GB2134109A - Method of preparing tetrahalobenzene compounds, chemical intermediates used therein and certain of the compounds themselves - Google Patents
Method of preparing tetrahalobenzene compounds, chemical intermediates used therein and certain of the compounds themselves Download PDFInfo
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Abstract
Tetrahalobenzene compounds of the formula (I): <IMAGE> in which X is independently chloro or, preferably, fluoro and Y is hydrogen or -N<+>R3A<-> in which each R is independently C1-4 alkyl and A is a radical capable of forming an anion A<->, are prepared by (a) alkylating a compound of formula (II): <IMAGE> or a salt thereof, to form a compound of formula (III): <IMAGE> (b) treating the compound of formula (III) with a quaternizing agent of formula RA to form a compound of formula (IV): <IMAGE> and (c) partially or completely reductively cleaving the compound of formula (IV) to replace one or both -N<+>R3A<-> groups by hydrogen. Compounds (I), in which Y is -N<+>R3A<->, (III) and (IV) are novel. Compound (I) is useful in the synthesis of insecticides.
Description
SPECIFICATION
Method of preparing tetrahalobenzene compounds, chemical intermediates used therein and certain of the compounds themselves
This invention relates to a method of preparing tetrahalobenzene compounds useful in the synthesis of insecticides, chemical intermediates used therein and certain of the compounds themselves.
According to the present invention there is provided a method of preparing tetrahalobenzene compounds of the formula (I):
in which each X is independently chloro or, preferably, fluoro and Y is hydrogen or -N+R3A in which each R is independently C,, alkyl, especially methyl or ethyl, and A is a radical capable of forming an anion A-, the method comprising the steps of (a) alkylating a compound of formula (ill):
or a salt thereof, to form a compound of formula (Ill):
(b) treating the compound of formula (III) with a quaternizing agent of formula RA to form a compound of formula (IV):
in which X and A have the meanings hereinbefore defined; and (c) partially or completely reductively cleaving the compound of formula (IV) to replace one or both -N+R3A groups by hydrogen.
The invention also includes the process steps (a), (b) and (c) individually and the combinations of steps (a) and (b) and (b) and (c), the intermediate compounds of the formulae (Ill) and (IV) and compounds of the formula (I) in which Y is-N+R3A.
Step (a) of the process may be carried out by any of the methods well known in the chemical art for the preparation of tertiary amines from primary amines, for example, by either
(a) (i) treating the compound of formula (II)
with one or more alkylating agents
containing the R radicals; or
(a) (ii) reductively alkylating the compound of
formula (II) or a salt thereof with one or more
aldehydes or ketones or a mixture of both in
the presence of a reducing agent, the R
radicals being formed by the reduction of the
aldehyde or ketone and amine reaction
products.
In step (a) (i), the compound of formula (II) may be treated with, typically, one or more alkyl halides in an alcoholic solution. The reaction mixture is made alkaline and the tertiary amine recovered, by, for example, distillation,
Conveniently, when the R radicals are to be the same, a single alkylating agent may be used in slight excess of the stoichiometric amount required to form the di-tertiary amine. However, it is also envisaged that different alkylating agents could be used, either in admixture or separately, to form a range of products having different combinations of alkyl groups attached to the nitrogen atoms of compound (III).
In alternative step (a) (ii), the compound of formula (II) or a salt thereof may be reacted with one or more aldehydes or ketones or mixtures thereof in the presence of, for example, hydrogen and a hydrogenation catalyst, such as palladium on carbon, at temperatures preferably above 450C to avoid too slow a reaction. Conveniently, when the R radicals are to be the same, a single aldehyde or ketone is used in slight excess of the stoichiometric amount required to form the ditertiary amine. However, it is also envisaged, although not preferred, that step (a) (ii) could proceed in stages using in each stage different aldehydes or ketones or mixtures thereof to provide different values of R.
Step (b) the quaternisation of the compound of formula (III), may be carried out by any of the methods well known in the chemical art for forming quaternary compounds. Conveniently, the compound of formula (III) is treated with an appropriate alkyl halide or sulphate, e.g.
dimethylsulphate, in an alcoholic solution and, as necessary, in the presence of an acid binding agent such as magnesium oxide. The acid binding agent is used to mop up any acid formed as a result of hydrolysis of the quaternising agent.
In a preferred aspect of the process of the invention, 1 ,4-bis(am inomethyl)-2,3,5,6-tetrafluorobenzene or a salt thereof is tetramethylated by step (a) (ii) in a single stage using formaldehyde as the aldehyde, and quaternised with a methyl halide.
The intermediate compound having the formula (V):
and the diquaternary salt obtained therefrom, having the formula (VI):
in which A- has the meaning hereinbefore defined are preferred compounds of the invention.
In step (c), the di-quaternary compound (IV) is partially or completely cleaved, that is deamminated, to form either the monoquaternary derivative, i.e. compound (I) in which Y is N+R3A-, or the dimethyltetrahalobenzene, i.e.
compound (i) in which Y is H. Deammination is achieved with a reducing agent such as hydrogen in the presence of a suitable catalyst. The most suitable catalyst is palladium, especially palladium on carbon, preferably having a metal loading of from 3 to 20% by weight of palladium on carbon and especially 5% and 10% palladium on carbon which are grades of catalyst commercially available. Catalyst usages will depend on the temperature and pressure of reduction and whether complete or partial deammination is desired. These factors are more fully discussed later.In general, however, catalyst usages will range from 1.25% for partial deammination to 5% by weight of metal in the catalyst on diquaternary compound (IV) for complete deammination, when reduction is carried out at elevated temperatures and pressures, and up to 10% when complete deammination is carried out at atmospheric pressure.
In a preferred method of complete deammination to form the dimethyltetrahaiobenzene, the diquaternary compound (IV) is electrolysed in a protic medium, preferably water.
Suitable materials for use as the cathode in this electrolytic method are lead, mercury and amalgamated metals such as amalgamated lead.
The anode is conveniently platinum. Reduction takes place at potentials more negative than --1.OV against a saturated calomel electrode.
Electrolysis is preferably carried out in a divided cell, for example, an H-celi or Filter Press (Plate-and-Frame) cell having a diaphragm which is suitably a cation exchange membrane, for instance a Nafion membrane. The diquaternary compound in the protic medium is used as the catholyte. When water is the protic medium, the concentration of diquaternary salt in the aqueous solution is preferably from 7.5% w/v up to a saturated solution, ideally about 20% w/v. The anolyte may be any suitable electrolyte, usually a salt solution such as a saturated aqueous solution of sodium sulphate. The voltage applied across the electrodes will normally be sufficient to give a current density of, typically, about 100 mAcm-2, deammination being completed in about 5 hours at ambient temperature.During the electrolysis, a portion of the 1 ,4-dimethyltetrahalobenzene separates from the aqueous trialkylamine, which is formed as a result of deammination, a portion dissolves in the aqueous solution and a portion sublimes onto the wall of the electrolytic cell. The portions are dissolved in ether and residual trialkylamine washed out of the ether with aqueous inorganic acid. The crude 1 ,4-dimethyl- tetrahalobenzene may be purified by distillation.
The monoquaternary salt having the formula (VII):
in which X, R and A have the meanings hereinbefore defined, may be obtained by terminating the deammination step (c) partway through. This is most conveniently done when hydrogen is used as the deamminating agent in the presence of a catalyst. Under pressures up to about 1 7 atmospheres, particularly in the range of from 3 to 1 7 atmospheres, temperatures in the range of from 70 to 1200C, particularly 75 to 850C and using a 5% palladium on carbon catalyst, the monoquaternary salt can be obtained. At lower pressures and/or temperatures, higher catalyst usages and/or metal loadings, e.g. 10% palladium on carbon, and extended reaction times are needed.At higher temperatures and/or pressures and/or catalyst usages deammination proceeds further and the 1 ,4-dimethyltetrahalobenzene is formed.
Whether the diquaternary compound (IV) is deamminated by a chemical or electrochemical reduction, there is no substantial loss of the ring fluorine atoms. In contrast, attempts to deaminate the diamine (II) and the tetra-alkylated compound (III) by catalytic hydrogenolysis using palladium catalysts have resulted in total and partial loss, respectively, of the ring halogen atoms.
The starting material, the diamine (II), may be obtained by a process which comprises reacting the appropriate 1 ,4-dicyanotetrahalobenzene with hydrogen in the presence of a hydrogenation catalyst under acid conditions, as described in UK
Patent Application No.8312493 (Publication No.
2120666). Conveniently, this process may be combined with step (a) (ii) of the present process without isolation of the compound (II). Thus, for instance, the 1 ,4-dicyanotetrahalobenzene may be reacted with hydrogen in a pressurised autoclave at an elevated temperature in the presence of a hydrogenation catalyst, e.g. 5% palladium on carbon, an inert solvent, suitably methanol, an acid, preferably sulphuric acid and, optionally, a small amount of water.When hydrogenation is judged complete, an appropriate quantity of aldehyde or ketone or mixture thereof may be introduced to the autoclave and reacted with the hydrogenation product to form the compound of formula (III). Alternatively, the process for preparing the 1,4-diaminomethyltetrahalobenzene and step (a) (ii) may be combined in a single stage, the aldehyde or ketone or mixture thereof being introduced to the autoclave before hydrogenation is commenced. In this case it is desirable to exclude water from the autoclave.
If the 4-methyl-2,3,5,6-tetrahalobenzyl ester of a carboxylic acid is desired, then rather than proceeding via the 1 ,4-dimethyltetrahalobenzene and the appropriate alcohol or halide the ester may be formed by direct reaction of the monoquaternary salt (VII) with the carboxylic acid or a reactive derivative thereof, such as an alkali metal salt, an ammonium salt or an alkylammonium salt, preferably in a suitable organic solvent.
1 ,4-Dicyanotetrafluorobenzene may be obtained by fluorinating the corresponding tetrachlorinated compound with potassium fluoride in a polar aprotic solvent. 1 ,4-Dicyanotetrachloro- benzene is, itself, obtained from the commercially available tetrachloroterephthaloyl chloride by treatment with aqueous ammonia to give the diamide followed by dehydration using phosphorus oxychloride.
The invention is illustrated by the following
Examples 1 to 12 in which percentages are by weight. Example 13 is included for comparative purposes only.
Preparation of 1 ,4-bis(dimethylam inomethyl)- 2,3,5,6-tetrafluorobenzene
Example 1
2g of 1 ,4-bis(aminomethyl)-2,3,5,6-tetra- fluorobenzene disulphate, 25 ml methanol, 25 ml water, 3 ml of 37% aqueous formaldehyde and 0.59 5% palladium on carbon catalyst were charged to a 100 ml flask fitted with a stirrer, an inlet connected to a supply of hydrogen and a gas outlet. The mixture was agitated while passing hydrogen through at 50 ml/min. After 3 days the mixture was added to strong sodium hydroxide solution. An ether extract was shown by gas liquid chromatography to contain none of the original diamine, but a substantial quantity of the N,N,N' ,N'-tetramethyl derivative, contaminated with about 12% of the corresponding N,Ndimethyl compound.
Example 2
5g of 1 ,4-dicyano-2,3 ,5,6-tetrafluorobenzene, 0.25 g of 5% palladium on carbon, 2 ml water, 70 ml methanol and 3.0 g sulphuric acid, were loaded to a glass-lined rotating autoclave which, after purging, was pressurised to 1 5 atmospheres with hydrogen. The autoclave was rotated for 6 hours at 750C (maximum autogeneous pressure, 1 7 atmospheres). The autoclave was cooled, vented, and, after 1 5 ml of 37% formaldehyde solution was added, pressurised again to 1 5 atmospheres and rotated for 6 hours at 750C.The reaction solution was filtered and the filtrate reduced in volume by evaporation at 500C at 6 cms Hg pressure. 5.8 g of crude 1,4-bis(dimethylaminomethyl)-2,3,5,6-tetrafluorobenzene was isolated by evaporating ether extracts of a strongly alkaline solution of the residue.
Example 3
5.0 g of 1 ,4-dicyano-2,3,5,6-tetrafluorobenzene, 70 ml of methanol, 5 ml of water, 3.5 g of sulphuric acid and 0.125 g 5% palladium on carbon (T37 dry powder obtained from Johnson
Matthey Chemicals Ltd.) were loaded into a glasslined rotating autoclave and hydrogenated for 6 hours at 1 30C and 30 atmospheres. 15 ml of 37% formalin solution were added and the mixture treated with hydrogen for 6 hours at 600C and 20 atmospheres. The product solution was filtered and methanol removed from the filtrate using a vacuum rotary evaporator, 700Tw caustic soda solution was added dropwise, and the precipitate (5.6 g) isolated. The isolated material (5.03 g) was recrystallised from 5 ml of toluene giving 3.0 g white solid having a melting point of 73.50C.
Elemental analysis of the solid gave C 54.2%,
H 6.4%, N 10.6%, F 29.2% against theory for 1,4 bis(dimethylaminomethyl)-2,3,5,6-tetrafluoro- benzene of C 54.5%, H 6.1%, N 10.6%, F 28.6%.
Analysis by nmr gave delta=2.19 (6 p,s) and delta=3.60 (2p,s) attributable to (CH3)2-N-C- and Ar-CH2-N protons, respectively. Anaylsis by UV (0.5 N HCI in 50/50 methanol/water) gave ,imam=279 nm, E=2.17x103, A min=237 nm.
The Infra Red spectrum of the solid (KBr disc) showed peaks at the following wavelengths: 2985, 2975, 2860,2820, 2780,2760, 1485, 1465,1440,1415, 1405,1375,1318,1277, 1255, 1177, 1154, 1096, 1030, 940, 873, 840, 700, 601 cm-'.
Example 4 5 9 of 1 ,4-dicyano-2,3,5,6-tetrafluoro- benzene, 0.5 g of 5% palladium on carbon, 3.5 g of sulphuric acid, 75 ml of methanol and 5 g formaldehyde were loaded to a glass-lined rotating autoclave, and, after purging, pressurised to 20 atmospheres with hydrogen. The autoclave was rotated at 750for 12 hours. 6.08 g crude material were isolated by the procedures described in Example 2, and consisted of 89.7% 1,4-bis(dimethylam inomethyl)-2,3,5,6tetrafluorobenzene (82.6% yield).
Quaternisation of I ,4bis(dimethylamino- methyl)-2,3,5,6-tetrafluorobenzene
Example 5
2.0 g of crude 1 ,4-bis(dimethylaminomethyl) 2,3,5,6-tetrafluorobenzene, 60 ml 80% ethanol and 1.6 g methyl chloride were heated to 400C for 23 hours in a flask fitted with a reflux condenser topped with a "Dri-Cold" finger.
Further methyl chloride was added and the mixture heated for another 24 hours. Only trace quantities of the starting tertiary amine remained.
Example 6
2.0 g of crude 1 ,4-bis(dimethylaminomethyl)- 2,3,5,6-tetrafluorobenzene (819/0 pure), 50 ml
75% aqueous ethanol and 0.3 g magnesium oxide were heated to 550C and a stream of methyl
chloride passed through for 24 hours. The
suspension was filtered, and the solvent removed from the filtrate to give 2.5 g of the crude
diquaternary compound. Potentiometric titration
gave a titre equivalent to about 1.5% of the
original diamine.
Example 7
100 g of 1 ,4-bis(dimethylaminomethyl)- 2,3 ,5,6-tetrafluorobenzene (average strength 96.2%), 300 ml 74 OP ethanol and 200 ml water,
were heated with methyl chloride at 68-750C until analysis indicated less than 2.5% half
quaternised material to be present in the reaction
mixture. The product solution was reduced to
about 180 ml and separated solid was
recrystallised from 100 ml of 50% aqueous
ethanol to give 20.2 g of white solid.
Elemental analysis of the white solid, which
was stable to at least 3000C, gave C 45.8%, H 6.1%, N 7.6%, Cl 19.5%, F 22.5% against theory
for 1 ,4-bis(trimethylammoniomethyl)-2,3,5,6 tetrafluorobenzene dichloride of C 46.0%, H 6.0%,
N 7.7%, Cl 19.5% and F 20.8%. Analysis by nmr
gave delta=3.32 (9 p,s) and delta=4.87 (2 p,s)
attributable to N(CH3)3 and Ar-CH2-N, protons
respectively. UV Amax=283 nm. The Infra Red
spectrum of the solid (KBr disc) showed peaks at the following wavelengths: 3100,2960, 1500, 1490,1450,1420,1390, 1355,1290,1145, 1050,985,960,900,865, 695, 600 cm-1.
Complete deammination of 1,4-bis(trimethyl- ammoniomethyl)-2,3,5,6-tetrafluorobenzene dichloride
(i) By hydrogenolysis
Example 8
25 ml of the product solution obtained from
Example 5 and 0.5 g of 5% palladium on charcoal powder, were charged to a glass-lined rotating autoclave, pressurised to 25 atmospheres with hydrogen, and rotated at 900for 10 hours. 19
ml of solution containing 0.219 1 ,4-dimethyl- 2,3,5,6-tetrafluorobenzene were recovered, with
no defluorination indicated in any of the products when examined by GLC/mass spectroscopy.
(ii) By reductive electrolysis
Example 9 (H Cell)
A solution of 1 ,4-bis(trimethylammonio- methyl)-2,3,5,6-tetrafluorobenzene dichloride (1.5 g) in 7.5 ml of water was introduced into the cathode compartment of an H cell of all-glass construction. A saturated aqueous solution of sodium sulphate (25 ml) was used as the anolyte.
The H cell had a lead cathode (2 cm2), a platinum on titanium anode and was divided by a Nafion membrane. A voltage of 11 v was applied across the electrodes for 2.6 hours at ambient temperature generating a current density of 1 00mAcm-2.
1,4-Dimethyl-2,3,5,6-tetrafluorobenzene separated from the catholyte giving a yield of
78%. The current effiency was 65.5%.
Example 10 (Filter Press cell)
A solution of 1 ,4-bis(trimethylammonio- methyl)-2,3,5,6-tetr fluorobenzene dichloride (20 g) in 100 ml water was used as the catholyte and a saturated aqueous solution of sodium sulphate
(250 ml) as the anolyte in a Filter Press (Plateand-Frame) divided cell. The cell had a lead cathode (30 cm2), a platinum anode (30 cm2) and a separating Nafion cation exchange membrane.
A voltage of 8 v was applied across the electrodes for 2.3 hours at ambient temperature generating
a current density of 100 mAcm-2.
Conversion of the bis quaternary salt to 1,4
dimethyl-2,3,5,6-tetrafluorobenzene was 76%
and the current efficiency was 66%.
Partial deammination of 1,4-bis(trimethyl- ammoniomethyl)-2,3,5,6-tetrafluorobenzene dichloride
Example 11
1.0 g of the diquaternary compound obtained from Example 6, 25 ml 75% aqueous ethanol, and
0.5 g of 5% palladium on carbon were stirred under hydrogen at 700C for 43 hours. Only a trace quantity of 1 ,4-dimethyltetrafluorobenzene was formed. Potentiometric titration indicated formation of an amount of trimethylamine consistent with deammination to (4-methyl 2,3,5,6-tetrafluorobenzyl)-trimethylammonium chloride. Ultraviolet spectroscopy showed formation of a compound with ajax=273 nm [cf
Amax=283 nm for the diquaternary compound (solvent 0.5N HCI in 50% aqueous methanol)l.
Example 12
6g of 1 ,4-bis(trimethylammoniomethyl)- 2,3,5,6-tetrafluorobenzene dichloride, 50 ml of ethanol, 7.5 ml of water and 1.5 g of 5% palladium on carbon (T87P dry powder obtained from Johnson Matthey Ltd.) were charged to a glass-lined rotating autoclave which was pressurised to about 6 atmospheres with hydrogen and rotated at 1 000C for 1 5 hours. The reaction mixture was filtered and solvent removed from the filtrate by evaporation to yield 5.9 g of solid material.This was extracted with 40 ml of acetone and the extract evaporated to give 7.7 g of a mixture of trimethylamine hydrochloride and a product identified in the mixture as (4-methyl 2,3,5,6-tetrafluorobenzyl)trimethylammonium chloride by proton nmr which gave delta=2.36 (3 p, poorly resolved triplet), delta=3.28 (9p, singlet), delta=-4.87 (2p, singlet), attributed to the CH3-, -N(CH3)3+, and -CH2-N protons respectively; UV Amax was 273 nm. Strength by nmr of the monoquaternary salt of the mixture was 69.4%..
Example 13 (For comparative purposes only)
Deamination of 1,4-bis(dimethylamino- methyl)-2,3,5,6-tetrafluorobenzene
1.0 g of crude 1 ,4-bis(dimethylaminomethyl)- 2,3,5,6-tetrafluorobenzene, 30 ml of 90% ethanol, and 1.0 g of 5% palladium on charcoal were heated under hydrogen at atmospheric pressure at 500C for 1 9 hours, with agitation.
Approximately 98% of the starting material was converted, mainly to p-xylene, monofluoro-pxylene, and N-dimethyl-p-methylbenzylamines containing 1 to 3 nuclear fluorine atoms.
Claims (14)
1. Method of preparing tetrahalobenzene compounds of the formula (I):
in which each X is independently chloro orfluoro and Y is hydrogen or -N+R3A- in which R is independently C14 alkyl, and A is a radical capable of forming an anion A-, the method comprising partially or completely reductively cleaving the compound of formula (IV):
to replace one or both -N+R3A- groups by hydrogen.
2. Method according to claim 1 in which compound (IV) is reductively cleaved by reaction with hydrogen in the presence of a palladium catalyst.
3. Method according to claim 1 in which compound (IV) is reductively cleaved completely to replace both -N+R3A- groups by hydrogen by electrolysing compound (IV) in a protic medium.
4. Method of preparing tetrahalobenzene compounds of the formula (I):
in which each X is independently chloro or fluoro and Y is hydrogen or -N+R3A- in which R is independently C14 alkyl, and A is a radical capable of forming an anion A-, the method comprising treating a compound of formula (III):
with a quaternising agent of formula RA to form a compound of formula (IV):
and partially or completely reductively cleaving the compound of formula (IV):
to replace one or both -N+R3A groups by hydrogen.
5. Method of preparing tetrahalobenzene compounds of the formula (I):
in which each X is independently chloro or fluoro and Y is hydrogen or -N+R3A in which each R is indpendently C14 alkyl, and A is a radical capable of forming an anion A-, the method comprising the steps of
(a)alkylating a compound of formula (ill):
or a salt thereof, to form a compound of formula (111):
(b) treating the compound of formula (III) with
a quaternizing agent of formula RA to form a
compound of formula (IV):
and
(c) partially or completely reductively cleaving
the compound of formula (IV) to replace one
or both -N+R3A groups by hydrogen.
6. A compound of the formula (III):
in which X is independently chloro or fluoro and each R is independently C,, alkyl.
7. A compound of the formula (V):
8. A method of preparting the compound (III) according to claim 6 which comprises alkylating a compound of the formula (II):
or a salt thereof.
9. A compound of the formula (IV):
in which X is independently chloro orfluoro, each
R is independently C,, alkyl and A is a radical capable of forming an anion A-.
10. A compound of the formula (Vl):
in which A is a radical capable of forming an anion
A-.
11. A method of preparing the compound (IV) according to claim 9 which comprises treating the compound of the formula (III):
in which X is independently chloro or fluoro and R is independently C1-4 alkyl, with a quaternising agent of formula RA.
12. A method of preparing the compound (IV) according to claim 9 which comprises alkylating a compound of the formula (II):
in which X is indpedently chloro or fluoro, or a salt thereof to form a compound of the formula (III):
and treating the compound (III) with a quaternising agent of formula RA.
13. A compound of the formula (Vll):
in which X is independently chloro or fluoro, each
R is independently C1~4 alkyl and A is a radical capable of forming an anion A-.
14. A compound of the formula (VIII):
in which A is a radical capable of forming an anion
A-.
Priority Applications (1)
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GB08400100A GB2134109B (en) | 1983-01-26 | 1984-01-04 | Method of preparing tetrahalobenzene compounds, chemical intermediates used therein and certain of the compounds themselves |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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GB838302155A GB8302155D0 (en) | 1983-01-26 | 1983-01-26 | Chemical process |
GB838329956A GB8329956D0 (en) | 1983-11-10 | 1983-11-10 | Chemical process |
GB08400100A GB2134109B (en) | 1983-01-26 | 1984-01-04 | Method of preparing tetrahalobenzene compounds, chemical intermediates used therein and certain of the compounds themselves |
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Publication Number | Publication Date |
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GB8400100D0 GB8400100D0 (en) | 1984-02-08 |
GB2134109A true GB2134109A (en) | 1984-08-08 |
GB2134109B GB2134109B (en) | 1986-09-10 |
Family
ID=27261936
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GB08400100A Expired GB2134109B (en) | 1983-01-26 | 1984-01-04 | Method of preparing tetrahalobenzene compounds, chemical intermediates used therein and certain of the compounds themselves |
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1984
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GB2134109B (en) | 1986-09-10 |
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