(c)Mはアルカリ金属、アルカリ土類金属またはアルカリ土類金属一ハロゲン化物である、
前記方法。 - シクロプロピルカルビノールの製造方法であって、アリルアルコラートの生成およびこのアリルアルコラートと(A)マグネシウム金属およびジブロモメタンならびに(B)ジブロモメタンおよび第三グリニャール試薬から選択される試薬系とのシクロプロパン化(ここで該シクロプロパン化はエーテル溶媒の存在下で行う)を含む、前記方法。
- Qが単結合を表し、アリルアルコールの置換が、以下の可能性(i)それらのα,γまたはβ,γ位において二置換されている、(ii)それらのα,β,γ位において三置換されている、(iii)α,β,γ,γ位において四置換されている、(iv)それらのα,α,β,γ,γ位において五置換されている、から選択される、請求項1に記載の方法。
- アルキル化およびシクロプロパン化を連続的な反応において行う、請求項1に記載の方法。
- エーテル溶媒が、THF、MTBEおよびジエチルエーテルからなる群から選択される、請求項1に記載の方法。
- 第三グリニヤール試薬がtert−ブチルマグネシウムクロリドまたは塩化tert−アミルマグネシウムである、請求項1に記載の方法。
- フレーバーまたはフレグランス成分の製造であって、アリルアルコラートを請求項1または2に記載の方法によりシクロプロパン化することを含む、前記製造。
- (1−メチル−2−(1,2,2−トリメチルビシクロ[3.1.0]−ヘキサ−3−イルメチル)シクロプロピル)メタノールの製造方法であって、2−エチル−4(2,2,3−トリメチルシクロペンチル−3−エニル)ブタ−2−エン−1−オールと、リチウム試薬ならびに次にマグネシウムおよびジブロモメタンとを、エーテル溶媒の存在下で反応させることを含む、前記方法。
- 以下の化合物:1−(2−エチルシクロプロピル)プロパン−2−オール;1−(5,5−ジメチル−ビシクロ[4.1.0]ヘプタン−1−イル)エタノール;ジスピロ[4.0.4.1]ウンデカン−4−オール;2,2,5a,7a−テトラメチルデカヒドロ−1H−ジシクロプロパ[b,d]ナフタレン−6a−イル)メタノール;5−エチル−1,2−ジメチルビシクロ[3.1.0]ヘキサン−2−オール。
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PCT/CH2008/000352 WO2009023980A1 (en) | 2007-08-21 | 2008-08-19 | Cyclopropanation process |
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WO2012105430A1 (ja) * | 2011-01-31 | 2012-08-09 | 小川香料株式会社 | 香料組成物 |
JP2014522395A (ja) * | 2011-05-25 | 2014-09-04 | ジボダン エス エー | フレグランス組成物および芳香製品における使用のためのテルペンアルコール |
JP6091028B1 (ja) * | 2015-11-11 | 2017-03-08 | 花王株式会社 | シクロプロパン化合物 |
Families Citing this family (6)
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GB0916363D0 (en) * | 2009-09-18 | 2009-10-28 | Givaudan Sa | Organic compounds |
US9296675B2 (en) * | 2013-03-12 | 2016-03-29 | Takasago International Corporation | Compound having cyclopropane ring, and flavor and/or fragrance composition containing same |
CN107848907A (zh) * | 2015-08-06 | 2018-03-27 | 国际香料和香精公司 | 取代烯烃的环丙烷化 |
US10584080B2 (en) | 2017-12-12 | 2020-03-10 | International Flavors & Fragrances Inc. | Cyclopropanation of substituted alkenes |
CN112920017B (zh) * | 2021-01-27 | 2022-09-02 | 格林生物科技股份有限公司 | 一种双环丙烷基衍生化合物的制备方法 |
WO2023232245A1 (en) | 2022-06-01 | 2023-12-07 | Symrise Ag | Fragrances with cyclopropyl structure |
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DE2517586A1 (de) | 1974-05-08 | 1975-11-20 | Hoffmann La Roche | Bicyclische verbindungen |
GB8729107D0 (en) * | 1987-12-14 | 1988-01-27 | Ici Plc | Chemical process |
ES2318571T3 (es) | 2004-12-24 | 2009-05-01 | Givaudan Sa | Proceso de ciclopropanacion. |
US7410942B2 (en) | 2005-02-24 | 2008-08-12 | International Flavors & Fragrances Inc. | Substituted 1-(2-ethyl-1-methyl-cyclopropyl)-one/ol derivatives |
GB0515926D0 (en) | 2005-08-03 | 2005-09-07 | Merck Sharp & Dohme | Chemical process |
WO2007117462A1 (en) | 2006-04-03 | 2007-10-18 | Flexitral, Inc. | Cyclopropanated aromachemicals |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2012105430A1 (ja) * | 2011-01-31 | 2012-08-09 | 小川香料株式会社 | 香料組成物 |
KR20140007419A (ko) * | 2011-01-31 | 2014-01-17 | 오가와코료 가부시키가이샤 | 향료 조성물 |
KR101711246B1 (ko) | 2011-01-31 | 2017-02-28 | 오가와코료 가부시키가이샤 | 향료 조성물 |
JP2014522395A (ja) * | 2011-05-25 | 2014-09-04 | ジボダン エス エー | フレグランス組成物および芳香製品における使用のためのテルペンアルコール |
JP6091028B1 (ja) * | 2015-11-11 | 2017-03-08 | 花王株式会社 | シクロプロパン化合物 |
WO2017082084A1 (ja) * | 2015-11-11 | 2017-05-18 | 花王株式会社 | シクロプロパン化合物 |
JP2017088552A (ja) * | 2015-11-11 | 2017-05-25 | 花王株式会社 | シクロプロパン化合物 |
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CN101784509A (zh) | 2010-07-21 |
US20110124924A1 (en) | 2011-05-26 |
BRPI0816237A2 (pt) | 2015-02-24 |
US8450533B2 (en) | 2013-05-28 |
MX2010001476A (es) | 2010-03-01 |
WO2009023980A1 (en) | 2009-02-26 |
CN101784509B (zh) | 2013-12-18 |
JP5442612B2 (ja) | 2014-03-12 |
EP2190803A1 (en) | 2010-06-02 |
GB0716232D0 (en) | 2007-09-26 |
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