WO1996016010A1 - Preparation of halogenated alcohols - Google Patents
Preparation of halogenated alcohols Download PDFInfo
- Publication number
- WO1996016010A1 WO1996016010A1 PCT/GB1995/002571 GB9502571W WO9616010A1 WO 1996016010 A1 WO1996016010 A1 WO 1996016010A1 GB 9502571 W GB9502571 W GB 9502571W WO 9616010 A1 WO9616010 A1 WO 9616010A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- strong base
- alkali metal
- preparation
- sodium
- Prior art date
Links
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
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/40—Halogenated unsaturated alcohols
- C07C33/42—Halogenated unsaturated alcohols acyclic
- C07C33/423—Halogenated unsaturated alcohols acyclic containing only double bonds as unsaturation
Definitions
- This invention relates to halogenated alcohols and more particularly to a process of preparing halogenated alcohols from haloal anes.
- halogenated alcohols such as l,l,l-trichloro-4- methyl-3-penten-2-ol
- a Grignard reagent such as isobutenylmagnesium chloride
- the Grignard reaction is essentially a laboratory procedure and is not inherently suitable for industrial production.
- An alternative known process involves the reaction of chloral with isobutylene under the conditions of the Prins reaction but this can lead to a mixture of the desired product with the iso eric 1,1,l-trichloro-4-methyl-4-pentene-2-ol and further treatment to isomerise this is required.
- the present invention is concerned with an improved process which is applicable to the preparation of the desired compounds and which is suitable for industrial manufacture.
- the present invention provides a process for preparing a halogenated alcohol of formula:
- X , X and X are halo, preferably chloro, bromo or fluoro,
- X , X and X are all chloro or all bromo.
- Particular examples of such compounds of formula (I) include 4-hydroxy-2-methyl-5,5,- 5-tribromopent-2-ene, and 4-hydroxy-2-meth l-5,5,5-trichloropent-2-ene.
- the compounds of formula (II) which are useful in the process of the invention are halomethanes containing a single hydrogen atom, such as chloroform, and bromofo ⁇ n.
- 3-Methylbut-2-en-l-al is also known as senecialdehyde.
- Suitable strong bases include alkali metal lower alkoxides, such as sodium or potassium alkoxides containing up to 6 carbon atoms, for example sodium isopropoxide, potasiurn isopropoxide, sodium £-butoxide and potassium t-butoxide, but other bases such as alkali metal hydrides, for example sodium hydride, and amides, for example soda ide, may also be used.
- alkali metal lower alkoxides such as sodium or potassium alkoxides containing up to 6 carbon atoms, for example sodium isopropoxide, potasiurn isopropoxide, sodium £-butoxide and potassium t-butoxide
- alkali metal hydrides for example sodium hydride
- amides for example soda ide
- the process is preferably conducted at low temperatures to avoid the production of unwanted by-products.
- a preferred temperature is within the range -80°C to 0°C, especially where a polar aprotic solvent is used.
- polar aprotic solvents which may be useful in the process include amides such as dimethylformamide, dimethylacetamide, dibutylacetamide, cyclic ethers such as tetrahydrofuran, tetrahydropyran and dioxan, glycol ethers such as ethylene glycol dimethyl ether, and ethylene glycol diethyl ether, and sulphoxides such as dimethyl sulphoxide.
- other inert solvents such as aromatic hydrocarbons e.g. toluene may also be used.
- the process is useful to produce the compounds of formula (I) in good yield and purity and allows for easy isolation of the desired product. Any unreacted or excess compound of formula (II) can be readily recovered and recycled.
- the compounds of formula (I) are useful as intermediates in a variety of synthetic procedures for the manufacture of useful products.
- 4-hydroxy-2-methyl-5,5,5-trichloropent-2-ene may be used in the manufacture of permethrin acid, a key intermediate for pyrethroid insecticides, by the process set out in UK Patent No. 1528944.
- This Example illustrates the preparation of 4-hydroxy-methyl-5,5,5- tribromopent-2-ene.
- aqueous and organic phases were separated and the aqueous phase extracted with dichloro ethane (2x20ml) and the extracts combined with the organic phase and dried over anhydrous sodium sulphate. After removal of the solvents by evaporation under reduced pressure the residue was dissolved in hexane (20ml) and the solution washed with brine (3x5ml) and dried over anhydrous sodium sulphate, and concentrated by removal of the solvent under reduced pressure.
- the residue was dissolved in a mixture of ethyl acetate and petroleum ether (boiling range 40-60°C) (1:6 parts by volume, 20ml) and purified by loading onto a short silica column (3.75cm) and eluting with the same mixture (400ml). Successive fractions (3) were examined by chromatography to establish that the desired product was present in the first two fractions.
- the eluate was concentrated by evaporation of the solvents under reduced pressure and the residue (1.14g) identified by nuclear magnetic resovance spectroscopy and gas chromatographic-mass spectral analysis as 4-hydroxy-2-methyl- 5,5,5-tribromopent-2-ene.
- This Example illustrates the preparation of 4-hydroxy-2-methyl-5,5.5- trichloropent-2-ene.
- Example 2 The procedure and quantities used were similar to those of Example 1 except that chloroform (0.54g) was used in place of bromoform. The product was obtained as a white crystalline solid (0.594g).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK95936011T DK0793635T3 (en) | 1994-11-24 | 1995-11-02 | Preparation of Halogenated Alcohols |
DE69512268T DE69512268T2 (en) | 1994-11-24 | 1995-11-02 | PRODUCTION OF HALOGENED ALCOHOLS |
JP8516638A JPH10509164A (en) | 1994-11-24 | 1995-11-02 | Method for producing halogenated alcohols |
EP95936011A EP0793635B1 (en) | 1994-11-24 | 1995-11-02 | Preparation of halogenated alcohols |
US08/765,532 US5907070A (en) | 1994-11-24 | 1995-11-02 | Preparation of halogenated alcohols |
GR990402281T GR3031212T3 (en) | 1994-11-24 | 1999-09-16 | Preparation of halogenated alcohols |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9423746A GB9423746D0 (en) | 1994-11-24 | 1994-11-24 | Preparation of halogenated alcohols |
GB9423746.8 | 1994-11-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996016010A1 true WO1996016010A1 (en) | 1996-05-30 |
Family
ID=10764927
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1995/002571 WO1996016010A1 (en) | 1994-11-24 | 1995-11-02 | Preparation of halogenated alcohols |
Country Status (12)
Country | Link |
---|---|
US (1) | US5907070A (en) |
EP (1) | EP0793635B1 (en) |
JP (1) | JPH10509164A (en) |
CN (1) | CN1067971C (en) |
AT (1) | ATE184587T1 (en) |
DE (1) | DE69512268T2 (en) |
DK (1) | DK0793635T3 (en) |
ES (1) | ES2136879T3 (en) |
GB (1) | GB9423746D0 (en) |
GR (1) | GR3031212T3 (en) |
HU (1) | HU214161B (en) |
WO (1) | WO1996016010A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109879718B (en) * | 2017-12-06 | 2021-09-17 | 中国科学院大连化学物理研究所 | Synthetic method of 5,5, 5-trichloro-2-methyl-2-pentene |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63211242A (en) * | 1987-02-27 | 1988-09-02 | Kanto Denka Kogyo Kk | Production of carbinol derivative |
GB2278352A (en) * | 1993-05-28 | 1994-11-30 | Zeneca Ltd | Preparation and use of halogenated alcohols |
-
1994
- 1994-11-24 GB GB9423746A patent/GB9423746D0/en active Pending
-
1995
- 1995-11-02 JP JP8516638A patent/JPH10509164A/en active Pending
- 1995-11-02 HU HU9603120A patent/HU214161B/en not_active IP Right Cessation
- 1995-11-02 ES ES95936011T patent/ES2136879T3/en not_active Expired - Lifetime
- 1995-11-02 WO PCT/GB1995/002571 patent/WO1996016010A1/en active IP Right Grant
- 1995-11-02 CN CN95196404A patent/CN1067971C/en not_active Expired - Fee Related
- 1995-11-02 AT AT95936011T patent/ATE184587T1/en not_active IP Right Cessation
- 1995-11-02 US US08/765,532 patent/US5907070A/en not_active Expired - Fee Related
- 1995-11-02 DE DE69512268T patent/DE69512268T2/en not_active Expired - Fee Related
- 1995-11-02 EP EP95936011A patent/EP0793635B1/en not_active Expired - Lifetime
- 1995-11-02 DK DK95936011T patent/DK0793635T3/en active
-
1999
- 1999-09-16 GR GR990402281T patent/GR3031212T3/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63211242A (en) * | 1987-02-27 | 1988-09-02 | Kanto Denka Kogyo Kk | Production of carbinol derivative |
GB2278352A (en) * | 1993-05-28 | 1994-11-30 | Zeneca Ltd | Preparation and use of halogenated alcohols |
Non-Patent Citations (4)
Title |
---|
H. KROPF:: "Methoden der organischen Chemie (Houben-Weyl), 4th edn., vol. VI/1a, Part 2", THIEME VERLAG, STUTTGART, DE * |
M. FUJITA, ET AL.:: "Fluoride ion-catalysed generation and carbonyl addition of alpha-halo carbanions from alpha-halo organosilicon compounds", TETRAHEDRON, vol. 44, no. 13, OXFORD, GB, pages 4135 - 4145 * |
PATENT ABSTRACTS OF JAPAN vol. 12, no. 501 (C - 556) 27 December 1988 (1988-12-27) * |
T. SHONO, ET AL.:: "Chain reactions induced by cathodic reduction", JOURNAL OF ORGANIC CHEMISTRY, vol. 50, no. 14, 12 July 1985 (1985-07-12), WASHINGTON, DC, US, pages 2527 - 2533 * |
Also Published As
Publication number | Publication date |
---|---|
HU214161B (en) | 1998-01-28 |
EP0793635B1 (en) | 1999-09-15 |
DE69512268D1 (en) | 1999-10-21 |
EP0793635A1 (en) | 1997-09-10 |
GR3031212T3 (en) | 1999-12-31 |
JPH10509164A (en) | 1998-09-08 |
DK0793635T3 (en) | 2000-03-27 |
ES2136879T3 (en) | 1999-12-01 |
GB9423746D0 (en) | 1995-01-11 |
US5907070A (en) | 1999-05-25 |
DE69512268T2 (en) | 2000-01-13 |
ATE184587T1 (en) | 1999-10-15 |
HUT75687A (en) | 1997-05-28 |
CN1166822A (en) | 1997-12-03 |
CN1067971C (en) | 2001-07-04 |
HU9603120D0 (en) | 1997-01-28 |
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