ES2602190T3 - Procedimiento para la preparación de (3E, 7E)-homofarnesol - Google Patents

Procedimiento para la preparación de (3E, 7E)-homofarnesol Download PDF

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Publication number
ES2602190T3
ES2602190T3 ES13715694.9T ES13715694T ES2602190T3 ES 2602190 T3 ES2602190 T3 ES 2602190T3 ES 13715694 T ES13715694 T ES 13715694T ES 2602190 T3 ES2602190 T3 ES 2602190T3
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formula
compound
general formula
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meanings indicated
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ES13715694.9T
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English (en)
Inventor
Melanie Bonnekessel
Hansgeorg Ernst
Wolfgang Siegel
Ekkehard Winterfeldt
Reinhard W. HOFFMANN
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BASF SE
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BASF SE
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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/34—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen reacting phosphines with aldehydes or ketones, e.g. Wittig reaction
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/92—Naphthofurans; Hydrogenated naphthofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Furan Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Procedimiento para la producción de compuestos de la fórmula general I**Fórmula** en la que R1 representa un radical hidrocarburo con 1 a 50 átomos de carbono, de cadena recta o ramificada, dado el caso con una o varias insaturaciones, conteniendo la cadena de hidrocarburo dado el caso heteroátomos y R2 representa H o alquilo C1-C6, en el que a) un compuesto carbonilo de la fórmula II**Fórmula** en la que R1 y R2 poseen los significados indicados anteriormente, se hace reaccionar por medio de la formación de olefina de Wittig hasta dar un ciclopropano de la fórmula general (III)**Fórmula** en la que R1 y R2 poseen los significados indicados anteriormente, b) se hace reaccionar el ciclopropano de la fórmula III con apertura de anillo hasta dar un compuesto de la fórmula IV**Fórmula** en la que R1 y R2 poseen los significados indicados anteriormente, y X representa halógeno o representa O-R', en donde R' representa H, acilo, Tf-acetilo o SO2-R", en donde R" representa alquilo o arilo; y c) se transforma el compuesto de la fórmula general IV en el compuesto de la fórmula general I.

Description

imagen1
imagen2
imagen3
imagen4
imagen5
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imagen7
-B: Acetonitrilo con 0,1 % vol H3PO4
Tiempo en min
% B Fluj o
0,0
70 1
10,0
80 1
13,0
100 1
Tiempo en min
% B Fluj o
17,0
100 1
17,1
70 1
Detector: Detector UV λ=197 nm, BW=4 nm Rata de flujo: 1 ml/min
5 Inyección: 1 µL Temperatura: 50 °C Duración: 20 minutos Presión: aproximadamente 160 bares
Procedimiento 2)
10 Ajustes del aparato y condiciones cromatográficas: Aparato: Agilent Series 1100 Columna: Chiralpak AD-RH 5 µm 150*4,6 mm de Daicel® Eluyente: -A: agua con 0,1 % vol H3PO4
-B: Acetonitrilo con 0,1 % vol H3PO4
Tiempo en min
% B Fluj o
0,0
30 1,2
25,0
70 1,2
30,0
100 1,2
40,0
100 1,2
40,1
30 1,2
15 Detector: Detector UV λ=205 nm, BW=5 nm Rata de flujo: 1,2 ml/min Inyección: 5 µL Temperatura: 40 °C
20 Duración: 45 minutos
9
imagen8
fase inferior 6 (UP6, 509 g, fase clara). Se evapora la fase superior 6 (303 g) en el evaporador rotativo (baño a 45 °C, vacío total en la bomba de aceite.)
Se obtienen 60,4 g de producto valioso (aceite amarillo). El producto deseado pudo ser aislado con una pureza de aproximadamente 97,2 % A (E&Z) y aproximadamente 93 % de rendimiento, referido a la geranilacetona, respecto a la sal de C3-fosfonio el rendimiento es de 84,0 %.
Procedimiento HPLC 2
RT
Sustancia % Fl
6,14
TPPO 1,51
10,7 9
E-Geranilacetona 0,24
RT
Sustancia % Fl
20,6 4
Z-C16-Ciclopropano 6,03
22,2 5
E-C16-Ciclopropano 91,2 1
Ejemplo 2: Reacción de Wittig partiendo de la sal de TPP-bromopropano con NaH
imagen9
10 Sustancias de entrada: 250 ml (3.082,3 mmol) I tetrahidrofurano 12,3 eq 222,25 g M = 72,11 g/mol 126,6 g (250 mmol) II sal C4 HPLC -91,67 % en peso 1 eq 22 g (550 mmol) III hidruro de sodio en aceite mineral al 60 % 2,2 eq
15 M = 24 g/mol
48,6 g 240,1 mmol IV Geranilacetona 0,96 eq ref. a (E) 90 %(E) y 6 %(Z) y (Z) M = 194,32 g/mol 0,9 225 mmol eq
20 ref. a (E) Se coloca la sal C4 (II) a temperatura ambiente en THF(I). Se lava tres veces el hidruro de sodio (III) con en cada caso 100 ml de n-hexano, se seca en corriente de nitrógeno y se agrega. Se agita adicionalmente la suspensión blanca por 4,5 horas a temperatura ambiente (control de rendimiento vía HPLC). Después se agrega geranilacetona (IV) y se calienta por 21 horas a 35 °C. Después se agregan a la suspensión amarillenta 500 ml de 25 n-heptano. A continuación se elimina el THF en el evaporador rotativo. A la suspensión remanente se añaden 500 ml de agua/metanol y se separan las fases. Se realiza extracción a la fase acuosa por dos veces con 250 ml de nheptano. Se lavan las fases orgánicas combinadas por seis veces con 250 ml de agua/metanol para separar NaBr y TPPO formados. Se seca la fase orgánica sobre sulfato de sodio y se concentra en el evaporador rotativo a 50 °C/10 mbar. Se obtienen 50,6 g de producto valioso como un aceite marrón, claro.
imagen10
11
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bolas. Se hace expresa referencia sobre la divulgación de los documentos impresos aquí mencionados.
18

Claims (1)

  1. imagen1
    imagen2
ES13715694.9T 2012-04-16 2013-04-12 Procedimiento para la preparación de (3E, 7E)-homofarnesol Active ES2602190T3 (es)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12164279 2012-04-16
EP12164279 2012-04-16
PCT/EP2013/057653 WO2013156398A1 (de) 2012-04-16 2013-04-12 Verbessertes verfahren zur herstellung von (3e, 7e)-homofarnesol

Publications (1)

Publication Number Publication Date
ES2602190T3 true ES2602190T3 (es) 2017-02-20

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EP (1) EP2838871B1 (es)
JP (1) JP6226954B2 (es)
CN (1) CN104245647B (es)
ES (1) ES2602190T3 (es)
MX (1) MX347882B (es)
WO (1) WO2013156398A1 (es)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104341255B (zh) * 2014-09-19 2016-08-24 江苏苏博特新材料股份有限公司 一种不饱和醇的制备方法
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
PL3319951T3 (pl) 2015-07-10 2022-02-28 Basf Se Sposób hydroformylowania 2-podstawionych butadienów oraz wytwarzania ich produktów pochodnych, w szczególności ambroksu
GB201618090D0 (en) * 2016-10-26 2016-12-07 Givaudan Sa Product
EP3585764B1 (de) * 2017-02-24 2021-01-27 Basf Se Verfahren zur herstellung von ungesättigten carbonsäuren durch carbonylierung von allylalkoholen und deren acylierungsprodukten
GB201917688D0 (en) 2019-12-04 2020-01-15 Givaudan Sa SHC enzymes and enzyme variants
GB201917694D0 (en) * 2019-12-04 2020-01-15 Givaudan Sa Enzyme mediated process
GB202010072D0 (en) 2020-07-01 2020-08-12 Givaudan Sa Enzyme-mediated process
GB202020330D0 (en) 2020-12-22 2021-02-03 Givaudan Sa Process of making organic compounds
GB202020331D0 (en) 2020-12-22 2021-02-03 Givaudan Sa Process of making organic compounds
WO2023175123A1 (en) 2022-03-17 2023-09-21 Givaudan Sa Shc enzymes and enzyme variants

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US5326888A (en) 1990-10-09 1994-07-05 Henkel Research Corporation Carbonylation of allylic alcohols and synthesis of an ambergris fragance compound
JP2004035496A (ja) * 2002-07-04 2004-02-05 Yoshinori Yamamoto ホモアリルハライドの合成方法
JP5236233B2 (ja) * 2007-09-04 2013-07-17 花王株式会社 （−）−アンブロキサンの製造方法
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MX2014012400A (es) 2015-01-12
MX347882B (es) 2017-05-17
EP2838871B1 (de) 2016-08-10
CN104245647A (zh) 2014-12-24
WO2013156398A1 (de) 2013-10-24
CN104245647B (zh) 2017-06-09
JP6226954B2 (ja) 2017-11-08
EP2838871A1 (de) 2015-02-25
JP2015518477A (ja) 2015-07-02

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