DK155001B - PROCEDURE FOR THE PREPARATION OF UNSATURED CARBOXYLIC ACIDS - Google Patents
PROCEDURE FOR THE PREPARATION OF UNSATURED CARBOXYLIC ACIDS Download PDFInfo
- Publication number
- DK155001B DK155001B DK492576AA DK492576A DK155001B DK 155001 B DK155001 B DK 155001B DK 492576A A DK492576A A DK 492576AA DK 492576 A DK492576 A DK 492576A DK 155001 B DK155001 B DK 155001B
- Authority
- DK
- Denmark
- Prior art keywords
- salt
- acid
- carboxylic acids
- preparation
- procedure
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 title claims description 4
- 239000002253 acid Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 3
- 230000008707 rearrangement Effects 0.000 claims description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- -1 alkaline earth metal salt Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- YUACDUKFVCTPKB-UHFFFAOYSA-N 2-(2,2-dichloroethenyl)cyclopropane-1-carboxylic acid Chemical class OC(=O)C1CC1C=C(Cl)Cl YUACDUKFVCTPKB-UHFFFAOYSA-N 0.000 description 1
- KGUVNWFNGFCCKR-UHFFFAOYSA-N 2-cyano-3,3-dimethylpent-4-enoic acid Chemical compound C=CC(C)(C)C(C#N)C(O)=O KGUVNWFNGFCCKR-UHFFFAOYSA-N 0.000 description 1
- SGLHJFPSURESKN-UHFFFAOYSA-N 2-cyanopent-4-enoic acid Chemical class OC(=O)C(C#N)CC=C SGLHJFPSURESKN-UHFFFAOYSA-N 0.000 description 1
- OGRUNLRQTBVLAP-UHFFFAOYSA-N 2-ethoxycarbonyl-3,3-dimethylpent-4-enoic acid Chemical compound CCOC(=O)C(C(O)=O)C(C)(C)C=C OGRUNLRQTBVLAP-UHFFFAOYSA-N 0.000 description 1
- LZLSUHMFFPVWGU-UHFFFAOYSA-N 3-methylbut-2-enyl 2-cyanoacetate Chemical compound CC(C)=CCOC(=O)CC#N LZLSUHMFFPVWGU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000006286 aqueous extract Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
DK 155001 BDK 155001 B
Den foreliggende opfindelse angår en fremgangsmåde til fremstilling af hidtil ukendte umættede carboxylsyrer, som er værdifulde kemiske mellemprodukter.The present invention relates to a process for the preparation of novel unsaturated carboxylic acids which are valuable chemical intermediates.
Den foreliggende opfindelse angår fremstilling af umættede carboxyl-5 syrer med den almene formel IThe present invention relates to the preparation of unsaturated carboxylic acids of general formula I
R1R1
HOOC -CH -C -CH - CHo IHOOC -CH -C -CH - CHo I
1 >2 10 X Rz hvor X betegner cyano eller alkoxycarbonyl, og og R2 hver for sig betegner alkyl, eller et salt af en sådan syre.1> 2 10 X R 2 where X represents cyano or alkoxycarbonyl, and and R 2 each represent alkyl, or a salt of such an acid.
Fremgangsmåden ifølge opfindelsen er ejendommelig ved, at et enolatsalt af en ester med den almene formel IIThe process of the invention is characterized in that an enolate salt of an ester of the general formula II
15 R1 015 R1 0
C = CH - CH2OC-CH2X IIC = CH - CH2OC-CH2X II
R2 20 hvor X, R*· og R2 har den ovenfor anførte betydning, omlejres termisk ved en temperatur mellem 100°C og 150°C, og syren om ønsket frigøres fra det således dannede salt ved syrning.R2, where X, R * and R2 have the meaning set forth above, is thermally rearranged at a temperature between 100 ° C and 150 ° C and the acid, if desired, is released from the salt thus formed by acidification.
Enolatsaltet er fortrinsvis et alkalimetal- eller jordalkalimetalsalt, som kan dannes ved omsætning af esteren med selve metallet 25 eller en basisk forbindelse deraf, f.eks. hydridet. Der foretrækkes især natriumsaltet, som bekvemt kan dannes ved omsætning af esteren med natriumhydrid.The enolate salt is preferably an alkali metal or alkaline earth metal salt which can be formed by reaction of the ester with the metal itself or a basic compound thereof, e.g. hydride. Particularly preferred is the sodium salt, which can be conveniently formed by reacting the ester with sodium hydride.
Den termiske omlejring udføres som anført ved en temperatur mellem 100 og 1500C. Der kan også forekomme et inert opløsningsmiddel, 30 f.eks. en flydende aromatisk forbindelse såsom toluen, xylen eller chlorbenzen.The thermal rearrangement is carried out as indicated at a temperature between 100 and 1500C. There may also be an inert solvent, e.g. a liquid aromatic compound such as toluene, xylene or chlorobenzene.
Produktet fra den termiske omlejring er et salt af syren med formlenThe product of the thermal rearrangement is a salt of the acid of the formula
DK 155001 BDK 155001 B
2 I, fra hvilket syren frigøres ved syrning med f.eks. en stark mineralsyre såsom saltsyre, fortrinsvis under vandige betingelser.2 I from which the acid is released by acidification with e.g. a strong mineral acid such as hydrochloric acid, preferably under aqueous conditions.
Som ovenfor anført kan forbindelserne med formlen I anvendes som mellemprodukter, især til fremstilling af pesticider. Således kan 2-5 cyano-4-pentensyrederivateme anvendes til fremstillingen af estere af 2-(2,2-dichlorvinyl)cyclopropancarboxylsyrer, som har interessante insecticide egenskaber, jfr. hollandsk patentansøgning nr. 7.307.130.As stated above, the compounds of formula I can be used as intermediates, especially for the preparation of pesticides. Thus, the 2-5 cyano-4-pentenoic acid derivatives can be used for the preparation of esters of 2- (2,2-dichlorovinyl) cyclopropane carboxylic acids which have interesting insecticidal properties, cf. Dutch Patent Application No. 7,307,130.
Opfindelsen belyses nærmere ved nedenstående eksempler, i hvilke NMR-spektreme er målt ved 60 MHz i deuterochloroformopløsning; absorp-10 tionerne er angivet i forhold til en tetramethylsilanstandard.The invention is further illustrated by the following examples in which the NMR spectra are measured at 60 MHz in deuterochloroform solution; the absorbances are given relative to a tetramethylsilane standard.
EKSEMPEL 1EXAMPLE 1
En opløsning af 30 g (0,2 mol) 3-methyl-2-butenyl-cyanoacetat i 50 ml en blanding af xylener (kogepunkt 137-143°C) sættes under omrøring i løbet af 15 minutter til en suspension af 5,0 g (0,2 mol) natrium-15 hydrid i 150 ml xylenblandingen. Suspensionen af det dannede enolatsalt fortyndes til 500 ml med yderligere xylenblanding og omrøres derefter ved 130°C i 2 1/2 time. Suspensionen afkøles derpå til 22°C og ekstraheres tre gange med hver gang 150 ml vand. Den vandige ekstrakt symes til pH-værdi 1 med vandig saltsyreopløsning, 20 og det dannede bundfald ekstraheres tre gange med hver gang 150 ml diethylether. Ekstrakterne tørres over natriumsulfat, og etheret af dampes under reduceret tryk, hvorved der fås den ønskede 2-cyano-3,3-dimethyl-4-pentensyre i form af en viskos olie i et udbytte på 86% af det teoretiske.A solution of 30 g (0.2 mole) of 3-methyl-2-butenyl cyanoacetate in 50 ml of a mixture of xylenes (bp 137-143 ° C) is stirred over 15 minutes to a suspension of 5.0 g (0.2 mole) of sodium hydride in the 150 ml xylene mixture. The suspension of the enolate salt formed is diluted to 500 ml with additional xylene mixture and then stirred at 130 ° C for 2 1/2 hours. The suspension is then cooled to 22 ° C and extracted three times with 150 ml of water each time. The aqueous extract is sieved to pH 1 with aqueous hydrochloric acid solution, and the precipitate formed is extracted three times with 150 ml of diethyl ether each time. The extracts are dried over sodium sulfate and the ether is evaporated under reduced pressure to give the desired 2-cyano-3,3-dimethyl-4-pentenoic acid in the form of a viscous oil in a yield of 86% of theory.
25 NMR-Spektret af forbindelsen viser følgende absorptioner: 8 = 1,30 ppm (singlet, >C(CH3)2) 8 = 3,41 ppm (singlet, >CHCN) 8 — 5,17 ppm (dobbelt dublet, =0¾) 8 = 5,95 ppm (dobbelt dublet, -CH=) 30 8 = 10,1 ppm (singlet, -COOH).The NMR spectrum of the compound shows the following absorptions: 8 = 1.30 ppm (singlet,> C (CH 3) 2) 8 = 3.41 ppm (singlet,> CHCN) 8 - 5.17 ppm (double doubled, = 0¾ 8 = 5.95 ppm (double doubled, -CH =) 8 = 10.1 ppm (singlet, -COOH).
EKSEMPEL 2EXAMPLE 2
DK 155001 BDK 155001 B
33
Der gås frem som beskrevet i eksempel 1 under anvendelse af toluen som fortyndingsmiddel, en reaktions temperatur på 110° C og en reaktionstid på 3 timer. Udbyttet af syre er 80% af det teoretiske.Proceed as described in Example 1 using toluene as the diluent, a reaction temperature of 110 ° C and a reaction time of 3 hours. The yield of acid is 80% of the theoretical.
5 EKSEMPEL 3EXAMPLE 3
Der gås frem som beskrevet i eksempel 1 under anvendelse af metallisk natrium i stedet for natriumhydrid. Udbyttet af syre er 40% af det teoretiske.Proceed as described in Example 1 using metallic sodium instead of sodium hydride. The yield of acid is 40% of theory.
EKSEMPEL 4 10 Der gås frem som beskrevet i eksempel 1 under anvendelse af chlor-benzen som fortyndingsmiddel og en reaktionstid på 1 time. Udbyttet af syre er 68% af det teoretiske.EXAMPLE 4 10 Proceed as described in Example 1 using chlorobenzene as diluent and a reaction time of 1 hour. The yield of acid is 68% of the theoretical.
EKSEMPEL 5EXAMPLE 5
Der gås frem som beskrevet i eksempel 1 under anvendelse af 3-methyl-15 2-butenyl-ethylmalonat som udgangsmateriale. Produktet, 2-ethoxycar-bonyl-3,3-dimethyl-4-pentensyre, dannes som en viskos olie i et udbytte på 40% af det teoretiske.Proceed as described in Example 1 using 3-methyl-2-butenyl-ethyl malonate as starting material. The product, 2-ethoxycarbonyl-3,3-dimethyl-4-pentenoic acid, is formed as a viscous oil in a yield of 40% of theory.
NMR-Spektret af denne forbindelse viser følgende absorptioner: 20 6 = 6,05 ppm (dobbelt dublet, HC=) δ = 5,05 ppm (dobbelt dublet, =CH2) δ « 4,2 ppm (kvartet, -0¾-O) C00 δ — 3,3 ppm (singlet, -CH ) 25 C00 8 = 1,28 ppm (singlet på triplet, tre CH3-grupper).The NMR spectrum of this compound shows the following absorbances: δ 6 = 6.05 ppm (double doubled, HC =) δ = 5.05 ppm (double doubled, = CH 2) δ δ 4.2 ppm (quartet, -0¾-O ) C00 δ - 3.3 ppm (singlet, -CH) C00 δ = 1.28 ppm (singlet on triplet, three CH3 groups).
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB4515575 | 1975-10-31 | ||
| GB45155/75A GB1556999A (en) | 1975-10-31 | 1975-10-31 | Unsaturated carboxylic acids |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK492576A DK492576A (en) | 1977-05-01 |
| DK155001B true DK155001B (en) | 1989-01-23 |
| DK155001C DK155001C (en) | 1989-06-05 |
Family
ID=10436104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK492576A DK155001C (en) | 1975-10-31 | 1976-10-29 | PROCEDURE FOR THE PREPARATION OF UNSATURED CARBOXYLIC ACIDS |
Country Status (19)
| Country | Link |
|---|---|
| JP (1) | JPS602296B2 (en) |
| AU (1) | AU502376B2 (en) |
| BR (1) | BR7607252A (en) |
| CA (1) | CA1086329A (en) |
| CH (1) | CH624380A5 (en) |
| DD (1) | DD127238A5 (en) |
| DE (1) | DE2649711C2 (en) |
| DK (1) | DK155001C (en) |
| ES (1) | ES452860A1 (en) |
| FR (1) | FR2329649A1 (en) |
| GB (1) | GB1556999A (en) |
| IL (1) | IL50795A (en) |
| IT (1) | IT1075871B (en) |
| MX (1) | MX3822E (en) |
| NL (1) | NL187205C (en) |
| SE (1) | SE7612068L (en) |
| SU (1) | SU668591A3 (en) |
| TR (1) | TR19157A (en) |
| ZA (1) | ZA766490B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1128958A (en) * | 1977-09-19 | 1982-08-03 | Johannes L.M. Syrier | Preparation of an alkenyl cyanoacetate |
| CA1182469A (en) * | 1981-12-11 | 1985-02-12 | William D. Emmons | Esters of michael addition homopolymers of acrylic acid |
| IL111484A (en) * | 1993-11-03 | 2001-06-14 | Commw Scient Ind Res Org | Polymerization process using allylic chain transfer agents for molecular weight control, the polymers obtained thereby and certain novel allylic compounds |
| AU688403B2 (en) * | 1993-11-03 | 1998-03-12 | Commonwealth Scientific And Industrial Research Organisation | Allylic chain transfer agents |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2326077C2 (en) * | 1972-05-25 | 1985-12-12 | National Research Development Corp., London | Unsaturated cyclopropanecarboxylic acids and their derivatives, their preparation and insecticides containing them |
-
1975
- 1975-10-31 GB GB45155/75A patent/GB1556999A/en not_active Expired
-
1976
- 1976-09-14 CA CA261,226A patent/CA1086329A/en not_active Expired
- 1976-10-27 TR TR19157A patent/TR19157A/en unknown
- 1976-10-28 NL NLAANVRAGE7611939,A patent/NL187205C/en not_active IP Right Cessation
- 1976-10-29 IL IL50795A patent/IL50795A/en unknown
- 1976-10-29 DK DK492576A patent/DK155001C/en not_active IP Right Cessation
- 1976-10-29 AU AU19145/76A patent/AU502376B2/en not_active Expired
- 1976-10-29 IT IT28901/76A patent/IT1075871B/en active
- 1976-10-29 MX MX765034U patent/MX3822E/en unknown
- 1976-10-29 CH CH1370076A patent/CH624380A5/en not_active IP Right Cessation
- 1976-10-29 ES ES452860A patent/ES452860A1/en not_active Expired
- 1976-10-29 FR FR7632778A patent/FR2329649A1/en active Granted
- 1976-10-29 SU SU762415403A patent/SU668591A3/en active
- 1976-10-29 ZA ZA766490A patent/ZA766490B/en unknown
- 1976-10-29 DD DD195534A patent/DD127238A5/xx unknown
- 1976-10-29 JP JP51129567A patent/JPS602296B2/en not_active Expired
- 1976-10-29 BR BR7607252A patent/BR7607252A/en unknown
- 1976-10-29 DE DE2649711A patent/DE2649711C2/en not_active Expired
- 1976-10-29 SE SE7612068A patent/SE7612068L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| SU668591A3 (en) | 1979-06-15 |
| CA1086329A (en) | 1980-09-23 |
| MX3822E (en) | 1981-07-31 |
| FR2329649A1 (en) | 1977-05-27 |
| JPS5257118A (en) | 1977-05-11 |
| DD127238A5 (en) | 1977-09-14 |
| FR2329649B1 (en) | 1979-09-21 |
| DE2649711C2 (en) | 1985-01-10 |
| DK492576A (en) | 1977-05-01 |
| NL7611939A (en) | 1977-05-03 |
| IL50795A (en) | 1980-02-29 |
| DK155001C (en) | 1989-06-05 |
| IL50795A0 (en) | 1976-12-31 |
| AU1914576A (en) | 1978-05-04 |
| BR7607252A (en) | 1977-09-13 |
| DE2649711A1 (en) | 1977-05-05 |
| SE7612068L (en) | 1977-05-01 |
| CH624380A5 (en) | 1981-07-31 |
| IT1075871B (en) | 1985-04-22 |
| AU502376B2 (en) | 1979-07-26 |
| GB1556999A (en) | 1979-12-05 |
| TR19157A (en) | 1978-06-01 |
| JPS602296B2 (en) | 1985-01-21 |
| NL187205B (en) | 1991-02-01 |
| ZA766490B (en) | 1977-10-26 |
| NL187205C (en) | 1991-07-01 |
| ES452860A1 (en) | 1977-10-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PBP | Patent lapsed |