SE433350B - ortho-halogenoalkyl-2-halogeno acetananilide derivatives which are intermediates in the production of ortho- (alkoxymethyl)-2-halogeno acetanilide herbicides. - Google Patents
ortho-halogenoalkyl-2-halogeno acetananilide derivatives which are intermediates in the production of ortho- (alkoxymethyl)-2-halogeno acetanilide herbicides.Info
- Publication number
- SE433350B SE433350B SE8002281A SE8002281A SE433350B SE 433350 B SE433350 B SE 433350B SE 8002281 A SE8002281 A SE 8002281A SE 8002281 A SE8002281 A SE 8002281A SE 433350 B SE433350 B SE 433350B
- Authority
- SE
- Sweden
- Prior art keywords
- bromine
- chlorine
- halogeno
- hydrogen
- ortho
- Prior art date
Links
- 239000000543 intermediate Substances 0.000 title claims abstract 3
- 229960001413 acetanilide Drugs 0.000 title description 3
- 239000004009 herbicide Substances 0.000 title description 2
- FZERHIULMFGESH-UHFFFAOYSA-N methylenecarboxanilide Natural products CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 31
- 239000000460 chlorine Substances 0.000 claims description 27
- 229910052794 bromium Inorganic materials 0.000 claims description 24
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 22
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 18
- 125000005997 bromomethyl group Chemical group 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 229910052740 iodine Chemical group 0.000 claims 1
- 239000011630 iodine Chemical group 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 20
- 239000002904 solvent Substances 0.000 description 14
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000004342 Benzoyl peroxide Substances 0.000 description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 6
- 230000031709 bromination Effects 0.000 description 5
- 238000005893 bromination reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 230000026030 halogenation Effects 0.000 description 4
- 238000005658 halogenation reaction Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- FRXJYUFHAXXSAL-UHFFFAOYSA-N 3-chloro-n-phenylpropanamide Chemical compound ClCCC(=O)NC1=CC=CC=C1 FRXJYUFHAXXSAL-UHFFFAOYSA-N 0.000 description 3
- 229910014265 BrCl Inorganic materials 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- -1 ethyl-n-propyl Chemical group 0.000 description 3
- 230000002140 halogenating effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 229960002317 succinimide Drugs 0.000 description 3
- DUOWXXDQITWHQV-UHFFFAOYSA-N 2,3-dibromo-N-methyl-N-phenylpropanamide Chemical compound CN(C1=CC=CC=C1)C(=O)C(CBr)Br DUOWXXDQITWHQV-UHFFFAOYSA-N 0.000 description 2
- MARXMDRWROUXMD-UHFFFAOYSA-N 2-bromoisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(Br)C(=O)C2=C1 MARXMDRWROUXMD-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000001743 benzylic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- JKJLCVZYVSZYAQ-UHFFFAOYSA-N n-bromo-n-methylacetamide Chemical compound CN(Br)C(C)=O JKJLCVZYVSZYAQ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JLUHIWYOWGCJRG-UHFFFAOYSA-N 2-bromo-N-[2-(bromomethyl)-6-tert-butylphenyl]-N-methylacetamide Chemical compound BrCC1=C(N(C(CBr)=O)C)C(=CC=C1)C(C)(C)C JLUHIWYOWGCJRG-UHFFFAOYSA-N 0.000 description 1
- UENGBOCGGKLVJJ-UHFFFAOYSA-N 2-chloro-1-(2,4-difluorophenyl)ethanone Chemical compound FC1=CC=C(C(=O)CCl)C(F)=C1 UENGBOCGGKLVJJ-UHFFFAOYSA-N 0.000 description 1
- BBQZKZIIRKKRBD-UHFFFAOYSA-N 2-chloro-n-(2-chloro-6-methylphenyl)acetamide Chemical compound CC1=CC=CC(Cl)=C1NC(=O)CCl BBQZKZIIRKKRBD-UHFFFAOYSA-N 0.000 description 1
- YHZUNJIVPRPTSP-UHFFFAOYSA-N 2-chloro-n-(chloromethyl)-n-(2,6-dimethylphenyl)acetamide Chemical compound CC1=CC=CC(C)=C1N(CCl)C(=O)CCl YHZUNJIVPRPTSP-UHFFFAOYSA-N 0.000 description 1
- PCJKDSWECWZMRV-UHFFFAOYSA-N 2-chloro-n-(chloromethyl)-n-phenylacetamide Chemical compound ClCC(=O)N(CCl)C1=CC=CC=C1 PCJKDSWECWZMRV-UHFFFAOYSA-N 0.000 description 1
- OZYNTGRWSDJASM-UHFFFAOYSA-N 2-chloro-n-[2-(chloromethyl)-6-methylphenyl]acetamide Chemical compound CC1=CC=CC(CCl)=C1NC(=O)CCl OZYNTGRWSDJASM-UHFFFAOYSA-N 0.000 description 1
- QUKFWAXIKVYCKS-UHFFFAOYSA-N 2-chloro-n-[2-methyl-6-(trifluoromethyl)phenyl]acetamide Chemical compound CC1=CC=CC(C(F)(F)F)=C1NC(=O)CCl QUKFWAXIKVYCKS-UHFFFAOYSA-N 0.000 description 1
- VUOFGWLJEBESHL-UHFFFAOYSA-N 2-chloro-n-methyl-n-phenylacetamide Chemical compound ClCC(=O)N(C)C1=CC=CC=C1 VUOFGWLJEBESHL-UHFFFAOYSA-N 0.000 description 1
- LPVAUTDBCYXZCP-UHFFFAOYSA-N 3-bromo-n-phenylpropanamide Chemical compound BrCCC(=O)NC1=CC=CC=C1 LPVAUTDBCYXZCP-UHFFFAOYSA-N 0.000 description 1
- WQWVQIVJGAOWDJ-UHFFFAOYSA-N 3-methoxy-n-phenylpropanamide Chemical compound COCCC(=O)NC1=CC=CC=C1 WQWVQIVJGAOWDJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-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
- 239000002841 Lewis acid Substances 0.000 description 1
- GZSGVBVDFWXXJS-UHFFFAOYSA-N N-(2-tert-butyl-6-methylphenyl)-2-chloro-N-(chloromethyl)acetamide Chemical compound C(C)(C)(C)C1=C(N(C(CCl)=O)CCl)C(=CC=C1)C GZSGVBVDFWXXJS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 150000008061 acetanilides Chemical class 0.000 description 1
- 229940051881 anilide analgesics and antipyretics Drugs 0.000 description 1
- 150000003931 anilides Chemical group 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000004970 halomethyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- SSKKKOHRVGLSCT-UHFFFAOYSA-N n-[2-(bromomethyl)phenyl]-2-chloroacetamide Chemical compound ClCC(=O)NC1=CC=CC=C1CBr SSKKKOHRVGLSCT-UHFFFAOYSA-N 0.000 description 1
- ZNOFWJBCCPFGNN-UHFFFAOYSA-N n-[2-tert-butyl-6-(dibromomethyl)phenyl]-2-chloroacetamide Chemical compound CC(C)(C)C1=CC=CC(C(Br)Br)=C1NC(=O)CCl ZNOFWJBCCPFGNN-UHFFFAOYSA-N 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
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 210000004357 third molar Anatomy 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/12—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
- C07C233/15—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
8002281-7, 2 Föreningarna enligt uppfinningen har formeln R _ 9 C - CH X \ / 2 N X ö 2 32 X1 där X är klor, brom eller jod; 5 R är väte, metyl, klormetyl eller brommetyl; ' ' R I är väte, halogen, tgig-butyl, trifluormetyl eller X2 _ C -_R2 X1 Rz är väte, klor, brom eller rakkedjig alkyl innehållande-l-till 4 kol- atomer; 10 Y 1 är väte, halogen, tÉQ-butyl,trifluormetyleller X2 - C - Rz X1 X1 och X2 oberoende_är väte, klor eller brom, förutsatt att, när Rz är rakkedjig alkyl innehållande l till ll kolatomer, endast en av X1 och X2 kan vara väte, klor eller brom och vidare förutsatt att Rz, X1 och X2 inte samtidigt kan vara klor eller brom. - l5 Uttrycket "rakkedjig alkyl innehållande l till 4 kolatomer" avser metyl, etyl-n-propyl och n-butyl. _ Uttrycket "halogen" avser klor-, brom-, fluor- och jodatomer. Klor och brom är föredragna. 8002281-7, 2 The compounds of the invention have the formula R _ 9 C - CH X R is hydrogen, methyl, chloromethyl or bromomethyl; R 1 is hydrogen, halogen, tgig-butyl, trifluoromethyl or X 2 -C 1 -R 2 X 1 R 2 is hydrogen, chlorine, bromine or straight chain alkyl containing 1 to 4 carbon atoms; Y 1 is hydrogen, halogen, tEQ-butyl, trifluoromethyl or X 2 - C - R 2 X 1 X 1 and X 2 are independently hydrogen, chlorine or bromine, provided that when R 2 is straight chain alkyl containing 1 to 11 carbon atoms, only one of X 1 and X 2 may be hydrogen, chlorine or bromine and further provided that Rz, X1 and X2 cannot simultaneously be chlorine or bromine. The term "straight chain alkyl containing 1 to 4 carbon atoms" refers to methyl, ethyl-n-propyl and n-butyl. The term "halogen" refers to chlorine, bromine, fluorine and iodine atoms. Chlorine and bromine are preferred.
Föreningarna enligt uppfinningen framställs enligt följande nya för- ZO farande: I 10 15 20 25 8002281 -7 3 0 o " u R c-cnzx R c-cazx \ H \ / v - I C12, Brz eller NBS. N 1:1 Ru çíRiu I C u i / X 2 v 1 y l II I där R" är väte, halogen, tert-butyl, trítluormetyl eller H _C_Rn H R"'är väte, eller rakkedjig alkyl innehållande 1 - 4 kolatomer, när n är noll, R är metyl och de övriga substituenterna har ovan angivna betydelser.The compounds of the invention are prepared according to the following new procedure: I C12, Brz or NBS. N 1: 1 Wherein R "is hydrogen, halogen, tert-butyl, tritluoromethyl or H - C_Rn HR" 'is hydrogen, or straight chain alkyl containing 1 to 4 carbon atoms, when n is zero, R is methyl and the other substituents have the meanings given above.
I enlighet med det ovanstående reaktionsschemat löses det lämpliga utgångsmaterialet, dvs. en förening av den med formel II beskrivna typen, i en lämplig volym lösningsmedel, som är inert mot halogenering. Exempel pä lämpliga lösningsmedel är koltetraklorid, kloroform, petroleunleter, metylen- klorid och liknande, företrädesvis koltetraklorid. Vid denna punkt kan eventuellt en katalysator, t.ex. bensoylklorid, sättas till blandningen för att underlätta reaktionen. Till denna blandning sätts en stökiometriskt ekvivalent mängd av ett halogeneringsmedel valt bland molekylärt klor, molekylärt brom, Nsuccinimid (NBS) eller andra N-brornekvivalenter, som tex. N-brom-N-metylacetamid eller N-bromftalimid. Man kan också använda mer än stökiometriskt ekvivalenta mängder halogeneringsmedel. Den resulterande blandningen utsätts för yttre och/eller inre ultraviolett och/eller vitt ljus och reaktionen tillåts att fortlöpa.In accordance with the above reaction scheme, the appropriate starting material is dissolved, i.e. a compound of the type described in formula II, in a suitable volume of solvent, which is inert to halogenation. Examples of suitable solvents are carbon tetrachloride, chloroform, petroleum ether, methylene chloride and the like, preferably carbon tetrachloride. At this point, a catalyst, e.g. benzoyl chloride, is added to the mixture to facilitate the reaction. To this mixture is added a stoichiometrically equivalent amount of a halogenating agent selected from molecular chlorine, molecular bromine, Nsuccinimide (NBS) or other N-bromine equivalents, such as e.g. N-bromo-N-methylacetamide or N-bromophthalimide. It is also possible to use more than stoichiometrically equivalent amounts of halogenating agents. The resulting mixture is exposed to external and / or internal ultraviolet and / or white light and the reaction is allowed to proceed.
Reaktanterna tillsätts vanligen vid rumstemperatur, dvs. cirka '25°C, och hålls sedan nära återflöde, men även lägre temperaturer kan användas, såsom illustreras i de följande exemplen.The reactants are usually added at room temperature, i.e. about '25 ° C, and then kept close to desolation, but even lower temperatures can be used, as illustrated in the following examples.
Den resulterande reaktionsprodukten separeras lätt från reaktionsbland- ningen med konventionella medel. T.ex. kan oreagerat halogeneringsmedel och succinimid tas bort genom filtrering, medan lösningsmedlet kan avlägsnas genom strippning eller destillation, företrädesvis lågtemperaturdestillation i vakuum.The resulting reaction product is easily separated from the reaction mixture by conventional means. For example. unreacted halogenating agent and succinimide can be removed by filtration, while the solvent can be removed by stripping or distillation, preferably low temperature distillation in vacuo.
Produkten renas vanligen genom kristallisation ur lämpliga lösningsmedel. aoozzafi-7 10 15 20 25 30 35 4 Utgångsmaterialen, dvs. föreningarna med formeln II, är kända, t.ex. från US-A-»B 442 945, 3 6737 847, 3 966 811 och GB-A-l 455 474.The product is usually purified by crystallization from suitable solvents. aoozza fi-7 10 15 20 25 30 35 4 The starting materials, ie. the compounds of formula II, are known, e.g. from US-A-B 442 945, 3,6737,847, 3,966,811 and GB-A-1,455,474.
I det ovan beskrivna' förfarandet leder inte klorering eller bromering av glo-alkyl-Z-halogenacetanilider, i motsats till grtq-alkoxi-Z-halogenacetanilider, till halogenering av fenylringen, dvs. kärnhalogenering. När halogeneringen utförs med molekylärt klor med användning av 2'-6'-dimetyl-Nfmetyl-Z-kloracetanilid som utgångsmaterial, kloreras både N-metyl- och ring(bensyD-metylgrupperna med jämförbara hastigheter. När de här beskrivna o_r*¿q-alkyl-Z-klor-acetanilider- na utsätts för bromering, är processen långsammare och mer selektiv än vid klorering. För optimala resultat sätts sålunda molekylärt brom (löst i CCI4) droppvis till en âterflödande och belyst (UV och/eller vitt ljus) lösning av amid innehållande cirka 0,196 bensoylperoxid. När Z-halogen-N-metyl-Zß ßdialkylace- tanilider bromeras med användning av Brz, bromeras i allmänhet endast fenylringens (bensyiiska) sidokedjekol.In the process described above, chlorination or bromination of glo-alkyl-Z-haloacetanilides, in contrast to grtq-alkoxy-Z-haloacetanilides, does not lead to halogenation of the phenyl ring, i.e. nuclear halogenation. When the halogenation is carried out with molecular chlorine using 2'-6'-dimethyl-N-methyl-Z-chloroacetanilide as starting material, both the N-methyl and ring (benzyl D-methyl groups are comparable at comparable rates. When the o_r * ¿q- described here The alkyl-Z-chloro-acetanilides are subjected to bromination, the process is slower and more selective than in chlorination, so for optimal results molecular bromine (dissolved in CCl 4) is added dropwise to a refluxing and illuminated (UV and / or white light) solution. of amide containing about 0.196 benzoyl peroxide When Z-halogen-N-methyl-Zβ-dialkyl acetanilides are brominated using Brz, generally only the side chain carbon of the phenyl ring is brominated.
I Bromering med molekylärt brom (Brz) av Z-kloracetanilider av den med formel II beskrivna typen ger i varierande grad upphov till halogenutbyte, med delvis bildning av Z-bromacetanilider. Sekundära och tertiära anilider är känsliga för detta utbyte när de framställs i stora mängder vid högre brom- och amidkoncentrationer. Bromet i Z-ställning härstammar från utbyte av klor med HBr för att ge HCl. Halogenutbytet kan minimeras genom kvävebehandling för att underlätta borttagning av brom (HBr). ' För att undvika halogenutbyte och fortfarande behålla fördelarna med bromeringen, är omkristalliserad N-bromsuccinimid (NBS) eller enuliknande N- bromekvivalent, som t.ex. N-brom-N-metylacetamid eller N-bromftalimid, even- tuellt med tillsatt bensoylperoxid, det föredragna reagenset. Endast ekvimolära mängder av detta lätthanterliga material behövs för att uteslutande ge bensylisk sidokedje-bromering, med bildning av biprodukten succinimid.Bromination with molecular bromine (Brz) of Z-chloroacetanilides of the type described in formula II gives rise to halogen exchange to varying degrees, with partial formation of Z-bromoacetanilides. Secondary and tertiary anilides are sensitive to this yield when produced in large quantities at higher bromine and amide concentrations. The bromine in the Z position is derived from the exchange of chlorine with HBr to give HCl. Halogen exchange can be minimized by nitrogen treatment to facilitate the removal of bromine (HBr). To avoid halogen exchange and still retain the benefits of bromination, recrystallized N-bromosuccinimide (NBS) or a similar N-bromine equivalent, e.g. N-bromo-N-methylacetamide or N-bromophthalimide, optionally with added benzoyl peroxide, the preferred reagent. Only equimolar amounts of this manageable material are needed to give exclusively benzylic side chain bromination, with the formation of the by-product succinimide.
Molekylärt brom eller NBSbromerar uteslutande en gítg-metylgrupp i närvaro av en grtg-t-butylgrupp. Klor å andra sidan är inte lika selektivt, med viss klorering av t-butyldelen.Molecular bromine or NBS bromines exclusively a gitg-methyl group in the presence of a grtg-t-butyl group. Chlorine, on the other hand, is not as selective, with some chlorination of the t-butyl moiety.
Det sätt, på vilket föreningarna enligt uppfinningen kan framställas, illustreras närmare i de följande exemplen. ' Exempel l ~ Framställning av 2'-6'-bis(l-brornetyl)-2-brom~N-metylacetanilid. 2-klor-N-metyl-2'-6'-dietylacetanilid (23,9 g, 0,l~mol) placerades i 300 ml koltetraklorid med 0,2 g bensoylperoxid. Efter upphettning till âterflöde sattes 16,0 g brom (0,2 mol) i 50 ml CCll* droppvís till blandningen, som sedan utsattes för både inre UV och yttre vitt ljus. Lösningsmedel borttogs i vakuum och 10 l5 20 25 30 35 8002281 -7 5 räprodukten löstes i etylacetat. Den fasta produkten omkristalliserades upprepat ur etylacetat för att ge 2'-6'-bis(l-brometyl)-2~brom-N-metyl-acetanilid, smält- punkt 1e2_164°c.The manner in which the compounds of the invention may be prepared is further illustrated in the following examples. Example 1 ~ Preparation of 2'-6'-bis (1-bromomethyl) -2-bromo-N-methylacetanilide. 2-Chloro-N-methyl-2'-6'-diethyl acetanilide (23.9 g, 0.1 mol) was placed in 300 ml of carbon tetrachloride with 0.2 g of benzoyl peroxide. After heating to reflux, 16.0 g of bromine (0.2 mol) in 50 ml of CCl 4 * were added dropwise to the mixture, which was then exposed to both internal UV and external white light. Solvent was removed in vacuo and the crude product was dissolved in ethyl acetate. The solid product was repeatedly recrystallized from ethyl acetate to give 2'-6'-bis (1-bromomethyl) -2-bromo-N-methyl-acetanilide, m.p. 1e2-164 ° C.
Analys. Beräknat för CUHMBrBNO: C, 35,32; Br, 54,24; N, 3,17 C, 35,18; Br, 54,29; N, 3,16.Analysis. Calculated for CUHMBrBNO: C, 35.32; Br, 54.24; N, 3.17 C, 35.18; Br, 54.29; N, 3.16.
Exemgel 2 Funnet: F ramstäilning av 2'-(brommetylLóßt-butyl-Z-brom-N-metylacetanilid.Example 2 Found: Preparation of 2 '- (bromomethylLoss-butyl-Z-bromo-N-methylacetanilide.
Till 38,0 g (0,15 moi) 2-klor-N,2'-dirnetyl-Q-t-butylacetanilid (33 g, 0,15 moi) löst i CCI4 sattes 0,2 g bensoyiperoxid och blandningen upphettades till äterflöde. Brom (24,0 g, 0,15 moi) i 50 ml CClu sattes droppvis till den ovanstående blandningen. Efter tilisatsen (1-l/2 h) och vidare åter-flöde (0,5 h) strippades materialet för att avlägsna lösningsmedel. Efter skrapning stelnade återstoden. Produkten omkristalliserades ur heptan och identifierades som 2'- (brornmetyl)-6'-_t-butyl-2-brom-N-metylacetanilid, smältpunkt 86-87°C, utbyte 65%.To 38.0 g (0.15 moi) of 2-chloro-N, 2'-dimethyl-Q-t-butylacetanilide (33 g, 0.15 moi) dissolved in CCl 4 was added 0.2 g of benzoyl peroxide and the mixture was heated to reflux. Bromine (24.0 g, 0.15 mol) in 50 ml of CClu was added dropwise to the above mixture. After the addition (1-1 / 2 h) and further reflux (0.5 h), the material was stripped to remove solvent. After scraping, the residue solidified. The product was recrystallized from heptane and identified as 2'- (bromomethyl) -6'-t-butyl-2-bromo-N-methylacetanilide, m.p. 86-87 ° C, yield 65%.
Analys. Beräknat för C 1 41-1 l9Br2NO: C, 44,59; Br, 42,38; N, 3,71 C, 44,62; Br, 42,27; N, 3,72.Analysis. Calculated for C 14 41-1 19 Br 2 NO: C, 44.59; Br, 42.38; N, 3.71 C, 44.62; Br, 42.27; N, 3.72.
Exemgel 3 Framställning av 2-klor-N,2'-6'-tris(brornmetyüacetanilid.Example Gel 3 Preparation of 2-chloro-N, 2'-6'-tris (bromomethylacetanilide.
Funnet: 2-klor-N-(klormetyl)-2'-6'-dimetylacetanilid (0,04 mol, 10 g) placerades i 100 ml CClq innehållande 0,14 g bensoyiperoxid och blandningen upphettades till återflöde med inre 0,2A UV belysning och yttre 150V/ vitt ljus. Till denna blandning sattes 13 g brom i 50 ml CCl4. Sedan teoretisk mängd brom tillsatts, tillsattes ytterligare 3,0 g brom. Blandningen kyldes, lösningsmedlet aviägsnades och den resulterande viskösa oljan revs med eter för att ge ett fast ämne, som genom NMR indikerade 2-klor-N-2'-6'-tris(brommetyDacetanilld. Råprodukten renades inte vidare, utan behandlades med 200 ml kokande metanol för att ge 2',6'-bis(brommetyll-Z-klor-N-(ntetoximetyUacetanilid, smältpunkt l27,5-l29°C.Found: 2-Chloro-N- (chloromethyl) -2'-6'-dimethylacetanilide (0.04 mol, 10 g) was placed in 100 ml of CCl 2 containing 0.14 g of benzoyl peroxide and the mixture was heated to reflux with internal 0.2A UV lighting and external 150V / white light. To this mixture was added 13 g of bromine in 50 ml of CCl 4. After the theoretical amount of bromine was added, an additional 3.0 g of bromine was added. The mixture was cooled, the solvent was removed and the resulting viscous oil was triturated with ether to give a solid which by NMR indicated 2-chloro-N-2'-6'-tris (bromomethyldacetanilide. The crude product was not further purified but treated with 200 ml boiling methanol to give 2 ', 6'-bis (bromomethyl) -Z-chloro-N- (nethoxymethylacetanilide, m.p. 127.5-129 ° C.
ExemEel 4 Framställning av 2'-(brommetyU-Z-klor-óßt-butylacetanilid. 2-klor-Zßmetyl-G-t-butylacetanilid (5,6 g, 0,025 mol) placerades i ca 120 ml CCll, med 0,15 g bensoylperoxld och upphettades till âterflöde. Brom (4,0 g, 0,025 moi) i 50'ml CClu tillsattes droppvis. Efter tillsatsen visade NMR- övervakning att reaktionen var fullständig. Efter borttagning av lösningsmedlet i vakuum utvanns 7,0 g vitt fast ämne. Efter succesiv omkristallisation ur isopropanol smälte produkten, 2'-(brommetyl)~2-k1ör-G-t-butylacetanilid, vid 14z-147°c. utbyte 23%. 10 15 20 25 30 35 8002281 -7 6 Analys: Beräknat för C BH ”BrCl NO: C, 49,00; Br, 35,08; Cl, ll,l3.Example 4 Preparation of 2 '- (bromomethyl-Z-chloro-β-butylacetanilide. 2-Chloro-β-methyl-Gt-butylacetanilide (5.6 g, 0.025 mol) was placed in about 120 ml of CCl Bromine (4.0 g, 0.025 mol) in 50 ml of CClu was added dropwise. After the addition, NMR monitoring showed that the reaction was complete. After removal of the solvent in vacuo, 7.0 g of white solid was recovered. recrystallization from isopropanol melted the product, 2 '- (bromomethyl) ~ 2-chloro-Gt-butylacetanilide, at 14z-147 ° C, yield 23%. 10 15 20 25 30 35 8002281 -7 6 Analysis: Calculated for C BH "BrCl NO: C, 49.00; Br, 35.08; Cl, 11.13.
Funnet: C, 47,93; Br, 24,50; Cl, 10,83.Found: C, 47.93; Br, 24.50; Cl, 10.83.
Exempel 5 Frarnställning av 2-klor-N,2',6'-tris(klormetyllacetanilid. 2~klor-N,2',óktri-metyl-acetanilid (2l,l g, 0,1 mol)» placerades i 200 ml CClq och en inre 0,2 A UV-källa belyste-i en 500 ml kolv. Klor (0,1 moi, 7,0 g) 'infördes under ytan med omrörning. Reaktionen var milt exotermisk, 'med temperatur stigande från 200 till 40°C. Sedan all klor tillsatts erhölls en väsentligen färglös lösning. Blandningen kyldes till cirka 5°C, och ytterligare 0,1 mol klor tillsattes. Slutligen sattes en tredje molekvivalent klor till blandningen. Materialet fick stå under cirka 48 h. Sedan borttogs lösningsmedlet för att ge en viskös olja. Portioner av denna olja omkristalliserades ur pentaneter för att ge kristaller identifierade som 2-klor-N,2',6'tris(klormetyDacetanilid, smälltpunkt 70-75°C. Räprodukten renades inte vidare, utan behandlades direkt med kokande metanol för att ge Z-ldor-N-(metoximetyl)-2',6'bis(klormetyl)ace- tanilid. Föreningen i Exempel 5 kan även framställas med användning av 2-klor~ N-(klormetyl)-2',6'-dimetylacetanilid som utgângsmaterial. i Exempel 6 _ Framställning av 2'-(Brommetyl)-6'-_t¿-butyl-2-klor-N-(klormetyllacetani- lid.Example 5 Preparation of 2-chloro-N, 2 ', 6'-tris (chloromethylacetanilide. 2-chloro-N, 2', octrimethyl-acetanilide (2.1l, 0.1 mol) »was placed in 200 ml of CCl and an internal 0.2 Å UV source was illuminated in a 500 ml flask. Chlorine (0.1 mol, 7.0 g) was introduced below the surface with stirring. The reaction was mildly exothermic, with temperatures rising from 200 to 40 g. After all the chlorine was added, a substantially colorless solution was obtained, the mixture was cooled to about 5 ° C, and an additional 0.1 mole of chlorine was added, and finally a third molar equivalent of chlorine was added to the mixture, and the material was allowed to stand for about 48 hours. Aliquots of this oil were recrystallized from pentanethers to give crystals identified as 2-chloro-N, 2 ', 6' tris (chloromethydacetanilide, m.p. 70-75 ° C. The shrimp product was not further purified, but treated directly with boiling methanol to give Z-ldor-N- (methoxymethyl) -2 ', 6'bis (chloromethyl) acetanilide The compound of Example 5 can also be prepared using 2-Chloro-N- (chloromethyl) -2 ', 6'-dimethylacetanilide as starting material. Example 6 Preparation of 2 '- (Bromomethyl) -6' - t-butyl-2-chloro-N- (chloromethylacetanalidide.
Till 17,3 g (0,06 mol) av 2-klor-N-klormetyl-2'-(metyl)-6'-§t-butyllaceta- nilid löst i 250 ml C614 sattes 11,2 g (0,063 mol) omkristalliserad N-bromsuccini- mid (NBS) och 0,25 g bensoylperoxid. Den resulterande blandningen upphettades till äterflöde och 500 ml 3-halskolven belystes genom låg-Ströms neddoppbar' UV och yttre vitt ljus. Reaktionen övervakades med NMR och var väsentligen fullständig på cirka 0,5 h. Efter att ha stått vid rumstemperatur under cirka 48 h isolerades 2,2 g av produkten, 2'-(brommetyl)-G-š-butyl Z-klor-N-(klormetyfi- acetanilid, smältpunkt l2Al-l25°C. Ytterligare mängd (7,9 g) utvanns efter delvis I indunstning av lösningsmedlet. Produkten renades inte vidare, utan reagerades med metanol för att ge 2'-(brommetyl)-2-l Exempel 7 Framställning av 2'-(brommetyll-GLÉ-butyl-Z-klor-N-metylacetanilid.To 17.3 g (0.06 mol) of 2-chloro-N-chloromethyl-2 '- (methyl) -6'-t-butyl acetanilide dissolved in 250 ml of C614 was added 11.2 g (0.063 mol). recrystallized N-bromosuccinimide (NBS) and 0.25 g of benzoyl peroxide. The resulting mixture was heated to desolation and 500 ml of the 3-neck flask was illuminated by low current dipping UV and external white light. The reaction was monitored by NMR and was substantially complete in about 0.5 hours. After standing at room temperature for about 48 hours, 2.2 g of the product was isolated, 2 '- (bromomethyl) -G-β-butyl Z-chloro-N (chloromethyl fi-acetanilide, m.p. 12Al-125 ° C. Additional amount (7.9 g) was recovered after partial evaporation of the solvent. The product was not further purified, but reacted with methanol to give 2 '- (bromomethyl) -2- Example 7 Preparation of 2 '- (bromomethyl) GLÉ-butyl-Z-chloro-N-methylacetanilide.
Z-klor-ßßt-butyl-N,2'-dimetylacetanilid (17,5 g, 0,069 mol) löstes i 250 ml CClg med 0,2 g bensoylperoxid och 13 g (0,072 mol) omkristalliserad NBS med användning av belysning och kolvstorlek som i Exempel 6. Reaktionen fullborda- des på cirka 0,5 h, med succinimid flytande ovanpå ClCllj-lösningen. Materialet filtrerades och filtratet tvättadés med vatten samt vakuumtorkades för att borttaga lösningsmedlet för att ge 24,9 g återstod. Återstoden omkristalliserades 10 15 20 25 30 35 8002281 -7 7 ur hexan för att ge 14,8 g produkt. En andra omkristallisation ur hexan gav 2'- (brommetyl)-6'-jc_-butyl-2-klor-N-metylacetanilid, smältpunkt ll2-ll4oC; utbyte 63%.Z-chloro-β-butyl-N, 2'-dimethylacetanilide (17.5 g, 0.069 mol) was dissolved in 250 ml of CCl 3 with 0.2 g of benzoyl peroxide and 13 g (0.072 mol) of recrystallized NBS using illumination and flask size as in Example 6. The reaction was completed in about 0.5 h, with succinimide fl superimposed on top of the ClCl 2 solution. The material was filtered and the filtrate was washed with water and vacuum dried to remove the solvent to give 24.9 g of residue. The residue was recrystallized from hexane to give 14.8 g of product. A second recrystallization from hexane gave 2'- (bromomethyl) -6'-β-butyl-2-chloro-N-methylacetanilide, mp 112-114 ° C; yield 63%.
Analys: Beräknat för C 141-1 Br Cl NO: »C, 50,54; Br, 24,02; Cl, 10,66. c, 50,33; ßr,'21+,e3; cl, 10,61. Égemgel 8 Framställning av 2'-(klormetyl)-6'-metyl-Z-kloracetanilid. 19 F unnet: 2',6'-dimetyl-Z-kloracetanllid klorerades enligt proceduren i Exempel 5 för att ge ett vitt fast ämne, identifierat som 2'-(klormetyl)~6'-metyl~2- kloracetanilid, srnältpunkt l33-134°C.Analysis: Calculated for C 141-1 Br Cl NO: »C, 50.54; Br, 24.02; Cl, 10.66. c, 50.33; ßr, '21 +, e3; cl, 10.61. Egemgel 8 Preparation of 2 '- (chloromethyl) -6'-methyl-Z-chloroacetanilide. Found: 2 ', 6'-Dimethyl-Z-chloroacetanylide was chlorinated according to the procedure of Example 5 to give a white solid, identified as 2' - (chloromethyl) -6'-methyl-2-chloroacetanilide, mp 133- 134 ° C.
Analys: Beräknat för C H ClZNO: m U C, 51,74; H, 4,77; N, 6,03.Analysis: Calculated for C H Cl 2 NO: m U C, 51.74; H, 4.77; N, 6.03.
C, 51,69; H, 4,66; N, 6,03. _ Exemgel 9 F ramställning av 2',6'-bis(brommetyl)-2-klor-N-(klormetyßacetanilid.C, 51.69; H, 4.66; N, 6.03. Example 9 Preparation of 2 ', 6'-bis (bromomethyl) -2-chloro-N- (chloromethylacetanilide.
Funnet: 2-klor-N-(l 100 ml CClg med 0,14 g bensoylperoxid. Materialet upphettades till återflöde och kolven belystes med lâgströms neddoppbar UV och yttre vitt ljus. Till blandningen sattes droppvis 13,0 g molekylärt brom i 50,0 ml CCl4. 3,0 g ytterligare brom tillsattes när NMR visade att reaktionen var fullständig. Blandningen kyldes och lösningsmedlet borttogs i vakuum. Den resulterande viskösa oljan revs med eter för att ge ett fast ämne, identifierat som 2',6'-bis(brommetyll-Z-klor-N- (klormetyDacetanilid. Produkten renades inte vidare, utan behandlades med metanol för att ge 2',6'-bis(brornmetyD-Z-klor-N-(metoximetyüacetanilid.Found: 2-chloro-N- (100 ml CCl 3 with 0.14 g benzoyl peroxide. The material was heated to reflux and the flask was illuminated with low current immersible UV and external white light. To the mixture was added dropwise 13.0 g molecular bromine in 50.0 g). 3.0 g of additional bromine were added when NMR showed that the reaction was complete, the mixture was cooled and the solvent was removed in vacuo The resulting viscous oil was triturated with ether to give a solid, identified as 2 ', 6'-bis ( bromomethyl-Z-chloro-N- (chloromethylacetanilide. The product was not further purified, but treated with methanol to give 2 ', 6'-bis (bromomethylD-Z-chloro-N- (methoxymethylacetanilide).
Exemgel 10 Framställning av 2'-(dibrommetyl)-6'-_t-butyl-2-kloracetanilid.Example 10 Preparation of 2 '- (dibromomethyl) -6'-t-butyl-2-chloroacetanilide.
Föreningen i Exempel 4 (9,54 g, 0,03 mol) sattes till 300 ml CClq innehållande 0,3 g bensoylperoxid. Två vita lampor användes för att bestråla reaktionskärlet. Sedan sattes 4,8 g brom i 50 ml CCI, droppvis till den bestrålade blandningen medan man höll en försiktig kvävgasstrilning i reaktionsmediet.The compound of Example 4 (9.54 g, 0.03 mol) was added to 300 ml of ClCl 3 containing 0.3 g of benzoyl peroxide. Two white lamps were used to irradiate the reaction vessel. Then 4.8 g of bromine was added in 50 ml of CCl, dropwise to the irradiated mixture while maintaining a gentle nitrogen spray in the reaction medium.
Bestrålningen borttogs efter cirka 1,5 h och blandningen fick stå och kallna under natten. Den fasta fällningen filtrerades för att ge 10,4 g av en första skörd och 1,4 g av en andra skörd. Det fasta materialet omkristalliserades ur isopropanol för att ge 2'-(dibrommetyll-(fl-t-butyl-2-kloracetanilid, smältpunkt 145-147°C, utbyte 99%. ~ Analys: Beräknat för Cl 31-1 16Br2Cl NO: Funnct: C, 39,28; H, 4,06; N, 3,52.The irradiation was removed after about 1.5 hours and the mixture was allowed to stand and cool overnight. The solid precipitate was filtered to give 10.4 g of a first crop and 1.4 g of a second crop. The solid was recrystallized from isopropanol to give 2 '- (dibromomethyl- (fl-t-butyl-2-chloroacetanilide, m.p. 145-147 ° C, 99% yield. ~ Analysis: Calculated for Cl 31-1 16Br 2 Cl NO: Funnct Found: C, 39.28; H, 4.06; N, 3.52.
C, 38,99; H, 4,10; N, 3,58. 10 15 20 25 30 35 58002281-7 8 ExemQel 11 Framställning av 2'-(brommetyl)-2,G-dikloracetanílid.C, 38.99; H, 4.10; N, 3.58. EXAMPLE 11 Preparation of 2 '- (bromomethyl) -2, G-dichloroacetanilide.
Till 300 ml C614 i en 500 ml kolv sattes 15,0 g 2,6'-diklor-2'- metylacetanilid (0.068 mol) och 0,5 g bensoylperoxid. Reaktionskärlet bestrâlades med tvâ yttre vita lampor. Reaktionsblandningen upphettades till âterflöde och sedan tillsattes 10,9 g brom (Brz) i 50 ml CCllbl med kvävestrilning. Ytterligare 2,5 g Brz tillsattes när NMR indikerade att reaktionen var ofullständig. Lösnings- medel borttogs i vakuum . och det råa fas-ta ämnet omkrlstalliserades ur isopropanol och vakuumsublimerades (0,05 mm) för att ge 2'-(brommetyl)-2,6'- dikiotacetannid, smältpunkt 155_159°c, utbyte 52%. a Analyst Beräknat för c9Hsßfc12 Not c, 36,40; H, 2,72; N, 4,72.To 300 ml of C614 in a 500 ml flask was added 15.0 g of 2,6'-dichloro-2'-methylacetanilide (0.068 mol) and 0.5 g of benzoyl peroxide. The reaction vessel was irradiated with two outer white lamps. The reaction mixture was heated to reflux and then 10.9 g of bromine (Brz) in 50 ml of CCl An additional 2.5 g of Brz was added when NMR indicated that the reaction was incomplete. Solvent was removed in vacuo. and the crude solid was recrystallized from isopropanol and vacuum sublimed (0.05 mm) to give 2 '- (bromomethyl) -2,6'-dichiotacetannide, mp 155-159 ° C, yield 52%. a Analyst Calculated for c9Hsßfc12 Note c, 36.40; H, 2.72; N, 4.72.
Funnet: C, 26,18; H, 2,72; N, 4,80. i Exemgel 12 Framställning av 2'-(brommetyl)-2,3'-diklor-G-t-butylacetanilid.Found: C, 26.18; H, 2.72; N, 4.80. in Example Gel 12 Preparation of 2 '- (bromomethyl) -2,3'-dichloro-G-t-butylacetanilide.
I en 1 literskolv löstes 2,_3'-diklor-2'-metyl-G-t-butylacetanilid (15,0 g, 0,055 fmol) i 600 ml CClq. Bestrâlning gavs genom tvâ yttre vita lampor.In a 1 liter flask, 2,3'-dichloro-2'-methyl-G-t-butylacetanilide (15.0 g, 0.055 mmol) was dissolved in 600 mL of CCl Irradiation was given by two external white lamps.
Reaktionsblandningen upphettades till âterflöde och sedan tillsattes 8,8 g molekylärt brom i 50 ml CCl4. Överskott av lösningsmedel borttogs i vakuum och den fasta produkten omkristalliserades två gånger för att ge 2'-(brommetyl)~2,3'- tfiklat-euí-butylacetannzd, smältpunkt 1s2_lsa°c, utbyte 65%.The reaction mixture was heated to reflux and then 8.8 g of molecular bromine in 50 ml of CCl 4 was added. Excess solvent was removed in vacuo and the solid product was recrystallized twice to give 2 '- (bromomethyl) ~ 2,3' - t-clath-eu-butyl acetane, melting point 1s2_lsa ° c, yield 65%.
Analys: Beräknat för C13H16BrCl2 NO: C, 44,22; H, 4,57; N, 3,97, Funnet: C, 44,09; H, 4,62; N, 3,96.Analysis: Calculated for C 13 H 16 BrCl 2 NO: C, 44.22; H, 4.57; N, 3.97. Found: C, 44.09; H, 4.62; N, 3.96.
ExemEel 13 Framställning av 2',3'-bis(brommetyl)-2-klor-GHI-butylacetanilid._ I en 1 litersflaska löstes 15 g (0,059 mol) 2-klor-2',3'~dimetyl-9-3- butylacetanilid i 600 ml CCI 4. Bestrålning gavs av två vita strålkastare.Example 13 Preparation of 2 ', 3'-bis (bromomethyl) -2-chloro-GHI-butylacetanilide. In a 1 liter ash, 15 g (0.059 mol) of 2-chloro-2', 3 '-dimethyl-9-3 were dissolved. - butyl acetanilide in 600 ml CCI 4. Irradiation was given by two white headlights.
Reaktionsblandningen upphettades till återflöde och behandlades med kväve.The reaction mixture was heated to reflux and treated with nitrogen.
Sedan tillsattes 9,44 g (0,059 mol) elementärt brom i 50 ml CCI, droppvis. Sedan en andra molekvivalent .molekylärt brom tillsatts, och efter cirka 48 h, filtrerades blandningen och det fasta ämnet omkristalliserades ur isopropanol för att ge 2',3'-bis(bromm'etyl)-Z-klor-Q-t-butylacetanilid, smältpunkt l80-l82°C (vakuumsublimering smältpunkt l95-l97oC). _ Analys: Beräknat för CL4Hl8Br2Cl NO: C, 40,85; H, 4,41; N, 3,40.Then 9.44 g (0.059 mol) of elemental bromine in 50 ml of CCl was added dropwise. After a second molar equivalent of molecular bromine was added, and after about 48 hours, the mixture was filtered and the solid was recrystallized from isopropanol to give 2 ', 3'-bis (bromomethyl) -Z-chloro-Qt-butylacetanilide, m.p. -182 ° C (vacuum sublimation m.p. 195-197 ° C). Analysis: Calculated for CL 4 H 18 Br 2 Cl NO: C, 40.85; H, 4.41; N, 3.40.
Funnet: C, 40,60; H, 4,37; N, 3,40.Found: C, 40.60; H, 4.37; N, 3.40.
Exemgel 14 Framställning av 2'-(brommetyl)-2-kloracetanilid.Example gel 14 Preparation of 2 '- (bromomethyl) -2-chloroacetanilide.
Z-klor-Zkmetylacietanilid (4,0 g, 0,02 mol) och N-bromsuccinimid (3,9 g, 10 15 20 25 30 35 8002281-7 9 0,02 mol) löstes i 300 ml CCI4 med 0,3 g 2,2'-azobis(Z-metyl-propionitrilJ.Z-chloro-Zm-methylacietanilide (4.0 g, 0.02 mol) and N-bromosuccinimide (3.9 g, 0.02 mol) were dissolved in 300 ml of CCl 4 with 0.3 g 2,2'-azobis (Z-methyl-propionitrile).
Blandningen belystes med en strålkastare och upphettades till återflöde under 2,5 h. Vid denna tidpunkt fick blandningen kallna till rumstemperatur, varefter den filtrerades, tvättades en gång med vatten, torkades över MgSOq, filtrerades igen och renades för att ge ett vitt fast ämne. Det fasta ämnet omkristallisera- des ur toluen för att ge 2,2 g produkt, 2'-(brommetyD-Z-kloracetanilid, smält- punk: 1z5_127°c, utbyte 32%. " Analys: Beräknat för C9H9BrCl NO: F unnet: C, 41,17; H, 3,46; N, 5,311.The mixture was illuminated with a spotlight and heated to reflux for 2.5 hours. At this time, the mixture was allowed to cool to room temperature, after which it was filtered, washed once with water, dried over MgSO 4, filtered again and purified to give a white solid. The solid was recrystallized from toluene to give 2.2 g of product, 2 '- (bromomethyl-D-chloroacetanilide, melting point: 125 DEG-127 DEG C., 32% yield. "Analysis: Calculated for C9 H9 BrCl NO: Found: C, 41.17; H, 3.46; N, 5.311.
C: 01,35; H, 3,40; N, 5,30.C: 01.35; H, 3.40; N, 5.30.
Exempel 15 Framställning av 2'-(brommetyl)~6'-(trifluormetyD-Z-kloracetanilid.Example 15 Preparation of 2 '- (bromomethyl) -6' - (trifluoromethyl-D-chloroacetanilide.
Till 12,5 g (0,05 mol) 2'-metyl-6'-(trifluormetyl)-2-kloracetanilid sattes 300 ml koltetraklorid och 10,0 g (0,056 mol) omkristalliserad NBS i en lliters kolv. Blandningen hölls vid rumstemperatur under cirka 1-1,5 h och hölls sedan vid 70-75°C under cirka 4-5 h. Råprodukten isolerades som ett fast ämne (frätande) 17,7 g; omkristallisation ur isopropanol gav 9,8 g produkt, 2'-(brom- rnetyl)-6'-(trifluormetyD-Z-kloracetanilid, smältpunkt 98-10l°C, 59,496 utbyte.To 12.5 g (0.05 mol) of 2'-methyl-6 '- (trifluoromethyl) -2-chloroacetanilide was added 300 ml of carbon tetrachloride and 10.0 g (0.056 mol) of recrystallized NBS in a 1 liter flask. The mixture was kept at room temperature for about 1-1.5 hours and then kept at 70-75 ° C for about 4-5 hours. The crude product was isolated as a solid (corrosive) 17.7 g; recrystallization from isopropanol gave 9.8 g of product, 2 '- (bromomethyl) -6' - (trifluoromethyl-Z-chloroacetanilide, m.p. 98-101 ° C, 59.449 yield.
Analys: Beräknat för C1OH8C1BrF O; C, 36,34; H, 2,#l+; N, 4,20.Analysis: Calculated for C 10 OH 8 Cl1 BrF 0; C, 36.34; H, 2, # 1 +; N, 4.20.
C, 35,94; H, 2,27; N, 4,19.C, 35.94; H, 2.27; N, 4.19.
Exempel 16 Framställning av 2-klor-N-klormetylacetanilid. 3 Funnet: 1 en lämplig kolv försedd med omrörare, gasinledningsrör, termometer och inre lâgtrycks-UV-lampa satsades 200,0 ml CClu-lösning innehållande 0,1 mol av 2-klor-N-metylacetanilid. En molekvivalent gasformigt klor infördes sakta vid rumstemperatur i kolven. Lösningen belystes sedan, och efter en kort begynnelse- period steg temperaturen på lösningen till 38°C på grund av den exotermiska kloreringen. NMR av CCM-lösningen visade fullständig reaktion sedan ett 10% överskott av klor hade införts. Efter vakuumbehandling för att avlägsna gaser och lösningsmedel erhölls 98% utbyte av Z-klor-N-(klormetyl)acetanilid som en värmekänslig olja, som hade följande NMR: I O (cbci3), 653,9 (s, zn, clcijzö, d 5,55 (s, 2H, cicnzn), J 7,6 (bred s, 51-1, Arn).Example 16 Preparation of 2-chloro-N-chloromethylacetanilide. Found: In a suitable flask equipped with a stirrer, gas inlet tube, thermometer and internal low pressure UV lamp was charged 200.0 ml of CClu solution containing 0.1 mol of 2-chloro-N-methylacetanilide. One molar equivalent of gaseous chlorine was slowly introduced at room temperature into the flask. The solution was then elucidated, and after a short initial period, the temperature of the solution rose to 38 ° C due to the exothermic chlorination. NMR of the CCM solution showed complete reaction after a 10% excess of chlorine had been introduced. After vacuum treatment to remove gases and solvents, 98% yield of Z-chloro-N- (chloromethyl) acetanilide was obtained as a heat sensitive oil, which had the following NMR: 10 (cbci3), 653.9 (s, zn, clcijzö, d , 55 (s, 2H, cicnzn), J 7.6 (broad s, 51-1, Arn).
Föreningarna enligt uppfinningen har befunnits uppvisa utmärkt herbicid aktivitet och vara användbara vid framställning av vissa gtg-(alkoximetyß-Z- halogenacetanilider, som är verksamma herbicider. Det förfarande, med vilket dessa senare föreningar framställs, innefattar att man reagerar de tidigare 10 8lIlÛ2281-7 10 beskrivna föreningarna med formelnI med en alkohol, företrädesvis i närvaro av metallkatjoner, tex. kalium, natrium, silver, bly, kvicksilver, etc., eller andra Lewissyror, Lex. AlCl3, SnCl4, ZnCIZ, etc. Vid användning av de nya föreningar- na enligt formelni visade det sig, att halogenen på glq-halogenalkylgrupperna, särskilt halogenmetyl, som var bundna till ringen (bensyliska) i Z-halogenacetani- lidmolekylen med formeln l, kunde ersättas selektivt med en lämplig alkohol utan att störa den annars labila Z-acetylhalogenen. Även om uppfinningen har beskrivits i samband med specifika utförings- former får detaljerna däri inte uppfattas som ' begränsningar, utan olika ekvivalenter, ändringar och modifikationer kan göras utan att man avviker från uppfinningens grundtanke och omfattning.The compounds of the invention have been found to exhibit excellent herbicidal activity and to be useful in the preparation of certain gtg- (alkoxymethyl-Z-haloacetanilides which are active herbicides. The process by which these latter compounds are prepared comprises reacting the former 8 Described compounds of formula I with an alcohol, preferably in the presence of metal cations, eg potassium, sodium, silver, lead, mercury, etc., or other Lewis acids, Lex. AlCl3, SnCl4, ZnCl2, etc. When using the new compounds It was found that the halogen on the glq-haloalkyl groups, especially halomethyl, which were attached to the ring (benzylic) in the Z-haloacetanilide molecule of formula I, could be selectively replaced by a suitable alcohol without disturbing the otherwise labile Z Although the invention has been described in connection with specific embodiments, the details therein should not be construed as limitations, but various valents, changes and modifications may be made without departing from the spirit and spirit of the invention.
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SE8002281A SE433350B (en) | 1980-03-25 | 1980-03-25 | ortho-halogenoalkyl-2-halogeno acetananilide derivatives which are intermediates in the production of ortho- (alkoxymethyl)-2-halogeno acetanilide herbicides. |
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