IL44446A - Process for the preparation of 1-alkyl-3-hydroxy-5-chloro-1,2,4-triazoles - Google Patents
Process for the preparation of 1-alkyl-3-hydroxy-5-chloro-1,2,4-triazolesInfo
- Publication number
- IL44446A IL44446A IL44446A IL4444674A IL44446A IL 44446 A IL44446 A IL 44446A IL 44446 A IL44446 A IL 44446A IL 4444674 A IL4444674 A IL 4444674A IL 44446 A IL44446 A IL 44446A
- Authority
- IL
- Israel
- Prior art keywords
- formula
- preparation
- alkyl
- hydroxy
- chloro
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000003701 inert diluent Substances 0.000 claims 1
- 239000012442 inert solvent Substances 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- -1 ester chloride Chemical class 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- ILULYDJFTJKQAP-UHFFFAOYSA-N hydron;propan-2-ylhydrazine;chloride Chemical compound [Cl-].CC(C)N[NH3+] ILULYDJFTJKQAP-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 150000003580 thiophosphoric acid esters Chemical class 0.000 description 2
- 150000000178 1,2,4-triazoles Chemical class 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- 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
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
The procesa for the preparation of l-alkyl-3 hydroxy-5-chloro-1 ,2 , 4-triazoleB C:- 42621 The present invention relates to a process for the preparation of 1,2,4-triazole derivatives which are of particular importance as intermediates for, e.g. the producing of active substances for pest-control agents.
It is known to produce 1,2,4-triazole derivatives by a process described in German patent specification No. 1.940.367. In this process an N-chlorocarbonyliminocarbonic acid ester chloride of the formula R- c wherein R is an alkyl group or an optionally substituted phenyl group is reacted with a substituted hydrazine, for example an alkylhydrazine in the presence of a base, for example excess hydrazine, to obtain the desired 1,2 ,4-triazoles .
If according to this process a N-chlorocarbonyliminocarbonic acid phenyl ester is reacted with excess alkylhydrazine, for example methylhydrazine , there is obtained a l-alkyl-3-phenoxy-1,2 ,4-triazole-5-one which can also be considered as the tautomeric l-alkyl-3-phenoxy-5-hydroxy-l, 2 ,4-triazole „ According to. this known reaction it was to be expected that the reaction of an alkyl hydrazine with N-chlorocarbonylisocyanidedichloride which contains an additional chlorine instead of the alkoxy or phenoxy group present in the N-chlorocarbonyliminocarbonic acid esters of the above formula would result in the formation of a l-alkyl-3-chloro-5- hydroxy-1,2 ,4-triazole.
Surprisingly, it has now been found that lralkyl-3-hydroxy-5-chloro-l,2,4-triazoles can be prepared by reacting an alkylhydrazine hydrochloride with N-chlorocarbonylisocyanidedichloride.
The 1 , 2, -triazoles prepared according to the / invention have the formula wherein represents a straight chain or branched alkyl radical having 1 to 6 carbon atoms.
Applicable alkyl radicals are, in particular, methyl, ethyl and n-propyl, isopropyl, n-, i- , sec.-, tert. -butyl, n-pentyl, n-hexyl.
Of particular importance is the preparation by the process according to the invention of the compound of formula I wherein represents isopropyl.
The compounds of formula I are prepared according to the invention by reaction of an alkylhydrazine hydrochloride of the formula R1-NH-NH2 · H CI (II) with N-chlorocarbonylisocyanidedichloride of the formula in formula II has the meaning given under formula I.
The reaction according to the invention can be performed in the presence or absence of solvents or diluents. For the obtainment of economic yields, it has proved advantageous for the reaction to be performed in the presence of a solvent or diluent.
Suitable solvents and/or diluents are, e.g. aliphatic and aromatic hydrocarbons or halogenated hydrocarbons, such as hexane, petroleum ether, chloroform, methylene chloride, halogenated ethanes, benzene, toluene, xylenes, ethers and ethereal compounds such as dialkyl ether, 1, 2-dimethoxyethane, .dioxane, tetrahydrofuran, N,N-dialkylated amides such as dimethylformamide, sulphoxides such as dimethylsulphoxide, nitriles such as acetonitrile, etc., or mixtures of such solvents .with each other; for the cyclisation reaction, it is also possible to use water or hydrous solvents. Particularly suitable are also two- phase reaction media consisting of water and an organic solvent not miscible with water, such as chloroform, methylene chloride and toluene.
The process according to the invention is performed under normal pressure and in a temperature range of -30 to 150° C, preferably between 0 and 80°C.
The reactants are used in the process in equimolecular amounts, whereby an excess of the one or of the other reaction partner can contribute towards- the completion of the reaction.
The compounds of formula I prepared according to the invention are* of importance as intermediates in the preparation of pesticides. They can be converted, in particular, by reaction with phosphoric acid ester haiides and thiophosphoric acid ester haiides into phosphoric acid esters and thiophosphoric acid esters, respectively, of the formula wherein Z represents oxygen or sulphur, 1*2 represents alkoxy, alkylthio,. amino, or mono- or dial amino, and represents alkyl, alkoxy, alkylthio, phenyl, phenoxy, aminOj^mono- or dialkylamino , and has "the meaning given under formula I.
These compounds have an excellent insecticidal action.
Preparation of l-isopropyl-5-chloro-3-hydroxy-l , 2 ,4- triazole 16.0 g of N-chlorocarbonylisocyanidedichloride is added dropwise at 20°C, with stirring, to 11.0 g of isopropylhydrazine-hydrochloride suspended in 100 ml of acetonitrile . The reaction proceeds exothermically and is controlled with an ice bath. The mixture is subsequently refluxed for 2 hours, with hydrochloric acid gas being released. On cooling to room temperature, there is precipitated a crystalline product; this is then filtered off, and dried in vacuo to yield an amount of 5.2 g. The mother liquor is concentrated in vacuo, and the residue boiled with 50 ml of water for 5 minutes . The precipitated product is again filtered off, and dried in vacuo to obtain an additional yield of 4 g of the compound of the formula having a melting point of 101 - 103°C.
Example 2 A solution of 5.5 g (0.05 mole) of isopropylhydrazine-hydrochloride in 80 ml of water is added dropwise, in the course of 2 hours, to a solution cooled to -5°C of 8.0 g (0.05 mole) of N-chlorocarbonylisocyanide-dichloride in 20 ml of toluene, with the temperature being maintained between -5°C and -10°C. The whole is subsequently concentrated to dryness by evaporation, and the residue extracted with 50 ml of ethanol. The resulting ethanolic solution is again concentrated to dryness by evaporation, and the residue recrystallised from 20 ml of water to obtain 2.39 g of l-isopropyl-3-hydroxy-5-chloro-l,2,4-triazole, M.P. 101 - 102°C. - 2A - Example 3 ^ 240 g (1.5 moles) of gaseous N-chlorocarbonylisocyanide-dichloride is introduced, in the course of 10 hours, into a solution cooled to -10°C of 110.5 g (1 mole) of isopropylhydrazine-hydrochloride in 250 ml of water.
After completion of the addition, the cooling bath is removed, and stirring maintained for a further 15 hours at room temperature. The residue obtained after concentration of the acid solution by evaporation to dryness is suspended in 150 ml of water; the pH-value of the suspension is adjusted to 4 by addition of sodium hydroxide solution, and the suspension then filtered: the resulting yield is 87.5 g of crude l-isopropyl-3-hydroxy-5-chloro-l, 2,4-triazole, M.P. 92-98°C, which melts at 101-103°C after recrystallisation from water. 7 - Jri - The following additional compounds are prepared in an analogous manner: Furthe substituted hydrazines suitable as starting materials for the process according to the invention are, for example: methylhydrazine, (3-cyano-ethyl) -hydrazine .
Claims (3)
1. Process for the preparation of compounds of the formula wherein represents a straight chain or branched alkyl radical having 1 to 6 carbon atoms in which process an alkylhydrazine hydrochloride of the formula R1-NH-NH2 · H CI (II) is reacted with N-chlorocarbonylisocyanidedichloride of the formula 0 wherein has the above-given meaning .
2. Process according to Claim 1, wherein the reaction of an alkylhydrazine hydrochloride with N-chlorocarbonylisocyanide-dichloride is performed in the presence of an inert solvent or diluent. 44446/2
3. Process according to Claim 1, wherein the reaction of an alkylhydrazine hydrochloride with N-chlorocarbonylisocyanide- ' dichloride is performed at a temperature between 0 and 80°C. Process according to Claims 1 to 4 for the preparation the compound of the formula HE:dn
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH549573A CH574427A5 (en) | 1973-04-17 | 1973-04-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL44446A0 IL44446A0 (en) | 1974-06-30 |
| IL44446A true IL44446A (en) | 1977-10-31 |
Family
ID=4294553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL44446A IL44446A (en) | 1973-04-17 | 1974-03-19 | Process for the preparation of 1-alkyl-3-hydroxy-5-chloro-1,2,4-triazoles |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5018468A (en) |
| AT (1) | AT332871B (en) |
| BE (1) | BE813749A (en) |
| CA (1) | CA1035362A (en) |
| CH (1) | CH574427A5 (en) |
| DE (1) | DE2417970A1 (en) |
| FR (1) | FR2226401B1 (en) |
| GB (1) | GB1464765A (en) |
| IL (1) | IL44446A (en) |
| NL (1) | NL7404841A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4404019A (en) * | 1980-12-24 | 1983-09-13 | Sumitomo Chemical Company, Limited | 3-Chloro-1-phenyl-1,2,4-triazolin-5-ones and their use as herbicides |
| JP2000178462A (en) | 1998-12-16 | 2000-06-27 | Konica Corp | Hydrazine compound, and silver halide photosensitive material containing the same, and image formation |
-
1973
- 1973-04-17 CH CH549573A patent/CH574427A5/xx not_active IP Right Cessation
-
1974
- 1974-03-19 IL IL44446A patent/IL44446A/en unknown
- 1974-03-22 CA CA195,709A patent/CA1035362A/en not_active Expired
- 1974-04-09 NL NL7404841A patent/NL7404841A/xx not_active Application Discontinuation
- 1974-04-11 DE DE19742417970 patent/DE2417970A1/en not_active Withdrawn
- 1974-04-16 BE BE143225A patent/BE813749A/en unknown
- 1974-04-16 GB GB1658674A patent/GB1464765A/en not_active Expired
- 1974-04-16 AT AT313874A patent/AT332871B/en not_active IP Right Cessation
- 1974-04-16 FR FR7413166A patent/FR2226401B1/fr not_active Expired
- 1974-04-16 JP JP49043257A patent/JPS5018468A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AT332871B (en) | 1976-10-25 |
| CA1035362A (en) | 1978-07-25 |
| CH574427A5 (en) | 1976-04-15 |
| DE2417970A1 (en) | 1974-11-07 |
| FR2226401B1 (en) | 1978-01-27 |
| NL7404841A (en) | 1974-10-21 |
| JPS5018468A (en) | 1975-02-26 |
| GB1464765A (en) | 1977-02-16 |
| ATA313874A (en) | 1976-02-15 |
| FR2226401A1 (en) | 1974-11-15 |
| IL44446A0 (en) | 1974-06-30 |
| BE813749A (en) | 1974-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0285893B1 (en) | Phenyltriazole derivative and insecticide | |
| MXPA05001117A (en) | Method for preparing 3-halo-4,5-dihydro-1<i>h</i>-pyrazoles. | |
| US4346097A (en) | Method for treating convulsions with pyrazole-4-carboxamide derivatives | |
| US4069252A (en) | Process for the preparation of certain acyl cyanide compounds | |
| CA1116607A (en) | PROCESS FOR THE PREPARATION OF N-SUBSTITUTED .alpha.-HALOGENOACETANILIDES | |
| EP1773783B1 (en) | Method for preparing n-piperidino-1,5-diphenylpyrazole-3-carboxamide derivatives | |
| US4632999A (en) | Process for the preparation of oxiranes | |
| EP0035087B1 (en) | Process for the preparation of 1h-azole derivatives | |
| IL44446A (en) | Process for the preparation of 1-alkyl-3-hydroxy-5-chloro-1,2,4-triazoles | |
| Al-Azmi et al. | Synthesis of 1, 4, 5-trisubstituted-1, 2, 3-triazoles via coupling reaction of diaminomaleonitrile with aromatic diazonium salts | |
| EP1805145B1 (en) | Process for the preparation of pyrazoles | |
| US5008398A (en) | Preparation of p-nitrophenyl-imidazoles | |
| JPH08283261A (en) | 3-Phenyltriazole derivative and insecticide, acaricide | |
| US4028409A (en) | Process for the preparation of α-oxothiodimethylamide compounds | |
| US3415840A (en) | Pyrazole-1-ethanol derivatives | |
| US4006157A (en) | Process for the preparation of 1,2,4-triazole derivatives | |
| US4581175A (en) | N'-acylhydrazine-N-thiocarboxylic acid O-carbamoylmethyl esters | |
| US5162529A (en) | Process for the preparation of 5-hydroxy-3,4,5,6-tetrahydro-pyrimidine derivatives | |
| US4123437A (en) | Process for preparing 1,2,4-triazole derivatives | |
| CA1119179A (en) | Process for preparing n-tritylimidazole compounds | |
| US4408044A (en) | Preparation of 3,6-disubstituted 4-amino-1,2,4-triazin-5-ones | |
| Cocco et al. | Amidrazones as precursors of biologically active compounds–synthesis of diaminopyrazoles for evaluation of anticancer activity | |
| US4456769A (en) | Preparation of hydrazidines | |
| US3923827A (en) | Preparation of 4-imidazolin-2-ones | |
| US4904811A (en) | (Z)-2-cyano-2-oximino-acetyl chlorides |