GB2226315A - Organometallic 2-fluoro-5-bromophenyl compound - Google Patents
Organometallic 2-fluoro-5-bromophenyl compound Download PDFInfo
- Publication number
- GB2226315A GB2226315A GB8927840A GB8927840A GB2226315A GB 2226315 A GB2226315 A GB 2226315A GB 8927840 A GB8927840 A GB 8927840A GB 8927840 A GB8927840 A GB 8927840A GB 2226315 A GB2226315 A GB 2226315A
- Authority
- GB
- United Kingdom
- Prior art keywords
- formula
- fluoro
- bromo
- organometallic
- dibromofluorobenzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Organometallic 2-fluoro-5-bromophenyl compound Chemical class 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000575 pesticide Substances 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- MKHDDTWHDFVYDQ-UHFFFAOYSA-N 2,4-dibromo-1-fluorobenzene Chemical group FC1=CC=C(Br)C=C1Br MKHDDTWHDFVYDQ-UHFFFAOYSA-N 0.000 description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 4
- RNTGKISRXVFIIP-UHFFFAOYSA-N 1,2-dibromo-4-fluorobenzene Chemical compound FC1=CC=C(Br)C(Br)=C1 RNTGKISRXVFIIP-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- IGBDPRKNAFOOGY-UHFFFAOYSA-N (5-bromo-2-fluorophenyl)boronic acid Chemical compound OB(O)C1=CC(Br)=CC=C1F IGBDPRKNAFOOGY-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- IQHSSYROJYPFDV-UHFFFAOYSA-N 2-bromo-1,3-dichloro-5-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC(Cl)=C(Br)C(Cl)=C1 IQHSSYROJYPFDV-UHFFFAOYSA-N 0.000 description 1
- MDIQXIJPQWLFSD-UHFFFAOYSA-N 3-(2,2-dibromoethenyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C=C(Br)Br)C1C(O)=O MDIQXIJPQWLFSD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910002476 CuII Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- DKYOUKMZAHSAHM-UHFFFAOYSA-M [Br-].FC1=C(C=C(C=C1)[Mg+])OC1=CC=CC=C1 Chemical compound [Br-].FC1=C(C=C(C=C1)[Mg+])OC1=CC=CC=C1 DKYOUKMZAHSAHM-UHFFFAOYSA-M 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 150000005171 halobenzenes Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/24—Halogenated derivatives
- C07C39/26—Halogenated derivatives monocyclic monohydroxylic containing halogen bound to ring carbon atoms
- C07C39/27—Halogenated derivatives monocyclic monohydroxylic containing halogen bound to ring carbon atoms all halogen atoms being bound to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
- C07C43/29—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/02—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A compound of formula IV, useful as an intermediate in the production of pesticides <IMAGE> in which formula IV, M represents a metallic moiety in particular Mg Br or Li. Such a compound is useful as an intermediate in the preparation of compounds claimed in GB 8927841.0 and GB 8705940.8 (GB 2187731A) <IMAGE>
Description
INTERMEDIATES USEFUL IN THE PRODUCTION OF PESTICIDES
This invention relates to production of intermediates useful in the manufacture of pesticides.
In International Patent Application No. CB 85/00146 there are disclosed methods for the preparation of compounds of formula I
I: RACH3=CR4CHDRB in which formula:
RA represents a group ArCRlR2 - in which Ar represents a phenyl or naphthyl group optionally substituted by one or more halogen, alkoxy, haloalkoxy, methylenedioxy, C1-C6 alkyl or haloalkyl groups;
R1 and R2 together with the carbon to which they are attached represent a C3-C6 cycloalkyl group optionally substituted by one or more halogen atoms or C1-C6 alkyl groups.
R3 and R4 which may be identical or differ, represent hydrogen, haloyen or C1 -C6 alkyl groups and
RB represents the residue of an alcohol RB CHDOH in which D is hydrogen or cyano and of which the EMIR, ) 2,2-dimethyl-3-(2,2-dibromovinyl) cyclopropane carboxylic ester is 'significantly insecticidal,
the configuration of RA and CHDRB about the double bond being mutually trans.
Compounds I in which RB represents 4-fluoro-3-phenoxyphenyl are of particular interest and may be prepared inter alia by reaction of the Grignard reagent, 4-fluoro-3-phenoxyphenyl magnesium bromide with a suitable substrate. The bromide required for preparation of this Grignard reagent (5-bromo-2-fluorodiphenyl either) (II), has, however, been available hitherto only with difficulty.
It has now however been found that the bromide and other Brmediates can be generated in good yield from 2,4-dibromoprobenzene, which is available commercially although generally aminated with the isomer 3,4-dibromofluorobenzene.
In UK Patent Application No. 8705940 of which the present
ication is a [)lvlsional Application there is described a ess for the production of a boronic acid of formula III,
ertible into 5-bromo-2-fluorodiphenyl ether (II), in which an nometallic of formula IV, obtainable from 2,4-dibromofluoroene,
zilch formula IV M represents a metallic moiety such as -MgX, zing a halogen) t an alkali metal such as lithium is treated
a trialkoxy borne of formula B(OR)3, R representing an
group (e.g. a C1-C6 alkyl group which is preferably methyl) he product is hydrolysed.
he present invention comprises a compound of formula IV oer has been fod that the boronic acid III crystallizes y and that bhe crystals are substantially free of impurities and particularly isomers of the acid III derived from metallation at the 4-bromo position of 2,4-dibromofluorobenzene or derived from 3,4-dibromofluorobenzene impurity in the starting material.
Preferably, therefore the boronic acid III is crystallised and the crystals are isolated prior to further treatment.
The amount of the metal or metal alkyl used to treat 2,4-dibromofluorobenzene and thus produce the organometallle IV may be reduced to 80% or less of the stoichiometric amount.
Under these conditions bromine at the 2-position in 2,4-dibromofluorobenzene may react in preference to bromine at the 4-position and 2,4-dibromofluorobenzene may react in preference to 3,4-dibromofluorobenzene present as a contaminant, so that a good yield of the desired isomer of formula IV is obtained. Amounts less than 60% of stoichiometric are undesirable as the yield Is unnecessarily decreased.
The boronic acid III may be converted Into the Intermediate 5-bromo---;luorodiphenyl ether II, by oxidation, suitably using hydrogen peroxide, to the corresponding phenol V the corresponding C1-C6 alkoxide of which VI reacts with a halobenzene, in' which the halogen is chlorine, bromine or iodine, under Ullmann conditions e.g. in the presence of a copper catalyst such as copper bronze or a CuI or CuII halide to give II
The Invention is illustrated by the following Example:: Di hvdroxv-(5-bromo-2-fluoroqhenvl )-borane A solution of 2,4-dibromofluorobenzene (12.79, containing 30% 3,4-dibromofluorobenzene) in dry tetrahydrofuran (THF) (lOml) is added over 5 min to a stirred suspension of magnesium turnings (l.l5g) in dry THF (50ml) under an atmosphere of nitrogen and cooled in a water bath. After 1 hour, when all the magnesium has reacted, this reagent is added over 20 min to a stirred solution of trimethoxyborane (7ml) in dry diethyl ether (80ml) under an atmosphere of nitrogen and cooled at 78"C for a further 15 min.
and glacial acetic acid (6ml) added followed by water (50ml).
The mixture Is warmed to room temperature, extracted with diethyl ether (x3), washed with water, dried and the solvent evaporated under reduced pressure. The residue Is stirred with carbon tetrachloride (30ml) > and then cooled at 0 C. The crystals of dihydroxy-(5-bromo-2-fluorophenyl)-borane are filtered off and washed with a little carbon tetrachloride. Yield 2.89 m.pt.
173-174"C. s 5-Bromo-2-flvoroDhenol To a stirred solution of dihydroxy-(5-bromo-2-fluorophenyl)- borane (2g) in diethyl ether (lOml) is added chloroform (lOml) and 30% hydrogen peroxide (lOml), The mixture is stirred for 18 hours at room temperature, diluted with water, extracted with diethyl ether (x3) and back extracted with 2M NaOH (or, in an alternative embodiment producing relatively increased yields, with stronger sodium hydroxide, e.g. 5M NaOH). The aqueous layer is acidified with aqueous 2N HCI extracted with diethyl ether (x3), dried and the solvent evaporated to give S-bromo-2-fluorophenol, yield 1.25g.A sample is purified by t.l.c. on silica gel eluted with 30% diethyl ether in petroleum ether b.p. 60-80"C nDl.5564. Alternatively, the product is distilled b.p. 52-54 /0.2 mm Hg.
S-Bromo-2-fluoro-diqhenvl ether
Sodium hydride (0.2g of 60% dispersion in oil) is added in small portions to a stirred solution of 5-bromo-2-fluorophenoi (lug) in 2-methoxyethyl ether (lml) under nitrogen and cooled in a water bath. Cuprous bromide (0.099 ) and a solution of bromobenzene (1.5ml) in 2-methoxymethyl ether (2ml) were added and the mixture refluxed for 6 hours. The mixture was poured onto water, extracted with petroleum ether b.p. 60-80 (x3), washed with water, dried, solvent evaporated and the residue distilled at 0.02 mm Hg b.pt. 80-82 C nD 1.5708, Yield 0.55g.
Claims (4)
1. A compound of formula IV,
in which formula IV, M represents a metallic moiety.
2. A compound according to Claim 1, in which M represents -MgX wherein X is a halogen.
3. A compound according to Claim 1, in which M represents an alkali metal.
4. A compound according to Claim 3, in which M represents lithium.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB868606292A GB8606292D0 (en) | 1986-03-13 | 1986-03-13 | Intermediates |
| GB868609590A GB8609590D0 (en) | 1986-04-18 | 1986-04-18 | Intermediates |
| GB8705940A GB2187731B (en) | 1986-03-13 | 1987-03-13 | Intermediates useful in the production of pesticides |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8927840D0 GB8927840D0 (en) | 1990-02-14 |
| GB2226315A true GB2226315A (en) | 1990-06-27 |
| GB2226315B GB2226315B (en) | 1991-02-06 |
Family
ID=27262955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8927840A Expired - Fee Related GB2226315B (en) | 1986-03-13 | 1987-03-13 | Intermediates useful in the production of pesticides |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2226315B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5962742A (en) * | 1996-06-14 | 1999-10-05 | American Cyanamid Company | Process for the preparation of 5-bromo-2 fluorobenzeneboronic acid |
| US6198008B1 (en) | 1997-06-06 | 2001-03-06 | American Cyanamid Company | Process for the preparation of 5-bromo-2-fluorobenzeneboronic acid |
| CN1087743C (en) * | 1996-06-14 | 2002-07-17 | 美国氰胺公司 | Process for prepn. of 5-bromo-2-fluorobenzeneboronic acid |
| GB2415193A (en) * | 2004-06-19 | 2005-12-21 | F2 Chemicals Ltd | Fluorinated arylboronic acids |
-
1987
- 1987-03-13 GB GB8927840A patent/GB2226315B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5962742A (en) * | 1996-06-14 | 1999-10-05 | American Cyanamid Company | Process for the preparation of 5-bromo-2 fluorobenzeneboronic acid |
| CN1087743C (en) * | 1996-06-14 | 2002-07-17 | 美国氰胺公司 | Process for prepn. of 5-bromo-2-fluorobenzeneboronic acid |
| US6198008B1 (en) | 1997-06-06 | 2001-03-06 | American Cyanamid Company | Process for the preparation of 5-bromo-2-fluorobenzeneboronic acid |
| GB2415193A (en) * | 2004-06-19 | 2005-12-21 | F2 Chemicals Ltd | Fluorinated arylboronic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2226315B (en) | 1991-02-06 |
| GB8927840D0 (en) | 1990-02-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20020313 |