CA1180018A - Halomethyltriazoles - Google Patents
HalomethyltriazolesInfo
- Publication number
- CA1180018A CA1180018A CA000397946A CA397946A CA1180018A CA 1180018 A CA1180018 A CA 1180018A CA 000397946 A CA000397946 A CA 000397946A CA 397946 A CA397946 A CA 397946A CA 1180018 A CA1180018 A CA 1180018A
- Authority
- CA
- Canada
- Prior art keywords
- formula
- triazole
- hal
- process according
- chloromethyl
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Abstract of the Disclosure The invention discloses halonethyltriuzoles of the formula I
Hal-CH2 -
Hal-CH2 -
Description
5-13321/=
Halomethyltriazoles The present invention relates to novel l-halomethyl-lH-1,2,4-triazoles and to a process for their production. The invention further relates to a novel process for obtaining the starting compound, l-hydroxy-.
methyl-lH-1,2,4-triazole.
The l-halamethyl-lH-1,2,4-triazoles have the general formula I
,N=
: 2 \ ~
wherein Hal is chlorine, bromine and iodine.
.
The compounds of formula I are employed as starting compounds for obtaining triazolylmethyl phosphonates of the formula II
~ ~ CH2 ~ N\ ~ (II), wherein each of the radicals Rl independently of the other is phenyl or Cl-C~alkyl, or triazoly].methyl phosphonium compo~mds of the ~ormula -.LII
Halomethyltriazoles The present invention relates to novel l-halomethyl-lH-1,2,4-triazoles and to a process for their production. The invention further relates to a novel process for obtaining the starting compound, l-hydroxy-.
methyl-lH-1,2,4-triazole.
The l-halamethyl-lH-1,2,4-triazoles have the general formula I
,N=
: 2 \ ~
wherein Hal is chlorine, bromine and iodine.
.
The compounds of formula I are employed as starting compounds for obtaining triazolylmethyl phosphonates of the formula II
~ ~ CH2 ~ N\ ~ (II), wherein each of the radicals Rl independently of the other is phenyl or Cl-C~alkyl, or triazoly].methyl phosphonium compo~mds of the ~ormula -.LII
2 ~ C~12 N\ I ~lal ~ (.tII), wherein each of the radicals R2 independent:Ly o:t one another is yhenyl or CL-C4aLkyl which i8 msul)stituted or subst:;tuted by hydroxyl, and Hal is as definecl for formula I.
5-l3321/=
: Abstract of the Disclosure : Halomethyltriazoles . . . _ .
The invention discloses halomethyltria~oles of the formula I
,N=-Hal - CH2 - ~
. =
wherein Hal is chlorine, bromine and iodine.
.
The compounds of formula I are important intermediates for obtaining highly active plant fungicides.
These compounds are used in turn for the production of fungicidal phenylethylenyltriazoles of the formula IV
Ar\ /N=.
~ C -- CH - N ¦ (IV), R \.=N
wherein Ar is phenyl which is unsubstituted or subs-tituted by Cl-C4alkyl, Cl-C4-alkoxy, cyano, nitro, trifluoromethyl, or by one to three halogen atoms, and R
is hydrogen, Cl-ClOalkyl, C2-C5alkenyl, C3-C8cycloalkyl, Cl-C4alkyl which is unsubstituted or substituted by C3-C8cycloalkyl or phenyl which is ~msubstitutedor substituted by halogen, Cl-C~alkyl or Cl-C4alkoxy, ancl plant fungicidal 1-(2-phenylethyl)triazoles of the formula V
N=.
Ar - CH - CH2 - N\ ¦ (V), R .=N
wherein Ar and R are as defined for fo-rmula IV.
The compounds II, III and IV, as well as the method of preparing the compounds V, form the subject matter of Canadian Patent Application No. 397,945.
The compounds of formula V are described in Canadian Patent No. 1,133,492.
The preferred compound of the formula I according to this invention is l-chloromethyl-lH-1,2,4-triazole.
The compounds of the formula I are obtained by the process of this invention by reacting l-hydroxymethyl-lH-1,2,4-triazole of the formula VI
/N=.
HO - CH - N l (VI), wlth a h~logenating agen~, and treatlng the resultant hydrohal:ldes ol the fo~mul~ VII
/N=~ .
2 \ ~N (VII), ~, wherein Hal is as defined for formula I, with a base.
Suitable bases are strong inorganic hydroxides such as sodium and potassium hydroxide.
Suitable halogenating agents are: phosgene, thionyl chloride, thionyl bromide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphoroxy chloride or hydriodic acid. Preferred halogenating agents are thionyl chloride and thionyl bromide, as the by-products formed are gaseous and therefore do not influence the reaction. The iodine compounds are conveniently obtained from already halogenated compounds by reacting these latter with hydriodic acid.
A further method of obtaining corresponding chlorides, bromides and iodides comprises reacting compounds of the formula VI with the corresponding trialkyl silyl halides.
The halogenation reaction is normally carried out in inert solvents, e.g. hydrocarbons such as hexane, cyclohexane, benzene, toluene or xylene, or ethers such as diethyl ether, tetrahydrofurane, dioxane or xylene or dimethoxy ethane. When using liquid halogenating agents, it is frequently possible to dispense with a solvent entirely. The reaction is then carried out in an excess of reagent, e.g. thionyI chloride or thionyl bromide.
The l-halomethyl-lH-1,2,4-triazoles of the formula I are compounds ; which are unstable at room temperature and also at 0C. Surprisingly, however, it has been found that solutions of l-halomethyl-lM-1,2,4-triazoles Oe the Eorm~lla I ln acetonltrLle can be s~ored Eor months without clecomposltion.
The start:Lng compound oE the eormllla VL Is known erom Kllim~
Geterosikl. Soedl., 1980~ 251 (English translfltion: Chem. ~leterocycl. Comp.
_.
1980, 189). In the process descrlbed thereln, the hydroxymethyl ,~,.
triazole is prepared using aqueous formalin solution.
Surprisingly, it has now been found that higher yields can be obtained by carrying out the synthesis using paraformaldehyde in a non-aqueous rnedium. This process also cons~itutes an object of the invention~
In the process of this invention, l-hydroxymethyl-lH-1,2,4-tria~ole is prepared by reacting lH-1,2,4-triazole in a non-aqueous medium, in the presence of catalytic amounts of a base9 with paraformaldehyde.
The reaction may be carried out in the presence or absence of an inert solvent.
Suitable solvents for this process are inert organic compounds, e.g.
ethers, preferably containing 2 or more oxygen atoms, such as dioxane or dimethoxy ethane. The reaction is carried out by boiling the reaction mixture under reflux. It is particularly advantageous~ how-ever, to carry out the reaction without a solvent in the melt of the reactants. The temperature is in the range from 40 to 150C~ with the preferred range being from 60 to 100C.
Suitable bases are: hydroxides such as sodium or potassium hydroxide, carbonates such as sodium or potassium carbonate, or amines such as triethylamine, quinoline and pyridine.
The following Examples illustrate the invention in more detail.
Pressures are given in milllbars tmb).
.xam ~ 1: Preparation of l-chlormethyl-lH-1,2,4-triaæole hydrochlorLde A melt of 195.3 g (1.74 moles) of l-hydro~ymethyl-lH-1,2,~-triaxole is added dropwise over 1 1/2 hours to 600 ml oE thionyl chloride.
Vigorous evolution of gas ensues and the reaction mixture begins to boil. After the melt has been completely added, the reaction mixture ls stirred under reflux for a further 2 hours and then cooled.
The precipitated yellow l-chloromethyl-lH-1,2,4-triazole hydrochloride is isolated by filtration and washed with two 300 ml portions of diethyl ether. Yield: 272 g (93.5 %). Melting point: 120-127C.
C H ClN ~ HCl (154) cal.: C 23.40 %; H 3.27 %; N 27.29 %
found: C 23.40 %; H 3.5 % ; N 27.30 %, H-NMR (CD30D): ~= 9.77 (s; lH, 5-CH); 8.55 (s; lH, 3-CH);
5.9 (s; 2H, CH2-Cl) and 5.06 (s; lH, HCl) ppm.
Example 2: Preparation of l-chloromethyl-lH-1,2,4-triazole With efficient stirring, 80 g of sodium hydroxide in 250 ml of water are added dropwise to 240.6 g (1.44 moles) of 1-chloromethyl-lH-1,2,4-triazole hydrochloride in a mixture of 600 ml of water and 400 ml of chloroform. The reaction mixture is saturated with sodium chloride and extracted three times with chloroform. The chloroform extracts are dried and concentrated. Fractional distillation of the residue yields 156.2 g (83.05 %) of 1-chloromethyl-lH-1,2,4-triazole w;th a boiling point of 52-54C/0.27 mb.
H-NMR (CDC13): S = 8.8 (s; lH, 5-CH); 8.3 (s; lH, 3-CH) and 6.3 (s; 2H, CH2Cl) ppm.
~xample 3- Preparation oE 1~ ~ roxymethy'1.-1~1~1,2,4-~riazole __ __ _ _ _ mlxture o~ 140 g (2 mo'Les) oE lH-1,2,4-triazole, 60 g oE parn-~ormaldehyde and 'L.5 ml oE triethylamine is hea~ed Eor ~ hours to Eorm a clear melt, which congeals on cooling. Recrystallisa~ion from acetone aEEords 195.3 g (98.5 %) oE l-hydroxymethyl-lH-1,2,~l-triazo'le with a melting point of 65-67C.
C3H5N30 (99.1) cal.; C 36.3 %; H 5.0 %; N 42.4 %
found: C 36.0 %; H 5.0 %; N 42.4 %.
H-NMR (CDC13): d = 8.47 (s; lH~ 5-CH); 8.0 (s; lH, 3-CH);
7.35 (s; lH, OH) and 5.67 (s; 2H, CH20) ppm.
5-l3321/=
: Abstract of the Disclosure : Halomethyltriazoles . . . _ .
The invention discloses halomethyltria~oles of the formula I
,N=-Hal - CH2 - ~
. =
wherein Hal is chlorine, bromine and iodine.
.
The compounds of formula I are important intermediates for obtaining highly active plant fungicides.
These compounds are used in turn for the production of fungicidal phenylethylenyltriazoles of the formula IV
Ar\ /N=.
~ C -- CH - N ¦ (IV), R \.=N
wherein Ar is phenyl which is unsubstituted or subs-tituted by Cl-C4alkyl, Cl-C4-alkoxy, cyano, nitro, trifluoromethyl, or by one to three halogen atoms, and R
is hydrogen, Cl-ClOalkyl, C2-C5alkenyl, C3-C8cycloalkyl, Cl-C4alkyl which is unsubstituted or substituted by C3-C8cycloalkyl or phenyl which is ~msubstitutedor substituted by halogen, Cl-C~alkyl or Cl-C4alkoxy, ancl plant fungicidal 1-(2-phenylethyl)triazoles of the formula V
N=.
Ar - CH - CH2 - N\ ¦ (V), R .=N
wherein Ar and R are as defined for fo-rmula IV.
The compounds II, III and IV, as well as the method of preparing the compounds V, form the subject matter of Canadian Patent Application No. 397,945.
The compounds of formula V are described in Canadian Patent No. 1,133,492.
The preferred compound of the formula I according to this invention is l-chloromethyl-lH-1,2,4-triazole.
The compounds of the formula I are obtained by the process of this invention by reacting l-hydroxymethyl-lH-1,2,4-triazole of the formula VI
/N=.
HO - CH - N l (VI), wlth a h~logenating agen~, and treatlng the resultant hydrohal:ldes ol the fo~mul~ VII
/N=~ .
2 \ ~N (VII), ~, wherein Hal is as defined for formula I, with a base.
Suitable bases are strong inorganic hydroxides such as sodium and potassium hydroxide.
Suitable halogenating agents are: phosgene, thionyl chloride, thionyl bromide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphoroxy chloride or hydriodic acid. Preferred halogenating agents are thionyl chloride and thionyl bromide, as the by-products formed are gaseous and therefore do not influence the reaction. The iodine compounds are conveniently obtained from already halogenated compounds by reacting these latter with hydriodic acid.
A further method of obtaining corresponding chlorides, bromides and iodides comprises reacting compounds of the formula VI with the corresponding trialkyl silyl halides.
The halogenation reaction is normally carried out in inert solvents, e.g. hydrocarbons such as hexane, cyclohexane, benzene, toluene or xylene, or ethers such as diethyl ether, tetrahydrofurane, dioxane or xylene or dimethoxy ethane. When using liquid halogenating agents, it is frequently possible to dispense with a solvent entirely. The reaction is then carried out in an excess of reagent, e.g. thionyI chloride or thionyl bromide.
The l-halomethyl-lH-1,2,4-triazoles of the formula I are compounds ; which are unstable at room temperature and also at 0C. Surprisingly, however, it has been found that solutions of l-halomethyl-lM-1,2,4-triazoles Oe the Eorm~lla I ln acetonltrLle can be s~ored Eor months without clecomposltion.
The start:Lng compound oE the eormllla VL Is known erom Kllim~
Geterosikl. Soedl., 1980~ 251 (English translfltion: Chem. ~leterocycl. Comp.
_.
1980, 189). In the process descrlbed thereln, the hydroxymethyl ,~,.
triazole is prepared using aqueous formalin solution.
Surprisingly, it has now been found that higher yields can be obtained by carrying out the synthesis using paraformaldehyde in a non-aqueous rnedium. This process also cons~itutes an object of the invention~
In the process of this invention, l-hydroxymethyl-lH-1,2,4-tria~ole is prepared by reacting lH-1,2,4-triazole in a non-aqueous medium, in the presence of catalytic amounts of a base9 with paraformaldehyde.
The reaction may be carried out in the presence or absence of an inert solvent.
Suitable solvents for this process are inert organic compounds, e.g.
ethers, preferably containing 2 or more oxygen atoms, such as dioxane or dimethoxy ethane. The reaction is carried out by boiling the reaction mixture under reflux. It is particularly advantageous~ how-ever, to carry out the reaction without a solvent in the melt of the reactants. The temperature is in the range from 40 to 150C~ with the preferred range being from 60 to 100C.
Suitable bases are: hydroxides such as sodium or potassium hydroxide, carbonates such as sodium or potassium carbonate, or amines such as triethylamine, quinoline and pyridine.
The following Examples illustrate the invention in more detail.
Pressures are given in milllbars tmb).
.xam ~ 1: Preparation of l-chlormethyl-lH-1,2,4-triaæole hydrochlorLde A melt of 195.3 g (1.74 moles) of l-hydro~ymethyl-lH-1,2,~-triaxole is added dropwise over 1 1/2 hours to 600 ml oE thionyl chloride.
Vigorous evolution of gas ensues and the reaction mixture begins to boil. After the melt has been completely added, the reaction mixture ls stirred under reflux for a further 2 hours and then cooled.
The precipitated yellow l-chloromethyl-lH-1,2,4-triazole hydrochloride is isolated by filtration and washed with two 300 ml portions of diethyl ether. Yield: 272 g (93.5 %). Melting point: 120-127C.
C H ClN ~ HCl (154) cal.: C 23.40 %; H 3.27 %; N 27.29 %
found: C 23.40 %; H 3.5 % ; N 27.30 %, H-NMR (CD30D): ~= 9.77 (s; lH, 5-CH); 8.55 (s; lH, 3-CH);
5.9 (s; 2H, CH2-Cl) and 5.06 (s; lH, HCl) ppm.
Example 2: Preparation of l-chloromethyl-lH-1,2,4-triazole With efficient stirring, 80 g of sodium hydroxide in 250 ml of water are added dropwise to 240.6 g (1.44 moles) of 1-chloromethyl-lH-1,2,4-triazole hydrochloride in a mixture of 600 ml of water and 400 ml of chloroform. The reaction mixture is saturated with sodium chloride and extracted three times with chloroform. The chloroform extracts are dried and concentrated. Fractional distillation of the residue yields 156.2 g (83.05 %) of 1-chloromethyl-lH-1,2,4-triazole w;th a boiling point of 52-54C/0.27 mb.
H-NMR (CDC13): S = 8.8 (s; lH, 5-CH); 8.3 (s; lH, 3-CH) and 6.3 (s; 2H, CH2Cl) ppm.
~xample 3- Preparation oE 1~ ~ roxymethy'1.-1~1~1,2,4-~riazole __ __ _ _ _ mlxture o~ 140 g (2 mo'Les) oE lH-1,2,4-triazole, 60 g oE parn-~ormaldehyde and 'L.5 ml oE triethylamine is hea~ed Eor ~ hours to Eorm a clear melt, which congeals on cooling. Recrystallisa~ion from acetone aEEords 195.3 g (98.5 %) oE l-hydroxymethyl-lH-1,2,~l-triazo'le with a melting point of 65-67C.
C3H5N30 (99.1) cal.; C 36.3 %; H 5.0 %; N 42.4 %
found: C 36.0 %; H 5.0 %; N 42.4 %.
H-NMR (CDC13): d = 8.47 (s; lH~ 5-CH); 8.0 (s; lH, 3-CH);
7.35 (s; lH, OH) and 5.67 (s; 2H, CH20) ppm.
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A l-halomethyl-lH-1,2,4-triazole of the general formula I
Hal - (I), wherein Hal is chlorine, bromine and iodine.
Hal - (I), wherein Hal is chlorine, bromine and iodine.
2. 1-Chloromethyl-lH-1,2,4-triazole according to claim 1.
3. A process for the production of a compound of the formula I according to claim 1, which process comprises reacting a 1-hydroxymethyl-lH-1,2,4-triazole of the formula VI
(VI) with a halogenating agent, and treating the resultant hydrohalide of the formula VII
Hal - CH2 - . HHal (VII), wherein Hal is as defined for formula I in claim 1, with a base.
(VI) with a halogenating agent, and treating the resultant hydrohalide of the formula VII
Hal - CH2 - . HHal (VII), wherein Hal is as defined for formula I in claim 1, with a base.
4. A process according to claim 3 for the production of 1-chloromethyl-lH-1,2,4-triazole, wherein the halogenating agent is thionyl chloride.
5. A process according to claim 3 wherein the required 1-hydroxymethyl-1H-1,2,4-triazole, is obtained by reacting lH-1,2,4-triazole in a non-aqueous medium, in the presence of catalytic amounts of a base, with paraformaldehyde.
6. A process according to claim 5, wherein the reaction is carried out in the melt of a mixture of the reactants.
7. A process according to claim 6, wherein the reaction temperature is in the range from 40° to 150°C.
8. A process according to claim 7, wherein the reaction temperature is in the range from 60° to 100°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH162281 | 1981-03-10 | ||
| CH1622/81-7 | 1981-03-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1180018A true CA1180018A (en) | 1984-12-27 |
Family
ID=4214745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000397946A Expired CA1180018A (en) | 1981-03-10 | 1982-03-09 | Halomethyltriazoles |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0060222B1 (en) |
| JP (1) | JPS57159773A (en) |
| AT (1) | ATE48419T1 (en) |
| CA (1) | CA1180018A (en) |
| DE (1) | DE3280049D1 (en) |
| HU (2) | HU198191B (en) |
| IL (1) | IL65191A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3311318A1 (en) * | 1983-03-29 | 1984-10-11 | Basf Ag, 6700 Ludwigshafen | AZOLATED HALOGEN-KETEN-O, N-ACETALE, METHOD FOR THE PRODUCTION THEREOF, THE FUNGICIDES CONTAINING THEM AND METHOD FOR CONTROLLING FUNGI WITH YOU |
| JPH0619206U (en) * | 1992-08-21 | 1994-03-11 | 市光工業株式会社 | Vehicle lighting |
-
1982
- 1982-03-04 AT AT82810097T patent/ATE48419T1/en not_active IP Right Cessation
- 1982-03-04 DE DE8282810097T patent/DE3280049D1/en not_active Expired - Lifetime
- 1982-03-04 EP EP82810097A patent/EP0060222B1/en not_active Expired
- 1982-03-08 IL IL65191A patent/IL65191A/en unknown
- 1982-03-09 CA CA000397946A patent/CA1180018A/en not_active Expired
- 1982-03-09 HU HU853938A patent/HU198191B/en not_active IP Right Cessation
- 1982-03-09 HU HU82727A patent/HU189567B/en not_active IP Right Cessation
- 1982-03-10 JP JP57037867A patent/JPS57159773A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| IL65191A0 (en) | 1982-05-31 |
| EP0060222A1 (en) | 1982-09-15 |
| JPH0250905B2 (en) | 1990-11-05 |
| EP0060222B1 (en) | 1989-12-06 |
| HU198191B (en) | 1989-08-28 |
| HU189567B (en) | 1986-07-28 |
| IL65191A (en) | 1985-07-31 |
| ATE48419T1 (en) | 1989-12-15 |
| JPS57159773A (en) | 1982-10-01 |
| DE3280049D1 (en) | 1990-01-11 |
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|---|---|---|---|
| MKEC | Expiry (correction) | ||
| MKEX | Expiry |