JP6733992B2 - シクロプロピルビニル前駆体のブレンステッド酸との反応によるホモアリル化合物の製造 - Google Patents
シクロプロピルビニル前駆体のブレンステッド酸との反応によるホモアリル化合物の製造 Download PDFInfo
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- JP6733992B2 JP6733992B2 JP2016549637A JP2016549637A JP6733992B2 JP 6733992 B2 JP6733992 B2 JP 6733992B2 JP 2016549637 A JP2016549637 A JP 2016549637A JP 2016549637 A JP2016549637 A JP 2016549637A JP 6733992 B2 JP6733992 B2 JP 6733992B2
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- homoallyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
- C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
- C12P17/02—Oxygen as only ring hetero atoms
- C12P17/04—Oxygen as only ring hetero atoms containing a five-membered hetero ring, e.g. griseofulvin, vitamin C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
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- General Engineering & Computer Science (AREA)
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- Genetics & Genomics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Description
特に驚くべきことは、本発明の転位反応が、遷移金属触媒、または水および/もしくはアルカン酸HQ以外のいかなる他の試薬もしくは溶媒(特に付加的な無極性有機溶媒、例えばジクロロメタン)をも必要とせずに進行したという発見であった。
− 40℃でのギ酸中の硫酸(G. Lucius, Chem. Ber. 93, 2663, 1960)、
− −15℃でのジクロロメタン中のメタンスルホン酸(DE 4301555、Henkel KGaA, 1993)、
− または0℃でのトルエン中の硫酸(EP 2048139、Kao Corporation, 2006)
の存在下で進行する。
本発明の特定の態様において、式
によるシクロプロパン化イソプレンを、提供する。
I)尿素、メチルアミン、NaNO2、および酸性の水性混合物を反応させて、MNUを生成すること、
II)MNUのための有機溶媒を加えて、二相混合物を生成し、MNUを有機溶媒中に分配すること;ならびに
III)有機溶媒に溶解したMNUを、アルケン基質、水性塩基および触媒を含む混合物上に移送し、それによってアルケン基質をシクロプロパン化すること
を含む、前記プロセスを提供する。
ここで、さらに本発明を例示する役割を果たす一連の例を後続させる。
無極性GCMS:50℃/2分、20℃/分 200℃、35℃/分 270℃。HP 7890A Series GCシステムを有するGC/MS Agilent 5975C MSD。無極性カラム:SGEからのBPX5、5%フェニル95%ジメチルポリシロキサン0.22mm×0.25mm×12m。キャリアガス:ヘリウム。インジェクタ温度:230℃。分割1:50。流量:1.0ml/分。移送ライン:250℃。MS−四重極:106℃。MS源:230℃。
Δ−ミルセン(1g、6.7mmol)および酢酸(2g、33.3mmol)を、圧力管中で150℃で12時間加熱する。完全な変換(GC)の後、均一な混合物を、水(100ml)およびtert−ブチルメチルエーテル(50ml)上に注ぐ。相分離の後、水相を、tert−ブチルメチルエーテル(50ml)で抽出する。合わせた有機相を、10%Na2CO3水溶液(50ml)および水(2×50ml)で洗浄し、MgSO4で乾燥し、減圧下で蒸発させる。粗製の生成物(1.4g)は、68%のE−ホモゲラニオールアセテート、25%のZ−ホモゲラニオールアセテートおよび4%のΔ−オシメンを含む。
Δ−オシメン(3g、20.2mmol)および酢酸(5g、0.1mol)を、圧力管中で3時間150℃に加熱する。例17に記載した後処理によって、GCMSによって73%のE−ホモゲラニオールアセテートおよび27%のZ−ホモゲラニオールアセテートを含む3.5gの暗赤色液体が得られる。100℃/0.05mbarでのバルブ・ツー・バルブ蒸留によって、2.2g(52%)のホモゲラニオールアセテートが無色液体として得られ、その分析的データは、例18において製造したホモゲラニオールアセテートから得られたものと同一である。
Δ−ヒドロキシミルセノール(0.5g、3mmol)および酢酸(0.9g、15mmol)を、150℃で10時間加熱する。例17に記載した後処理によって、GCによって75%の純度を有する0.6gの粗製の酢酸塩(E/Z 72:28)が得られる。メタノール(6ml)および30%KOH水溶液(1.7ml)を、残留物に加える。25℃で1時間撹拌した後、濃NaCl水溶液(50ml)およびtert−ブチルメチルエーテル(50ml)を加える。相を分離し、水相をtert−ブチルメチルエーテル(50ml)で抽出する。有機相を合わせ、水(50ml)で洗浄し、MgSO4で乾燥し、ろ過し、減圧下で蒸発させて、0.44gの粗製のジオール(E/Z 72:28)を得、それを、溶離液ヘキサン/tert−ブチルメチルエーテル 1:1でのシリカゲル上のフラッシュクロマトグラフィーによって精製して、(E)−4,8−ジメチルノナ−3−エン−1,8−ジオール(0.28g、50%)を無色オイルとして得る。
Claims (8)
- ホモアリル化合物2をシクロプロピルビニル前駆体1からブレンステッド酸HQの存在下で生成する方法であって、
前記方法。 -
- E/Z比率が70:30より大きい、請求項2に記載のホモアリルアルコールを生成する方法。
- 残基Rが炭素−炭素不飽和を含む、請求項1〜3のいずれか一項に記載の方法。
- 基質1がポリプレノイド
である、請求項1〜4のいずれか一項に記載の方法。 - 基質1がシクロプロパン化ファルネセンである、請求項5に記載の方法。
- Ambrox
- シクロプロピル前駆体1
から転位生成物2’
転位生成物2’のエステル交換および/または求核置換により、ホモアリル化合物2のエステル
を得、ホモアリル化合物のエステル2を水性塩基で加水分解してホモアリルアルコール3
Applications Claiming Priority (3)
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GB1318894.1 | 2013-10-25 | ||
GBGB1318894.1A GB201318894D0 (en) | 2013-10-25 | 2013-10-25 | Improvements in or relating to organic compounds |
PCT/EP2014/072891 WO2015059293A1 (en) | 2013-10-25 | 2014-10-24 | Preparation of homoallylic compounds by reaction of cyclopropylvinyl precursors with bronstedt acids |
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JP2016540036A JP2016540036A (ja) | 2016-12-22 |
JP2016540036A5 JP2016540036A5 (ja) | 2017-12-07 |
JP6733992B2 true JP6733992B2 (ja) | 2020-08-05 |
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US (1) | US9884803B2 (ja) |
EP (1) | EP3060542B1 (ja) |
JP (1) | JP6733992B2 (ja) |
CN (1) | CN105683146B (ja) |
BR (1) | BR112016008895B1 (ja) |
ES (1) | ES2669213T3 (ja) |
GB (1) | GB201318894D0 (ja) |
IL (1) | IL244928B (ja) |
MX (1) | MX2016005052A (ja) |
SG (1) | SG11201602722YA (ja) |
WO (1) | WO2015059293A1 (ja) |
Families Citing this family (8)
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GB201507207D0 (en) | 2015-04-24 | 2015-06-10 | Givaudan Sa | Enzymes and applications thereof |
GB201507170D0 (en) | 2015-04-24 | 2015-06-10 | Givaudan Sa | Process |
GB201516396D0 (en) | 2015-09-16 | 2015-10-28 | Givaudan Sa | Improvements in or relating to organic compounds |
GB201618090D0 (en) | 2016-10-26 | 2016-12-07 | Givaudan Sa | Product |
EP3476822A1 (en) * | 2017-10-31 | 2019-05-01 | Givaudan SA | Process of making organic compounds |
CN107828709B (zh) * | 2017-11-09 | 2021-06-25 | 天津大学 | 异源合成龙涎香醇的重组大肠杆菌及其构建方法 |
CN110963877B (zh) * | 2019-12-18 | 2022-10-04 | 河北旭阳能源有限公司 | 1-氯-1-氯乙酰基环丙烷的制备方法 |
GB202020331D0 (en) | 2020-12-22 | 2021-02-03 | Givaudan Sa | Process of making organic compounds |
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US5854405A (en) | 1997-11-13 | 1998-12-29 | Aerojet-General Corporation | Continuous process for diazomethane from an n-methyl-n-nitrosoamine and from methylurea through n-methyl-n-nitrosourea |
EP2438182B1 (de) | 2009-06-05 | 2018-10-10 | Basf Se | Biokatalytische herstellung von ambroxan |
US20130273619A1 (en) * | 2012-04-16 | 2013-10-17 | Basf Se | Process for the Preparation of (3E, 7E)-Homofarnesol |
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Publication number | Publication date |
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JP2016540036A (ja) | 2016-12-22 |
CN105683146B (zh) | 2018-02-06 |
MX2016005052A (es) | 2016-08-17 |
US9884803B2 (en) | 2018-02-06 |
IL244928A0 (en) | 2016-05-31 |
ES2669213T3 (es) | 2018-05-24 |
BR112016008895A8 (pt) | 2020-03-24 |
US20160251298A1 (en) | 2016-09-01 |
EP3060542A1 (en) | 2016-08-31 |
IL244928B (en) | 2019-09-26 |
EP3060542B1 (en) | 2018-02-21 |
WO2015059293A1 (en) | 2015-04-30 |
GB201318894D0 (en) | 2013-12-11 |
CN105683146A (zh) | 2016-06-15 |
BR112016008895B1 (pt) | 2021-11-03 |
SG11201602722YA (en) | 2016-05-30 |
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