HRP940883A2 - Process for the preparation of n-arylhalopyrolidones - Google Patents
Process for the preparation of n-arylhalopyrolidones Download PDFInfo
- Publication number
- HRP940883A2 HRP940883A2 HRP-1021/84A HRP940883A HRP940883A2 HR P940883 A2 HRP940883 A2 HR P940883A2 HR P940883 A HRP940883 A HR P940883A HR P940883 A2 HRP940883 A2 HR P940883A2
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- Croatia
- Prior art keywords
- amine
- hydrogen
- chlorine
- haloamide
- copper
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 32
- 238000002360 preparation method Methods 0.000 title claims description 4
- 239000003054 catalyst Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 23
- 150000001412 amines Chemical class 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 239000000460 chlorine Chemical group 0.000 claims description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 150000002431 hydrogen Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 150000003335 secondary amines Chemical class 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical group CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Chemical group 0.000 claims description 6
- 239000011737 fluorine Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 150000003141 primary amines Chemical class 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 101100037762 Caenorhabditis elegans rnh-2 gene Proteins 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004769 (C1-C4) alkylsulfonyl group Chemical group 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 238000007363 ring formation reaction Methods 0.000 claims description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 2
- 125000004768 (C1-C4) alkylsulfinyl group Chemical group 0.000 claims 1
- KQTOYEUYHXUEDB-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanamide Chemical compound NC(=O)C(F)(F)C(F)(F)F KQTOYEUYHXUEDB-UHFFFAOYSA-N 0.000 claims 1
- 239000005751 Copper oxide Substances 0.000 claims 1
- 229910000431 copper oxide Inorganic materials 0.000 claims 1
- 125000004093 cyano group Chemical group *C#N 0.000 claims 1
- 125000002346 iodo group Chemical group I* 0.000 claims 1
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 7
- 229940045803 cuprous chloride Drugs 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 229960003280 cupric chloride Drugs 0.000 description 6
- 229960004643 cupric oxide Drugs 0.000 description 6
- 150000003512 tertiary amines Chemical class 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- -1 trifluoromethyl iodo Chemical group 0.000 description 5
- 239000005749 Copper compound Substances 0.000 description 4
- 229960001413 acetanilide Drugs 0.000 description 4
- 150000001880 copper compounds Chemical class 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- OQZCSNDVOWYALR-UHFFFAOYSA-N flurochloridone Chemical compound FC(F)(F)C1=CC=CC(N2C(C(Cl)C(CCl)C2)=O)=C1 OQZCSNDVOWYALR-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- SUTWPJHCRAITLU-UHFFFAOYSA-N 6-aminohexan-1-ol Chemical group NCCCCCCO SUTWPJHCRAITLU-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 150000003940 butylamines Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HMMPCBAWTWYFLR-UHFFFAOYSA-N n-pyridin-2-ylpyridin-2-amine Chemical compound C=1C=CC=NC=1NC1=CC=CC=N1 HMMPCBAWTWYFLR-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003139 primary aliphatic amines Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Description
Osnova izuma The basis of the invention
U ovom izumu je opisan poboljšan postupak za dobivanje N-arilhalopirolidona u prisustvu katalizatora koji obuhvaća spoj bakra zajedno s aminom. The present invention describes an improved process for the preparation of N-arylhalopyrrolidone in the presence of a catalyst comprising a copper compound together with an amine.
Poznato je da su neki N-arilhalopirolidoni korisni kao herbicidi opće primjene. Ovakvi spojevi i njihova korisnost otkriveni su, na primjer, u U.S. Patentu 4,110,105 Eugena G. Teach-a. Some N-arylhalopyrrolidones are known to be useful as general purpose herbicides. Such compounds and their utility are disclosed, for example, in U.S. Pat. Patent 4,110,105 to Eugene G. Teach.
Jedan postupak za njihovo dobivanje otkriven je u U.S. Patentu 4,110,105 i dodatnom U.S. Patentu 4,210,589, koji je dio prethodnog. Prema ovim referencama, spojevi se dobivaju intramolekularnom ciklizacijom N-2-alkenilamida koji sadrži α -halogen u prisustvu katalitičke količine fero željeza. One process for obtaining them is disclosed in the U.S. Patent 4,110,105 and additional U.S. Pat. Patent 4,210,589, which is part of the previous one. According to these references, the compounds are obtained by intramolecular cyclization of α -halogen-containing N-2-alkenylamide in the presence of a catalytic amount of ferrous iron.
Jedan drugi U.S. Patent No. 4,132,713 Michael-a D. Broadhurst-a, otkriva poboljšan postupak za dobivanje ovakvih spojeva koristeći druge katalizatore a ne fero željezo. Naročito, katalizator iz U.S. Patenta 4,132,713 sadrži jedan ili više prijelaznih metala vanadij, molibden, rutenij, srebro i bakar. Spoj koji sadrži metal može biti u nekoliko oblika obuhvaćajući komplekse s uobičajenim reagensima za formiranje kompleksa kao što su trifenilfosfin, ugljik monoksid, i tercijarni amini. Primjeri tercijarnih amina za koje je otkriveno da su korisni u ovom postupku su piridin, 2,2'-dipiridil, 2,2'-dipiridilamin i tetrametilendiamin. Posljednji spomenuti spoj je međutim, stvarno bifunkcionalni primarni amin, koji ima formulu N2N(CH2)4NH2. Među spojevima koji sadrže bakar specifično otkriveni u ovom patentu su kupro klorid i kupri oksid. Another U.S. Patent No. 4,132,713 to Michael D. Broadhurst, discloses an improved process for making such compounds using catalysts other than ferric iron. In particular, the catalyst from the U.S. Patent 4,132,713 contains one or more of the transition metals vanadium, molybdenum, ruthenium, silver and copper. The metal-containing compound can be in several forms including complexes with common complexing reagents such as triphenylphosphine, carbon monoxide, and tertiary amines. Examples of tertiary amines found to be useful in this process are pyridine, 2,2'-dipyridyl, 2,2'-dipyridylamine and tetramethylenediamine. The last mentioned compound, however, is really a bifunctional primary amine, having the formula N2N(CH2)4NH2. Among the copper-containing compounds specifically disclosed in this patent are cupric chloride and cupric oxide.
Kada se koriste katalizatori koji sadrže bakar s tercijarnim aminom, reagensom za formiranje kompleksa, postupak se može izvesti na temperaturi od oko 60ºC do oko 200ºC, prvenstveno od oko 80ºC do oko 150ºC. Tablica II. u U.S. Patentu 4,132,713 pokazuje rezultate za dobivanje spoja 3-kloro-4-klorometil-1-(m-trifluorometilfenil)-2-pirolidona When using catalysts containing copper with a tertiary amine complexing reagent, the process can be carried out at a temperature of from about 60°C to about 200°C, preferably from about 80°C to about 150°C. Table II. in the US Patent 4,132,713 shows results for obtaining the compound 3-chloro-4-chloromethyl-1-(m-trifluoromethylphenyl)-2-pyrrolidone
[image] [image]
koristeći kupri oksid i kupro klorid različito kompleksirane sa nekoliko tercijarnih amina. Postupak je izvođen pri vremenima koja su se kretala od 2,5 do 11 sati s prinosima koji su dostizali do 65% teorijskog. Dobivanje proizvoda u većem opsegu opisano je u primjeru 14 patenta. Drugi primjeri prikazuju dobivanje srodnih spojeva ovom tehnikom. using cuprous oxide and cuprous chloride differently complexed with several tertiary amines. The procedure was performed at times ranging from 2.5 to 11 hours with yields reaching up to 65% of the theoretical. Obtaining the product on a larger scale is described in example 14 of the patent. Other examples show the preparation of related compounds by this technique.
Izvod iz izuma Extract from the invention
Sada je nađeno da se poboljšanje u odnosu na postupak opće opisan u U.S. Patentu 4,132,713 može postići izvođenjem reakcije u prisustvu katalizatora koji obuhvaća spoj bakra zajedno s aminom odabranim iz grupe koja se sastoji od: It has now been found that an improvement over the process generally described in the U.S. Patent 4,132,713 can be achieved by performing the reaction in the presence of a catalyst comprising a copper compound together with an amine selected from the group consisting of:
(a) primarnih amina koji imaju formulu RNH2, u kojoj je R alkil grupa normalnog ili račvastog lanca, koja ima 1 do 20 ugljikovih atoma, opcijski supstituirana sa hidroksi; ili (a) primary amines having the formula RNH2, in which R is a normal or branched chain alkyl group having 1 to 20 carbon atoms, optionally substituted with hydroxy; or
(b) sekundarnih amina koji imaju formulu R1NHR2 u kojoj su R1 i R2 neovisno alkil grupe s normalnim ili račvastim lancem, koje imaju od 1 do 20 ugljikovih atoma, opcijski supstituirane s hidroksi, isključi alkil grupe račvastog lanca koje imaju račvanj alfa ugljikovom atomu. (b) secondary amines having the formula R1NHR2 in which R1 and R2 are independently normal or branched chain alkyl groups having from 1 to 20 carbon atoms, optionally substituted with hydroxy, excluding branched chain alkyl groups having a branch at an alpha carbon atom.
Detaljan opis izuma Detailed description of the invention
N-2-alkil-α-haloamid koji se upotrebljava kao polazni materijal u postupku prema predmetnom izumu može se dobiti bilo kojom konvencionalnom tehnikom poznatom u znanosti. Nekoliko tehnika je dano u U.S: Patentu 4,132,713. The N-2-alkyl-α-haloamide used as a starting material in the process according to the present invention can be obtained by any conventional technique known in science. Several techniques are given in U.S. Patent 4,132,713.
N-arilhalopiridoni koji se dobivaju prema predmetnom izumu imaju opću formulu: The N-arylhalopiridones obtained according to the present invention have the general formula:
[image] [image]
X je odabrano iz grupe koja se sastoji od vodika, klora, broma i fluora; X is selected from the group consisting of hydrogen, chlorine, bromine and fluorine;
Y je odabrano iz grupe koja se sastoji od vodika, klora, broma i fluora; Y is selected from the group consisting of hydrogen, chlorine, bromine and fluorine;
Z je odabrano iz grupe koja se sastoji od klora i broma; Z is selected from the group consisting of chlorine and bromine;
R! je odabrano iz grupe koja se sastoji od vodika i C1-C4 alkil; R! is selected from the group consisting of hydrogen and C1-C4 alkyl;
R2 je odabrano iz grupe koja se sastoji od vodika, C1-C4 alkil, acetil, klora, broma, fluora, joda trifluorometila, nitro, cijano C1-C4 alkilsulfinil, C1-C4 alkilsulfonil, trifluorometiltio, trifluorometilsulfinil, trifluorometilsulfonil, pentafluoropropionamido, i 3-metilureido; i R2 is selected from the group consisting of hydrogen, C1-C4 alkyl, acetyl, chlorine, bromine, fluorine, trifluoromethyl iodo, nitro, cyano C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, pentafluoropropionamido, and 3 -methylureido; and
R3je odabrano iz grupe koja se sastoji od vodika, C1-C4 alkila, klora i trifluorometila. R 3 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, chlorine and trifluoromethyl.
Klasa prvenstvenih proizvoda su oni u kojima je R3 trifluorometil i R2 je vodik ili fluoro. Jedan prvenstven proizvod je 3-kloro-4-klorometil-1-(m-trifluorometilfenil)-2-pirolidon (X = klor, Y = vodik, Z = klor, R1 = vodik, R2 = vodik, R3 = 3-trifluorometil). A class of preferred products are those in which R3 is trifluoromethyl and R2 is hydrogen or fluoro. One primary product is 3-chloro-4-chloromethyl-1-(m-trifluoromethylphenyl)-2-pyrrolidone (X = chlorine, Y = hydrogen, Z = chlorine, R1 = hydrogen, R2 = hydrogen, R3 = 3-trifluoromethyl) .
Ciklizacija N-2-alkenil-α-haloamida se izvodi u prisustvu katalizatora koji uključuje spoj bakra. Spoj bakra je prvenstveno kupro klorid, kupri klorid ili kupri oksid, sa kupro kloridom najpogodnija. The cyclization of N-2-alkenyl-α-haloamide is carried out in the presence of a catalyst that includes a copper compound. The copper compound is primarily cupric chloride, cupric chloride or cupric oxide, with cupric chloride being the most suitable.
Katalizator može biti prisutan ili kao neotopljen krut u reakcijskoj smjesi, ili kao otopljen u otopini s polaznim amidom ili otapalom, kada se upotrebljava otapalo. Uopće, katalizator je prvenstveno otopljen. Reakcija će protjecati bez miješanja, bilo da je katalizator neotopljen ili je u otopini. Međutim, kada je upotrijebljeno miješanje, tijek reakcije će biti znatno potpomognut. Miješanje se može postići bilo kojim konvencionalnim načinom, na primjer, miješanjem, propuštanjem inertnog plina, upotrebom pregrada u reakcijskoj posudi, ili izvođenjem reakcije pri refluksu. The catalyst can be present either as an undissolved solid in the reaction mixture, or as dissolved in a solution with the starting amide or solvent, when a solvent is used. In general, the catalyst is primarily dissolved. The reaction will proceed without stirring, whether the catalyst is undissolved or in solution. However, when stirring is used, the course of the reaction will be greatly aided. Mixing can be achieved by any conventional means, for example, stirring, passing an inert gas, using baffles in the reaction vessel, or performing the reaction at reflux.
Količina katalizatora koji sadrži bakar koja će činiti katalitičku količinu, bit će ona količina koja služi da poveća brzinu reakcije. Veće količine će izazvati veće povećanje. Količina koja se upotrebljava u svakoj pojedinačnoj primjeni bit će određena u velikoj mjeri individualnim potrebama proizvodnje. Osim razmatranja kao što su ocjena, potrebnog reakcijskoj vremena i kapaciteta sustava količina katalizatora nije kritična odlika izuma i može varirati preko širokog opsega. Najpogodnije, upotrebljava se količina katalizatora koja obuhvaća od oko 0,1 do oko 20 mol postotaka, na osnovi početne količine N-2-alkenilamida. The amount of copper-containing catalyst that will make up the catalytic amount will be the amount that serves to increase the reaction rate. Larger amounts will cause a larger increase. The amount used in each individual application will be determined to a large extent by individual production needs. Apart from considerations such as grade, required reaction time and system capacity, the amount of catalyst is not a critical feature of the invention and can vary over a wide range. Most conveniently, an amount of catalyst is used that comprises from about 0.1 to about 20 mole percent, based on the initial amount of N-2-alkenylamide.
Prvenstvene količine katalizatora su: za kupro ili kupri klorid - od oko 1 do 10 mol postotaka; za kupri oksid - od oko 1 do oko 5 mol postotaka. The primary amounts of catalyst are: for cupro or cupric chloride - from about 1 to 10 mol percent; for cupric oxide - from about 1 to about 5 mol percent.
Amini za koje je nađeno da su korisni u poboljšanom postupku prema ovom izumu su neki primarni i sekundarni alifatični amini. Amines found to be useful in the improved process of this invention are some primary and secondary aliphatic amines.
Primarni amini su tipa RNH2, gdje je R alkil grupa normalnog ili račvastog lanca, koja ima od 1 do 20 ugljikovih atoma, opcijski supstituiran s hidroksi. Ovakvi amini obuhvaćaju, na primjer, etilamin, propilamin, različite butilamine, i amine koji sadrže više alkil grupe. Jedan primjer hidroksidom supstituiranog alkil amina je 6-hidroksiheksilamin. Primary amines are of the RNH2 type, where R is a normal or branched chain alkyl group, having from 1 to 20 carbon atoms, optionally substituted with hydroxy. Such amines include, for example, ethylamine, propylamine, various butylamines, and amines containing multiple alkyl groups. One example of a hydroxide substituted alkyl amine is 6-hydroxyhexylamine.
Sekundarni amini su R1NHR2, gdje su R1 i R2 alkil grupe prvenstveno 1 do 12 ugljikovih atoma. Ove alkil grupe mogu biti grupe normalnog ili račvastog lanca, opcijski supstituirane s hidroksi, pod uvjetom da ako su račvastog lanca, račvanje je drugačije nego na alfa ugljikovom atomu. Sekundarni amini koji sadrže alfa račvaste alkil grupe, kao što je izopropil, sek-butil i slične, ne daju povoljne rezultate u ovom postupku. Alkil grupe R1 ̧i R2 mogu biti iste ili različite, prvenstveno one su iste. Prvenstvena klasa sekundarnih amina su one u kojima su R1 i R2 identične alkil grupe normalnog lanca koje imaju od 1 do 12 ugljikovih atoma. Prvenstveni članovi ove klase su di(n-butil) i di(n-propil)amini. Secondary amines are R1NHR2, where R1 and R2 are alkyl groups preferably of 1 to 12 carbon atoms. These alkyl groups may be straight chain or branched chain groups, optionally substituted with hydroxy, provided that if they are branched chain, the branching is other than at the alpha carbon atom. Secondary amines containing alpha branched alkyl groups, such as isopropyl, sec-butyl and the like, do not give favorable results in this process. Alkyl groups R1 and R2 can be the same or different, primarily they are the same. A primary class of secondary amines are those in which R1 and R2 are identical normal chain alkyl groups having from 1 to 12 carbon atoms. The primary members of this class are di(n-butyl) and di(n-propyl)amines.
Ukoliko je potrebno, mogu se upotrijebiti različita otapala u ovoj reakciji. Takva otapala mogu obuhvatiti alifatične spojeve kao što su heptan ili oktan, alkohola kao što je tercijarni butil alkohol, i aromatične spojeve kao što su toluol ili ksiolol. Prvenstvena otapala su toluol i tercijarni butil alkohol. Druga otapala kao što su oni spomenuti u U.S. Patentu 4,132,713 mogu se upotrijebiti ako je potrebno. If necessary, different solvents can be used in this reaction. Such solvents may include aliphatic compounds such as heptane or octane, alcohols such as tertiary butyl alcohol, and aromatic compounds such as toluene or xylene. The primary solvents are toluene and tertiary butyl alcohol. Other solvents such as those mentioned in U.S. Patent 4,132,713 can be used if necessary.
Količina amina koja je upotrebljena može široko varirati prema cijenama i željenim efektima. Uopće, amin se upotrebljava u količini od oko 5 do 60 mol postotaka na osnovi polaznog N-alkenil-α-haloamida, i prvenstveno od oko 10 do oko 40 mol postotaka. The amount of amine used can vary widely according to cost and desired effects. In general, the amine is used in an amount of about 5 to 60 mol percent based on the starting N-alkenyl-α-haloamide, and preferably from about 10 to about 40 mol percent.
Temperatura na kojoj se izvodi postupak je uglavnom od oko 50°C do oko 150°C. Prvenstvena opcijska područja će varirati u ovisnosti od prirode katalizatora koji sadrži bakar, amina, otapala (ukoliko ga ima), koncentracije α-haloamida u supstratu. Uopće, kupro kloridi i amini manje molekulske težine koji sadrže do osam ugljikovih atoma po alkil grupi, su najbolji na temperaturama od oko 60 do oko 90°C. The temperature at which the procedure is performed is generally from about 50°C to about 150°C. The primary optional regions will vary depending on the nature of the copper-containing catalyst, the amine, the solvent (if any), the α-haloamide concentration in the substrate. In general, cupro chlorides and lower molecular weight amines containing up to eight carbon atoms per alkyl group are best at temperatures from about 60 to about 90°C.
Pošto se reakcija odigrava u tekućoj fazi, radni tlak nije značajan parametar, i može se kretati široko, u ovisnosti od pogodnosti, ekonomičnosti i materijala konstrukcije. Najpogodnije je da se reakcija izvodi na ili blizu tlaka okoline. Since the reaction takes place in the liquid phase, the operating pressure is not a significant parameter, and can vary widely, depending on convenience, economy and construction materials. The reaction is most conveniently carried out at or near ambient pressure.
Ukoliko se reakcija izvodi u prisustvu otapala, pod refluksom ili na blizu atmosferskog tlaka temperatura može da bude normalna temperatura refluksa otapala, ili može biti niža. Temperatura od oko 85°C su nađene da su pogodne za otapala kao što su toluil i tercijarni butil alkohol. If the reaction is carried out in the presence of a solvent, under reflux or at close to atmospheric pressure, the temperature can be the normal reflux temperature of the solvent, or it can be lower. A temperature of about 85°C has been found to be suitable for solvents such as toluene and tertiary butyl alcohol.
Koncentracija α-haloamida u otapalu može da varira. Međutim, kako se koncentracija povećava sa oko 20 tež.% na oko 60 tež. % selektivnost - prinos reakcije obično opadaju, uz dobivanje manje poželjnih proizvoda i većih količina “smola”. Ovo je naročito tako kod amina s većim molekulskim težinama i kupri oksid katalizatorima. Stoga, za dobre rezultate, koncentracije amida u otapalu treba biti na maksimumu od oko 65 te. % najpogodnije oko 40 tež. %. The concentration of α-haloamide in the solvent can vary. However, as the concentration increases from about 20 wt.% to about 60 wt. % selectivity - reaction yields usually decrease, with less desirable products and larger amounts of "resin" being obtained. This is especially true for amines with higher molecular weights and cupric oxide catalysts. Therefore, for good results, the amide concentration in the solvent should be at a maximum of about 65 te. % most suitable around 40 wt. %.
Redosljed dodavanja materijala nije značajan parametar. Međutim, poželjno je da se prethodno izmiješaju katalizator i amin, i zatim se doda α-haloamid, pošto se ovo može proizvesti u malo poboljšanom prinosu. The order of adding materials is not a significant parameter. However, it is preferable to premix the catalyst and amine, and then add the α-haloamide, as this can be produced in slightly improved yield.
Prvenstveni zbroj parametara za izvođenje ovog postupka je: The primary sum of parameters for performing this procedure is:
bakreni katalizator : 3 - 8 mol % copper catalyst: 3 - 8 mol %
amin : 20 - 40 mol % amine: 20 - 40 mol %
otapalo : toluol solvent: toluene
temperatura : 75 - 95°C temperature: 75 - 95°C
koncentracija amida u otapalu : 15 - 30 % concentration of amide in the solvent: 15 - 30 %
Pirolidon dobiven reakcijom može da se regenerira iz reakcijske smjese bilo kojom konvencionalnom tehnikom, kao što je ekstrakcija otapalom, kristalizacija, sublimacija, ili destilacija. The pyrrolidone obtained by the reaction can be regenerated from the reaction mixture by any conventional technique, such as solvent extraction, crystallization, sublimation, or distillation.
U usporedbi s bakar/tercijarni amin kompleksima opisanim u U.S. Patentu 4,132,713, upotreba bakarnog katalizatora s primarnim ili sekundarnim alifatičkim aminom, tipa opisanog ovdje proizvodi željeni spoj s većim prinosom, s odgovarajućim smanjenjem proizvodnje neisparljivih nus proizvoda (“smola”), i uopće smanjenje potrebnog reakcijskog vremena. Compared to the copper/tertiary amine complexes described in U.S. Pat. In Patent 4,132,713, the use of a copper catalyst with a primary or secondary aliphatic amine of the type described herein produces the desired compound in higher yield, with a corresponding reduction in the production of non-volatile side products ("resin"), and an overall reduction in the required reaction time.
Slijedeći primjeri ilustriraju tijek postupka, u odnosu na dobivanje spoja 3-kloro-4-klormetil-1(m-trifluoro-metilfenil)-2-pirolidona. The following examples illustrate the course of the procedure, in relation to obtaining the compound 3-chloro-4-chloromethyl-1(m-trifluoro-methylphenyl)-2-pyrrolidone.
Primjer 1 Example 1
U balonu se pomiješa 200 (g) (0,567 mola) N-alil-3’-trifluormetil-2,2-dikloracetanilida, 2,79 g (0,028 mola) kupro klorida, 28,5 mililitara (ml) (0,169 mola) di-(n-butil)-amina, i 891 ml toluola. Smjesa se zagrijava do temperature od 85-90°C i miješa se 2 sata i 25 minuta. Na kraju ovog vremena, jedan uzorak reakcijske smjese se analizira plinskom kroamtografijom i pokazuje 95,0 površinskog postotka željenog proizvoda. 200 (g) (0.567 mol) N-allyl-3'-trifluoromethyl-2,2-dichloroacetanilide, 2.79 g (0.028 mol) cuprous chloride, 28.5 milliliters (ml) (0.169 mol) di -(n-butyl)-amine, and 891 ml of toluene. The mixture is heated to a temperature of 85-90°C and stirred for 2 hours and 25 minutes. At the end of this time, a sample of the reaction mixture is analyzed by gas chromatography and shows 95.0 surface percent of the desired product.
Reakcijska smjesa je oprana tri puta sa 125 ml 3,0 M klorovodične kiseline. Zatim je smjesa odvojena u faze i usisavana s aspiratorom jedan sat na 40°C i pod visokim vakuumom jedan sat na 55°C, dajući sirovi prinos od 192,89 g. Analiza plinskom kromatografijom pokazala je čistoću od 86,8%, što odgovara korigiranom prinosu od 94,5% željenog proizvoda. Destilacija uzorka pokazala je da proizvod sadrži 5,8 težinskih % neisparljivih smola. Struktura željenog proizvoda potvrđena je masenom spektroskopijom. The reaction mixture was washed three times with 125 ml of 3.0 M hydrochloric acid. The mixture was then separated into phases and vacuumed with an aspirator for one hour at 40°C and under high vacuum for one hour at 55°C, giving a crude yield of 192.89 g. Gas chromatography analysis showed a purity of 86.8%, corresponding to corrected yield of 94.5% of the desired product. Distillation of the sample showed that the product contains 5.8% by weight of non-volatile resins. The structure of the desired product was confirmed by mass spectroscopy.
Usporedni primjer 1 Comparative example 1
Ovaj primjer ilustrira tijek postupka koji koristi kupri oksid/piridin katalizator kao u U.S. Patentu 4,132,713. This example illustrates a process flow using a cupric oxide/pyridine catalyst as in the U.S. Patent 4,132,713.
U balonu se pomiješa 200 g (0,586 mola) N-alil-3’-tri-fluorometil-2,2-dikloroacetanilida, 8,25 g (0,058 mola) kupri oksida, 18,7 ml (0,023 mola) piridina i 135 ml toluola. Smjesa se zagrijava do refluksa na 115°C, i miješa ukupno jedan sat, 20 minuta. Smjesa se filtrira, tada pere tri puta sa 100 ml 3,0 M klorovodične kiseline. Zatim se smjesa odvoji od faze i izvlači prvo s aspiratorom, zatim pod visokim vakuumom jedan sat na 55°C da da sirov prinos od 186,80 g. Plinskom kromatografijom, pokazano je da je proizvod 80,0% čistoće, što odgovara korigiranom prinosu od 81,7% željenog proizvoda. Proizvod je sadržao 14,8 težinskih % smola, kao što je određeno destilacijom. Struktura željenog proizvoda je potvrđena masenom spektroskopijom. 200 g (0.586 mol) of N-allyl-3'-trifluoromethyl-2,2-dichloroacetanilide, 8.25 g (0.058 mol) of cupric oxide, 18.7 ml (0.023 mol) of pyridine and 135 ml of toluene. The mixture is heated to reflux at 115°C, and stirred for a total of one hour, 20 minutes. The mixture is filtered, then washed three times with 100 ml of 3.0 M hydrochloric acid. The mixture was then dephased and extracted first with an aspirator, then under high vacuum for one hour at 55°C to give a crude yield of 186.80 g. By gas chromatography, the product was shown to be 80.0% pure, corresponding to the corrected yield of 81.7% of the desired product. The product contained 14.8% resins by weight, as determined by distillation. The structure of the desired product was confirmed by mass spectroscopy.
Primjer 2 Example 2
U balonu se pomiješa 0,157 g (0,00158 mola) kupro klorida, 1,6 ml (0,0091 mola) di-(n-butil)amina, i 40 ml toluola. Smjesa se miješa da se otopi kupro klorid. Tada se doda 11,22 g (0,0334 mola) acetanilida korištenog u primjeru 1, zajedno s dodatnim 10 ml toluola. Dobivena smjesa je zagrijavana do 85-95°C i miješana 1,5 sati. 0.157 g (0.00158 mol) of cuprous chloride, 1.6 ml (0.0091 mol) of di-(n-butyl)amine, and 40 ml of toluene are mixed in a flask. The mixture is stirred to dissolve the cuprous chloride. 11.22 g (0.0334 mol) of the acetanilide used in Example 1 was then added, along with an additional 10 ml of toluene. The resulting mixture was heated to 85-95°C and stirred for 1.5 hours.
Na kraju ovog vremena smjesa je ohlađena oprana sa 3 M klorovodičnom kiselinom i isisana pod vakuumom, da bi dala 11,81 g oranž ulja, koje je analizirano masenom spektroskopijom i pokazalo da je željeni pirolidon proizvod. Plinsko kromatografska analiza proizvoda pokazala je da je 85,4% čist, što odgovara korektnom prinosu od 96,7%. Destilacijom jedne količine proizvoda pokazan je da sadrži 3,1% težinski “smola”. At the end of this time, the mixture was cooled, washed with 3 M hydrochloric acid and suctioned under vacuum to give 11.81 g of an orange oil, which was analyzed by mass spectroscopy and shown to be the desired pyrrolidone product. Gas chromatographic analysis of the product showed that it is 85.4% pure, which corresponds to a correct yield of 96.7%. Distillation of one quantity of the product showed that it contains 3.1% by weight of "resin".
Primjer 3 - 12 Example 3 - 12
Slijedeći primjeri predstavljaju tijek postupka prema ovom izumu, s drugim primarnim i sekundarnim alkil aminima. Ovi primjeri su svi izvedeni prema sljedećem postupku. The following examples represent the process of the present invention, with other primary and secondary alkyl amines. These examples are all performed according to the following procedure.
Isti acenilid kao u primjerima 1 i 2 pomiješan je s 5 mol postotaka kupro klorida i 28 mol postotaka navedenog amina, koristeći tercijarni butil alkohol ili toluol kao otapalo. Reakcije su vršene na prosječno 85°C, ili oko 115°C kada je ukazano, za ukazano vrijeme. Koncentracija acetanilida u otapalu je bila oko 20-21 težinskih % osim gdje je ukazano. The same acenilide as in examples 1 and 2 was mixed with 5 mol percent of cuprous chloride and 28 mol percent of said amine, using tertiary butyl alcohol or toluene as solvent. Reactions were performed at an average of 85°C, or about 115°C when indicated, for the indicated time. The concentration of acetanilide in the solvent was about 20-21% by weight except where indicated.
Reakcijska smjesa je isprana s razblaženom vodenom otopinom klorovodične kiseline, otapalo je uklonjeno i proizvodi destilirani. Reakcijski proizvodi su analizirani za postotak težinski željenog pirolidona, i ne-isparljivih nus-proizvoda (“smola”). Rezultati ovih eksperimenata su prikazani u slijedećoj tablici I. The reaction mixture was washed with dilute aqueous hydrochloric acid, the solvent was removed and the products distilled. The reaction products were analyzed for percentage by weight of the desired pyrrolidone, and non-volatile by-products (“resin”). The results of these experiments are shown in the following table I.
Tablica I Table I
[image] [image]
* Korigirano za neizreagirani polazni materijal, ako ga ima. * Corrected for unreacted starting material, if any.
** Toluol upotrebljen kao otapalo. ** Toluene used as solvent.
*** Toluol upotrebljen kao otapalo, temperature = 115°C, koncentracija acetonilida u otapalu 61 tež. %. *** Toluene used as solvent, temperature = 115°C, concentration of acetonilide in the solvent 61 wt. %.
Usporedni primjer 2 Comparative example 2
Postupak se izvodi kao što je opisano za primjere 3-12 gore sa tercijarnim butil alkoholom, i kupro kloridom, na 85°C, ali upotrebljavajući piridin kao amin, prije nego primarni ili sekundarni amin. Dobiveni rezultati su bili sljedeći: The procedure is carried out as described for Examples 3-12 above with tertiary butyl alcohol, and cuprous chloride, at 85°C, but using pyridine as the amine, rather than the primary or secondary amine. The obtained results were as follows:
- pirolidon prinos (korigiran za neizreagiran polazni materijal 89,0 tež. - pyrrolidone yield (corrected for unreacted starting material 89.0 wt.
- smole (korigirano za neizreagirani polazni materijal 6,5 tž. - resins (corrected for unreacted starting material 6.5 wt.
- vrijeme za reakciju 320 min - reaction time 320 min
Tako, kada se upotrebljava piridin, tercijarni amin opisan u U.S. Patentu 4,132,713, s istom količinom kupro klorida kao u primjerima 3-14, za završavanje reakcije da se dobiju upotrebljivi prinosi, potrebno je skoro 2,5 puta toliko dugo kao sa primarnim i sekundarnim aminima. Thus, when using pyridine, the tertiary amine described in U.S. Pat. Patent 4,132,713, with the same amount of cuprous chloride as in Examples 3-14, required nearly 2.5 times as long to complete the reaction to obtain usable yields as with primary and secondary amines.
Primjeri 15 - 18 Examples 15 - 18
Ovi primjeri demonstriraju tijek postupka koristeći kupri klorid u kombinaciji s aminima niže i više molekulske težine. Postupak se izvodi kao gore; eksperimenti koji koriste tercijarni butil alkohol kao otapalo vršeni su na 85°C, sa koncentracijom acetanilida od 21 težinskih %, oni kod kojih se koristi toluol kao otapalo vršeni su na 115°C, s koncentracijom acetanilida od 61 težinskih postotaka. Rezultati su sumirani u slijedećoj Tablici II. These examples demonstrate a process flow using cupric chloride in combination with lower and higher molecular weight amines. The procedure is performed as above; experiments using tertiary butyl alcohol as a solvent were performed at 85°C, with an acetanilide concentration of 21% by weight, those using toluene as a solvent were performed at 115°C, with an acetanilide concentration of 61% by weight. The results are summarized in the following Table II.
Tablica II Table II
[image] [image]
* korigirano za neizreagirani polazni materijal, ako ga ima. * corrected for unreacted starting material, if any.
Prethodni primjeri su namijenjeni da ilustriraju tijek predmetnog postupka, i nisu namijenjeni da ograniče opseg izuma, osim kao što je definirano u slijedećim zahtjevima. The foregoing examples are intended to illustrate the flow of the subject process, and are not intended to limit the scope of the invention, except as defined in the following claims.
Claims (9)
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