NO172116B - PROCEDURE FOR THE PREPARATION OF ACYLCYANIDES IN ANNUAL MEDIUM - Google Patents
PROCEDURE FOR THE PREPARATION OF ACYLCYANIDES IN ANNUAL MEDIUM Download PDFInfo
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- NO172116B NO172116B NO902140A NO902140A NO172116B NO 172116 B NO172116 B NO 172116B NO 902140 A NO902140 A NO 902140A NO 902140 A NO902140 A NO 902140A NO 172116 B NO172116 B NO 172116B
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- acid halide
- amount
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- solvent
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 150000001264 acyl cyanides Chemical class 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 16
- -1 alkali metal cyanides Chemical class 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 25
- 150000004820 halides Chemical class 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical group ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000001266 acyl halides Chemical class 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- 150000005840 aryl radicals Chemical group 0.000 abstract 1
- 125000000753 cycloalkyl group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- GJQBHOAJJGIPRH-UHFFFAOYSA-N benzoyl cyanide Chemical compound N#CC(=O)C1=CC=CC=C1 GJQBHOAJJGIPRH-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Chemical group 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 150000008045 alkali metal halides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-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
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-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
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/04—Preparation of carboxylic acid nitriles by reaction of cyanogen halides, e.g. ClCN, with organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Saccharide Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
Description
Foreliggende oppfinnelse angår en fremgangsmåte for syntese av acylcyanider i vannfritt medium. Denne fremgangsmåte består i å omsette syrehalogenider med et alkalimetallcyanid. Acylcyanider er mellomprodukter ved organisk syntese av for eksempel herbicider. The present invention relates to a method for the synthesis of acyl cyanides in an anhydrous medium. This method consists in reacting acid halides with an alkali metal cyanide. Acyl cyanides are intermediate products in the organic synthesis of, for example, herbicides.
FR-PS 2.353.524 beskriver en syntese av benzoylcyanid C5H5COCN ved omsetning av benzoylklorid med natriumcyanid i et molart overskudd i nærvær av et nitril av karboksylsyre og kobbercyanid. FR-PS 2.346.323 beskriver en tilsvarende men meget mere generell reaksjon fordi den sistnevnte angår en hel gruppe azylcyanider og består i å omsette natriumcyanid med et syrehalogenid i overskudd i nærvær av kobber- eller sinkcyanid. Disse prosesser har mangelen av at de krever nærvær av tunge metaller og krever derfor også kompliserte behandlinger for å unngå disse metallers nærvær i avløpet. I "TETRAHEDRON LETTERS" (Pergamon Press), nr. 26, sidene 2275-2278 (1974) finnes det en prosess som er begrenset til syntese av benzoylcyanid ved omsetning av natriumcyanid med benzoylklorid i oppløsning i metylenklorid og i oppløsning i metylenklorid i oppløsning i metylenklorid og i nærvær av tetrabutylammoniumbromid; utbytte av C5H5COCN beregnet på C6H5COCI overskrider ikke 60 %. FR-PS 2.364.894 beskriver en syntese av C5H5COCN fra C5H5COCI med NaCN i et oppløsnings-middel i nærvær av benzosyreanhydrid (C5H5CO-O- CO- C^ E^) eller av produkter som kan gi benzosyreanhydrid under reaksj onsbetingelsene. FR-PS 2,353,524 describes a synthesis of benzoyl cyanide C5H5COCN by reaction of benzoyl chloride with sodium cyanide in a molar excess in the presence of a nitrile of carboxylic acid and copper cyanide. FR-PS 2,346,323 describes a similar but much more general reaction because the latter concerns a whole group of azyl cyanides and consists in reacting sodium cyanide with an acid halide in excess in the presence of copper or zinc cyanide. These processes have the disadvantage that they require the presence of heavy metals and therefore also require complicated treatments to avoid the presence of these metals in the effluent. In "TETRAHEDRON LETTERS" (Pergamon Press), No. 26, pages 2275-2278 (1974) there is a process limited to the synthesis of benzoyl cyanide by the reaction of sodium cyanide with benzoyl chloride in solution in methylene chloride and in solution in methylene chloride in solution in methylene chloride and in the presence of tetrabutylammonium bromide; yield of C5H5COCN calculated for C6H5COCI does not exceed 60%. FR-PS 2,364,894 describes a synthesis of C5H5COCN from C5H5COCI with NaCN in a solvent in the presence of benzoic anhydride (C5H5CO-O- CO- C^ E^) or of products which can give benzoic anhydride under the reaction conditions.
Den foretrukne mengde benzosyreanhydrid er mellom 0,03 og 0,1 mol pr. mol benzoylklorid. Dette nærvær av benzosyreanhydrid kompliserer gjenvinningen av benzoylcyanid. Det er nu funnet en fremgangsmåte som gjør det mulig å omdanne benzoylklorid til benzoylcyanid og som ikke gir benzosyreanhydrid som biprodukt. The preferred amount of benzoic anhydride is between 0.03 and 0.1 mol per moles of benzoyl chloride. This presence of benzoic anhydride complicates the recovery of benzoyl cyanide. A process has now been found which makes it possible to convert benzoyl chloride into benzoyl cyanide and which does not give benzoic anhydride as a by-product.
Oppfinnelsen angår derfor en fremgangsmåte for syntese av acylcyanider med formel (I): der R er en arylrest, idet resten eventuelt er substituert, omfattende å omsette acylhalogenider med formel (II): The invention therefore relates to a process for the synthesis of acyl cyanides of formula (I): where R is an aryl residue, the residue being optionally substituted, comprising reacting acyl halides of formula (II):
der R har en ovenfor angitte betydning og X betyr halogen, med alkalimetallcyanider, og denne fremgangsmåte karakteri-seres ved at reaksjonen gjennomføres: where R has a meaning given above and X means halogen, with alkali metal cyanides, and this method is characterized by the fact that the reaction is carried out:
a) i et vannfritt oppløsningsmiddelmedium, a) in an anhydrous solvent medium,
b) i nærvær av et produkt inneholdende mellom 2 og 200 alkylenoksydenheter valgt blant etylenoksyd og propylen-oksyd; og c) i nærvær av et polart produkt valgt blant glycerol, etylenglykol, formamid og sukkerderivater, idet vann er b) in the presence of a product containing between 2 and 200 alkylene oxide units selected from ethylene oxide and propylene oxide; and c) in the presence of a polar product selected from glycerol, ethylene glycol, formamide and sugar derivatives, water being
utelukket. excluded.
Reaksjonen ifølge oppfinnelsen skjer i henhold til formelen: The reaction according to the invention takes place according to the formula:
der M angir et alkalimetall. Efter reaksjonen blir alkali-metallhalogenid og eventuelt overskudd av alkalimetallcyanid fjernet ved filtrering og vasking med oppløsningsmiddel. Det rene acylcyanid oppnås ved destillasjonen av den filtrerte reaksjonsblanding. where M denotes an alkali metal. After the reaction, alkali metal halide and any excess alkali metal cyanide are removed by filtration and washing with solvent. The pure acyl cyanide is obtained by the distillation of the filtered reaction mixture.
Syrehalogenidene som benyttes som utgangsmateriale defineres ved formel (II). I denne formel angir R fortrinnsvis en lineær eller forgrenet C^_4-alkylrest som kan substitueres; The acid halides used as starting material are defined by formula (II). In this formula, R preferably denotes a linear or branched C 1-4 alkyl radical which can be substituted;
R angir også fortrinnsvis en C5_^-cykloalkylrest som kan substitueres; R also preferably denotes a C 5 -cycloalkyl radical which can be substituted;
R angir også fortrinnsvis en fenyl- eller en naftylrest som kan substitueres; R also preferably denotes a phenyl or a naphthyl residue which can be substituted;
R angir også fortrinnsvis en pentagonal eller heksagonal heterocyklisk rest som kan være substituert hvis dette er hensiktsmessig. R also preferably denotes a pentagonal or hexagonal heterocyclic residue which can be substituted if this is appropriate.
I formel (II) angir X fortrinnsvis klor eller brom. In formula (II), X preferably denotes chlorine or bromine.
Alkalimetall-, fortrinnsvis natrium- eller kaliumcyanid, benyttes i støkiometrisk mengde eller ellers i overskudd, i en andel på 1-2 mol pr. mol syrehalogenid; den foretrukne mengde er fra 1-1,25 mol pr. mol syrehalogenid. Alkali metal, preferably sodium or potassium cyanide, is used in a stoichiometric amount or otherwise in excess, in a proportion of 1-2 mol per moles of acid halide; the preferred amount is from 1-1.25 mol per moles of acid halide.
Syrehalogenidet tilsettes fortrinnsvis litt efter litt til reaksjonsblandingen. Det tilsettes enten rent eller fortynnet med reaksjonsoppløsningsmiddelet. Tilsetningsperioden kan variere fra noen minutter til flere timer. The acid halide is preferably added little by little to the reaction mixture. It is added either neat or diluted with the reaction solvent. The addition period can vary from a few minutes to several hours.
Den foretrukne varighet er ca. 1/2 time. The preferred duration is approx. 1/2 hour.
Reaksjonen skjer i nærvær av et oppløsningsmiddel i til-strekkelig mengde til å tillate god omrøring av faststoff- og væskereaktantene. The reaction takes place in the presence of a solvent in sufficient quantity to allow good stirring of the solid and liquid reactants.
Et hvilket som helst oppløsningsmiddel som ikke reagerer med syrehalogenidet eller med alkalimetallcyanidet under reaksjonsbetingelsene, kan benyttes. Det er foretrukket med oppløsningsmidler med meget lav polaritet. Any solvent which does not react with the acid halide or with the alkali metal cyanide under the reaction conditions can be used. Solvents with very low polarity are preferred.
Som oppløsningsmiddel som kan benyttes i reaksjonen skal nevnes: aromatiske hydrokarboner som benzen, toluen, xylen og lignende og halogenerte aromatiske hydrokarboner som Solvents that can be used in the reaction include: aromatic hydrocarbons such as benzene, toluene, xylene and similar and halogenated aromatic hydrocarbons such as
klorbenzen, diklorbenzen og lignende; chlorobenzene, dichlorobenzene and the like;
alifatiske hydrokarboner som cykloheksan, ligroin og aliphatic hydrocarbons such as cyclohexane, naphtha and
lignende; the like;
halogenerte alifatiske hydrokarboner som trikloretylen, halogenated aliphatic hydrocarbons such as trichloroethylene,
tetrakloretan og lignende. tetrachloroethane and the like.
De foretrukne oppløsningsmidler for omsetningen er toluen og xylen. The preferred solvents for the reaction are toluene and xylene.
Mengden oppløsningsmiddel kan variere innen vide grenser. Fra 200-500 ml pr.mol syrehalogenid er vanligvis tilstrekke-lig. The amount of solvent can vary within wide limits. From 200-500 ml per mole of acid halide is usually sufficient.
Man går ikke utenfor oppfinnelsens ramme hvis man benytter en større mengde oppløsningsmiddel men det vil da være nødvendig å destillere av en større mengde for å gjenvinne syrehalogenidet . One does not go outside the scope of the invention if a larger amount of solvent is used, but it will then be necessary to distill a larger amount in order to recover the acid halide.
Reaksjonen kan gjennomføres ved temperaturer mellom 60 og 150°C, de foretrukne temperaturer ligger mellom 80 og 120°C. The reaction can be carried out at temperatures between 60 and 150°C, the preferred temperatures being between 80 and 120°C.
Reaksjonen gjennomføres med fordel ved atmosfærisk trykk og under et oppløsningsmiddeldamptrykk eller under et inert gasstrykk. The reaction is advantageously carried out at atmospheric pressure and under a solvent vapor pressure or under an inert gas pressure.
Reaksjonen er vanligvis ferdig i løpet 2 timer. The reaction is usually complete within 2 hours.
Imidlertid er det fordelaktig å fortsette oppvarmingen i et tidsrom på 2-8 timer for å fjerne eventuelle spor av benzylklorid. Ved 95 °C er for eksempel den foretrukne reaksjonsperiode fra 5-7 timer. However, it is advantageous to continue heating for a period of 2-8 hours to remove any traces of benzyl chloride. At 95 °C, for example, the preferred reaction period is from 5-7 hours.
Det er for eksempel et produkt inneholdene en eller flere polyoksyetylenkjeder med formelen: There is, for example, a product containing one or more polyoxyethylene chains with the formula:
-0-(CH2-CH2-0)n-CH2-CH2-0H -O-(CH2-CH2-O)n-CH2-CH2-OH
der summen av n eller n'ene er mellom 2 og 200. where the sum of n or n's is between 2 and 200.
Etylenoksydenhetene. kan erstattes med propylenoksydenheter eller en blanding av disse to enheter. Blant de polyoksy-alkylerte derivater som er regnet skal nevnes: enkle polyetylenglykoler med formelen: The ethylene oxide units. can be replaced with propylene oxide units or a mixture of these two units. Among the polyoxy-alkylated derivatives that have been counted should be mentioned: simple polyethylene glycols with the formula:
0H-(CH2-CH20)n-CH2-CH2OH OH-(CH 2 -CH 2 O) n -CH 2 -CH 2 OH
med en molekylvekt mellom 100 og 4000, with a molecular weight between 100 and 4000,
polyetylenglykoler kondensert med stearinsyre med formelen: polyethylene glycols condensed with stearic acid with the formula:
CH3-(CH2)216-C00-(CH2-CH20)n-CH2-CH2-0H CH3-(CH2)216-C00-(CH2-CH20)n-CH2-CH2-OH
der n er mellom 20 og 150, where n is between 20 and 150,
- triglycerld-derIvater av polyetylenglykoler, - triglyceride derivatives of polyethylene glycols,
- polyoksyetylerte alkylfenolermed formelen: - polyoxyethylated alkylphenols with the formula:
Ri Ride
-0(CH2-CH20)n-CH2-CH2OH -O(CH2-CH2O)n-CH2-CH2OH
der n er mellom 10 og 200 of R^angir et alkyl med opptil 20 karbonatomer. where n is between 10 and 200 or R^ denotes an alkyl with up to 20 carbon atoms.
Denne ikke-begrensende liste inkluderer alle polyetylen-glykolderivatene som ikke har mer enn 10 etylen-enheter. This non-limiting list includes all polyethylene glycol derivatives having no more than 10 ethylene units.
Produkter som ligner de ovenfor angitte produkter kan benyttes, der etylenoksydenheten er erstattet med en propylenoksydenhet eller en blanding av etylenoksyd- og propylenoksydenheter. Products similar to the above-mentioned products can be used, where the ethylene oxide unit is replaced by a propylene oxide unit or a mixture of ethylene oxide and propylene oxide units.
Mengden av dette produkt kan variere fra 0,1 til 10 g pr. mol syrehalogenid, den foretrukne mengde er fra 0,4 til 2 g. The amount of this product can vary from 0.1 to 10 g per moles of acid halide, the preferred amount being from 0.4 to 2 g.
Produktet tilsettes generelt til reaksjonsoppløsningsmiddelet men kan også tilsettes helt eller delvis med det rene eller oppløsningsmiddelfortynnede syrehalogenid. The product is generally added to the reaction solvent but can also be added in whole or in part with the pure or solvent-diluted acid halide.
Når reaksjonen skjer i et rent vannfritt medium med om-hyggelig dehydratiserte reaktanter er graden av omdanning og utbytte meget lavt; en meget liten mengde av et polart produkt, for eksempel formamid, glycerol eller etylenglycol, må tilsettes til reaktantene for å oppnå et høyt utbytte og en høy omdanningsgrad. When the reaction takes place in a pure anhydrous medium with carefully dehydrated reactants, the degree of conversion and yield is very low; a very small amount of a polar product, for example formamide, glycerol or ethylene glycol, must be added to the reactants to obtain a high yield and a high degree of conversion.
Det polare produkt er fortrinnsvis dårlig oppløselig i reaksjonsoppløsningsmidlet men må ikke gi grunn til dannelse av anhydrid eller syre ved omsetning med syrehalogenidet. Produkter hvis dielektrisitetskonstant er over 30 benyttes med hell, bortsett fra vann. The polar product is preferably poorly soluble in the reaction solvent but must not give rise to the formation of an anhydride or acid upon reaction with the acid halide. Products whose dielectric constant is above 30 are successfully used, except for water.
Mengden polart produkt som tilsettes ligger mellom 0,1 og 10 g pr. 1 mol syrehalogenid. The amount of polar product that is added is between 0.1 and 10 g per 1 mole of acid halide.
Den foretrukne mengde er mellom 0,25 og 2 g pr. mol syrehalogenid. The preferred amount is between 0.25 and 2 g per moles of acid halide.
Den måte på hvilket det polare produkt innføres må sikre god fordeling derav over reaktantene. The manner in which the polar product is introduced must ensure good distribution thereof over the reactants.
Efter omsetningen blir overskudd av cyanid og alkalimetall-halogenid som dannes, fjernet ved filtrering. Rent syrehalogenid oppnås ved destillasjon av den filtrerte reaksjonsblanding. After the reaction, the excess of cyanide and alkali metal halide that is formed is removed by filtration. Pure acid halide is obtained by distillation of the filtered reaction mixture.
I de følgende eksempler uttrykker omdanningsgraden den mengde av syrehalogenid som er forsvunnet, beregnet på den opprinnelige mengde, og utbytte uttrykker forholdet mellom antall mol oppnådd syrehalogenid og antall mol syrehalogenid som opprinnelig var tilstede. In the following examples, the degree of conversion expresses the amount of acid halide that has disappeared, calculated on the original amount, and the yield expresses the ratio between the number of moles of acid halide obtained and the number of moles of acid halide originally present.
I eksemplene er sammensetningen i filtratet gitt i mol, beregnet i forhold til det benyttede benzoylklorid. In the examples, the composition of the filtrate is given in moles, calculated in relation to the benzoyl chloride used.
Eksempel 1 Example 1
29,4 g eller 0,6 mol vannfri natriumcyanid og 0,5 g glycerol tilsettes til en glassreaktor utstyrt med rørverk og kondensator og inneholdende 150 cm<5>xylen og 0,5 g polyoksy-etylenert nonylfenol "ANTAROX CO 990". Dette oppvarmes til 95"C under omrøring og 70,3 g eller 0,5 mol benzoylklorid tilsettes så i løpet av 1/2 time, temperaturen holdes ved 95°C i 6 timer og efter avkjøling blir filtrering og vasking med xylen gjenomført og man oppnår et uorganiske precipitat i en mengde av 34,5 g samt et filtrat på 241,9 g. 29.4 g or 0.6 mol of anhydrous sodium cyanide and 0.5 g of glycerol are added to a glass reactor equipped with tubing and condenser and containing 150 cm<5>xylene and 0.5 g of polyoxy-ethyleneted nonylphenol "ANTAROX CO 990". This is heated to 95°C with stirring and 70.3 g or 0.5 mol of benzoyl chloride is then added over the course of 1/2 hour, the temperature is maintained at 95°C for 6 hours and after cooling the filtration and washing with xylene is repeated and obtains an inorganic precipitate in an amount of 34.5 g and a filtrate of 241.9 g.
Det organiske filtrat organiseres ved gassfasekromatografi og bestemmes ved bruk av en indre standard. The organic filtrate is organized by gas phase chromatography and determined using an internal standard.
Molar sammensetning i filtratet: Molar composition in the filtrate:
Dette betyr et utbytte på 93,3 % og en omdanningsgrad av benzoylklorid på 99,6 %. This means a yield of 93.3% and a conversion rate of benzoyl chloride of 99.6%.
Eksempel 2 Example 2
Prosedyren er som i eksempel 1 men glycerol erstattes med en tilsvarende mengde etylenglykol. The procedure is as in example 1, but glycerol is replaced with a corresponding amount of ethylene glycol.
229,1 g organisk filtrat oppnås og dette inneholder i mol-#, beregnet på opprinnelig benzoylklorid: 229.1 g of organic filtrate is obtained and this contains in mol-#, calculated on original benzoyl chloride:
Dette betyr et utbytte på 91,6 % og en omdanningsgrad av benzoylklorid på 99,8 %. This means a yield of 91.6% and a conversion rate of benzoyl chloride of 99.8%.
Eksempel 3 Example 3
Prosedyren er som i eksempel 1 men glycerol erstattes med 1,25 g formamid. Efter at benzoylklorid er tilsatt i løpet av 1 time og oppvarmingen er fortsatt i 2 timer oppnås det et uorganisk precipitat på 33,4 g og et organisk filtrat på 274,5 g og dette inneholder: The procedure is as in example 1 but glycerol is replaced with 1.25 g of formamide. After benzoyl chloride is added over the course of 1 hour and the heating is continued for 2 hours, an inorganic precipitate of 33.4 g and an organic filtrate of 274.5 g are obtained and this contains:
Dette betyr et utbytte på 76 % og en omdanningsgrad av benzoylklorid på 96,7 %. This means a yield of 76% and a conversion rate of benzoyl chloride of 96.7%.
Eksempel 4 Example 4
Prosedyren er som i eksempel 1 men glycerol erstattes med 0,5 g glycose. Det oppnås en omdanningsgrad på 92 %, et utbytte på 73,4 % og et benzosyreanhydridinnhold på 0,65 % (molart) i filtratet. The procedure is as in example 1 but glycerol is replaced with 0.5 g of glucose. A conversion rate of 92%, a yield of 73.4% and a benzoic anhydride content of 0.65% (molar) in the filtrate is achieved.
Eksempel 5 Example 5
Prosedyren er nøyaktig som i eksempel 1 men man reduserer mengden oppløsningsmiddel: 75 cm<5>xylen i stedet for 150 cm5 . Man oppnår 34,4 g av et organisk precipitat og også 182,2 g av et organisk filtrat som inneholder: The procedure is exactly as in example 1 but the amount of solvent is reduced: 75 cm<5>xylene instead of 150 cm5 . 34.4 g of an organic precipitate is obtained and also 182.2 g of an organic filtrate containing:
Dette betyr et utbytte på 79 # og en omdanningsgrad av benzoylklorid på 85,2 %. This means a yield of 79 # and a conversion rate of benzoyl chloride of 85.2%.
Eksempel 6 (ikke ifølge oppfinnelsen) Example 6 (not according to the invention)
Prosedyren er nøyaktig som i eksempel 2 men man utelater tilsetningen av "ANTAROX CO 990". The procedure is exactly as in example 2, but the addition of "ANTAROX CO 990" is omitted.
36,6 g av et uorganisk precipitat oppnås og 243,4 g oppnås av et organisk filtrat som inneholder: 36.6 g of an inorganic precipitate is obtained and 243.4 g is obtained of an organic filtrate containing:
Dette betyr et utbytte på 39,5 1o og en omdanningsgrad av benzoylklorid på 42,2 <t>. This means a yield of 39.5 10 and a degree of conversion of benzoyl chloride of 42.2 <t>.
Eksempel 7 (ikke ifølge oppfinnelsen) Example 7 (not according to the invention)
Prosedyren er som i eksempel 1 men man unnlater tilsetning av polart derivat. Man oppnår 30,8 g av et uorganisk precipitat og 229 g av et organisk filtrat som i mol-& inneholder: The procedure is as in example 1, but the addition of polar derivative is omitted. 30.8 g of an inorganic precipitate and 229 g of an organic filtrate are obtained, which in mol-& contains:
Eksempel 8 Example 8
Prosedyren er som i eksempel 2 men man erstatter "ANTAROX CO 990" med den samme mengde polyetylenglykol triglycerid inneholdende 150 etylenerte enheter av typen atlas og med betegnelsen "G 1295". The procedure is the same as in example 2, but "ANTAROX CO 990" is replaced with the same amount of polyethylene glycol triglyceride containing 150 ethyleneized units of the atlas type and with the designation "G 1295".
Det oppnås 34,9 g av et uorganisk precipitat og man oppnår et organisk filtrat som i mol-#, beregnet på det opprinnelige benzoylklorid, inneholder: 34.9 g of an inorganic precipitate is obtained and an organic filtrate is obtained which in mol-#, calculated on the original benzoyl chloride, contains:
Dette vil si et utbytte på 92,3 <j> med en omdanningsgrad på 98,1 *. This means a yield of 92.3 <j> with a conversion rate of 98.1 *.
Claims (8)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8906563A FR2647109B1 (en) | 1989-05-19 | 1989-05-19 | PROCESS FOR THE PREPARATION OF ACYLATE CYANIDES IN ANHYDROUS MEDIA |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| NO902140D0 NO902140D0 (en) | 1990-05-14 |
| NO902140L NO902140L (en) | 1990-11-20 |
| NO172116B true NO172116B (en) | 1993-03-01 |
| NO172116C NO172116C (en) | 1993-06-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| NO902140A NO172116C (en) | 1989-05-19 | 1990-05-14 | PROCEDURE FOR THE PREPARATION OF ACYLCYANIDES IN ANNUAL MEDIUM |
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| Country | Link |
|---|---|
| EP (1) | EP0398782B1 (en) |
| JP (1) | JPH0686414B2 (en) |
| KR (1) | KR940000062B1 (en) |
| CN (1) | CN1027260C (en) |
| AT (1) | ATE111442T1 (en) |
| CA (1) | CA2015998C (en) |
| DE (1) | DE69012424T2 (en) |
| DK (1) | DK0398782T3 (en) |
| ES (1) | ES2058839T3 (en) |
| FI (1) | FI103572B (en) |
| FR (1) | FR2647109B1 (en) |
| IE (1) | IE69053B1 (en) |
| NO (1) | NO172116C (en) |
| PT (1) | PT94087B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK0493711T3 (en) * | 1990-12-31 | 1996-11-11 | Basf Ag | Process for the preparation of E-oximeters of phenylglyoxylic esters |
| DE69427419T2 (en) * | 1993-03-22 | 2001-10-18 | Fuji Xerox Co., Ltd. | Triarylamine compounds, processes for their preparation and electrophotographic photoreceptors containing these triarylamine compounds |
| CZ287198B6 (en) * | 1994-11-24 | 2000-10-11 | Basf Ag | Process for preparing derivatives of halomethylbenzoyl cyanides |
| CN102642363A (en) * | 2012-04-28 | 2012-08-22 | 河南永威安防股份有限公司 | Production method of high-strength high-pressure decorating plate |
| CN109651193A (en) * | 2019-01-22 | 2019-04-19 | 江苏佳麦化工有限公司 | A kind of synthetic method of benzoyl cyanide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE2614242C3 (en) * | 1976-04-02 | 1986-11-13 | Bayer Ag, 5090 Leverkusen | Process for the production of acyl cyanides |
| DE2624891C2 (en) * | 1976-06-03 | 1982-11-18 | Degussa Ag, 6000 Frankfurt | Process for the production of benzoyl cyanide |
| DE2642140C2 (en) * | 1976-09-20 | 1982-10-28 | Degussa Ag, 6000 Frankfurt | Process for the production of benzoyl cyanide |
| DE3015587A1 (en) * | 1980-04-23 | 1981-10-29 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING ACYLCYANIDES |
-
1989
- 1989-05-19 FR FR8906563A patent/FR2647109B1/en not_active Expired - Lifetime
-
1990
- 1990-05-03 CA CA002015998A patent/CA2015998C/en not_active Expired - Fee Related
- 1990-05-09 DK DK90401222.6T patent/DK0398782T3/en active
- 1990-05-09 DE DE69012424T patent/DE69012424T2/en not_active Expired - Fee Related
- 1990-05-09 AT AT90401222T patent/ATE111442T1/en not_active IP Right Cessation
- 1990-05-09 EP EP90401222A patent/EP0398782B1/en not_active Expired - Lifetime
- 1990-05-09 ES ES90401222T patent/ES2058839T3/en not_active Expired - Lifetime
- 1990-05-14 NO NO902140A patent/NO172116C/en not_active Application Discontinuation
- 1990-05-18 PT PT94087A patent/PT94087B/en not_active IP Right Cessation
- 1990-05-18 FI FI902473A patent/FI103572B/en active IP Right Grant
- 1990-05-18 IE IE180190A patent/IE69053B1/en not_active IP Right Cessation
- 1990-05-19 JP JP2130107A patent/JPH0686414B2/en not_active Expired - Fee Related
- 1990-05-19 KR KR1019900007191A patent/KR940000062B1/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| KR940000062B1 (en) | 1994-01-05 |
| FI103572B1 (en) | 1999-07-30 |
| JPH0686414B2 (en) | 1994-11-02 |
| CA2015998C (en) | 1996-09-03 |
| CA2015998A1 (en) | 1990-11-19 |
| DK0398782T3 (en) | 1995-02-13 |
| IE69053B1 (en) | 1996-08-07 |
| FR2647109A1 (en) | 1990-11-23 |
| PT94087B (en) | 1997-01-31 |
| NO902140L (en) | 1990-11-20 |
| PT94087A (en) | 1991-01-08 |
| ATE111442T1 (en) | 1994-09-15 |
| ES2058839T3 (en) | 1994-11-01 |
| IE901801L (en) | 1990-11-19 |
| NO902140D0 (en) | 1990-05-14 |
| EP0398782A1 (en) | 1990-11-22 |
| CN1047282A (en) | 1990-11-28 |
| NO172116C (en) | 1993-06-09 |
| EP0398782B1 (en) | 1994-09-14 |
| CN1027260C (en) | 1995-01-04 |
| FR2647109B1 (en) | 1991-07-26 |
| DE69012424T2 (en) | 1995-04-20 |
| FI902473A0 (en) | 1990-05-18 |
| KR900018011A (en) | 1990-12-20 |
| FI103572B (en) | 1999-07-30 |
| JPH035448A (en) | 1991-01-11 |
| DE69012424D1 (en) | 1994-10-20 |
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