GB1570937A - Process for the production of n - (2 - methyl - 4 - chlorophenyl) - formamidine derivatives - Google Patents
Process for the production of n - (2 - methyl - 4 - chlorophenyl) - formamidine derivatives Download PDFInfo
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- GB1570937A GB1570937A GB862477A GB862477A GB1570937A GB 1570937 A GB1570937 A GB 1570937A GB 862477 A GB862477 A GB 862477A GB 862477 A GB862477 A GB 862477A GB 1570937 A GB1570937 A GB 1570937A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
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Abstract
A process is described for the preparation of N-(2-methyl-4-chlorophenyl)formamidine derivative of the formula <IMAGE> in which R1 denotes hydrogen or an alkyl group having 1 to 4 carbon atoms and R2 denotes an alkyl group having 1 to 4 carbon atoms, which is based on reacting an alkyl formamide with an inorganic acid chloride, condensation of the resulting intermediate with o-toluidine and chlorination of the resulting N-(2-methylphenyl)formamidine derivative. The essential feature of the process is that all reaction steps are carried out in a halogenated hydrocarbon. The N-(2-methyl-4-chlorophenyl)formamidine derivatives of the above formula which can be prepared by this process are pesticides, in particular acaricides.
Description
(54) PROCESS FOR THE PRODUCTION OF N-(2-METHYL-4
CHLOROPHENYL)-FORMAMIDINE DERIVATIVES
(71) We, CIBA-GEIGY AG, a Swiss body corporate, of Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to a process for the production of N-(2-methyl-4chlorophenyl) -formamidine derivatives of formula I
wherein R1 is hydrogen or an alkyl radical having 1 to 4 carbon atoms, and R2 is an alkyl radical of 1 to 4 carbon atoms.
The N - (2 - methyl - 4 - chlorophenyl) - formamidine derivatives of formula I possess a strong selective toxicity against acarids in all stages of development as it is described in detail in U.S. Patents Nos. 3,378,437 and 3,502,720.
According to a method known from the aforementioned patents the N-(2-methyl4-chlorophenyl)-formamidine derivatives of formula I are prepared by reacting an alkylformamide of formula II
wherein R1 and R2 have the meaning given above, with phosphorus oxychloride to form a salt-like intermediate which is, without isolation, immediately further reacted with 2 - amino - 5 - chlorotoluene to the desired N - (2 - methyl - 4 - chlorophenyi)- formamidine derivatives of formula I. The structure of the salt-like intermediate formed by reaction on an alkylformamide of formula II and phosphorus oxychloride most likely corresponds to formula
as it is described by H. Bredereck et al in Chem. Ber. 92, 837-849 (1959).Since other acid halogenides are reported to form analogous products of formula III
wherein R1 and R2 have the meaning given above and Ac is an acyl group which corresponds to the acid chloride used, will be ascribed to the salt-like intermediates referred to in this specification.
The known process referred to above is disadvantageous in that the 2-amino5-chlorotoluene needed as intermediate has to be prepared from o-toluidine in a multistep process. According to this process o-toluidine is converted into its N-acyl compound, for example by reaction with acetyl chloride. The 2-acetylamino-toluene thus obtained is then chlorinated to form 2-acetylamino-5-chlorotoluene which is hydrolysed to 2-amino-5-chlorotoluene. This process has the further disadvantage that large quantities of by-products, namely 2-acetylamino-3-chlorotoluene and 2-acetylamino3,5-dichlorotoluene, are formed on chlorination of 2-acetylaminotoluene which have to be separated from the desired product together with unchlorinated product.
In view of these difficulties encountered in the preparation of 2-amino-5-chlorotoluene it has already been proposed to prepare the N-(2-methyi-4-chlorophenyl)- formamidine derivatives of formula I by chlorination of the corresponding N-(2methylphenyl)-formamidine derivatives which in turn are obtained according to the afore-mentioned method by reacting an alkylformamide of formula II with phosphorus oxychloride and further reacting the salt-like intermediate formed with o-toluidine.
According to this method described in U.S. Patent No. 3,911,012 the chlorination of
N - (2 - methylphenyl) - N,N - dialkylformamidines is preferably performed in an aqueous reaction medium. Further, it is mentioned that the chlorination can also be performed in organic solvents such as alcohols or glacial acetic acid.
This process is objectionable in that the preparation of the salt-like intermediate obtained by reaction of an alkyl-formamide of formula II with phosphorus oxychloride and/or the preparation of the N - (2 - methylphenyl) - N',N' - dialkylformamidine and-the-chlorinatio-n must We carried,ut in different soiven4s, and, as a consequence thereof, at least one of these products must be isolated and transferred into another solvent Further, if the chlorination is carried out in glacial acetic acid additional alkali metal hydroxide is necessery to neutralize the reaction mixture in order to make the isolation of the chlorinated product possible.
It is, therefore, the object of the present invention to provide a process for the production of N - (2 - methyl - 4 - chlorophenyl) - formamidine derivatives of formula I in which all reaction steps involved, namely formation of the salt-like intermediate, condensation of this intermediate with o-toluidine to a N- (2-methyl- phenyl)-formamidine derivative and chlorination of the latter to the desired N-(2 methyl-4-chlorophenyl) -formamidine derivative of formula I, can be performed in the same solvent.
Particularly, it is the object of the present invention to provide a process for the production of N-(2-methyl-4-chlorophenyl)-formamidine derivatives of formula I in which all reaction steps involved are performed in the same solvent in which all intermediates formed are soluble, i.e. the whole process is performed in a homogeneous reaction medium.
It has been found that all reaction steps involved in the production of N-(2 methyl-4-chlorophenyl) -formamidine derivatives of formula I can be performed in a solvent selected from halogenated hydrocarbons.
Accordingly, the present invention comprises a process for the production of N (2-methyl-4-chlorophenyl)-formamidine derivatives of formula I wherein the steps of reacting an alkylformamide of formula II
with an inorganic acid chloride selected from phosphorus oxychloride, thionyl chloride and phosgene to form a salt-like intermediate of formula IIIa
wherein X represents --OO-POCI,, -OSOCI or chlorine respectively, condensing this intermediate with o-toluidine and chlorinating the hydrochloride of the N-(2methylphenyl)-formamidine derivative formed to a N-(2-methyl-4-chlorophenyl)- formamidine derivative of formula I are performed in the same solvent which is selected from halogenated hydrocarbons.
Suitable halogenated hydrocarbons are for example 1,2-dichloroethane, 1,1,1trichloroethane, tetrachloroethane, chlorobenzene, o-dichlorobenzene, carbon tetrachloride and, preferably, chloroform.
Among the inorganic acid chlorides mentioned above phosgene is preferred. The salt-like intermediate primarily formed bv reacting phosgene with an alkylformamide of formula II corresponds to formula III. wherein Ac is -COCI. However, this product is unstable under the reaction conditions and decomposes according to the equation:
The salt-like intermediate of formula IIIa is formed by reacting an alkylformamide of formula II with one of the aforementioned acid chlorides, preferably with phosgene, in one of the aforementioned halogenated hydrocarbons, preferably in chloroform, usually at a temperature within the range of from - 10 to +SO"C, preferably from 10 to 300C.
The molar ratio of acid chloride to alkylformamide of formula II is essentially 1:1. However, each of the reactants can be used in excess of up to 20 mol /O. The molar ratio of phosgene to alkylformamide of formula II is preferably 0.95 to 0.98:1:
The condensation of a salt-like intermediate of formula IIIa with o-toluidine is usually carried out at a temperature of from 0 to 600 C, preferably 20 to 400 C. It is favorable to provide an excess salt-like intermediate of formula IIIa in order to complete the reaction.The chlorination of the hydrochlorides of the N-(2-methylphenyl)-formamidine derivatives formed by condensation of a salt-like intermediate of formula IIIa with an alkylformamide of formula II is usually carried out at a temperature of from 0 to 500 C, preferably 5 to 25 0C. The chlorination is preferably effected with chlorine gas. However other chlorinating agents, such as hypochlorites and N-chloro compounds, can also be used.According to a preferred embodiment of the present invention the N - (2 - methyl - 4 - chlorophenyl) - formamidine derivatives of formula I are prepared by reacting phosgene with an alkylformamide of formula II in a molar ratio of 0.95--0.98:1 at a temperature of 10 to 30"C in chloroform to form a salt-like intermediate of formula IIa, wherein X is chlorine, condensing this intermediate at 20 to 40"C with o-toluidine and subsequently chlorinating the hydrochloride of the N - (2 - methylphenyl) - formamidine derivative formed at a temperature of from 5 to 25 C.
As illustrated by Example 3 hereinafter, the o-toluidine can be charged to a
reactor vessel at the start of the process, along with the alkylformamide. It does not
enter into reaction until the salt-like intermediate is formed.
The N - (2 - methyl - 4 - chlorophenyl) - formamidine derivatives of formula I
can be isolated from the reaction mixture in the usual way, for example by adding an
aqueous solution of an alkali metal hydroxide to the reaction mixture, separating the
two layers formed and evaporating the solvent from the organic layer to obtain the
free N - (2 - methyl - 4 - chlorophenyl) - formamidine derivative of formula I.On
the other hand if phosgene or thionyl chloride was used for the formation of the salt
like intermediate of formula IIIa, it is also possible to remove the solvent completely
or partially from the reaction mixture to obtain the crystalline hydrochloride of a
N - (2 - methyl - 4 - chlorophenyl) - formamidine derivative or to extract the reaction
mixture with water to obtain an aqueous solution of the hydrochloride of an N - (2 methyl - 4 - chlorophenyl) - formamidine derivative of formula I. The process according to the present invention is particularly suitable for the production of N - (2methyl - 4 - chlorophenyl) - N',N' - dimethylformamidine and N - (2 - methyl - 4chlorophenyl) - N' - methyl - N' - n - butylformamidine.
The main advantage of the process according to the invention over the previously known methods is that all operations involved can be carried out in the same solvent.
Additional advantages are gained if the whole process is performed in chloroform which is the preferred solvent according to the present invention and with phosgene as acid chloride which is also preferred. If carried out in chloroform the whole process can be performed in a homogeneous reaction medium because all intermediates and the
final products present as hydrochlorides are soluble in the reaction mixture. This is particularly advantageous for the continuous performance of the process. Further, solvent losses are reduced to a minimum because chloroform is readily absorbed in alkylformamides of formula II. Therefore, the carbon dioxide emerging from the reaction mixture which is saturated with chloroform can be treated with the alkylformamide of formula II which is subsequently transformed into the salt-like intermediate of formula IIIa to absorb the chloroform.This is both an economical advantage as well as an ecological advantage.
The process according to the present invention is further illustrated by the following examples.
Example 1.
At a temperature of 18-220C 99 kg (1000 moles) of phosgene are introduced into a solution of 74.5 kg (1019 moles) of dimethylformamide in 360 kg dry chloroform which is placed in an enamelled reaction vessel provided with a stirrer. The
carbon dioxide emerging from the reaction mixture is freed from chloroform and traces
of phosgene by washing with dimethylformamide. Then 101.3 kg (945 moles) of o- toluidine are introduced into the homogeneous solution obtained within two hours at an
inner temperature of 22--27"C. After addition of the o-toluidine the homogeneous solution formed is stirred for 30 minutes. Thereafter, at a temperature of 15-200C 67 kg (945 moles) of chlorine are introduced within 4 hours.During the addition of chlorine the pressure in the reaction vessel increases from 1 atmosphere to 1.3 atmospheres. After addition of the chlorine the homogeneous solution is stirred for one hour.
Thereafter 150 kg of water are added whereby two layers are formed. After separation the aqueous layer is heated to 100--105"C to remove residual chloroform and excess
hydrogen chloride. Then a 25% by weight aqueous sodium hydroxide solution is added the cooled solution until a pH value of 11 is reached. The crude oily product is separated and purified by fractional distillation. There are obtained:
7.7 kg (5% of the theoretical amount) of N - (2 - methylphenyl) - N',N' - di
methylformamidine, b.p. 128--1300C/11 torr.
11.0 kg (5% of the theoretical amount of N - (2 - methyl - 6 - chlorophenyl)
N',N' - dimethylformamidine, b.p. 144-1460C/11 torr.
147.0 kg (80% of the theoretical amount) of N - (2 - methyl - 4 - chlorophenyl)
N',N' - dimethylformamidine b.p. 159-1610C/11 torr.
It is also possible to isolate the N - (2 - methyl - 4 - chlorophenyl) dimethylformamidine as hydrochloride. For this purpose the third part of the chloroform present in the solution obtained after chlorination is distilled off and the same volume of xylene is added. The precipitated hydrochloride is separated by filtration, washed with xylene and dried.
Example 2.
At a temperature of 25--30"C, 71 kg (718 moles) of phosgene are introduced within 5 hours into a solution of 54.1 kg (740 moles) of dry dimethylformamide in
280 kg of chlorobenzene which is placed in an enamelled reaction vessel provided with
a stirrer. After addition of the phosgene the reaction mixture is stirred for 30 minutes
at 25-300C. Then, at a temperature of 4550 C, 74 kg (690 moles) of o-toluidine are added within 2 hours and the reaction mixture is stirred for an additional hour at 75-800C. The mixture is cooled to 30"C and a solution of 1 kg of triethanolamine in 1 kg of chlorobenzene is added.Subsequently the pressure in the reaction vessel is reduced to 200 torr and 52.5 kg (740 moles) of chlorine are introduced within 6 hours at 30-350C in the following manner: First an amount of chlorine is introduced which is sufficient to increase the pressure in the reaction vessel to 1140 torr. Then the addition of chlorine is stopped and the mixture is stirred for 1 hour. Thereafter, the pressure is again reduced to 200 torr and the residual chlorine is introduced. After addition of the chlorine the reaction mixture is stirred for 2 hours at 30--350C. Then, after equalisation of the pressure 150 kg of water are added to the suspension of N (2 - methyl - 4 - chlorophenyl) - N',N' - dimethylformamidine hydrochloride obtained while the temperature is kept below 50 C by cooling.Thereafter, residual chlorine is removed by addition of an aqueous sodium bisulfite solution and, after separating of the two layers a 25 / by weight aqueous solution of sodium hydroxide is added to the aqueous layer until a pH value of 11 is reached. The crude oily product is then separated and purified by fractional distillation. 115 kg (80% of the theoretical amount) of N - (2 - methyl - 4 - chlorophenyl) - N',N' - dimethylformamidine, b.p. 1411430C/0.5 torr are obtained.
Example 3.
In an enamelled reaction vessel provided with a stirrer a mishlre of 235 1. of chloroform, 45.5 kg (395 moles) N - Methvl - N - n - butylformamide and 40 kg (374 moles) of o-toluidine is heated to 60"C. To this solution 52 kg (437 moles) of thionyl chloride are added within 1 hour while the temperature is kept at 60"C. After stirring for 1 additional hour the reaction mixture is cooled to S-100C and after addition of 0.4 kg of iodine, 37.5 kg (530 moles) of chlorine are introduced within 4 hours and the mixture obtained is stirred for additional 12 hours at 200 C. Subsequently hydrogen chloride and excess chlorine are removed by bubbling a stream of nitrogen through the reaction mixture.The whole mixture is then poured onto 140 kg of ice and 15 kg of a 24% by weight aqueous solution of sodium bisulphite while stirring at a temperature not exceeding 15"C. After adjusting a pH value of 10-11 by addition of a 30% by weight aqueous solution of sodium hydroxide the whole is stirred for 1 hour. Then the organic layer is separated and, after washing with 70 kg of water, the solvent is evaporated in vacuo.The crude product thus obtained is purified by distillation in vacuo. 85 kg of a product, b.p. 130-1350C/0.5 torr are obtained containing
86% of N - (2 - methyl - 4 - chlorophenyl) - N' - methyl - N' - n - butylform
amidine 1% of N - (2 - methylphenyl) - N' - methyl - N' - n - butylformamidine
7.2% of N - (2 - methyl - 6 - chlorophenyl) - N' - methyl - N' - n - butyl
formamidine
2% of N - (2 - methyl - 4,6 - dichlorophenyl) - N' - methyl - N' - n - butyl
formamidine
0.2% of 2 - amino - 5 - chlorotoluene
0.2% of N - methyl - N n - butylformamide
3% of non-identified by products
(all percentages by weight)
Example 4.
At a temperature of 20-400C 370 kg of phosgene are introduced within in 3 hours into a mixture of 1150 kg of o-dichlorobenzene and 249 kg of dry dimethylformamide which is placed in an enamelled reaction vessel provided with a stirrer.
After addition of the phosgene the pressure in the reaction vessel is reduced to 200 torr in order to remove unreacted phosgene. Then 300 kg of o-toluidine are added whereby care is taken that the temperature does not exceed 60"C. Subsequently the reaction mixture is heated to 800C and kept at this temperature for 2 hours.
Then 25 kg of triethanolamine are added and 235 kg of chlorine are introduced at a temperature of 20-40"C. The hydrogen chloride formed during chlorination is led to a caustic soda/sodium thiosuiphate scrubber. Then, after stirring the reaction mixture for two hours, 650 kg of water are added while cooling and excess chlorine present in the reaction mixture is removed by addition of sodium bisulphite. After separation of the organic phase 280 kg of toluene are added to the aqueous phase and the mixture is stirred for 10 minutes. Then, after separation of the toluene, 400 kg of fresh toluene are added and the pH value of the whole mixture is adjusted to 10 by addition of 820 kg of 30% by weight aqueous sodium hydroxide. The addition of sodium hydroxide is made at such a rate that the whole mixture has a temperature of 35400C at the end of the addition. After addition of the sodium hydroxide the whole mixture is stirred for 2 hours at 3546oC and thereafter the two layers are separated. The organic layer which contains the product is worked up by distillation.
At first a water-containing fraction is obtained under slightly reduced pressure. Then the toluene is distilled off in vacuo. Finally, by raising the temperature, about 10 kg of a third fraction are obtained which consists essentially of o-dichlorobenzene. The distillation is stopped when a temperature of 145"C at the bottom and 85-900C at the head of the column is reached. The crude N - (2 - methyl - 4 - chlorophenyl) N',N' - dimethylformamidine obtained as residue is purified by distillation in vacuo.
455 kg (74.3% of theory) of N - (2 - methyl - 4 - chlorophenyl) -N',N' - dimethylformamidine, b.p. 159-1610C/11 torr are obtained.
WHAT WE CLAIM IS:
1. A process for the production of N - (2 - methyl - 4 - chlorophenyl) - formamidine derivatives of formula I
wherein R1 is hydrogen or an alkyl radical having 1 to 4 carbon atoms, and R2 is an alkyl radical having 1 to 4 carbon atoms, wherein the steps of reacting an alkylformamide of formula II
with an inorganic acid chloride selected trom phosphorus oxychlorlde, tnionyl cmoricie and phosgene to form a salt-like intermediate of formula IIIa
wherein X represents --OO-POCI,, --OSOC1 or chlorine respectively, condensing this intermediate with o-toluidine and chlorinating the hydrochloride of the N-(2methylphenyl)-formamidine derivative formed to a N-(2-methyl-4-chlorophenyl)- formamidine derivative of formula I are performed in the same solvent which is selected from halogenated hydrocarbons.
2. A process according to claim 1 which is performed in a solvent selected from 1,2-dichloroethane, 1,1,1 -trichioroethane, tetrachioroethane, chlorobenzene, o-dichlorobenzene, carbon tetrachloride and chloroform.
3. A process according to claim 1, wherein chloroform is used as solvent.
4. A process according to claim 1, 2 or 3, wherein phosgene is used as inorganic acid chloride.
5. A process according to claim 4, wherein phosgene is reacted with an alkylformamide of formula II in a molar ratio of 0.95-0.98:1 at a temperature of 10 to 30"C in chloroform to form a salt-like intermediate of formula IIIa, wherein X is chlorine, condensing this intermediate at 20 to 400C with o-toluidine and subsequently chlorinating the hydrochloride of the N - (2 - methylphenyl) - formamidine derivative formed at a temperature of from 5 to 250C.
6. A process according to any one of claims 1 to 5, wherein N,N-dimethylformamide is used as alkylformamide of formula II.
7. A process according to any one of claims 1 to 5, wherein N-methyl-N-n-butylformamide is used as alkylformamide of formula II.
8. A process according to any preceding claim, wherein the chlorination is effected with chlorine gas.
9. A process according to claim 1 substantially as described in any one of
Examples 1 to 4.
10. N - (2 - Methyl - 4 - chlorophenyl)formamide derivatives of the formula I when produced by the process of any of claims 1 to 9.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (10)
- **WARNING** start of CLMS field may overlap end of DESC **.of a third fraction are obtained which consists essentially of o-dichlorobenzene. The distillation is stopped when a temperature of 145"C at the bottom and 85-900C at the head of the column is reached. The crude N - (2 - methyl - 4 - chlorophenyl) N',N' - dimethylformamidine obtained as residue is purified by distillation in vacuo.455 kg (74.3% of theory) of N - (2 - methyl - 4 - chlorophenyl) -N',N' - dimethylformamidine, b.p. 159-1610C/11 torr are obtained.WHAT WE CLAIM IS: 1. A process for the production of N - (2 - methyl - 4 - chlorophenyl) - formamidine derivatives of formula Iwherein R1 is hydrogen or an alkyl radical having 1 to 4 carbon atoms, and R2 is an alkyl radical having 1 to 4 carbon atoms, wherein the steps of reacting an alkylformamide of formula IIwith an inorganic acid chloride selected trom phosphorus oxychlorlde, tnionyl cmoricie and phosgene to form a salt-like intermediate of formula IIIawherein X represents --OO-POCI,, --OSOC1 or chlorine respectively, condensing this intermediate with o-toluidine and chlorinating the hydrochloride of the N-(2methylphenyl)-formamidine derivative formed to a N-(2-methyl-4-chlorophenyl)- formamidine derivative of formula I are performed in the same solvent which is selected from halogenated hydrocarbons.
- 2. A process according to claim 1 which is performed in a solvent selected from 1,2-dichloroethane, 1,1,1 -trichioroethane, tetrachioroethane, chlorobenzene, o-dichlorobenzene, carbon tetrachloride and chloroform.
- 3. A process according to claim 1, wherein chloroform is used as solvent.
- 4. A process according to claim 1, 2 or 3, wherein phosgene is used as inorganic acid chloride.
- 5. A process according to claim 4, wherein phosgene is reacted with an alkylformamide of formula II in a molar ratio of 0.95-0.98:1 at a temperature of 10 to 30"C in chloroform to form a salt-like intermediate of formula IIIa, wherein X is chlorine, condensing this intermediate at 20 to 400C with o-toluidine and subsequently chlorinating the hydrochloride of the N - (2 - methylphenyl) - formamidine derivative formed at a temperature of from 5 to 250C.
- 6. A process according to any one of claims 1 to 5, wherein N,N-dimethylformamide is used as alkylformamide of formula II.
- 7. A process according to any one of claims 1 to 5, wherein N-methyl-N-n-butylformamide is used as alkylformamide of formula II.
- 8. A process according to any preceding claim, wherein the chlorination is effected with chlorine gas.
- 9. A process according to claim 1 substantially as described in any one of Examples 1 to 4.
- 10. N - (2 - Methyl - 4 - chlorophenyl)formamide derivatives of the formula I when produced by the process of any of claims 1 to 9.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66230576A | 1976-03-01 | 1976-03-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1570937A true GB1570937A (en) | 1980-07-09 |
Family
ID=24657205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB862477A Expired GB1570937A (en) | 1976-03-01 | 1977-03-01 | Process for the production of n - (2 - methyl - 4 - chlorophenyl) - formamidine derivatives |
Country Status (3)
| Country | Link |
|---|---|
| CH (1) | CH626333A5 (en) |
| DE (1) | DE2708616A1 (en) |
| GB (1) | GB1570937A (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL302685A (en) * | 1963-01-18 | |||
| US3502720A (en) * | 1963-12-20 | 1970-03-24 | Schering Ag | N-(2-methyl-4-chlorophenyl)-formamidines |
| US3911012A (en) * | 1970-07-14 | 1975-10-07 | Schering Ag | Method of preparing 4-chloro-derivatives of phenylformamidine and salts thereof |
| DE2139046C3 (en) * | 1970-08-27 | 1975-04-10 | Ciba-Geigy Ag, Basel (Schweiz) | Formamidines and their salts, production of the same and compositions containing them for combating insects and representatives of the order Akarina |
| DE2417669A1 (en) * | 1974-04-11 | 1975-10-16 | Hoechst Ag | METHOD OF PREPARING N (HALOGENARYL) -N ', N'-DIALKYLAMIDINES |
-
1977
- 1977-02-25 CH CH239777A patent/CH626333A5/en not_active IP Right Cessation
- 1977-02-28 DE DE19772708616 patent/DE2708616A1/en not_active Ceased
- 1977-03-01 GB GB862477A patent/GB1570937A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2708616A1 (en) | 1977-09-08 |
| CH626333A5 (en) | 1981-11-13 |
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