GB2027705A - Preparation of 2-substituted- semicarbazones and carbalkoxy hydrazones - Google Patents
Preparation of 2-substituted- semicarbazones and carbalkoxy hydrazones Download PDFInfo
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- GB2027705A GB2027705A GB7926300A GB7926300A GB2027705A GB 2027705 A GB2027705 A GB 2027705A GB 7926300 A GB7926300 A GB 7926300A GB 7926300 A GB7926300 A GB 7926300A GB 2027705 A GB2027705 A GB 2027705A
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- alkyl
- general formula
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- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims description 15
- 150000007857 hydrazones Chemical class 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 4
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims abstract description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 239000000460 chlorine Substances 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 229910052740 iodine Chemical group 0.000 claims abstract description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000003444 phase transfer catalyst Substances 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 230000002051 biphasic effect Effects 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 238000005804 alkylation reaction Methods 0.000 abstract description 8
- 150000007659 semicarbazones Chemical class 0.000 abstract description 7
- 230000029936 alkylation Effects 0.000 abstract description 6
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 7
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229940093499 ethyl acetate Drugs 0.000 description 4
- 235000019439 ethyl acetate Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229940100198 alkylating agent Drugs 0.000 description 3
- 239000002168 alkylating agent Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 2
- MDTUWBLTRPRXBX-UHFFFAOYSA-N 1,2,4-triazol-3-one Chemical class O=C1N=CN=N1 MDTUWBLTRPRXBX-UHFFFAOYSA-N 0.000 description 1
- YCOYDSQEOWWYDT-UHFFFAOYSA-N 3,3-dichloroprop-2-enal Chemical compound ClC(Cl)=CC=O YCOYDSQEOWWYDT-UHFFFAOYSA-N 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- -1 propargyl halides Chemical class 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/02—Compounds containing any of the groups, e.g. carbazates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/06—Compounds containing any of the groups, e.g. semicarbazides
- C07C281/08—Compounds containing any of the groups, e.g. semicarbazides the other nitrogen atom being further doubly-bound to a carbon atom, e.g. semicarbazones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Compounds of the general formula: <IMAGE> in which R represents an alkyl, allyl, propargyl or benzyl group, which groups may be substituted, R<1> and R<2> independently represent a hydrogen atom or an alkyl, aryl or vinyl group, which groups may be substituted, and Y represents NH2 or O-alkyl, are prepared by reacting compounds of general formula: <IMAGE> with compounds of the formula: R-X in which X represents a chlorine, bromine or iodine atom or the group SO4R. The alkylation is exclusively oriented towards the 2-position and no alkylation products in the 1- or 4- position are observed. The selectivity is maintained even when the semicarbazone contains unsaturated substituents.
Description
SPECIFICATION
Preparation of 2-substituted-semicarbazones and carbalkoxy hydrazones
The present invention relates to the synthesis of semicarbazones and carbalkoxy-hydrazones, substituted in the 2-position and more particularly to the synthesis of such compounds by alkylation of the corresponding semicarbazones and carbalkoxy-hydrazones.
The synthesis of 2-alkyl-semicarbazones.(l) in general is achieved by addition of an alkyl-hydrazine (II) to an alkaline cyanate in an aqueous medium thereby yielding a semicarbazide (III) which, in its turn, is reacted with an aldehyde or a ketone (see, for example, "Chemistry of Carbon Compound", Ed. E. H.
Rodd, Vol. 1 B, pages 918-919 (1952)) according to the following reaction scheme:
(Scheme 1).
This process, which is well known to organic chemistry, suffers for the disadvantage of having the alkyl-hydrazines used as starting materials which are very expensive compounds and difficult to prepare, particularly when the alkyl group is a primary group.
The main methods for the preparation of alkyl-hydrazines include: 1) reaction of an alkyl-urea with hypochlorite and then with sodium hydroxide, see United States
Patent Specification No. 2 91 7 545. However, this method has the drawbacks of operating in
diluted solutions and giving rather low yields.
2) reaction of methyl sulphate with an azine obtained by the reaction of hydrazine with benzaldehyde
and then by hydrolizing the quaternary salt obtained, see Organic Synthesis, Collective Vol. Ií, 395
(1950). The reaction scheme is as follows:
This method, besides being rather complicated, has the disadvantage of being limited to the preparation of methyl-hydrazine, in fact, different alkylating agents do not quaternise with the azine.
Furthermore, the direct alkylation of hydrazine is not suited for obtaining mono-alkyi-hydrazine with acceptable yields.
The preparation of the 2-alkyl-semicarbazones may be achieved by preparing, independently from the alkyl-hydrazine, the 2-alkyl-semicarbazide (Compound ill, scheme 1). However, the method of preparation usually used, which is the catalytic reduction of alkyl-nitrous-urea of the formula:
(see United States Patent Specification No. 3 387 030, has two major disadvantages, namely the necessity to use compounds that carry the group
which is recognised as being carcinogenous, and it is impossible to achieve high yields.
The preparation of 2-alkyl-carbalkoxy-hydrazones (V) is usually achieved by reacting an aldehyde or ketone with a 2-alkyl-2-carbalkoxy-hydrazone (IV)
2-alkyl-2-carbalkoxy-hydrazines (IV) however are prepared starting from alkyl-hydrazines (II) with the above reported drawbacks.
According to the present invention there is provided a process for the preparation of compounds of general formula:
in which R represents an alkyl, allyl, propargyl or benzyl group, which groups may be substituted.
R1 and R2 independently represent a hydrogen atom or an alkyl, aryl or vinyl group, which groups may be substituted, and
Y represents NH2 or O-alkyl, in which a compound of general formula:
in which R1, R2 and Y are as defined above, is reacted with a compound of the formula: R-x in which X represents a chlorine, bromine or iodine atom or the group SO4R, and
R is as defined above.
This method is surprisingly endowed with a high selectivity. In fact, the alkylation is exclusively oriented towards the 2-position and no alkylation products in the 1- or 4-position can be observed. This great selectivity is even more surprisingly maintained also when the semicarbazone molecule contains olefinic substituents, which may be attacked by the alkylating agent.
The synthesis method of the invention proves to be of a general validity in as much as the alkylation reaction may be carried out on semicarbazones or carbalkoxy hydrazones of various carbonyl derivatives, by using as alkylating agents alkyl, benzyl, allyl or propargyl halides.
The reaction scheme is as follows:
in which R, R1, R2, X and Y are as defined above.
The reaction may be carried out in a homogeneous phase by using aprotic polar solvents in the presence of an alkaline base or in a biphasic system consisting of an organic solvent immiscible with water and an aqueous solution of an alkaline base, in the presence of a phase-transfer catalyst such as a quaternary ammonium salt.
The duration of the reaction is generally in the range 3 to 4 hours and a slight heating (50 to 6O0C) facilitates the reaction.
The 2-alkyl-semicarbazones are intermediates which are useful in the synthesis of pesticides.
Cyclization of the 2-alkyl-semicarbazones yields 1 ,2,4-triazol-5-ones from which it is possible to obtain phosphoric esters endowed with an insecticide, nematocide and acaricide activity, as described in our copending British Patent Application No. 47948/77.
2-alkyl-carbalkoxy-hydrazones are useful intermediates for the preparation of alkyl-hydrazines (by hydrolysis) or of 2-alkyl-semicarbazones (by treatment with NH3).
The invention will now be illustrated by the following Examples.
Some of the Examples are of alkylation reactions conducted on a semicarbazone, namely ss,ss- dichloroacrylidene-semicarbazone (obtained by condensation between ss,ss-dichloroacrolein and semicarbazide) showing how the selectivity of the reaction of the invention is maintained when the semicarbazone molecule contains unsaturated groups of an olefinic nature.
EXAMPLE 1
Preparation of the ss,ss-dichloroacrylidene-2-ethyl-semicarbazone in an homogeneous phase
1.82 g of ss,ss-dichloroacrylidene-semicarbazone (1) were dissolved in 30 ml of N,Ndimethylformamide and thereafter 2.3 g of K2CO3 and 1.93 g of C2H5I were added. The reaction mixture was subjected to stirring for 3 hours at 50 to 600C and thereafter cooled to 200 C, additioned with 120 ml of H20 and extracted with ethylacetate (2 x1 00 ml). The organic solution was then dried with anhydrous Na2SO4, and the solvent was then evaporated.
1.1 g of a yellowish solid consisting of ss,ss-dichloroacrylidene-2-ethyl-semicarbazone (2) was obtained when recrystallized from ethyl ether exhibiting a melting point of 127 to 1280C (Compound
No. 3, Table 1).
EXAMPLE 2
Preparation of the ss,ss-dichloroacrylidene-2-methyl-semicarbazone
1.8 g of ss,ss-dichloroacrylidene-semicarbazone, 1,5 ml of (CH3)2SO4 and 0.1 g of trimethylcetylammonium bromide were dissolved in 20 ml of methylene chloride. An aqueous solution or NaOH (50% concentration, 3 ml) was added to the solution and the heterogeneous reaction mixture was vigorously stirred for 3 to 4 hours and then additioned with 20 ml of water. The organic phase was separated dried with anhydrous Na2SO4 and filtered, whereupon the solvent was evaporated to yield 1.7 g of a white solid consisting of ss,ss-dichloro-acrylidene-2-methyl-semicarbazone (2) which was recrystallised from benzene. Melting point 130 to 1326C. (Compound No. 1, Table 1).
EXAMPLE 3
Adopting the same procedure as Examples 1 and 2, the ss,ss-dichloro-2-alkyl-semicarbazones reported in the following Table 1 were prepared.
TABLE 1 Compounds of the formula:
Elementary Analysis (%) Yield on Melting Theoretical Found converted Compound point product No. R Y ( C) C N C N (%) 1 CH3 NH2 130-132 30.63 21.43 31.20 22.10 95 2 CH3 OC2H5 77-78 37.35 12.45 38.28 12.71 90 3 C2H5 NH2 127-128 34.20 20.00 34.90 20.12 95 4 CH2-CH=CH2 NH2 107-108 37.86 18.92 38.17 18.70 80 5 CH2-C=CH NH2 38.20 19.09 38.12 18.79 80 6 CH2-C6H5 NH2 128-130 48.55 15.44 49.65 15.70 60 EXAMPLE 4
The following Example illustrates the high selectivity of the process of the invention.
Preparation of }5,,B-dichloroacrylidene-2-ethyl-semicarbazone
2.3 g of KzCOB and 1.93 g of C2H5l were added to a solution of 1.82 g of ,B"B-dichloroacrylidene- semicarbazone (I) in 30 ml of N,N-dimethyl-formamide. The reaction mixture was stirred for 3 hours at 50 to 600 C, cooled to 20 C and additioned with 120 ml of H20. A solid product separated which was collected by filtration, washed with water and dried. 2 g of a yellowish solid were obtained which was then suspended in ethyl-acetate (100 ml).The insoluble product was collected by filtration and washed with ethyl-acetate (30 ml) to yield 0.8 g of unreacted P,P-dichloroacrylidene-semicarbazone.
The ethyl-acetate solutions were gathered and the solvent was evaporated to yield 1.1 g of ss,ss dichloroacrylidene-2-ethyl-semicarbazone as a yellow solid, melting at 1 27 to 1 28 OC.
Conversion: 55%, yield on converted product: 95%.
EXAMPLE 5
Preparation of benziliden-2-methyl-semicarbazone (2)
1.63 g of benziliden-semicarbazone (1), 1.5 ml of (CH3)2SO4 and 0.1 g of trimethylcetylammonium bromide were dissolved in 20 ml of methylene chloride. An aqueous solution of NaOH (50% concentration, 3 ml) was added and the resulting heterogeneous mixture was stirred for 3 hours.
20 ml of water was then added to the mixture and the organic phase was separated and dried on an anhydrous Na2SO4 and filtered. The solvent was evaporated to yield 1.7 g of (2) having a melting point of 1600 C. Yield on converted product 97%.
Claims (9)
1. A process for the preparation of compounds of general formula:
in which R represents an alkyl, allyl, propargyl or benzyl group, which groups may be substituted,
R1 and R2 independently represent a hydrogen atom or an alkyl, aryl or vinyl group, which groups may be substituted, and
Y represents NH2 or O-alkyl, in which a compound of the general formula:
in which R1, R2 and Y are as defined above, is reacted with a compound of the formula: R-X in which X represents a chlorine, bromine or iodine atom of the group SO4R, and
R is as defined above.
2. A process as claimed in Claim 1, in which the reaction between the compound of general formula (Vl) and R-X is conducted in the presence of an alkaline base and in an aprotic polar solvent
3. A process as claimed in Claim 2, in which the aprotic polar solvent is dimethylformamide.
4. A process as claimed in Claim 2 or Claim 3, in which the alkaline base is potassium carbonate (K2CO3).
5. A process as claimed in any preceding claim, in which the reaction between the compound of general formula (Vl) and R-X is conducted at 50 to 600C for a period of time of 3 to 4 hours.
6. A process as claimed in Claim 1, in which the reaction between the compound of general formula (VI) and R-X is conducted in a biphasic system consisting of an organic solvent immiscible with water and an aqueous solution of an alkaline base, in the presence of a phase-transfer catalyst.
7. A process as claimed in Claim 6, in which the organic solvent is methylene chloride (CH2CI2).
8. A process as claimed in Claim 6 or Claim 7, in which the aqueous solution of the alkaline base is an aqueous NaOH solution at about a 50% concentration.
9. A process as claimed in any one of claims 6 to 8, in which the phase-transfer catalyst is a quaternary ammonium salt.
1 0. A process as claimed in any one of claims 6 to 9, in which the reaction mixture is subjected to vigorous agitation for a period of 3 to 4 hours.
1 1.A process for the preparation of compounds of formula VII substantially as herein described with reference to any one of the Examples.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT26231/78A IT1097754B (en) | 1978-07-28 | 1978-07-28 | PREPARATION OF 2-ALCHIL-SEMICARBAZONI AND 2-ALCHIL-CARBALCOSSI-IDRAZONI |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2027705A true GB2027705A (en) | 1980-02-27 |
| GB2027705B GB2027705B (en) | 1982-11-10 |
Family
ID=11219003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7926300A Expired GB2027705B (en) | 1978-07-28 | 1979-07-27 | Preparation of 2-substituted-semicarbazones and carbalkoxy hydrazones |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5520778A (en) |
| DE (1) | DE2930169A1 (en) |
| GB (1) | GB2027705B (en) |
| IT (1) | IT1097754B (en) |
| SU (1) | SU1003753A3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0254461A2 (en) * | 1986-07-17 | 1988-01-27 | Schering Aktiengesellschaft | Combatting plant nematodes using substituted hydrazones |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56139246A (en) * | 1981-03-16 | 1981-10-30 | Ono Naifu Seisakusho:Kk | Caulking machine |
-
1978
- 1978-07-28 IT IT26231/78A patent/IT1097754B/en active
-
1979
- 1979-07-25 DE DE19792930169 patent/DE2930169A1/en not_active Withdrawn
- 1979-07-27 JP JP9515879A patent/JPS5520778A/en active Pending
- 1979-07-27 SU SU792789703A patent/SU1003753A3/en active
- 1979-07-27 GB GB7926300A patent/GB2027705B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0254461A2 (en) * | 1986-07-17 | 1988-01-27 | Schering Aktiengesellschaft | Combatting plant nematodes using substituted hydrazones |
| EP0254461A3 (en) * | 1986-07-17 | 1990-06-13 | Schering Aktiengesellschaft | Combatting plant nematodes using substituted hydrazones |
| US4983755A (en) * | 1986-07-17 | 1991-01-08 | Schering Aktiengesellschaft | Substituted hydrazones, process for the preparation and their use as pesticide |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2930169A1 (en) | 1980-02-07 |
| GB2027705B (en) | 1982-11-10 |
| SU1003753A3 (en) | 1983-03-07 |
| IT7826231A0 (en) | 1978-07-28 |
| IT1097754B (en) | 1985-08-31 |
| JPS5520778A (en) | 1980-02-14 |
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