DE1047763B - Process for the conversion of organic halogen compounds into their homologous aldehydes - Google Patents
Process for the conversion of organic halogen compounds into their homologous aldehydesInfo
- Publication number
- DE1047763B DE1047763B DEB36853A DEB0036853A DE1047763B DE 1047763 B DE1047763 B DE 1047763B DE B36853 A DEB36853 A DE B36853A DE B0036853 A DEB0036853 A DE B0036853A DE 1047763 B DE1047763 B DE 1047763B
- Authority
- DE
- Germany
- Prior art keywords
- parts
- triphenylphosphine
- halogen compounds
- hours
- bromide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001299 aldehydes Chemical class 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 6
- 150000002896 organic halogen compounds Chemical class 0.000 title claims description 4
- 238000006243 chemical reaction Methods 0.000 title description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 31
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 150000002366 halogen compounds Chemical class 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000012433 hydrogen halide Substances 0.000 claims description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 4
- 150000004714 phosphonium salts Chemical group 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 claims description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 2
- 150000003003 phosphines Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 34
- 239000000243 solution Substances 0.000 description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- -1 chloroacetic acid ester Chemical class 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- SFDZETWZUCDYMD-UHFFFAOYSA-N monosodium acetylide Chemical compound [Na+].[C-]#C SFDZETWZUCDYMD-UHFFFAOYSA-N 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000012259 ether extract Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RAHOAHBOOHXRDY-UHFFFAOYSA-M (4-chlorophenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].C1=CC(Cl)=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 RAHOAHBOOHXRDY-UHFFFAOYSA-M 0.000 description 1
- XDYZRPUBRBBAQL-UHFFFAOYSA-N (4-chlorophenyl)methylidene-triphenyl-$l^{5}-phosphane Chemical compound C1=CC(Cl)=CC=C1C=P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XDYZRPUBRBBAQL-UHFFFAOYSA-N 0.000 description 1
- YQXBNCFNXOFWLR-UHFFFAOYSA-M (4-methoxyphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].C1=CC(OC)=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 YQXBNCFNXOFWLR-UHFFFAOYSA-M 0.000 description 1
- BHWXTNDORACTIJ-UHFFFAOYSA-N (4-methoxyphenyl)methylidene-triphenyl-$l^{5}-phosphane Chemical compound C1=CC(OC)=CC=C1C=P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BHWXTNDORACTIJ-UHFFFAOYSA-N 0.000 description 1
- ZYECOAILUNWEAL-NUDFZHEQSA-N (4z)-4-[[2-methoxy-5-(phenylcarbamoyl)phenyl]hydrazinylidene]-n-(3-nitrophenyl)-3-oxonaphthalene-2-carboxamide Chemical compound COC1=CC=C(C(=O)NC=2C=CC=CC=2)C=C1N\N=C(C1=CC=CC=C1C=1)/C(=O)C=1C(=O)NC1=CC=CC([N+]([O-])=O)=C1 ZYECOAILUNWEAL-NUDFZHEQSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
- MOHYOXXOKFQHDC-UHFFFAOYSA-N 1-(chloromethyl)-4-methoxybenzene Chemical compound COC1=CC=C(CCl)C=C1 MOHYOXXOKFQHDC-UHFFFAOYSA-N 0.000 description 1
- MMYKTRPLXXWLBC-UHFFFAOYSA-N 1-bromo-2-ethoxyethane Chemical compound CCOCCBr MMYKTRPLXXWLBC-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- JQZAEUFPPSRDOP-UHFFFAOYSA-N 1-chloro-4-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1 JQZAEUFPPSRDOP-UHFFFAOYSA-N 0.000 description 1
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- MWSNYBOKRSGWAN-UHFFFAOYSA-N 2-(4-chlorophenyl)acetaldehyde Chemical compound ClC1=CC=C(CC=O)C=C1 MWSNYBOKRSGWAN-UHFFFAOYSA-N 0.000 description 1
- NRIVMXXOUOBRAG-UHFFFAOYSA-N 2-(4-methoxyphenyl)acetaldehyde Chemical compound COC1=CC=C(CC=O)C=C1 NRIVMXXOUOBRAG-UHFFFAOYSA-N 0.000 description 1
- APISVOVOJVZIBA-UHFFFAOYSA-N 2-(triphenyl-$l^{5}-phosphanylidene)acetonitrile Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=CC#N)C1=CC=CC=C1 APISVOVOJVZIBA-UHFFFAOYSA-N 0.000 description 1
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- AKGUXECGGCUDCV-POHAHGRESA-N [(z)-benzylideneamino]urea Chemical compound NC(=O)N\N=C/C1=CC=CC=C1 AKGUXECGGCUDCV-POHAHGRESA-N 0.000 description 1
- ZDVDCDLBOLSVGM-UHFFFAOYSA-N [chloro(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(Cl)C1=CC=CC=C1 ZDVDCDLBOLSVGM-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WPUJEWVVTKLMQI-UHFFFAOYSA-N benzene;ethoxyethane Chemical compound CCOCC.C1=CC=CC=C1 WPUJEWVVTKLMQI-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- AQNQQHJNRPDOQV-UHFFFAOYSA-N bromocyclohexane Chemical group BrC1CCCCC1 AQNQQHJNRPDOQV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- YYDZNOUMWKJXMG-UHFFFAOYSA-N chloro(phenyl)phosphane Chemical compound ClPC1=CC=CC=C1 YYDZNOUMWKJXMG-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ARPLQAMUUDIHIT-UHFFFAOYSA-M cyanomethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC#N)C1=CC=CC=C1 ARPLQAMUUDIHIT-UHFFFAOYSA-M 0.000 description 1
- KVFDZFBHBWTVID-UHFFFAOYSA-N cyclohexanecarbaldehyde Chemical compound O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 description 1
- MPFNASIQENFSMB-UHFFFAOYSA-N cyclohexylidene(triphenyl)-$l^{5}-phosphane Chemical compound C1CCCCC1=P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 MPFNASIQENFSMB-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000002350 geranyl group Chemical group [H]C([*])([H])/C([H])=C(C([H])([H])[H])/C([H])([H])C([H])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- UCFFGYASXIPWPD-UHFFFAOYSA-N methyl hypochlorite Chemical compound COCl UCFFGYASXIPWPD-UHFFFAOYSA-N 0.000 description 1
- AZFQCTBZOPUVOW-UHFFFAOYSA-N methyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 AZFQCTBZOPUVOW-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- JHYGKRLFANBDIF-UHFFFAOYSA-N phosphane;triphenylphosphane Chemical compound P.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 JHYGKRLFANBDIF-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000005375 primary alkyl halides Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000005376 secondary alkyl halides Chemical class 0.000 description 1
- 150000007659 semicarbazones Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 1
- 150000002266 vitamin A derivatives Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
- C07C403/10—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by etherified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5456—Arylalkanephosphonium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Description
DEUTSCHESGERMAN
Es wurde gefunden, daß man organische Halogenverbindungen in ihre homologen Aldehyde überführen kann, indem man die Halogenverbindungen mit tertiären Phosphinen, insbesondere Triphenylphosphin, zu quartäxen Phosphoniumsalzen umsetzt, letztere durch Behandeln mit halogenwasserstoffbindenden Mitteln in die entsprechenden Phosphoniumylide umwandelt, auf letztere Ameisensäureester einwirken läßt und das Reaktionsprodukt hydrolysiert. It has been found that organic halogen compounds can be converted into their homologous aldehydes, by quataxing the halogen compounds with tertiary phosphines, especially triphenylphosphine Converts phosphonium salts, the latter by treatment with hydrogen halide binding agents in the corresponding Converts phosphonium ylides, allows formic acid esters to act on the latter and hydrolyzes the reaction product.
Die Reaktionsfolge läßt sich z.B. im Falle der Ver-Wendung von Benzylchlorid und Triphenylphosphin als Ausgangsstoffe von Natriumacetylid als halogenwasserstoffbindendes Mittel und von Ameisensäuremethylester als letzte Komponente wie folgt formulieren:The reaction sequence can be formulated as follows, for example in the case of using benzyl chloride and triphenylphosphine as starting materials for sodium acetylide as the hydrogen halide binding agent and methyl formate as the last component:
C6H6- CHaaC 6 H 6 - CH a a
* [■* [■
CBH5-CH2-P<C6H5)3|aC B H 5 -CH 2 -P <C 6 H 5 ) 3 | a
b) IC6H8- CH2-P(C6H5)SJ er·b) IC 6 H 8 - CH 2 -P (C 6 H 5 ) S J er
+ NaC = CH - ++ NaC = CH - +
»» C6H5-CH-P (C6H5),»» C 6 H 5 -CH-P (C 6 H 5 ),
+ NaCl+ C2H2 + NaCl + C 2 H 2
+ CH3O-CH=O+ CH 3 O-CH = O
♦- C4H5-CH-P(C6H5J3
CH8O-CH-O"♦ - C 4 H 5 -CH-P (C 6 H 5 J 3
CH 8 O-CH-O "
d) C6H5-CH-d) C 6 H 5 -CH-
i
CH3O-CH-O i
CH 3 O-CH-O
— CH- CH
+ OP(C6HJ3 + OP (C 6 HJ 3
CILO-CHCILO-CH
e) C6H5-CH=CH-OCH3
+ H2O C6H5 e) C 6 H 5 -CH = CH-OCH 3
+ H 2 OC 6 H 5
V + CH8OH V + CH 8 OH
CH2-CH =CH 2 -CH =
Als Ausgangsstoffe kann man die verschiedensten aliphatischen, cycloaliphatischen oder araliphatischen Halogenverbindungen verwenden, die an dem das Halogenatom tragenden Kohlenstoffatom noch mindestens ein Wasserstoff atom besitzen; die Halogenverbindungen können gesättigt sein oder eine oder mehrere isolierte oder konjugierte Doppel- und bzw. oder Dreifachbin-Verfahren zur ÜberführungA wide variety of aliphatic, Use cycloaliphatic or araliphatic halogen compounds which are attached to the halogen atom bearing carbon atom still have at least one hydrogen atom; the halogen compounds can be saturated or one or more isolated or conjugated double and / or triple bin processes for transfer
organischer Halogenverbindungenorganic halogen compounds
in ihre homologen Aldehydeinto their homologous aldehydes
Anmelder:Applicant:
Badische Anilin- & Soda-FabrikAniline & Soda Factory in Baden
Aktiengesellschaft,Corporation,
Ludwigshafen/RheinLudwigshafen / Rhine
Dr, Horst Pommer, Ludwigshafen/Rhem,
und Dr. Georg Wittig, Heidelberg,
sind als Erfinder genannt wordenDr, Horst Pommer, Ludwigshafen / Rhem,
and Dr. Georg Wittig, Heidelberg,
have been named as inventors
düngen und auch solche Substituenten tragen, die die Ylidbildimg gemäß Reaktion b) des obigen Schemas nicht stören. Es kommen also beispielsweise in Betracht geradkettig© und verzweigte primäre und sekundäre Alkylhalogenide, wie Methyl-, Propyl-, Isopropyl-, Hexyl-, DodeeylcMorid, Cydohexylchlorid, Benzyl- und Diphenylmethyichiorid, Methoxy-, Chlor- oder Carbäthoxybemzylbromid, ÄHylbromid, jS-Cyclogeranylbromid, lonylbromid, Äthoxyäthylbromid, Cnloressigsäur-eester, Chloracetonitril, 1,4-Dichlorbutan oderÄthylenbromid; letztere können mit 1 oder 2 Mol Triphenylphosphin umgesetzt werden. Die Umsetzung zu den quartären Phosphoniumsalzen gemäß a) .erfolgt in üblicher Weise, z. B. durch Lösen der Komponenten in Äther, Benzol, Tetrahydrofuran oder Dimethylformamid und Erwärmen, erforder- lichenfaMs im Druckgefäß (Kosolapoff: »Organophosphorous Compounds«, 1950, S. 78 und 79).fertilize and also carry those substituents that the Ylidbildimg according to reaction b) of the above scheme do not interfere. So, for example, they come into consideration straight-chain © and branched primary and secondary alkyl halides, such as methyl, propyl, isopropyl, hexyl, Dodecyl chloride, cyclohexyl chloride, benzyl and diphenyl methyl chloride, Methoxy, chlorine or carbethoxybemzyl bromide, ÄHylbromid, jS-Cyclogeranylbromid, Ionylbromid, Ethoxyethyl bromide, chloroacetic acid ester, chloroacetonitrile, 1,4-dichlorobutane or ethylene bromide; latter can be reacted with 1 or 2 moles of triphenylphosphine. The implementation to the quaternary phosphonium salts according to a) .does in the usual way, e.g. B. by dissolving the components in ether, benzene, tetrahydrofuran or dimethylformamide and heating, required LichenfaMs in the pressure vessel (Kosolapoff: »Organophosphorous Compounds ", 1950, pp. 78 and 79).
Als halogenwasserstoffbindende Mittel für 4ie Bildung der Phosphoniumylide gemäß b) kann man metallorganische Verbindungen, wie Methyl-, Butyl- oder Phenyllithium, Methyl- oder Phenylmagnesiumbromid, Calcium- oder Natriumacetylid, ferner Natrium- oder Kaliumamid und Alkali- oder Erdalkalimetallalkoholate verwenden (G. Wittig und U. Schöllkopf, Ber. 87 [1954], S. 1318 ff; deutsche Patente 1003 730 und 943 648).As a hydrogen halide binding agent for formation the phosphonium ylides according to b) can be organometallic compounds such as methyl, butyl or phenyllithium, Methyl or phenyl magnesium bromide, calcium or sodium acetylide, also sodium or potassium amide and use alkali or alkaline earth metal alcoholates (G. Wittig and U. Schöllkopf, Ber. 87 [1954], P. 1318 ff; German patents 1003 730 and 943 648).
Auch ist aus den deutschen Patentschriften 1 001256, 954247 und 957 942 die Umsetzung von YMden des Phosphors mit Carbonylverbindungen zu solchen der Vitamin-Α- und yS-Carotin-Reihe bekannt. Nachdem weiterhin bekannt ist, daß sich Carbonsäureester, ζ. Β.Also from the German patents 1 001256, 954247 and 957 942 the implementation of YMden of phosphorus with carbonyl compounds to those of Vitamin-Α and yS-carotene series known. After this It is also known that carboxylic acid esters, ζ. Β.
809 727/471809 727/471
■■■-■■ 3 ; 4■■■ - ■■ 3; 4th
Essigester oder BenzoesÄuäMfhylester, mit Yliden des Triphenylphosphoniummethylid teilweise kristallin aus; Phosphors nicht zu ungesättigten Verbindungen um- zum größten Teil bleibt es jedoch gelöst. Nun werdenEthyl acetate or benzoic acid, partially crystalline with ylides of triphenylphosphonium methylide; Phosphorus does not turn into unsaturated compounds - for the most part, however, it remains dissolved. Well be
setzen (vgl. G. Wittig und U. Schöllkopf, Ber. 87 vorsichtig 105 Teile Ameisensäurebutylester zugegeben, [1954], S. 1318 ff.), war es überraschend, daß die Ester wobei die Heftigkeit der Reaktion durch zeitweisesset (cf. G. Wittig and U. Schöllkopf, Ber. 87, carefully added 105 parts of butyl formate, [1954], pp. 1318 ff.), It was surprising that the esters, whereby the violence of the reaction by intermittent
der Ameisensäure in dem beanspruchten Sinne reagieren. 5 Kühlen gemildert wird. Nach 12 Stunden Rühren beireact the formic acid in the claimed sense. 5 cooling is mitigated. After stirring for 12 hours at
Die erhaltenen Ylide werden, zweckmäßig ohne sie gewöhnlicher Temperatur wird das Gemisch nochThe ylides obtained are, advantageously without them, the usual temperature, the mixture is still
aus den Lösungen oder Suspensionen zu isolieren, mit 3 Stunden zum Sieden erhitzt, dann abgekühlt, vomisolate from the solutions or suspensions, heated to boiling for 3 hours, then cooled, dated
Ameisensäureestern, wie Methyl-, Äthyl-, Benzyl- oder ausgefallenen Triphenylphosphinoyd abfiltriert und das !Phenylformiat, umgesetzt. Dabei bildet sich anscheinend Filtrat an einer j Kolonne destilliert, wobei 62 TeileFormic acid esters, such as methyl, ethyl, benzyl or precipitated triphenylphosphinoyd filtered off and that ! Phenyl formate, implemented. In the process, filtrate appears to be formed on a column distilled, with 62 parts
zunächst nach c) ein Additioäsprodukt, das, insbesondere io Vinylbutyläther übergehen. Er läßt sich in bekannterfirst after c) an additive product which, in particular, go over vinyl butyl ether. He lets himself be known in
beim Erwärmen, gemäß d) unter Bildung von Phosphin- Weise mit Säuren; zum Acetaldehyd hydrolysieren,on heating, according to d) with formation of phosphine-manner with acids; to hydrolyze acetaldehyde,
oxyd und Vinyläther zerfallt. Letzterer kann in an sich ; .Oxide and vinyl ether break down. The latter can in itself; .
bekannter Weise zum entsprechenden Aldehyd hydroly- , Beispiel 4known manner to hydrolyze the corresponding aldehyde, Example 4
siert werden, z.B. durch Erwärmen mit verdünnter Wie im Beispiel 3 werden 385 Teile n-Propyl-triphenyl-be sated, e.g. by heating with dilute As in Example 3, 385 parts of n-propyl-triphenyl-
Mineralsäure. 15 phosphoniumbromid, das durch Umsetzen von Triphenyl-Mineral acid. 15 phosphonium bromide, which is produced by reacting triphenyl
Das neue synthetische Verfahren ist breitester Anwen- phosphin mit n-Propylbromid hergestellt wurde, mitThe new synthetic process is broadest applied phosphine with n-propyl bromide was produced with
dung fähig. Es gestattet die Synthese vieler, bisher zum n-Butyllithium in Äther zu Propenylideii-triphenyl-capable. It allows the synthesis of many, previously n-butyllithium in ether to propenylideii-triphenyl-
Teil nicht oder wesentlich umständlicher zugänglicher phosphin und weiter mit 80 Teilen Ämeisensäureäthyl-Part of phosphine that is not or much more difficult to access and then with 80 parts of ethyl formic acid
Aldehyde aus leicht zugänglichen Ausgangsstoffen; so ester umgesetzt. Nach 12 Stunden Rühren wird äbge-Aldehydes from easily accessible starting materials; so ester implemented. After stirring for 12 hours, the
kann es z. B. zur Herstellung von /?,y-ungesättigten 20 saugt und das Filtrat durch Destillation an' einer kleinencan it e.g. B. for the production of / ?, y-unsaturated 20 sucks and the filtrate by distillation to 'a small
Aldehyden aus a,j8-ungesätligten Halogenverbindungen ·'· Kolonne vom Lösungsmittel befreit. Der Rückstand wirdAldehydes from a, j8-unsaturated halogen compounds · '· column freed from solvent. The residue will
dienen. Solche ^,^-ungesättigte Aldehyde sind wichtige mit 10 Teilen Oxalsäure versetzt und mit Wasserdampfto serve. Such ^, ^ - unsaturated aldehydes are important with 10 parts of oxalic acid and steam
Zwischenprodukte für Synthesen in der Vitamin-A-Reihe destilliert. Das Wasserdampfdestillat wird an einerIntermediate products for syntheses in the vitamin A series are distilled. The steam distillate is at a
(vgl. z. B. O. Isler, Chimia, Bd. 4 [1950], S. 116 ff., und Kolonne destilliert, wobei man bis 95° C übergehende(See, for example, O. Isler, Chimia, Vol. 4 [1950], p. 116 ff., and the column is distilled, passing over at up to 95 ° C
Zeitschrift für Angewandte Chemie, Bd. 68 [1956], S. 547 25 Anteile auffängt. Der im Destillat enthaltene n-Butyr-Zeitschrift für Angewandte Chemie, Vol. 68 [1956], p. 547 25 shares. The n-butyr- contained in the distillate
bis 553). ^ - -;"_;■ aldehyd wird durch Überführung in die Bisulfitverbin-to 553). ^ - -; "_; ■ aldehyde is converted into the bisulfite compound
Die in den Beispielen.genannten Teile sind Gewichts- dung abgetrennt und aus dieser durch Behandlung mitThe parts mentioned in the examples are separated by weight and removed from them by treatment with
teile. .'. ■ . Natriumcarbonat (vgl. Lipp, Liebigs Ann. Chem., Bd.2O5share. . '. ■. Sodium carbonate (see Lipp, Liebigs Ann. Chem., Vol. 205
Beispiel 1 [1880], S. 2) in Freiheit gesetzt. Es werden so 52 TeileExample 1 [1880], p. 2) set free. It will be 52 parts
Man setzt 217 Teile ß-Cyclogeranylbromid in üblicher 30 n-Butyraldehyd vom Kp.76O = 75 bis 76° C erhalten.217 parts of β-cyclogeranyl bromide are used in conventional n-butyraldehyde with a boiling point of 76O = 75 to 76 ° C.
Weise mit 268 Teilen Triphenylphosphin zum quartären , .Way with 268 parts of triphenylphosphine to the quaternary,.
Phosphoniumsalz um. Von dem erhaltenen /J-Cyclo- BeispielPhosphonium salt. From the obtained / J-Cyclo example
geranyl-triphenylpliosphoniumbfomid löst man 90 Teile Wie im Beispiel 4 werden 385 Teile Isopropyl-triphenylin
200 Teilen Dimethylformamid und fügt unter Stick- phosphoniumbromid, das durch Umsetzen-von Triphenylstoff
10 Teile feingepulvertes Natriumacetylid hinzu. 35 phosphin mit Isopropylbfomid hergestellt wurde, mit
Nach lstündigem Rühren bei.20° C gibt man zu der ent- n-ButyUithium in Äther zu Isopropyliden-triphenylstandenen
tiefroten Lösung des Triphenylphosphonium- phosphin und weiter mit 80 Teilen Ameisensäureäthyl-/?-eyelogeranylids
30 Teile Ameisensäureäthy !ester und ester umgesetzt. Bei analoger Aufarbeitung wie im Beierwärmt
5 Stunden auf 60° Q. Nach dem Abkühlen ver- spiel 4 werden 48 Teile Isobutyraldehyd vom Kp.7G0 = 62
setzt man mit 50 Teilen 100/,jiger Schwefelsäure, destilliert 40 bis 6*4° C erhalten,
mit Wasserdampf alle flüchtigen Reaktionsprodukte über Beismel 6
und--extrahiert das Destillat mit Methylenchlorid. Nach ^90 parts of geranyl triphenylpliosphonium bomide are dissolved. As in Example 4, 385 parts of isopropyl triphenylin are added to 200 parts of dimethylformamide and, under nitrogen phosphonium bromide, 10 parts of finely powdered sodium acetylide are added. 35 phosphine was prepared with isopropyl bomide, after stirring for 1 hour at 20 ° C, one adds to the ent-n-butyUithium in ether to isopropylidene-triphenyl-state deep red solution of triphenylphosphonium phosphine and further with 80 parts of ethyl formic acid - /? - eyelogeranylid 30 parts Formic acid ethers and esters reacted. In similar working up as in Beier-warming for 5 hours at 60 ° Q. After cooling comparable game 4 48 parts of isobutyraldehyde, bp. 7G0 = 62 are employed with 50 parts of 10 0 /, jiger sulfuric acid, distilled 40-6 * 4 ° C obtain,
with steam all volatile reaction products over Beismel 6
and - extracting the distillate with methylene chloride. After ^
Verdampfen des Extraktionsmittels wird der Rück- Zu einer Lösung von 95 Teilen Dodeeyl-triphenyl-Evaporation of the extractant is the back To a solution of 95 parts of dodecyl triphenyl
stand fraktioniert destilliert, wobei nach einem unter phosphoniumchlorid, das durch Umsetzen von Dodecyl-stood fractionally distilled, after a phosphonium chloride, which is obtained by reacting dodecyl-
14 mm Druck bei etwa 67 ,bis 80° C siedenden Vorlauf 45 bromid mit Triphenylphosphin hergestellt wurde, in14 mm pressure at about 67, up to 80 ° C boiling forerun 45 bromide with triphenylphosphine was made in
19Teile 2',6',6'-Trimethyleyelohexen-(l')-yl-(l')-a.cet- . 250 Teilen absolutem Tetrahydrofuran läßt man bei ge-19Parts 2 ', 6', 6'-trimethyleyelohexen- (l ') - yl- (l') - a.cet-. 250 parts of absolute tetrahydrofuran are allowed to
aldehyd vom Kp. 14 = 108 bis 112° C übergehen. Das in wohnlicher Temperatur allmählich eine 1,4 Teile Lithiumaldehyde of b.p. 14 = 108 to 112 ° C. That in a comfortable temperature gradually a 1.4 parts of lithium
üblicher Weise hergestellte Phenylsemicarbazon des enthaltende absolut ätherische Lösung von Phenyl-conventionally produced phenylsemicarbazone containing absolutely essential solution of phenyl
Aldehyds schmilzt bei;157°C. lithium zufließen. Die Bildung des tief gelben Dode-Aldehyde melts at; 157 ° C. lithium flow in. The formation of the deep yellow dodec-
' Λ _-..?- 1 _ 50 cyliden-triphenylphosphins findet Λ fast augenblicklich'Λ _- ..? - 1 _ 50 cylidene-triphenylphosphine finds Λ almost instantly
eisPie . ■-..-. statt. Zu der klaren gelben Lösung gibt man nun all- ice P ie . ■ -..-. instead of. Now add all-
Män setzt in üblicher Weise 127 Teile Benzylchlorid mählich 20 Teile Ameisensäureäthylesteu und rührtMan sets in the usual way 127 parts of benzyl chloride gradually 20 parts of ethyl formic acid and stirs
mit 268 Teilen Triphenylphosprnn zum quartären Phos- 24 Stunden bei gewöhnlicher Temperatur. Nach Abdestil-with 268 parts of triphenylphosphine to form the quaternary phosphate for 24 hours at ordinary temperature. According to Abdestil-
phoniumsalz um. 90 Teile des erhaltenen Benzyl-tri- lieren der Lösungsmittel extrahiert man den Rückstandphonium salt around. 90 parts of the resulting benzyl trilating of the solvent are extracted and the residue is extracted
phenylphosphoniumchlorids werden in 200 Teilen Di- 55 mit Petroläther, wobei das gebildete Triphenylphosphin-phenylphosphonium chloride in 200 parts of di- 55 with petroleum ether, the triphenylphosphine formed
methylformamid gelöst und'dann unter Stickstoff mit oxyd weitgehend ungelöst bleibt. Den Petrolätherextraktmethylformamide dissolved and then largely undissolved under nitrogen with oxide. The petroleum ether extract
10 Teilen Natriumacetylid in das Tripbenylphosphonium- schüttelt man 18 Stunden mit einer 20%igen wäßrigen10 parts of sodium acetylide in the tripbenylphosphonium are shaken for 18 hours with a 20% strength aqueous solution
benzylid umgewandelt. Die erhaltene rote Lösung ver- Phosphorsäurelösung. Nach Abtrennen der Petroläther-converted to benzylide. The red solution obtained is a phosphoric acid solution. After separating the petroleum ether
setzt man mit 30 Teilen Ameisensäureäthylester. Bei der schicht wird diese mehrmals mit Wasser gewaschen, über30 parts of ethyl formate are added. The layer is washed over several times with water
Aufarbeitung wie im Beispiel 1 erhält man 18 Teile 60 Natriumsulfat getrocknet und der nach Abdunsten desWorking up as in Example 1 gives 18 parts of 60 dried sodium sulfate and that after the evaporation of the
Phenylacetaldehyd vom Kp.15 = 88° C. Petroläthers erhaltene Rückstand im Vakuum destilliert,Phenylacetaldehyde with a boiling point of 15 = 88 ° C. The residue obtained from petroleum ether is distilled in vacuo,
-r, .. "■"■.',» Bei 18 Torr Druck destilliert der so erhaltene Tridecen--r, .. "■" ■. ', »At 18 Torr pressure, the tridecen-
tfeispiel ό aldehyd bei 147 bis 150° C über. Das Destillat erstarrtExample ό aldehyde at 147 to 150 ° C over. The distillate solidifies
. Zu einer Suspension von 350 Teilen Methyl-triphenyl- beim Abkühlen kristallin und schmilzt dann bei 13. To a suspension of 350 parts of methyl triphenyl crystalline on cooling and then melts at 13
phosphoniumbromid, das durch Umsetzen von Triphenyl- 65 bis 14° C. . .phosphonium bromide, which by reacting triphenyl 65 to 14 ° C.. .
phosphin mit Methylbromid hergestellt wurde, in 1200 Beispiel 7phosphine was made with methyl bromide in 1200 Example 7
Teilen absolutem Äther läßt man langsam unter Kühlung Zu einer Suspension von 425 Teilen Cyclohexyl-tri-Parts of absolute ether are left slowly with cooling to a suspension of 425 parts of cyclohexyl-tri-
eine 7 Teile Lithium enthaltende Lösung von η-Butyl- phenylphosphoniumbromid, das durch Umsetzen vona 7 parts of lithium containing solution of η-butyl phenylphosphonium bromide, which by reacting
lithium in absolutem Äther fließen. Während das Salz Cyclohexylbromid mit Triphenylphosphin hergestelltlithium flow in absolute ether. While the salt is cyclohexyl bromide made with triphenylphosphine
allmählich in Lösung geht, scheidet sich das tief gelbe 70 wurde, in 1200 Teilen absolutem Äther läßt man langsamgradually dissolves, the deep yellow 70 becomes separated, in 1200 parts of absolute ether one leaves slowly
1 U4/ /bo 1 U4 / / bo
eine 7 Teile Lithium enthaltende ätherische Lösung von n-ButyUithium fließen. Nach 6 Stunden Rühren ist die Bildung des Cyclohexyliden-triphenylphosphins beendet, und es werden 80 Teile Ameisensäureäthylester vorsichtig zugegeben. Nach 24· Stunden Rühren bei gewöhnlicher Temperatur wird das Gemisch noch 3 Stunden unter Rückfluß erhitzt, dann abgekühlt und vom ausgeschiedenen Triphenylphosphinoxyd abfiltriert. Das Filtrat wird vom Lösungsmittel befreit und nach Zugabe von 10 Teilen Oxalsäure rasch mit Wasserdampf destilliert. Das Wasserdampfdestillat wird ausgeäthert und der Ätherextrakt nach Zugabe von 0,1 Teil Hydrochinon destilliert, wobei 61 Teile Hexahydrobenzaldehyd vom Kp.18 = 72 bis 74° C erhalten werden.an ethereal solution of n-ButyUithium containing 7 parts of lithium. After 6 hours of stirring, the formation of cyclohexylidene-triphenylphosphine is complete, and 80 parts of ethyl formate are carefully added. After stirring for 24 hours at normal temperature, the mixture is refluxed for a further 3 hours, then cooled and the triphenylphosphine oxide which has precipitated out is filtered off. The filtrate is freed from the solvent and, after adding 10 parts of oxalic acid, rapidly distilled with steam. The steam distillate is extracted with ether and, after the addition of 0.1 part of hydroquinone, the ether extract is distilled, 61 parts of hexahydrobenzaldehyde with a b.p. 18 = 72 to 74 ° C. being obtained.
Zu einer Suspension von 150 Teilen 1,4-Butan-bis-triphenylphosphoniumbromid (hergestellt durch Umsetzen von 1 Moll,4-Dibrombutanrnit2 Mol Triphenylphosphin) in 500 Teilen absolutem Tetrahydrofutan gibt man eine ao 2,8 Teile Lithium enthaltende ätherische Lösung von Methyllithium. Nach 4 Stunden Rühren ist das Salz in Lösung gegangen und die Bildung des tief gelben 1,4-Butadien-(l,3)-bis-triphenylphosphins beendet. Nach Zugabe von 16 Teilen Ameisensäureäthylester wird das Gemisch 48 Stunden bei gewöhnlicher Temperatur gerührt, worauf man das Lösungsmittel abdestilliert, 12 Teile Oxalsäure hinzufügt und dann mit Wasserdampf destilliert. Aus dem stechend scharf riechenden Destillat gewinnt man den Adipindialdehyd in guter Ausbeute.To a suspension of 150 parts of 1,4-butane-bis-triphenylphosphonium bromide (produced by reacting 1 Moll, 4-dibromobutane with 2 moles of triphenylphosphine) in 500 parts of absolute tetrahydrofutane, an ethereal solution containing 2.8 parts of lithium is added Methyl lithium. After 4 hours of stirring, the salt has gone into solution and the formation of the deep yellow 1,4-butadiene- (1,3) -bis-triphenylphosphine completed. After adding 16 parts of ethyl formate, the mixture is stirred for 48 hours at ordinary temperature. whereupon the solvent is distilled off, 12 parts of oxalic acid are added and then with steam distilled. The adipine dialdehyde is obtained in good yield from the pungent pungent smelling distillate.
Zu einer Lösung von 340 Teilen Cyanomethyl-triphenylphosphoniumchlorid (hergestellt durch Umsetzen von Cyanmethylchlorid mit Triphenylphosphin) in 1000 Teilen absolutem Alkohol gibt man eine aus 23 Teilen Natrium bereitete konzentrierte alkoholische Natriumäthylatlösung. Fast momentan findet die Bildung von Cyanomethylen-triphenylphosphin statt, das teilweise als dicker Niederschlag ausfällt. Nach Zugabe von 80 Teilen Ameisensäureäthylester wird das Gemisch 48 Stunden bei gewöhnlicher Temperatur gerührt, wonach man den Alkohol im Vakuum weitgehend abdestilliert und den Rückstand mit einer konzentrierten wäßrigen Oxalsäurelösung 6 Stunden schüttelt. Dann wird mit Äther extrahiert und der ätherische Extrakt an einer kleinen Kolonne fraktioniert destilliert, wobei 31 Teile Formylacetonitril vom Κρ.7β0 = 71 bis 73° C erhalten werden.A concentrated alcoholic sodium ethylate solution prepared from 23 parts of sodium is added to a solution of 340 parts of cyanomethyl triphenylphosphonium chloride (prepared by reacting cyanomethyl chloride with triphenylphosphine) in 1000 parts of absolute alcohol. Almost instantly the formation of cyanomethylene triphenylphosphine takes place, some of which precipitates out as a thick precipitate. After adding 80 parts of ethyl formate, the mixture is stirred for 48 hours at ordinary temperature, after which the alcohol is largely distilled off in vacuo and the residue is shaken with a concentrated aqueous oxalic acid solution for 6 hours. Then it is extracted with ether and the ethereal extract is fractionally distilled on a small column, with 31 parts of formylacetonitrile from Κρ. 7β0 = 71 to 73 ° C can be obtained.
Zu einer Lösung von 260 Teilen ß-Ionyl-triphenylphosphoniumbromid, das durch Umsetzen von ß-Ionylbromid mit Triphenylphosphin hergestellt wurde, in 500 Teilen Dimethylformamid gibt man 90 Teile einer 30%igen Lösung von Natriummethylat in Methanol. Unter geringer Wärmeentwicklung findet Bildung des rotvioletten /3-Ionyliden-triphenylphosphins statt. Nach 3 Stunden Rühren bei gewöhnlicher Temperatur werden 40 Teile Ameisensäureäthylester zugegeben. Man rührt weitere 24 Stunden, extrahiert das Gemisch dann erschöpfend mit Petroläther und destilliert den Extrakt nach dem Waschen mit Wasser und Zugabe von 10 Teilen Oxalsäure mit Wasserdampf. Das Destillat schüttelt man mit Petroläther aus, wäscht die hellgelbe Petrolätherlösung mit Wasser, trocknet sie über Natriumsulfat und destilliert. Bei 0,05 Torr und 75 bis 90° C destilliert ein Gemisch von sogenannten /S-C14-Aldehyd und dem 4- [2', 6', 6' -Trimethylcyclohexen- (1') -yl- (1')] -1 -äthoxy-2-methylbutadien-(l,3) über. Zur Trennung wird in wenig Petroläther gelöst und an Aluminiumoxyd (standardisiert nach Brockmann) chromatographiert.- Dabei werden mit Petroläther 22 Teile ß-C^-Aldehyd (4-[2',6',6'-Trimethylcyclohexen-(l') -yl- (I')] -2-methylbuten- (2) -al- (1) elüiert, Kp.0)05 = 76 bis 77° C, Phenyisemicarbazon, F. 184° C. ; ."··: ,·'-■ -90 parts of a 30% solution of sodium methylate in methanol are added to a solution of 260 parts of ß-ionyl triphenylphosphonium bromide, which has been prepared by reacting ß-ionyl bromide with triphenylphosphine, in 500 parts of dimethylformamide. The red-violet / 3-ionylidene-triphenylphosphine is formed with little heat generation. After stirring for 3 hours at ordinary temperature, 40 parts of ethyl formate are added. The mixture is stirred for a further 24 hours, the mixture is then extracted exhaustively with petroleum ether and, after washing with water and adding 10 parts of oxalic acid, the extract is distilled with steam. The distillate is extracted with petroleum ether, the light yellow petroleum ether solution is washed with water, dried over sodium sulfate and distilled. A mixture of so-called / SC 14 aldehyde and 4- [2 ', 6', 6 '-trimethylcyclohexen- (1') -yl- (1 ')] - distills at 0.05 Torr and 75 to 90 ° C. 1-ethoxy-2-methylbutadiene- (l, 3) over. For separation, it is dissolved in a little petroleum ether and chromatographed on aluminum oxide (standardized according to Brockmann). 22 parts of β-C ^ aldehyde (4- [2 ', 6', 6'-trimethylcyclohexene (l ') - yl- (I ')] -2-methylbutene- (2) -al- (1) eluted, bp 0) 05 = 76 to 77 ° C, phenyisemicarbazone, m.p. 184 ° C; . "··:, · '- ■ -
Mit Petroläther-Benzol (2: 1) eluiert man 34 Teile 4- [2', 6', 6' -Trimethylcyclohexan- (1') -yl- (1')] -1 -äthoxy-2-methylbutadien-l,3, lmax 258 bis 259 mμ (e = 15000); Kp.OiO5 = 71 bis 73° C.34 parts of 4- [2 ', 6', 6 '-trimethylcyclohexan (1') -yl- (1 ')] -1-ethoxy-2-methylbutadiene-1 are eluted with petroleum ether-benzene (2: 1), 3, l max 258 to 259 mμ (e = 15,000); Bp . OiO5 = 71 to 73 ° C.
In gleicher Weise wie im Beispiel 10 werden 260 Teile jS-Ionyl-triphenylphosphoniumbromid mit 90 Teilen einer 30°/0igen Natriummethylatlösung und dann mit 40 Teilen Ameisensäureäthylester umgesetzt. Nach der erschöpfenden Extraktion mit Petroläther wird das Reaktionsprodukt direkt destilliert, wobei 61 Teile 4-[2',6',6'-Trimethylcyclohexen- (I') -yl- (I')] -I -äthoxy-2-methylbutadien-(l,3) vom Kp.0,05 = 71 bis 73° C, Xmax = 258 ηιμ (ε = 14 500) erhalten werden; der Vinyläther wird dann für sich in üblicher Weise mit Säure zum freien /3-C14-Aldehyd verseift.In the same manner as in Example 10 260 parts be jS-Ionyl bromide with 90 parts of a 30 ° / 0 sodium methylate solution and then reacted with 40 parts of ethyl formate. After the exhaustive extraction with petroleum ether, the reaction product is distilled directly, with 61 parts of 4- [2 ', 6', 6'-trimethylcyclohexen- (I ') -yl- (I')] -I -ethoxy-2-methylbutadiene- (l, 3) = 0 are obtained, bp, 05 71 to 73 ° C, X max = 258 ηιμ (ε = 14 500). the vinyl ether is then saponified in the usual way with acid to give the free / 3-C 14 aldehyde.
Eine Suspension von 206 Teilen 4-Chlorbenzyl-triphenylphosphoniumchlorid, das durch Umsetzen von 4-Chlorbenzylchlorid mit Triphenylphosphin hergestellt wurde, in 1000 Teilen absolutem Benzol wird mit 200 Teilen einer ungefähr 30%igen Suspension von Natriumamid in absolutem Benzol 48 Stunden geschüttelt. Dabei entweicht Ammoniak, und es bildet sich das orangerote 4-Chlorbenzyliden-triphenylphosphin. Unter Feuchtigkeitsausschluß wird das überschüssige Natriumamid und das ausgeschiedene Natriumchlorid abfiltriert. Die erhaltene klare orangerote Benzollösung versetzt man mit 40 Teilen Ameisensäureäthylester und rührt 48 Stunden bei gewöhnlicher Temperatur. Dann destilliert man das Lösungsmittel ab und rührt nach Zugabe von 300 Teilen einer 10°/0igen Phosphorsäurelösung 10 Stunden bei gewöhnlicher Temperatur. Das Reaktionsgemisch wird dann mit Petroläther extrahiert, der Petrolätherextrakt mit Wasser gewaschen, über Natriumsulfat bei —5° C getrocknet und destilliert. Bei Kp.13 = 114 bis 116° C gehen 34 Teile 4-Chlorphenylacetaldehyd über.A suspension of 206 parts of 4-chlorobenzyl triphenylphosphonium chloride, which was prepared by reacting 4-chlorobenzyl chloride with triphenylphosphine, in 1000 parts of absolute benzene is shaken with 200 parts of an approximately 30% suspension of sodium amide in absolute benzene for 48 hours. Ammonia escapes and the orange-red 4-chlorobenzylidene triphenylphosphine is formed. The excess sodium amide and the precipitated sodium chloride are filtered off with exclusion of moisture. The clear orange-red benzene solution obtained is mixed with 40 parts of ethyl formate and stirred for 48 hours at ordinary temperature. Then, the solvent is distilled off and, after addition of 300 parts of a 10 ° / 0 phosphoric acid solution for 10 hours at ordinary temperature. The reaction mixture is then extracted with petroleum ether, the petroleum ether extract is washed with water, dried over sodium sulfate at -5 ° C. and distilled. At b.p. 13 = 114 to 116 ° C., 34 parts of 4-chlorophenylacetaldehyde pass over.
Zu einer Suspension von 205 Teilen 4-Methoxybenzyltriphenylphosphoniumchlorid, das durch Umsetzen von 4-Methoxybenzylchlorid mit Triphenylphosphin hergestellt wurde, in 1000 Teilen absolutem Tetrahydrofuran gibt man 12 Teile Magnesium enthaltende Lösung von Äthylmagnesiumbromid in Tetrahydrofuran. Nach 5 Stunden Rühren ist die Bildung des orangeroten 4-MethoxybenzyIiden-triphenylphosphins beendet. Man fügt 40 Teile Ameisensäureäthylester vorsichtig hinzu, rührt 24 Stunden bei gewöhnlicher Temperatur und arbeitet weiter wie im Beispiel 12. Man erhält 36 Teile 4-Methoxyphenylacetaldehyd vom Kp.13 = 142 bis 143° C; sein Semicarbazon schmilzt bei 180 bis 181° C.To a suspension of 205 parts of 4-methoxybenzyltriphenylphosphonium chloride, which was prepared by reacting 4-methoxybenzyl chloride with triphenylphosphine, in 1000 parts of absolute tetrahydrofuran is added 12 parts of a magnesium-containing solution of ethylmagnesium bromide in tetrahydrofuran. After stirring for 5 hours, the formation of the orange-red 4-methoxybenzylidene-triphenylphosphine has ended. 40 parts of ethyl formate are carefully added, the mixture is stirred for 24 hours at ordinary temperature and the procedure is continued as in Example 12. 36 parts of 4-methoxyphenylacetaldehyde with a boiling point of 13 = 142 to 143 ° C. are obtained; its semicarbazone melts at 180 to 181 ° C.
Claims (1)
Priority Applications (5)
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NL98208D NL98208C (en) | 1955-08-13 | ||
NL209594D NL209594A (en) | 1955-08-13 | ||
DEB36853A DE1047763B (en) | 1955-08-13 | 1955-08-13 | Process for the conversion of organic halogen compounds into their homologous aldehydes |
GB22484/56A GB790823A (en) | 1955-08-13 | 1956-07-20 | Process for the conversion of organic halogen compounds into their homologous aldehydes |
FR1160365D FR1160365A (en) | 1955-08-13 | 1956-08-13 | Process for the conversion of halogenated organic compounds into their vinyl ethers or their homologous aldehydes |
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DEB36853A DE1047763B (en) | 1955-08-13 | 1955-08-13 | Process for the conversion of organic halogen compounds into their homologous aldehydes |
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DE1047763B true DE1047763B (en) | 1958-12-31 |
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DEB36853A Pending DE1047763B (en) | 1955-08-13 | 1955-08-13 | Process for the conversion of organic halogen compounds into their homologous aldehydes |
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DE (1) | DE1047763B (en) |
FR (1) | FR1160365A (en) |
GB (1) | GB790823A (en) |
NL (2) | NL209594A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0109606A1 (en) * | 1982-11-18 | 1984-05-30 | Bayer Ag | Process for the formylation of aryl halides |
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US3130219A (en) * | 1955-08-13 | 1964-04-21 | Basf Ag | Production of alkyl vinyl ethers |
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DE954247C (en) * | 1954-10-20 | 1956-12-13 | Basf Ag | Process for the production of ª ‰ -carotene or 15, 15'-dehydro-ª ‰ -carotene |
DE957942C (en) * | 1957-01-24 | Badische Arnim- &. Soda Fabrik Aktiengesellschaft Ludwigs hafen/Rhem | Process for the preparation of compounds of the vitamin A series |
-
0
- NL NL98208D patent/NL98208C/xx active
- NL NL209594D patent/NL209594A/xx unknown
-
1955
- 1955-08-13 DE DEB36853A patent/DE1047763B/en active Pending
-
1956
- 1956-07-20 GB GB22484/56A patent/GB790823A/en not_active Expired
- 1956-08-13 FR FR1160365D patent/FR1160365A/en not_active Expired
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DE957942C (en) * | 1957-01-24 | Badische Arnim- &. Soda Fabrik Aktiengesellschaft Ludwigs hafen/Rhem | Process for the preparation of compounds of the vitamin A series | |
DE954247C (en) * | 1954-10-20 | 1956-12-13 | Basf Ag | Process for the production of ª ‰ -carotene or 15, 15'-dehydro-ª ‰ -carotene |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0109606A1 (en) * | 1982-11-18 | 1984-05-30 | Bayer Ag | Process for the formylation of aryl halides |
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FR1160365A (en) | 1958-07-15 |
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