JPH0346456B2 - - Google Patents
Info
- Publication number
- JPH0346456B2 JPH0346456B2 JP19556983A JP19556983A JPH0346456B2 JP H0346456 B2 JPH0346456 B2 JP H0346456B2 JP 19556983 A JP19556983 A JP 19556983A JP 19556983 A JP19556983 A JP 19556983A JP H0346456 B2 JPH0346456 B2 JP H0346456B2
- Authority
- JP
- Japan
- Prior art keywords
- peak
- group
- compound
- ethylidene
- multiplet
- 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
- -1 bicyclic methylol Chemical class 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 20
- 239000003205 fragrance Substances 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical group C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 32
- 150000001875 compounds Chemical class 0.000 description 32
- 239000007788 liquid Substances 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 238000009835 boiling Methods 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 7
- 239000002453 shampoo Substances 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MBZRJSQZCBXRGK-UHFFFAOYSA-N 4-tert-Butylcyclohexyl acetate Chemical compound CC(=O)OC1CCC(C(C)(C)C)CC1 MBZRJSQZCBXRGK-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 235000019501 Lemon oil Nutrition 0.000 description 4
- GUUHFMWKWLOQMM-NTCAYCPXSA-N alpha-hexylcinnamaldehyde Chemical compound CCCCCC\C(C=O)=C/C1=CC=CC=C1 GUUHFMWKWLOQMM-NTCAYCPXSA-N 0.000 description 4
- GUUHFMWKWLOQMM-UHFFFAOYSA-N alpha-n-hexylcinnamic aldehyde Natural products CCCCCCC(C=O)=CC1=CC=CC=C1 GUUHFMWKWLOQMM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000001926 citrus aurantium l. subsp. bergamia wright et arn. oil Substances 0.000 description 4
- 239000010501 lemon oil Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 description 3
- 239000001875 1-phenylethyl acetate Substances 0.000 description 3
- NFAVNWJJYQAGNB-UHFFFAOYSA-N 2-methylundecanal Chemical compound CCCCCCCCCC(C)C=O NFAVNWJJYQAGNB-UHFFFAOYSA-N 0.000 description 3
- MTDAKBBUYMYKAR-UHFFFAOYSA-N 3,7-dimethyloct-6-enenitrile Chemical compound N#CCC(C)CCC=C(C)C MTDAKBBUYMYKAR-UHFFFAOYSA-N 0.000 description 3
- HTLBMZKXJYNJSK-UHFFFAOYSA-N 3-naphthalen-2-yl-1,2-oxazol-5-amine Chemical compound O1C(N)=CC(C=2C=C3C=CC=CC3=CC=2)=N1 HTLBMZKXJYNJSK-UHFFFAOYSA-N 0.000 description 3
- HXQPUEQDBSPXTE-UHFFFAOYSA-N Diisobutylcarbinol Chemical compound CC(C)CC(O)CC(C)C HXQPUEQDBSPXTE-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 235000019502 Orange oil Nutrition 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- JKRWZLOCPLZZEI-UHFFFAOYSA-N alpha-Trichloromethylbenzyl acetate Chemical compound CC(=O)OC(C(Cl)(Cl)Cl)C1=CC=CC=C1 JKRWZLOCPLZZEI-UHFFFAOYSA-N 0.000 description 3
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 description 3
- 235000000484 citronellol Nutrition 0.000 description 3
- 239000001111 citrus aurantium l. leaf oil Substances 0.000 description 3
- JRUYYVYCSJCVMP-UHFFFAOYSA-N coumarin 30 Chemical compound C1=CC=C2N(C)C(C=3C4=CC=C(C=C4OC(=O)C=3)N(CC)CC)=NC2=C1 JRUYYVYCSJCVMP-UHFFFAOYSA-N 0.000 description 3
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 3
- XSNQECSCDATQEL-UHFFFAOYSA-N dihydromyrcenol Chemical compound C=CC(C)CCCC(C)(C)O XSNQECSCDATQEL-UHFFFAOYSA-N 0.000 description 3
- 229930008394 dihydromyrcenol Natural products 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000001299 ferula galbaniflua resinoid Substances 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- ONKNPOPIGWHAQC-UHFFFAOYSA-N galaxolide Chemical compound C1OCC(C)C2=C1C=C1C(C)(C)C(C)C(C)(C)C1=C2 ONKNPOPIGWHAQC-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000010502 orange oil Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000010668 rosemary oil Substances 0.000 description 3
- 229940058206 rosemary oil Drugs 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000002597 Solanum melongena Nutrition 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
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- SDQFDHOLCGWZPU-UHFFFAOYSA-N lilial Chemical compound O=CC(C)CC1=CC=C(C(C)(C)C)C=C1 SDQFDHOLCGWZPU-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VPKMGDRERYMTJX-CMDGGOBGSA-N 1-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-1-penten-3-one Chemical compound CCC(=O)\C=C\C1C(C)=CCCC1(C)C VPKMGDRERYMTJX-CMDGGOBGSA-N 0.000 description 1
- YBUIAJZFOGJGLJ-SWRJLBSHSA-N 1-cedr-8-en-9-ylethanone Chemical compound C1[C@]23[C@H](C)CC[C@H]3C(C)(C)[C@@H]1C(C)=C(C(C)=O)C2 YBUIAJZFOGJGLJ-SWRJLBSHSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OJOWICOBYCXEKR-UHFFFAOYSA-N 5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=CC)CC1C=C2 OJOWICOBYCXEKR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 240000007436 Cananga odorata Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 235000015164 Iris germanica var. florentina Nutrition 0.000 description 1
- 235000015265 Iris pallida Nutrition 0.000 description 1
- 244000050403 Iris x germanica Species 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 229940022663 acetate Drugs 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019568 aromas Nutrition 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- HRGPYCVTDOECMG-RHBQXOTJSA-N methyl cedryl ether Chemical compound C1[C@@]23[C@H](C)CC[C@H]2C(C)(C)[C@]1([H])[C@@](OC)(C)CC3 HRGPYCVTDOECMG-RHBQXOTJSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000010666 rose oil Substances 0.000 description 1
- 235000019719 rose oil Nutrition 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
- Cosmetics (AREA)
Description
本発明は新規な二環式メチロール誘導体ならび
にこれを含有する香料組成物に関する。
本発明者は、以前から、石油化学製品として入
手容易な次式()、
で表わされる2−エチリデンビシクロ〔2.2.1〕
ヘプト−5−エン(以下、「EBH」と略称する)
を原料として種々の誘導体を合成し、その有用性
を評価する研究を行つてきた。そして、その研究
の過程において、本発明者は、EBHをヒドロホ
ルミル化すると極めて高選択率かつ高収率で次式
()
で表わされる2−エチリデン−5(又は6)−ホル
ミルビシクロ〔2.2.1〕ヘプタン(以下、
「EFBH」と略称する)が得られること、並びに
これが優れた香気を有することを見出した(特願
昭57−94460号、同57−220886号、特開昭57−
142937号)。
また、EFBHの誘導体としては、次式()、
()及び()の化合物が香気を有し、賦香成
分として有用であることが知られている(特願昭
57−94460号、特開昭57−142933号、同58−32833
号)。
(式中、Rはメチル基又はエチル基を示す)
斯かる実情において、本発明者は、EFBHの誘
導体について更に鋭意研究を行つた結果、次の一
般式()、
(式中、ROCH2−基はノルボルナン環の5位
又は6位に置換し、Rは炭素数1〜6の直鎖又は
分岐鎖のアルキル基又は炭素数1〜7の直鎖又は
分岐鎖のアシル基を示し、点線は単結合又は二重
結合であることを示す)で表わされる二環式メチ
ロール誘導体、すなわち二環式メチロールのエス
テル又はエーテル化合物が優れた香気を有するこ
とを見出し、本発明を完成した。
従つて、本発明の目的は新規な()式で表わ
される二環式メチロール誘導体を提供せんとする
にある。本発明の他の目的は二環式メチロール誘
導体を含有する香料組成物を提供せんとするにあ
る。
式()において、置換基Rとしては、メチル
基、エチル基、プロピル基、イソプロピル基、n
−ブチル基、sec−ブチル基、tert−ブチル基、
n−アミル基、イソアミル基、sec−アミル基等
のアルキル基;ホルミル基、アセチル基、プロピ
オニル基、ブチリル基、イソブチリル基、n−ペ
ンタノイル基、sec−ペンタノイル基、tert−ペ
ンタノイル基、n−ヘキサノイル基、イソヘキサ
ノイル基、sec−ヘキサノイル基、tert−ヘキサ
ノイル基、n−ヘプタノイル基、ベンゾイル基等
のアシル基が挙げられる。
本発明化合物()は、例えば、次の反応式に
従つて2−エチリデン−5(又は6)−ヒドロキシ
メチルビシクロ〔2.2.1〕ヘプタン(a)又は
2−エチル−5(又は6)−ヒドロキシメチルビシ
クロ〔2.2.1〕ヘプタン(b)〔藤倉ら:特願昭
57−94460号〕を自体公知の方法でエステル又は
エーテル化することによつて容易に製造される。
(式中、Rは前記に同じ)
原料化合物(a)は、例えばEBH()にロ
ジウム触媒の存在下一酸化炭素及び水素を反応さ
せて2−エチリデン−5(又は6)−ホルミルビシ
クロ〔2.2.1〕ヘプタン()を製造し、次いで
()に金属水素化合物を反応させて製造される。
更に(a)に金属触媒の存在下水素を作用させ
ることにより原料化合物(b)が製造される
(特願昭57−94460号)。
本発明のエステル類を製造するには、自体よく
知られたエステル化法、すなわち(1)強酸の存在下
対応するカルボン酸とメチロール化合物(a,
b)を混合し、エステルとする方法、(2)(1)と同
様な条件下、水と共沸するベンゼン等の溶媒を加
え、共沸脱水によりエステル化する方法、(3)酸ハ
ライドもしくは酸無水物とメチロール化合物(
a,b)を反応させる方法によつて行なわれ
る。
また、エーテル類を製造するには、メチロール
化合物(a,b)をアルカリ金属又はアルカ
リ金属ハイドライドと反応させてアルカリ金属ア
ルコラート(アルカリ金属としては、Na,K)
とした後、これに目的とするエーテルに対応する
アルキルハライド(ハライドとしては、Br,I
が好ましい)を反応させ、エーテルとするウイリ
アムソンのエーテル合成法が簡便である。
また、本発明化合物()の内、点線が単結合
で表わされる飽和体(b)は、不飽和体(
a)を金属触媒の存在下水素化することによつて
も合成できる。この場合、水素化触媒としては、
通常オレフインの水素化反応に用いる触媒であれ
ばどれでも良い。例えば、ラネーニツケル、パラ
ジウム/活性炭、酸化白金等を用いる。
本発明化合物()において、エステル類は大
まかな区分によればハーバル様の香りに分類さ
れ、エーテル類はグリーンでハーバル様の香りに
分類され、両者とも優れた香気を有する。その用
途としては、高級な香料組成物、香水、石鹸、シ
ヤンプー、ヘアリンス、洗剤、化粧品、スプレ
ー、芳香剤等の賦香を必要とされるものに広汎に
使用できる。
以下に実施例を挙げて説明するが、本発明はこ
れらの実施例に限定されるものではない。
実施例 1
2−エチリデン−ビシクロ〔2.2.1〕ヘプト−
5(又は6)−イルメチルホルメート:
500mlナスフラスコに2−エチリデン−5(又は
6)−ヒドロキシメチルビシクロ〔2.2.1〕ヘプタ
ン(30.0g、0.197mol)、ギ酸(182.16g、
3.96mol)、濃硫酸(3.89g、0.0385mol)の順に
加え、この混合物を室温で1.5時間撹拌した。反
応後水(100ml)を加え、n−ヘキサン(100ml)
で3回抽出した。n−ヘキサン層を炭酸水素ナト
リウム飽和水溶液でアルカリ性になるまで洗浄
し、その後飽和食塩水(100ml)で1回洗浄した。
n−ヘキサン層を無水硫酸マグネシウム上で乾燥
し、濾別後、濃縮し、分留して上記化合物8.74g
(収率24.6%)を得た。このものはオリス様の香
りを有する無色透明液体であつた。
沸点:42.0〜43.0℃/0.05mmHg
元素分析(C11H16O2として)
計算値(%):C,73.30:H,8.95
実測値(%):C,73.54:H,8.90
IR(液膜,cm-1):2950,1720,1170
1H−NMR(CDCl3溶媒、TMS内部標準、
δ):
8.08(一重線、1H,HCO−)
5.24(複雑な多重線、1H,=CH−CH3)
3.98〜3.85(多重線、2H,−O−CH 2−CH
)
2.90〜1.00(複雑な多重線、12H)
MS(相対強度)
この化合物には少なくとも4種類の異性体が存
在するが、キヤピラリーカラム〔横河・ヒユーレ
ツト・パツカード(株)のPEG20Mフユーズドシリ
カ、カラム長50m〕を用いたガスマス測定の結果
を次に示す。
ピーク1(18%):180(M+,33),119(38),106
(43),105(43),93(100),92(38),91(65),
79(63),78(35),77(39)
ピーク2(62%):180(M+,34),119(42),106
(45),105(41),94(31),93(100),92(36),
91(68),79(60),77(38)
ピーク3(16%):180(M+,34),119(60),106
(34),105(40),94(39),93(100),92(36),
91(65),79(57),77(35)
ピーク4(4%):180(M+,29),119(54),106
(27),105(40),94(37),93(100),92(36),
91(61),79(58),77(35)
実施例 2
2−エチリデン−ビシクロ〔2.2.1〕ヘプト−
5(又は6)−イルメチルアセテート:
200mlナスフラスコに2−エチリデン−5(又は
6)−ヒドロキシメチルビシクロ〔2.2.1〕ヘプタ
ン(20.0g、0.131mol)、トリエチルアミン
(20.04g、0.198mol)、乾燥ベンゼン(130ml)を
加え、これに氷冷下でアセチルクロリド(12.40
g、0.158mol)の乾燥ベンゼン(20ml)溶液を
20分間で滴下した。滴下後、還流冷却器と塩化カ
ルシウム管をとりつけて、この混合物を室温で20
分間撹拌した後、100℃で1.5時間加熱還流した。
冷却後エーテル(250ml)を加え、水(200ml)で
2回、飽和炭酸水素ナトリウム水溶液(100ml)
で2回、最後に水(100ml)で2回洗浄した。エ
ーテル層を無水硫酸マグネシウム上で乾燥し、濾
別後、濃縮し、分留して上記化合物24.48g(収
率96.2%)を得た。このものはハーバル様、オリ
ス的な木香様の香りを有する無色透明液体であつ
た。
沸点:48.5℃/0.05mmHg
元素分析(C12H18O2として)
計算値(%):C,74.19:H,9.34
実測値(%):C,74.08:H,9.43
IR(液膜,cm-1):2950,1735,1230,1030
1H−NMR(CDCl3溶媒、TMS内部標準、
δ):
5.24(複雑な多重線、1H,=CH−CH3)
3.91〜3.79(多重線、2H,−O−CH 2−CH
)
2.90〜1.00(複雑な多重線、15H)
MS(相対強度)
この化合物には少なくとも4種類の異性体が存
在するが、キヤピラリーカラム〔実施例1と同
様〕を用いたガスマス測定の結果を次に示す。
ピーク1(13%):194(M+,21),134(65),119
(72),106(68),105(60),93(100),92(64)
,
91(89),79(98),43(76)
ピーク2(38%):194(M+,21),134(73),119
(77),105(61),94(45),93(100),92(57),
91(91),79(87),43(61)
ピーク3(38%):194(M+,24),119(100),
106(40),105(61),94(44),93(87),92
(53),91(76),79(60),43(44)
ピーク4(11%):194(M+,22),119(98),106
(43),105(61),94(48),93(100),92(63),
91(84),79(68),43(61)
実施例 3
2−エチリデン−ビシクロ〔2.2.1〕ヘプト−
5(又は6)−イルメチルプロピオネート:
実施例2のアセチルクロリドの代わりにプロピ
オニルクロリド(14.62g、0.158mol)を用いる
以外は同様に操作して上記化合物26.62g(収率
97.5%)を得た。このものはハーバル様、花様の
香りを有する無色透明液体であつた。
沸点:57.0〜58.5℃/0.05mmHg
元素分析(C13H20O2として)
計算値(%):C,74.96:H,9.68
実測値(%):C,74.65:H,9.55
IR(液膜,cm-1):2950,1730,1180,1075,
1010
1H−NMR(CDCl3溶媒、TMS内部標準、
δ):
5.24(複雑な多重線、1H,=CH−CH3)
3.90〜3.79(多重線、2H,−O−CH 2−CH
)
2.88〜1.00(複雑な多重線、17H)
MS(相対強度)
この化合物には少なくとも4種類の異性体が存
在するがキヤピラリーカラム〔実施例1と同様〕
を用いたガスマス測定の結果を次に示す。
ピーク1(13%):208(M+,17),134(78),119
(77),106(69),105(56),92(71),91(79),
79(86),78(42),57(100)
ピーク2(38%):208(M+,15),134(88),119
(77),106(76),105(54),93(100),92(61)
,
91(77),79(79),57(89)
ピーク3(38%):208(M+,20),134(47),119
(100),106(45),105(60),93(99),92(63)
,
91(71),79(57),57(51)
ピーク4(11%):208(M+,19),119(97),106
(43),105(58),94(47),93(100),92(63),
91(70),79(59),57(61)
実施例 4
2−エチル−ビシクロ〔2.2.1〕ヘプト−5(又
は6)−イルメチルホルメート:
2−エチリデン−ビシクロ〔2.2.1〕ヘプト−
5(又は6)−イルメチルホルメート(10.0g、
55.5mmol)、5wt%Pd/C(0.5g、0.25wt%Pd)、
ベンゼン(40ml)をオートクレーブ中に加える。
オートクレーブ中の空気を窒素で置換した後、
H2100気圧に加圧し、次いでオートクレーブを80
℃まで加熱し撹拌する。ガス吸収が止まる時点を
反応終了とする。この間、約3時間を要した。オ
ートクレーブを室温まで冷却し、常圧に戻した
後、内容物を取り出す。これを濃縮し、分留して
上記化合物8.62g(収率85.2%)を得た。このも
のはオリス的で木香様の香りを有する無色透明液
体であつた。
沸点:37.0〜38.0℃/0.05mmHg
元素分析(C11H18O2として)
計算値(%):C,72.49:H,9.95
実測値(%):C,72.54:H,9.88
IR(液膜,cm-1):2950,1725,1170
1H−NMR(CDCl3溶媒、TMS内部標準、
δ):
8.02(一重線、1H,HCO−)
3.96〜3.84(多重線、2H,−O−CH 2−CH
)
2.34〜0.50(複雑な多重線、15H)
MS(相対強度)
この化合物には少なくとも4種類の異性体が存
在するが、キヤピラリーカラム〔実施例1と同
様〕を用いたガスマス測定の結果を次に示す。
ピーク1(49%):153(1),123(28),107(64),
95(58),94(89),93(35),81(66),80(100)
,
79(97),67(66)
ピーク2(29%):153(1),123(38),107(77),
95(51),94(100),93(28),81(66),80(61)
,
79(96),67(70)
ピーク3(8%):141(1),107(100),95(77),
94(86),93(38),81(57),80(64),79(100)
,
67(84),41(32)
ピーク4(14%):181(M−1,1),123(37),
107(90),95(38),94(100),93(40),81
(79),80(84),79(98),67(96)
実施例 5
2−エチル−ビシクロ〔2.2.1〕ヘプト−5(又
は6)−イルメチルアセテート:
実施例4の2−エチリデン−ビシクロ〔2.2.1〕
ヘプト−5(又は6)−イルメチルホルメートの代
わりに2−エチリデン−ビシクロ〔2.2.1〕ヘプ
ト−5(又は6)−イルメチルアセテート(10.0
g、51.5mmol)を用いる以外は同様に操作して
上記化合物9.48g(収率93.8%)を得た。このも
のはハーバル様、オリス的で木香様、果実様の香
りを有する無色透明液体であつた。
沸点:50.0〜51.0℃/0.2mmHg
元素分析(C12H20O2として)
計算値(%):C,73.43:H,10.27
実測値(%):C,73.21:H,10.32
IR(液膜,cm-1):2950,1740,1230,1030
1H−NMR(CDCl3溶媒、TMS内部標準、
δ):
3.92〜3.76(多重線、2H,−O−CH 2−CH
)
2.20〜0.50(複雑な多重線、18H)
MS(相対強度)
この化合物には少なくとも4種類の異性体が存
在するが、キヤピラリーカラム〔実施例1と同
様〕を用いたガスマス測定の結果を次に示す。
ピーク1(37%):155(1),107(49),95(28),9
4
(80),93(31),81(54),80(100),79(74),
67(42),43(43)
ピーク2(14%):154(3),136(26),107(48),
95(28),94(100),81(52),88(53),79(71)
,
67(45),43(47)
ピーク3(13%):181(1),136(36),107(99),
94(100),93(36),81(58),80(66),79(97)
,
67(60),43(68)
ピーク4(36%):181(1),107(93),95(34),9
4
(100),93(33),81(66),80(74),79(83),
67(64),43(56)
実施例 6
2−エチル−ビシクロ〔2.2.1〕−ヘプト−5
(又は6)−イルメチルプロピオネート:
実施例4の2−エチリデン−ビシクロ〔2.2.1〕
ヘプト−5(又は6)−イルメチルホルメートの代
わりに2−エチリデン−ビシクロ〔2.2.1〕ヘプ
ト−5(又は6)−イルメチルプロピオネート
(10.0g、48.0mmol)を用いる以外は同様に操作
して上記化合物9.55g(収率94.6%)を得た。こ
のものはハーバル様、花様の香りを有する無色透
明液体であつた。
沸点:50.0〜50.5℃/0.03mmHg
元素分析(C13H22O2として)
計算値(%):C,74.24:H,10.54
実測値(%):C,74.52:H,10.41
IR(液膜,cm-1):2950,1740,1180,1080,
1010
1H−NMR(CDCl3溶媒、TMS内部標準、
δ):
3.90〜3.72(多重線、2H,−O−CH 2−CH
)
2.49〜0.45(複雑な多重線、20H)
MS(相対強度)
この化合物には少なくとも4種類の異性体が存
在するが、キヤピラリーカラム〔実施例1と同
様〕を用いたガスマス測定の結果を次に示す。
ピーク1(39%):181(1),136(27),107(44),
94(74),93(27),88(51),80(100),79(59)
,
67(35),57(49)
ピーク2(12%):154(3),136(30),107(42),
95(26),94(100),81(45),80(44),79(55)
,
67(33),57(46)
ピーク3(13%):181(1),136(40),107(88),
94(100),93(33),81(49),80(57),79(82)
,
67(49),57(71)
ピーク4(36%):181(1),136(38),107(92),
95(34),94(100),81(59),80(66),79(72)
,
67(51),57(58)
実施例 7
2−エチリデン−5(又は6)−メトキシメチル
ビシクロ〔2.2.1〕ヘプタン:
還流冷却器、塩化カルシウム管及び滴下ロート
を備えた14つ口フラスコに、水素化ナトリウ
ム(油性、50%含有品、19.0g、0.396mol)、乾
燥テトラヒドロフラン(500ml)を加え、これに
室温で2−エチリデン−5(又は6)−ヒドロキシ
メチルビシクロ〔2.2.1〕ヘプタン(30.0g、
0.197mol)とヨウ化メチル(224.93g、
1.584mol)の混合溶液を20分間で滴下した。こ
の際反応温度が上がらないように注意した。滴下
後、この混合物を室温で2時間撹拌した。分液ロ
ート内の氷(500g)に、得られた反応混合物を
注ぎ、エーテル(500ml)を加えて分液後エーテ
ル層を5%希塩酸(100ml)、10%チオ硫酸ナトリ
ウム水溶液(200ml)、飽和炭酸水素ナトリウム水
溶液(100ml)、飽和食塩水(200ml)の順で、そ
れぞれ1回洗浄した。エーテル層を無水硫酸マグ
ネシウム上で乾燥し、濾別後、濃縮し、分留して
上記化合物29.23g(収率89.3%)を得た。この
ものはグリーン様、ハーバル様、柑橘様の香りを
有する無色透明液体であつた。
沸点:32.0〜33.0℃/0.1mmHg
元素分析(C11H18O2として)
計算値(%):C,79.47:H,10.91
実測値(%):C,79.69:H,10.82
IR(液膜,cm-1):2950,1110
1H−NMR(CDCl3溶媒、TMS内部標準、
δ):
5.24(複雑な多重線、1H,=CH−CH3)
3.33〜3.03(多重線、5H,CH 3−O−CH 2
−)
2.90〜0.78(複雑な多重線、12H)
MS(相対強度)
この化合物には少なくとも4種類の異性体が存
在するが、キヤピラリーカラム〔横河・ヒユーレ
ツト・パツカード(株)のPEG20Mフユーズドシリ
カ、カラム長50m〕を用いたガスマス測定の結果
を次に示す。
ピーク1(13%):166(M+,48),121(95),110
(28),109(27),106(28),105(26),93
(100),91(64),79(64),77(35)
ピーク2(53%):166(M+,56),121(75),119
(36),106(32),105(35),93(100),92(21)
,
91(66),79(61),77(35)
ピーク3(23%):166(M+,92),134(40),119
(100),106(46),105(84),93(95),92(34)
,
91(91),79(90),77(38)
ピーク4(11%):166(M+,62),121(42),119
(64),106(37),105(57),94(32),93(100)
,
91(84),79(83),77(40)
実施例 8
2−エチリデン−5(又は6)−エトキシメチル
ビシクロ〔2.2.1〕ヘプタン:
実施例7のヨウ化メチルの代わりにヨウ化エチ
ル(247.06g、1.584mol)を用いる以外は同様に
操作して上記化合物34.40g(収率96.8%)を得
た。このものはグリーン様、ハーバル様の香りを
有する無色透明液体であつた。
沸点:41.0℃/0.06mmHg
元素分析(C12H20Oとして)
計算値(%):C,79.94:H,11.18
実測値(%):C,79.63:H,11.22
IR(液膜,cm-1):2950,1105
1H−NMR(CDCl3溶媒、TMS内部標準、
δ):
5.24(複雑な多重線、1H,=CH−CH3)
3.63〜3.10(多重線、4H,−CH 2−O−CH 2
−)
2.93〜0.77(複雑な多重線、15H)
MS(相対強度)
この化合物には少なくとも4種類の異性体が存
在するが、キヤピラリーカラム〔実施例1と同
様〕を用いたガスマス測定の結果を次に示す。
The present invention relates to a novel bicyclic methylol derivative and a fragrance composition containing the same. The present inventor has long been aware of the following formula (), which is easily available as a petrochemical product. 2-ethylidene bicyclo [2.2.1]
Hept-5-ene (hereinafter abbreviated as "EBH")
We have been conducting research to synthesize various derivatives using this as a raw material and evaluate their usefulness. In the course of the research, the present inventor discovered that when EBH is hydroformylated, the following formula () can be obtained with extremely high selectivity and yield. 2-ethylidene-5 (or 6)-formylbicyclo[2.2.1]heptane (hereinafter referred to as
We have discovered that it is possible to obtain ``EFBH'' (abbreviated as "EFBH") and that it has an excellent aroma (Japanese Patent Application No. 57-94460, 57-220886, JP-A-57-
No. 142937). In addition, as a derivative of EFBH, the following formula (),
It is known that the compounds () and () have a fragrance and are useful as fragrance ingredients (Patent Application Showa).
No. 57-94460, Japanese Patent Publication No. 57-142933, No. 58-32833
issue). (In the formula, R represents a methyl group or an ethyl group.) Under these circumstances, the present inventor further conducted intensive research on derivatives of EFBH, and as a result, the following general formula (), (In the formula, the ROCH 2 - group is substituted at the 5th or 6th position of the norbornane ring, and R is a straight or branched alkyl group having 1 to 6 carbon atoms or a straight or branched chain having 1 to 7 carbon atoms. It has been discovered that a bicyclic methylol derivative represented by an acyl group and a dotted line indicates a single bond or a double bond, that is, an ester or ether compound of bicyclic methylol, has an excellent aroma, and the present invention is based on the present invention. completed. Therefore, an object of the present invention is to provide a novel bicyclic methylol derivative represented by the formula (). Another object of the present invention is to provide a perfume composition containing a bicyclic methylol derivative. In formula (), the substituent R is a methyl group, an ethyl group, a propyl group, an isopropyl group, n
-butyl group, sec-butyl group, tert-butyl group,
Alkyl groups such as n-amyl group, isoamyl group, sec-amyl group; formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, n-pentanoyl group, sec-pentanoyl group, tert-pentanoyl group, n-hexanoyl group and acyl groups such as isohexanoyl group, sec-hexanoyl group, tert-hexanoyl group, n-heptanoyl group, and benzoyl group. The compound of the present invention () can be prepared, for example, by 2-ethylidene-5 (or 6)-hydroxymethylbicyclo[2.2.1]heptane (a) or 2-ethyl-5 (or 6)-hydroxy Methylbicyclo[2.2.1]heptane (b) [Fujikura et al.: Tokugansho
57-94460] by a method known per se. (In the formula, R is the same as above.) Starting compound (a) can be obtained, for example, by reacting EBH () with carbon monoxide and hydrogen in the presence of a rhodium catalyst to produce 2-ethylidene-5 (or 6)-formylbicyclo [2.2 .1] Heptane () is produced, and then () is reacted with a metal hydride.
Furthermore, raw material compound (b) is produced by reacting hydrogen with hydrogen in the presence of a metal catalyst (Japanese Patent Application No. 57-94460). In order to produce the esters of the present invention, a well-known esterification method is used, namely (1) a corresponding carboxylic acid and a methylol compound (a,
(2) Under the same conditions as (1), add a solvent such as benzene that is azeotropic with water and esterify by azeotropic dehydration; (3) Acid halide or Acid anhydrides and methylol compounds (
It is carried out by a method of reacting a and b). In addition, to produce ethers, the methylol compounds (a, b) are reacted with an alkali metal or an alkali metal hydride to form an alkali metal alcoholate (the alkali metals include Na and K).
After that, add the alkyl halide corresponding to the desired ether (the halide is Br, I
Williamson's ether synthesis method, which involves reacting (preferably) to form an ether, is simple. Moreover, among the compounds of the present invention (), the saturated compound (b) in which the dotted line is represented by a single bond is the unsaturated compound (
It can also be synthesized by hydrogenating a) in the presence of a metal catalyst. In this case, the hydrogenation catalyst is
Any catalyst that is normally used in the hydrogenation reaction of olefins may be used. For example, Raney nickel, palladium/activated carbon, platinum oxide, etc. are used. In the compound () of the present invention, esters are roughly classified as having a herbal-like aroma, and ethers are classified as having a green, herbal-like aroma, and both have excellent aromas. It can be used in a wide range of applications that require fragrance, such as high-grade fragrance compositions, perfumes, soaps, shampoos, hair rinses, detergents, cosmetics, sprays, and fragrances. Examples will be described below, but the present invention is not limited to these examples. Example 1 2-ethylidene-bicyclo[2.2.1]hept-
5 (or 6)-yl methyl formate: In a 500 ml eggplant flask, add 2-ethylidene-5 (or 6)-hydroxymethylbicyclo[2.2.1]heptane (30.0 g, 0.197 mol), formic acid (182.16 g,
3.96 mol) and concentrated sulfuric acid (3.89 g, 0.0385 mol) were added in this order, and the mixture was stirred at room temperature for 1.5 hours. After the reaction, add water (100ml) and add n-hexane (100ml).
Extracted three times. The n-hexane layer was washed with a saturated aqueous solution of sodium hydrogen carbonate until it became alkaline, and then washed once with saturated brine (100 ml).
The n-hexane layer was dried over anhydrous magnesium sulfate, filtered, concentrated, and fractionated to give 8.74 g of the above compound.
(yield 24.6%). This product was a colorless and transparent liquid with an orris-like odor. Boiling point: 42.0-43.0℃/0.05mmHg Elemental analysis (as C 11 H 16 O 2 ) Calculated value (%): C, 73.30: H, 8.95 Actual value (%): C, 73.54: H, 8.90 IR (liquid film , cm -1 ): 2950, 1720, 1170 1 H-NMR (CDCl 3 solvent, TMS internal standard,
δ): 8.08 (singlet, 1H, H CO-) 5.24 (complex multiplet, 1H, = CH - CH3 ) 3.98-3.85 (multiplet, 2H, -O- CH2 - CH
) 2.90 to 1.00 (complex multiplet, 12H) MS (relative intensity) There are at least four isomers of this compound. , column length 50 m] are shown below. Peak 1 (18%): 180 (M + , 33), 119 (38), 106
(43), 105 (43), 93 (100), 92 (38), 91 (65),
79 (63), 78 (35), 77 (39) Peak 2 (62%): 180 (M + , 34), 119 (42), 106
(45), 105 (41), 94 (31), 93 (100), 92 (36),
91 (68), 79 (60), 77 (38) Peak 3 (16%): 180 (M + , 34), 119 (60), 106
(34), 105 (40), 94 (39), 93 (100), 92 (36),
91 (65), 79 (57), 77 (35) Peak 4 (4%): 180 (M + , 29), 119 (54), 106
(27), 105 (40), 94 (37), 93 (100), 92 (36),
91(61), 79(58), 77(35) Example 2 2-ethylidene-bicyclo[2.2.1]hept-
5 (or 6)-yl methyl acetate: In a 200 ml eggplant flask, add 2-ethylidene-5 (or 6)-hydroxymethylbicyclo[2.2.1]heptane (20.0 g, 0.131 mol), triethylamine (20.04 g, 0.198 mol), Dry benzene (130ml) was added, and acetyl chloride (12.40ml) was added to this under ice cooling.
g, 0.158 mol) in dry benzene (20 ml).
It was added dropwise over 20 minutes. After the addition, a reflux condenser and calcium chloride tube were attached, and the mixture was heated at room temperature for 20 minutes.
After stirring for a minute, the mixture was heated under reflux at 100°C for 1.5 hours.
After cooling, add ether (250 ml), add water (200 ml) twice, and saturated aqueous sodium bicarbonate solution (100 ml).
and finally twice with water (100 ml). The ether layer was dried over anhydrous magnesium sulfate, filtered, concentrated, and fractionally distilled to obtain 24.48 g (yield 96.2%) of the above compound. This substance was a colorless and transparent liquid with a herbal-like, orris-like wood scent. Boiling point: 48.5℃/0.05mmHg Elemental analysis (as C 12 H 18 O 2 ) Calculated value (%): C, 74.19: H, 9.34 Actual value (%): C, 74.08: H, 9.43 IR (liquid film, cm -1 ): 2950, 1735, 1230, 1030 1 H-NMR (CDCl 3 solvent, TMS internal standard,
δ): 5.24 (complex multiplet, 1H, = CH - CH 3 ) 3.91 - 3.79 (multiplet, 2H, -O- CH 2 -CH
) 2.90-1.00 (complex multiplet, 15H) MS (relative intensity) There are at least four types of isomers in this compound, but the results of gas mass measurement using a capillary column [same as Example 1] The following is shown. Peak 1 (13%): 194 (M + , 21), 134 (65), 119
(72), 106 (68), 105 (60), 93 (100), 92 (64)
,
91 (89), 79 (98), 43 (76) Peak 2 (38%): 194 (M + , 21), 134 (73), 119
(77), 105 (61), 94 (45), 93 (100), 92 (57),
91 (91), 79 (87), 43 (61) Peak 3 (38%): 194 (M + , 24), 119 (100),
106 (40), 105 (61), 94 (44), 93 (87), 92
(53), 91 (76), 79 (60), 43 (44) Peak 4 (11%): 194 (M + , 22), 119 (98), 106
(43), 105 (61), 94 (48), 93 (100), 92 (63),
91(84), 79(68), 43(61) Example 3 2-ethylidene-bicyclo[2.2.1]hept-
5 (or 6)-ylmethylpropionate: The above compound was produced in the same manner as in Example 2, except that propionyl chloride (14.62 g, 0.158 mol) was used instead of acetyl chloride, yielding 26.62 g (yield) of the above compound.
97.5%). This substance was a colorless and transparent liquid with a herbal-like and flower-like scent. Boiling point: 57.0-58.5℃/0.05mmHg Elemental analysis (as C 13 H 20 O 2 ) Calculated value (%): C, 74.96: H, 9.68 Actual value (%): C, 74.65: H, 9.55 IR (liquid film , cm -1 ): 2950, 1730, 1180, 1075,
1010 1 H-NMR (CDCl 3 solvent, TMS internal standard,
δ): 5.24 (complex multiplet, 1H, = CH - CH 3 ) 3.90 - 3.79 (multiplet, 2H, -O- CH 2 -CH
) 2.88 to 1.00 (complex multiplet, 17H) MS (relative intensity) There are at least four isomers of this compound, but capillary column [same as Example 1]
The results of gas mass measurements using the following are shown below. Peak 1 (13%): 208 (M + , 17), 134 (78), 119
(77), 106 (69), 105 (56), 92 (71), 91 (79),
79 (86), 78 (42), 57 (100) Peak 2 (38%): 208 (M + , 15), 134 (88), 119
(77), 106 (76), 105 (54), 93 (100), 92 (61)
,
91 (77), 79 (79), 57 (89) Peak 3 (38%): 208 (M + , 20), 134 (47), 119
(100), 106 (45), 105 (60), 93 (99), 92 (63)
,
91 (71), 79 (57), 57 (51) Peak 4 (11%): 208 (M + , 19), 119 (97), 106
(43), 105 (58), 94 (47), 93 (100), 92 (63),
91(70), 79(59), 57(61) Example 4 2-ethyl-bicyclo[2.2.1]hept-5(or 6)-yl methylformate: 2-ethylidene-bicyclo[2.2.1] hepto
5 (or 6)-yl methyl formate (10.0 g,
55.5mmol), 5wt%Pd/C (0.5g, 0.25wt%Pd),
Add benzene (40ml) into the autoclave.
After replacing the air in the autoclave with nitrogen,
Pressurize H2 to 100 atm and then autoclave to 80 atm.
Heat to ℃ and stir. The reaction ends when gas absorption stops. This took about 3 hours. After the autoclave is cooled to room temperature and returned to normal pressure, the contents are taken out. This was concentrated and fractionally distilled to obtain 8.62 g (yield: 85.2%) of the above compound. This product was a colorless and transparent liquid with an orris-like and woody scent. Boiling point: 37.0-38.0℃/0.05mmHg Elemental analysis (as C 11 H 18 O 2 ) Calculated value (%): C, 72.49: H, 9.95 Actual value (%): C, 72.54: H, 9.88 IR (liquid film , cm -1 ): 2950, 1725, 1170 1 H-NMR (CDCl 3 solvent, TMS internal standard,
δ): 8.02 (singlet, 1H, H CO-) 3.96-3.84 (multiplet, 2H, -O-C H 2 -CH
) 2.34-0.50 (complex multiplet, 15H) MS (relative intensity) There are at least four types of isomers in this compound, but the results of gas mass measurement using a capillary column [same as Example 1] The following is shown. Peak 1 (49%): 153 (1), 123 (28), 107 (64),
95 (58), 94 (89), 93 (35), 81 (66), 80 (100)
,
79 (97), 67 (66) Peak 2 (29%): 153 (1), 123 (38), 107 (77),
95 (51), 94 (100), 93 (28), 81 (66), 80 (61)
,
79 (96), 67 (70) Peak 3 (8%): 141 (1), 107 (100), 95 (77),
94 (86), 93 (38), 81 (57), 80 (64), 79 (100)
,
67 (84), 41 (32) Peak 4 (14%): 181 (M-1,1), 123 (37),
107 (90), 95 (38), 94 (100), 93 (40), 81
(79), 80(84), 79(98), 67(96) Example 5 2-ethyl-bicyclo[2.2.1]hept-5(or 6)-ylmethyl acetate: 2-ethylidene of Example 4 −Bicyclo [2.2.1]
2-ethylidene-bicyclo[2.2.1]hept-5(or 6)-yl methyl acetate (10.0
9.48 g (yield: 93.8%) of the above compound was obtained in the same manner except that 51.5 mmol) was used. This product was a colorless and transparent liquid with a herbal, orris, woody, and fruity aroma. Boiling point: 50.0-51.0℃/0.2mmHg Elemental analysis (as C 12 H 20 O 2 ) Calculated value (%): C, 73.43: H, 10.27 Actual value (%): C, 73.21: H, 10.32 IR (liquid film , cm -1 ): 2950, 1740, 1230, 1030 1 H-NMR (CDCl 3 solvent, TMS internal standard,
δ): 3.92 to 3.76 (multiplet, 2H, -O- CH2 - CH
) 2.20 to 0.50 (complex multiplet, 18H) MS (relative intensity) There are at least four types of isomers in this compound, but the results of gas mass measurement using a capillary column [same as Example 1] The following is shown. Peak 1 (37%): 155 (1), 107 (49), 95 (28), 9
Four
(80), 93 (31), 81 (54), 80 (100), 79 (74),
67 (42), 43 (43) Peak 2 (14%): 154 (3), 136 (26), 107 (48),
95 (28), 94 (100), 81 (52), 88 (53), 79 (71)
,
67 (45), 43 (47) Peak 3 (13%): 181 (1), 136 (36), 107 (99),
94 (100), 93 (36), 81 (58), 80 (66), 79 (97)
,
67 (60), 43 (68) Peak 4 (36%): 181 (1), 107 (93), 95 (34), 9
Four
(100), 93 (33), 81 (66), 80 (74), 79 (83),
67(64), 43(56) Example 6 2-ethyl-bicyclo[2.2.1]-hept-5
(or 6)-ylmethylpropionate: 2-ethylidene-bicyclo [2.2.1] of Example 4
Same except that 2-ethylidene-bicyclo[2.2.1]hept-5(or 6)-ylmethylpropionate (10.0 g, 48.0 mmol) is used instead of hept-5(or 6)-yl methylformate. 9.55 g (yield 94.6%) of the above compound was obtained. This substance was a colorless and transparent liquid with a herbal-like and flower-like aroma. Boiling point: 50.0-50.5℃/0.03mmHg Elemental analysis (as C 13 H 22 O 2 ) Calculated value (%): C, 74.24: H, 10.54 Actual value (%): C, 74.52: H, 10.41 IR (liquid film , cm -1 ): 2950, 1740, 1180, 1080,
1010 1 H-NMR (CDCl 3 solvent, TMS internal standard,
δ): 3.90 to 3.72 (multiplet, 2H, -O-C H 2 -CH
) 2.49-0.45 (complex multiplet, 20H) MS (relative intensity) There are at least four types of isomers in this compound, but the results of gas mass measurement using a capillary column [same as Example 1] The following is shown. Peak 1 (39%): 181 (1), 136 (27), 107 (44),
94 (74), 93 (27), 88 (51), 80 (100), 79 (59)
,
67 (35), 57 (49) Peak 2 (12%): 154 (3), 136 (30), 107 (42),
95 (26), 94 (100), 81 (45), 80 (44), 79 (55)
,
67 (33), 57 (46) Peak 3 (13%): 181 (1), 136 (40), 107 (88),
94 (100), 93 (33), 81 (49), 80 (57), 79 (82)
,
67 (49), 57 (71) Peak 4 (36%): 181 (1), 136 (38), 107 (92),
95 (34), 94 (100), 81 (59), 80 (66), 79 (72)
,
67(51), 57(58) Example 7 2-ethylidene-5(or 6)-methoxymethylbicyclo[2.2.1]heptane: In a 14-necked flask equipped with a reflux condenser, calcium chloride tube, and dropping funnel. , sodium hydride (oil-based, 50% content, 19.0 g, 0.396 mol) and dry tetrahydrofuran (500 ml) were added, and to this was added 2-ethylidene-5 (or 6)-hydroxymethylbicyclo[2.2.1]heptane at room temperature. (30.0g,
0.197mol) and methyl iodide (224.93g,
A mixed solution of 1.584 mol) was added dropwise over 20 minutes. At this time, care was taken not to raise the reaction temperature. After the addition, the mixture was stirred at room temperature for 2 hours. Pour the obtained reaction mixture into ice (500 g) in a separatory funnel, add ether (500 ml) and separate the ether layer. It was washed once each with an aqueous sodium hydrogen carbonate solution (100 ml) and a saturated saline solution (200 ml) in that order. The ether layer was dried over anhydrous magnesium sulfate, filtered, concentrated, and fractionally distilled to obtain 29.23 g (yield: 89.3%) of the above compound. This product was a colorless and transparent liquid with a green, herbal, and citrus scent. Boiling point: 32.0-33.0℃/0.1mmHg Elemental analysis (as C 11 H 18 O 2 ) Calculated value (%): C, 79.47: H, 10.91 Actual value (%): C, 79.69: H, 10.82 IR (liquid film , cm -1 ): 2950, 1110 1 H-NMR (CDCl 3 solvent, TMS internal standard,
δ): 5.24 (complex multiplet, 1H, = CH - CH 3 ) 3.33 - 3.03 (multiplet, 5H, CH 3 -O- CH 2
-) 2.90 to 0.78 (complex multiplet, 12H) MS (relative intensity) There are at least four types of isomers for this compound, but the capillary column [PEG20M fused The results of gas mass measurements using silica, column length 50 m are shown below. Peak 1 (13%): 166 (M + , 48), 121 (95), 110
(28), 109 (27), 106 (28), 105 (26), 93
(100), 91 (64), 79 (64), 77 (35) Peak 2 (53%): 166 (M + , 56), 121 (75), 119
(36), 106 (32), 105 (35), 93 (100), 92 (21)
,
91 (66), 79 (61), 77 (35) Peak 3 (23%): 166 (M + , 92), 134 (40), 119
(100), 106 (46), 105 (84), 93 (95), 92 (34)
,
91 (91), 79 (90), 77 (38) Peak 4 (11%): 166 (M + , 62), 121 (42), 119
(64), 106 (37), 105 (57), 94 (32), 93 (100)
,
91(84), 79(83), 77(40) Example 8 2-ethylidene-5(or 6)-ethoxymethylbicyclo[2.2.1]heptane: Ethyl iodide in place of methyl iodide in Example 7 (247.06 g, 1.584 mol) was used in the same manner to obtain 34.40 g (yield 96.8%) of the above compound. This substance was a colorless and transparent liquid with a green-like and herbal-like aroma. Boiling point: 41.0℃/0.06mmHg Elemental analysis (as C 12 H 20 O) Calculated value (%): C, 79.94: H, 11.18 Actual value (%): C, 79.63: H, 11.22 IR (liquid film, cm - 1 ): 2950, 1105 1 H-NMR (CDCl 3 solvent, TMS internal standard,
δ): 5.24 (complex multiplet, 1H, = CH - CH 3 ) 3.63 - 3.10 (multiplet, 4H, -CH 2 -O - CH 2
−) 2.93 to 0.77 (complex multiplet, 15H) MS (relative intensity) This compound has at least 4 types of isomers, but the results of gas mass measurement using a capillary column [same as Example 1] is shown below.
【表】
実施例 9
2−エチリデン−5(又は6)−n−プロピルオ
キシメチルビシクロ〔2.2.1〕ヘプタン:
実施例7のヨウ化メチルの代わりにヨウ化n−
プロピル(269.26g、1.584mol)を用いる以外は
同様に操作して上記化合物35.18g(収率91.9%)
を得た。このものはグリーン様、花様でやや金属
的な香りを有する無色透明液体であつた。
沸点:50.0〜52.0℃/0.1mmHg
元素分析(C13H22Oとして)
計算値(%):C,80.36:H,11.41
実測値(%):C,80.54:H,11.31
IR(液膜,cm-1):2950,1110
1H−NMR(CDCl3溶媒、TMS内部標準、
δ):
5.23(複雑な多重線、1H,=CH−CH3)
3.44〜3.06(多重線、4H,−CH 2−O−CH 2
−)
2.92〜0.68(複雑な多重線、17H)
MS(相対強度)
この化合物には少なくとも4種類の異性体が存
在するが、キヤピラリーカラム〔実施例1と同
様〕を用いたガスマス測定の結果を次に示す。[Table] Example 9 2-ethylidene-5(or 6)-n-propyloxymethylbicyclo[2.2.1]heptane: n-iodide in place of methyl iodide in Example 7
The above compound 35.18g (yield 91.9%) was obtained by the same procedure except that propyl (269.26g, 1.584mol) was used.
I got it. This substance was a colorless and transparent liquid with a green, flower-like, and slightly metallic aroma. Boiling point: 50.0-52.0℃/0.1mmHg Elemental analysis (as C 13 H 22 O) Calculated value (%): C, 80.36: H, 11.41 Actual value (%): C, 80.54: H, 11.31 IR (liquid film, cm -1 ): 2950, 1110 1 H-NMR (CDCl 3 solvent, TMS internal standard,
δ): 5.23 (complex multiplet, 1H, = CH - CH 3 ) 3.44 - 3.06 (multiplet, 4H, -CH 2 -O - CH 2
−) 2.92 to 0.68 (complex multiplet, 17H) MS (relative intensity) This compound has at least four isomers, but the results of gas mass measurement using a capillary column [same as Example 1] is shown below.
【表】
実施例 10
2−エチル−5(又は6)−メトキシメチルビシ
クロ〔2.2.1〕ヘプタン:
2−エチリデン−5(又は6)−メトキシメチル
ビシクロ〔2.2.1〕−ヘプタン(10.0g、
60.1mmol)、5wt%Pd/C(0.5g、0.25wt%Pd)、
ベンゼン(40ml)をオートクレーブ中に加える。
オートクレーブ中の空気を窒素で置換した後、
H2100気圧に加圧し、次いでオートクレーブを80
℃まで加熱し撹拌する。ガス吸収が止まる時点を
反応終了とする。この間、約3時間を要した。オ
ートクレーブを室温まで冷却し、常圧に戻した
後、内容物を取り出す。これを濃縮し、分留して
上記化合物6.28g(収率62.1%)を得た。このも
のはグリーン様、ハーバル様、グレープフルーツ
様の香りを有する無色透明液体であつた。
沸点:90.0〜91.0℃/13mmHg
元素分析(C11H20Oとして)
計算値(%):C,78.51:H,11.98
実測値(%):C,78.73:H,11.76
IR(液膜,cm-1):2950,1105
1H−NMR(CDCl3溶媒、TMS内部標準、
δ):
3.33〜3.04(多重線、5H,CH 3−O−CH 2
−)
2.90〜0.70(多重線、15H)
MS(相対強度)
この化合物には少なくとも4種類の異性体が存
在するが、キヤピラリーカラム〔実施例1と同
様〕を用いたガスマス測定の結果を次に示す。
ピーク1(35%):168(M+,0.2),136(23),
123(100),107(14),94(24),81(91),80
(15),79(28),67(59),45(15)
ピーク2(15%):168(M+,0.4),136(19),
123(100),122(12),94(12),81(85),79
(26),67(61),45(14),41(12)
ピーク3(14%):168(M+,0.2),136(34),
123(58),107(36),94(38),81(100),80
(27),79(40),67(77),45(23)
ピーク4(36%):168(M+,0.1),136(28),
123(69),107(26),94(38),81(100),80
(22),79(31),67(67),45(18)
実施例 11
2−エチル−5(又は6)−エトキシメチルビシ
クロ〔2.2.1〕ヘプタン:
実施例10の2−エチリデン−5(又は6)−メト
キシメチルビシクロ〔2.2.1〕ヘプタンの代わり
に2−エチリデン−5(又は6)−エトキシメチル
ビシクロ〔2.2.1〕ヘプタン(10.0g、55.5mol)
を用いる以外は同様に操作して上記化合物8.76g
(収率86.6%)を得た。このものはグリーン様、
ハーバル様、アルデヒド様の香りを有する無色透
明液体であつた。
沸点:32.0〜33.0℃/0.05mmHg
元素分析(C12H22Oとして)
計算値(%):C,79.06:H,12.16
実測値(%):C,79.28:H,12.31
IR(液膜,cm-1):2950,1110
1H−NMR(CDCl3溶媒、TMS内部標準、
δ):
3.60〜3.04(多重線、4H,−CH 2−O−CH 2
−)
2.93〜0.47(複雑な多重線、18H)
MS(相対強度)
この化合物には少なくとも4種類の異性体が存
在するが、キヤピラリーカラム〔実施例1と同
様〕を用いたガスマス測定の結果を次に示す。[Table] Example 10 2-ethyl-5(or 6)-methoxymethylbicyclo[2.2.1]heptane: 2-ethylidene-5(or 6)-methoxymethylbicyclo[2.2.1]-heptane (10.0 g,
60.1mmol), 5wt%Pd/C (0.5g, 0.25wt%Pd),
Add benzene (40ml) into the autoclave.
After replacing the air in the autoclave with nitrogen,
Pressurize H2 to 100 atm and then autoclave to 80 atm.
Heat to ℃ and stir. The reaction ends when gas absorption stops. This took about 3 hours. After the autoclave is cooled to room temperature and returned to normal pressure, the contents are taken out. This was concentrated and fractionally distilled to obtain 6.28 g (yield 62.1%) of the above compound. This product was a colorless, transparent liquid with a green, herbal, and grapefruit-like aroma. Boiling point: 90.0-91.0℃/13mmHg Elemental analysis (as C 11 H 20 O) Calculated value (%): C, 78.51: H, 11.98 Actual value (%): C, 78.73: H, 11.76 IR (liquid film, cm -1 ): 2950, 1105 1 H-NMR (CDCl 3 solvent, TMS internal standard,
δ): 3.33-3.04 (multiplet, 5H, CH3 - O - CH2
-) 2.90 to 0.70 (multiplet, 15H) MS (relative intensity) There are at least four types of isomers in this compound, but the results of gas mass measurement using a capillary column [same as Example 1] are as follows. Shown below. Peak 1 (35%): 168 (M + , 0.2), 136 (23),
123 (100), 107 (14), 94 (24), 81 (91), 80
(15), 79 (28), 67 (59), 45 (15) Peak 2 (15%): 168 (M + , 0.4), 136 (19),
123 (100), 122 (12), 94 (12), 81 (85), 79
(26), 67 (61), 45 (14), 41 (12) Peak 3 (14%): 168 (M + , 0.2), 136 (34),
123 (58), 107 (36), 94 (38), 81 (100), 80
(27), 79 (40), 67 (77), 45 (23) Peak 4 (36%): 168 (M + , 0.1), 136 (28),
123 (69), 107 (26), 94 (38), 81 (100), 80
(22), 79 (31), 67 (67), 45 (18) Example 11 2-ethyl-5 (or 6)-ethoxymethylbicyclo[2.2.1]heptane: 2-ethylidene-5 of Example 10 2-ethylidene-5(or 6)-ethoxymethylbicyclo[2.2.1]heptane (10.0g, 55.5mol) instead of (or 6)-methoxymethylbicyclo[2.2.1]heptane
8.76g of the above compound was prepared in the same manner except that
(yield 86.6%). This is Mr. Green.
It was a colorless and transparent liquid with a herbal-like and aldehyde-like aroma. Boiling point: 32.0-33.0℃/0.05mmHg Elemental analysis (as C 12 H 22 O) Calculated value (%): C, 79.06: H, 12.16 Actual value (%): C, 79.28: H, 12.31 IR (liquid film, cm -1 ): 2950, 1110 1 H-NMR (CDCl 3 solvent, TMS internal standard,
δ): 3.60-3.04 (multiplet, 4H, -CH2 - O - CH2
−) 2.93 to 0.47 (complex multiplet, 18H) MS (relative intensity) This compound has at least four isomers, but the results of gas mass measurement using a capillary column [same as Example 1] is shown below.
【表】
実施例 12
2−エチル−5(又は6)−n−プロピルオキシ
メチルビシクロ〔2.2.1〕−ヘプタン:
実施例10の2−エチリデン−5(又は6)−メト
キシメチルビシクロ〔2.2.1〕ヘプタンの代わり
に2−エチリデン−5(又は6)−n−プロピルオ
キシメチルビシクロ〔2.2.1〕ヘプタン(10.0g、
51.5mmol)を用いる以外は同様に操作して上記
化合物6.03g(収率59.6%)を得た。このものは
グリーン様、アルデヒド様の香りを有する無色透
明液体であつた。
沸点:36.0〜38.0℃/0.03mmHg
元素分析(C13H24Oとして)
計算値(%):C,79.53:H,12.32
実測値(%):C,79.21:H,12.44
IR(液膜,cm-1):2950,1110
1H−NMR(CDCl3溶媒、TMS内部標準、
δ):
3.42〜3.03(多重線、4H,−CH 2−O−CH 2
−)
2.92〜0.48(複雑な多重線、20H)
MS(相対強度)
この化合物には少なくとも4種類の異性体が存
在するが、キヤピラリーカラム〔実施例1と同
様〕を用いたガスマス測定の結果を次に示す。
ピーク1(31%):139(0.1),136(29),123
(83),107(18),95(21),94(34),81(100),
80(16),79(22),67(52)
ピーク2(12%):138(0.1),136(26),123
(93),95(19),94(24),81(100),79(22),
67(57),43(18),41(17)
ピーク3(12%):167(0.1),136(39),123
(39),107(41),95(29),94(46),81(100),
80(25),79(34),67(58)
ピーク4(29%):138(0.1),136(37),123
(51),107(37),95(25),94(47),81(100),
80(24),79(28),67(59)
ピーク5(2%):195(M−1,3),194(24),
121(100),106(30),105(19),93(81),91
(42),79(51),77(24),43(20)
ピーク6(8%):195(M−1,3),194(27),
121(100),106(28),105(20),93(82),91
(41),79(49),77(21),43(16)
ピーク7(5%):195(M−1,6),194(38),
119(62),106(38),105(62),93(100),92(34
),
91(63),79(68),43(44)
ピーク8(1%):195(M−1,6),194(38),
119(64),106(43),105(64),93(100),92
(35),91(67),79(76),43(48)
実施例 13
フローラル調香料組成物:
ベンジルアセテート 50(重量%)
α−ヘキシルシンナミツクアルデヒド
100
メチルヨノンγ 70
セドリルメチルエーテル 30
ヒアシンスベース 20
p−tert−ブチル−α−メチルヒドロシンナミ
ツクアルデヒド 100
(4−ヒドロキシ−4−メチルペンチル)−3
−シクロヘキサン−1−カルボキシアルデヒド
100
p−tert−ブチルシクロヘキシルアセテート
100
アセチルセドレン 100
イランイラン油 30
ベルガモツト油 100
レモン油 100
ローズ油ブルガリアン 20 ロジノール 70
990
上記フレーラル調香料組成物990部に2−エチ
リデンビシクロ〔2.2.1〕ヘプト−5(又は6)−
イルメチルホルメート(実施例1)10部を加える
ことにより、著しくこくのある香りになり、高級
感のある新規フローラル調香料組成物が得られ
た。
実施例 14
ハーバル調シヤンプー用香料組成物:
ガラクソライド*50%DEP** 15(重量%)
ローズフエノン 20
クマリン 30
ガルバナムレジノイド 10
ベルガモツト油 145
レモン油 100
オレンジ油 30
α−ヘキシルシンナミツクアルデヒド
100
プチグレイン油 40
ジイソブチルカルビノール 30
ローズマリー油 35
ステイラリルアセテート 35
p−tert−ブチルシクロヘキシルアセテートハ
イシス 30
パチユリ油 20
ジヒドロミルセノール 15
シトロネリルニトリル 25
メチルノニルアセトアルデヒド 10
シトロネロール 30
p−tert−ブチル−α−メチルヒドロシンナミ
ツクアルデヒド 50 (4−ヒドロキシ−4−メチルペンチル)−3
−シクロヘキサン−1−カルボキシアルデヒド
50
820
上記ハーバル調香料組成物820部に2−エチリ
デンビシクロ〔2.2.1〕ヘプト−5(又は6)−イ
ルメチルプロピオネート(実施例3)180部を加
えることにより、より甘さが増し、新鮮な新規ハ
ーバル調シヤンプー用香料組成物が得られた。
*インターナシヨナル・フレーバース・アン
ド・フレグランシス社商品名
** ジエチルフタレートで50%に希釈
実施例 15
ハーバル調シヤンプー用香料組成物:
1,3,4,6,7,8−ヘキサヒドロ−4,
6,6,7,8,8−ヘキサメチルシクロペン
タ−γ−2−ベンゾピラン 15(重量%)
ローズフエノン 20
クマリン 30
ガルバナムレジノイド 10
ハーボキサン** 180
ベルガモツト油 145
レモン油 100
オレンジ油 30
α−ヘキシルシンナミツクアルデヒド
100
プチグレイン油 40
ジイソブチルカルビノール 30
ローズマリー油 35
ステイラリルアセテート 35
p−tert−ブチルシクロヘキシルアセテートハ
イシス 30
パチユリ油 20
ジヒドロミルセノール 15
シトロネリルニトリル 25
メチルノニルアセトアルデヒド 10 シトロネロール 30
900
上記ハーバル調香料組成物900部に2−エチリ
デン−5(又は6)−メトキシメチルビシクロ
〔2.2.1〕ヘプタン(実施例7)100部を加えるこ
とにより更に新鮮さの増した新規ハーバル調シヤ
ンプー用香料組成物が得られた。
** ナールデン社商品名
実施例 16
ハーバル調シヤンプー用香料組成物:
1,3,4,6,7,8−ヘキサヒドロ−4,
6,6,7,8,8−ヘキサメチルシクロペン
タ−γ−2−ベンゾピラン 15(重量%)
ローズフエノン 20
クマリン 30
ガルバナムレジノイド 10
ハーボキサン** 180
ベルガモツト油 145
レモン油 100
オレンジ油 30
α−ヘキシルシンナミツクアルデヒド
100
プチグレイン油 40
ジイソブチルカルビノール 30
ローズマリー油 35
ステイラリルアセテート 35
p−tert−ブチルシクロヘキシルアセテートハ
イシス 30
パチユリ油 20
ジヒドロミルセノール 15
シトロネリルニトリル 25
メチルノニルアセトアルデヒド 10 シトロネロール 30
900
上記ハーバル調香料組成物900部に2−エチル
−5(又は6)−エトキシメチルビシクロ〔2.2.1〕
ヘプタン(実施例11)100部を加えることにより、
よりグリーンさの増した力強い感じの新規ハーバ
ル調シヤンプー用香料組成物が得られた。
** ナールデン社商品名 [Table] Example 12 2-ethyl-5(or 6)-n-propyloxymethylbicyclo[2.2.1]-heptane: 2-ethylidene-5(or 6)-methoxymethylbicyclo[2.2. 1] 2-ethylidene-5 (or 6)-n-propyloxymethylbicyclo[2.2.1] heptane (10.0 g,
6.03 g (yield 59.6%) of the above compound was obtained in the same manner except that 51.5 mmol) was used. This product was a colorless and transparent liquid with a green-like, aldehyde-like odor. Boiling point: 36.0-38.0℃/0.03mmHg Elemental analysis (as C 13 H 24 O) Calculated value (%): C, 79.53: H, 12.32 Actual value (%): C, 79.21: H, 12.44 IR (liquid film, cm -1 ): 2950, 1110 1 H-NMR (CDCl 3 solvent, TMS internal standard,
δ): 3.42-3.03 (multiplet, 4H, -CH2 - O - CH2
−) 2.92 to 0.48 (complex multiplet, 20H) MS (relative intensity) This compound has at least four isomers, but the results of gas mass measurement using a capillary column [same as Example 1] is shown below. Peak 1 (31%): 139 (0.1), 136 (29), 123
(83), 107 (18), 95 (21), 94 (34), 81 (100),
80 (16), 79 (22), 67 (52) Peak 2 (12%): 138 (0.1), 136 (26), 123
(93), 95 (19), 94 (24), 81 (100), 79 (22),
67 (57), 43 (18), 41 (17) Peak 3 (12%): 167 (0.1), 136 (39), 123
(39), 107 (41), 95 (29), 94 (46), 81 (100),
80 (25), 79 (34), 67 (58) Peak 4 (29%): 138 (0.1), 136 (37), 123
(51), 107 (37), 95 (25), 94 (47), 81 (100),
80 (24), 79 (28), 67 (59) Peak 5 (2%): 195 (M-1, 3), 194 (24),
121 (100), 106 (30), 105 (19), 93 (81), 91
(42), 79 (51), 77 (24), 43 (20) Peak 6 (8%): 195 (M-1, 3), 194 (27),
121 (100), 106 (28), 105 (20), 93 (82), 91
(41), 79 (49), 77 (21), 43 (16) Peak 7 (5%): 195 (M-1, 6), 194 (38),
119 (62), 106 (38), 105 (62), 93 (100), 92 (34
),
91 (63), 79 (68), 43 (44) Peak 8 (1%): 195 (M-1, 6), 194 (38),
119 (64), 106 (43), 105 (64), 93 (100), 92
(35), 91 (67), 79 (76), 43 (48) Example 13 Floral fragrance composition: Benzyl acetate 50 (wt%) α-hexyl cinnamic aldehyde
100 Methylionone γ 70 Cedryl methyl ether 30 Hyacinth base 20 p-tert-butyl-α-methylhydrocinnamic aldehyde 100 (4-hydroxy-4-methylpentyl)-3
-cyclohexane-1-carboxaldehyde
100 p-tert-butylcyclohexyl acetate
100 Acetyl Cedrene 100 Ylang Ylang Oil 30 Bergamot Oil 100 Lemon Oil 100 Rose Oil Bulgarian 20 Rhodinol 70 990 Add 2-ethylidenebicyclo[2.2.1]hept-5 (or 6) to 990 parts of the above floral fragrance composition.
By adding 10 parts of yl methyl formate (Example 1), a novel floral fragrance composition with a significantly richer aroma and a luxurious feel was obtained. Example 14 Flavor composition for herbal shampoo: Galaxolide * 50% DEP ** 15 (% by weight) Rosephenone 20 Coumarin 30 Galbanum resinoid 10 Bergamot oil 145 Lemon oil 100 Orange oil 30 α-hexylcinnamic aldehyde
100 Petitgrain oil 40 Diisobutylcarbinol 30 Rosemary oil 35 Styralyl acetate 35 p-tert-butylcyclohexyl acetate hycis 30 Pachylily oil 20 Dihydromyrcenol 15 Citronellyl nitrile 25 Methylnonylacetaldehyde 10 Citronellol 30 p-tert-Butyl -α-Methylhydrocinnamic aldehyde 50 (4-hydroxy-4-methylpentyl)-3
-cyclohexane-1-carboxaldehyde
50 820 By adding 180 parts of 2-ethylidenebicyclo[2.2.1]hept-5(or 6)-ylmethylpropionate (Example 3) to 820 parts of the above herbal fragrance composition, the sweetness was further increased. A fresh new herbal shampoo fragrance composition was obtained. *Product name of International Flavors & Fragrances ** Dilution to 50% with diethyl phthalate Example 15 Flavor composition for herbal shampoo: 1,3,4,6,7,8-hexahydro-4 ,
6,6,7,8,8-Hexamethylcyclopenta-γ-2-benzopyran 15 (wt%) Rosephenone 20 Coumarin 30 Galbanum resinoid 10 Herboxane ** 180 Bergamot oil 145 Lemon oil 100 Orange oil 30 α-hexyl cinnamic aldehyde
100 Petitgrain oil 40 Diisobutylcarbinol 30 Rosemary oil 35 Styralyl acetate 35 p-tert-butylcyclohexyl acetate hysis 30 Pachylily oil 20 Dihydromyrcenol 15 Citronellyl nitrile 25 Methylnonylacetaldehyde 10 Citronellol 30 900 The above herbal fragrances By adding 100 parts of 2-ethylidene-5 (or 6)-methoxymethylbicyclo[2.2.1]heptane (Example 7) to 900 parts of the composition, a new herbal shampoo fragrance composition with even greater freshness was obtained. Obtained. **Nalden product name Example 16 Herbal shampoo fragrance composition: 1,3,4,6,7,8-hexahydro-4,
6,6,7,8,8-Hexamethylcyclopenta-γ-2-benzopyran 15 (wt%) Rosephenone 20 Coumarin 30 Galbanum resinoid 10 Herboxane ** 180 Bergamot oil 145 Lemon oil 100 Orange oil 30 α-hexyl cinnamic aldehyde
100 Petitgrain oil 40 Diisobutylcarbinol 30 Rosemary oil 35 Styralyl acetate 35 p-tert-butylcyclohexyl acetate hysis 30 Pachylily oil 20 Dihydromyrcenol 15 Citronellyl nitrile 25 Methylnonylacetaldehyde 10 Citronellol 30 900 The above herbal fragrances 2-ethyl-5 (or 6)-ethoxymethylbicyclo [2.2.1] to 900 parts of the composition
By adding 100 parts of heptane (Example 11),
A new herbal shampoo fragrance composition with a stronger green feel was obtained. ** Naarden product name
Claims (1)
又は6位に置換し、Rは炭素数1〜6の直鎖又は
分岐鎖のアルキル基又は炭素数1〜7の直鎖又は
分岐鎖のアシル基を示し、点線は単結合又は二重
結合であることを示す)で表わされる二環式メチ
ロール誘導体。 2 一般式 ()、 (式中、ROCH2−基はノルボルナン環の5位
又は6位に置換し、Rは炭素数1〜6の直鎖又は
分岐鎖のアルキル基又は炭素数1〜7の直鎖又は
分岐鎖のアシル基を示し、点線は単結合又は二重
結合であることを示す)で表わされる二環式メチ
ロール誘導体を含有することを特徴とする香料組
成物。[Claims] 1. General formula (), (In the formula, the ROCH 2 - group is substituted at the 5th or 6th position of the norbornane ring, and R is a straight or branched alkyl group having 1 to 6 carbon atoms or a straight or branched chain having 1 to 7 carbon atoms. A bicyclic methylol derivative represented by an acyl group, and a dotted line indicates a single bond or a double bond. 2 General formula (), (In the formula, the ROCH 2 - group is substituted at the 5th or 6th position of the norbornane ring, and R is a straight or branched alkyl group having 1 to 6 carbon atoms or a straight or branched chain having 1 to 7 carbon atoms. A fragrance composition characterized by containing a bicyclic methylol derivative represented by an acyl group (where a dotted line indicates a single bond or a double bond).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19556983A JPS6087236A (en) | 1983-10-19 | 1983-10-19 | Bicyclic methylol derivative and perfume composition containing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19556983A JPS6087236A (en) | 1983-10-19 | 1983-10-19 | Bicyclic methylol derivative and perfume composition containing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6087236A JPS6087236A (en) | 1985-05-16 |
JPH0346456B2 true JPH0346456B2 (en) | 1991-07-16 |
Family
ID=16343301
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP19556983A Granted JPS6087236A (en) | 1983-10-19 | 1983-10-19 | Bicyclic methylol derivative and perfume composition containing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6087236A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4862908B2 (en) * | 2009-03-25 | 2012-01-25 | 株式会社大林組 | Retaining wall structure, method for constructing retaining wall structure |
US20160355751A1 (en) * | 2015-06-01 | 2016-12-08 | Takasago International Corporation (Usa) | Derivatives of 2-ethylidene norbornene and their use in fragrance and flavor applications |
WO2024027922A1 (en) | 2022-08-05 | 2024-02-08 | Symrise Ag | A fragrance mixture (ii) |
-
1983
- 1983-10-19 JP JP19556983A patent/JPS6087236A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS6087236A (en) | 1985-05-16 |
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