DE1768179C3 - Chlorocarbonyl isocyanate and process for making isocyanates - Google Patents
Chlorocarbonyl isocyanate and process for making isocyanatesInfo
- Publication number
- DE1768179C3 DE1768179C3 DE19681768179 DE1768179A DE1768179C3 DE 1768179 C3 DE1768179 C3 DE 1768179C3 DE 19681768179 DE19681768179 DE 19681768179 DE 1768179 A DE1768179 A DE 1768179A DE 1768179 C3 DE1768179 C3 DE 1768179C3
- Authority
- DE
- Germany
- Prior art keywords
- dichloride
- isocyanide
- acid
- isocyanates
- aryl
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 7
- 150000002513 isocyanates Chemical class 0.000 title claims description 5
- VBBUFMFZDHLELS-UHFFFAOYSA-N N-(oxomethylidene)carbamoyl chloride Chemical compound ClC(=O)N=C=O VBBUFMFZDHLELS-UHFFFAOYSA-N 0.000 title 1
- 239000002253 acid Substances 0.000 claims description 11
- RLAROPIDCNCRNR-UHFFFAOYSA-L dichloride;cyanide Chemical class [Cl-].[Cl-].N#[C-] RLAROPIDCNCRNR-UHFFFAOYSA-L 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000006414 CCl Chemical group ClC* 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- IIMIOEBMYPRQGU-UHFFFAOYSA-L Picoplatin Chemical compound N.[Cl-].[Cl-].[Pt+2].CC1=CC=CC=N1 IIMIOEBMYPRQGU-UHFFFAOYSA-L 0.000 description 17
- -1 alkyl radicals Chemical class 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- 125000004432 carbon atoms Chemical group C* 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N Carbon tetrachloride Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N [N-]=C=O Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- CKDWPUIZGOQOOM-UHFFFAOYSA-N carbamoyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- KHUXNRRPPZOJPT-UHFFFAOYSA-N $l^{1}-oxidanylbenzene Chemical compound O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- GAIQXJPZLRWQRH-UHFFFAOYSA-N 2-chloroacetyl isocyanide Chemical compound ClCC(=O)[N+]#[C-] GAIQXJPZLRWQRH-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- AWNGEPWONQTBRL-UHFFFAOYSA-N 2-phenylacetyl isocyanide Chemical compound [C-]#[N+]C(=O)CC1=CC=CC=C1 AWNGEPWONQTBRL-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N Benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- FNYBYIBSBFYZOG-UHFFFAOYSA-N BrCC(=O)[N+]#[C-] Chemical compound BrCC(=O)[N+]#[C-] FNYBYIBSBFYZOG-UHFFFAOYSA-N 0.000 description 1
- MFBYWMXCAKXPTA-UHFFFAOYSA-N C1(=CC=CC=C1)OC(=O)[N+]#[C-] Chemical compound C1(=CC=CC=C1)OC(=O)[N+]#[C-] MFBYWMXCAKXPTA-UHFFFAOYSA-N 0.000 description 1
- SSJRSXYUNBVNTF-UHFFFAOYSA-N COC1=C(C=CC=C1)OC(=O)[N+]#[C-] Chemical compound COC1=C(C=CC=C1)OC(=O)[N+]#[C-] SSJRSXYUNBVNTF-UHFFFAOYSA-N 0.000 description 1
- ICKYLXVWKKUQKF-UHFFFAOYSA-N ClC1=CC=C(C(=O)[N+]#[C-])C=C1 Chemical compound ClC1=CC=C(C(=O)[N+]#[C-])C=C1 ICKYLXVWKKUQKF-UHFFFAOYSA-N 0.000 description 1
- AFUZWDSCYVGWIV-UHFFFAOYSA-N FC(F)(F)C(=O)[N+]#[C-] Chemical compound FC(F)(F)C(=O)[N+]#[C-] AFUZWDSCYVGWIV-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N Fluorosulfuric acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N Methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N Trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- KETSXKGCGOYEJC-UHFFFAOYSA-N [N+](=O)([O-])C=1C=C(C(=O)[N+]#[C-])C=CC=1 Chemical compound [N+](=O)([O-])C=1C=C(C(=O)[N+]#[C-])C=CC=1 KETSXKGCGOYEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- OHWFZCUCQSPPSJ-UHFFFAOYSA-N benzoyl isocyanide Chemical compound [C-]#[N+]C(=O)C1=CC=CC=C1 OHWFZCUCQSPPSJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- WVPKAWVFTPWPDB-UHFFFAOYSA-N dichlorophosphinic acid Chemical compound OP(Cl)(Cl)=O WVPKAWVFTPWPDB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- BPRFCEZKJYIFJZ-UHFFFAOYSA-N ethyl isocyanoformate Chemical compound CCOC(=O)[N+]#[C-] BPRFCEZKJYIFJZ-UHFFFAOYSA-N 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- FURSOPUPGJBTMU-UHFFFAOYSA-N methyl isocyanoformate Chemical compound COC(=O)[N+]#[C-] FURSOPUPGJBTMU-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OZIFPTREIZAKDB-UHFFFAOYSA-N propanoyl isocyanide Chemical compound CCC(=O)[N+]#[C-] OZIFPTREIZAKDB-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Description
CI-C — N = C = OCI-C - N = C = O
Es ist bekannt, Isocyanid-dichloride mit Carbonsäureanhydriden unter Isocyanat-Bildung umzusetzen (Angew. Chemie, 77 [19651S. 1031).It is known to use isocyanide dichlorides with carboxylic anhydrides to react with isocyanate formation (Angew. Chemie, 77 [19651S. 1031).
Demgegenüber wurde nun ein neues chemisch eigenartiges Verfahren zur Herstellung von Isocyanaten gefunden, welches darin besteht, daß man Isocyaniddichloride der allgemeinen FormelIn contrast, a new chemically peculiar process for the production of isocyanates has now been developed found, which consists in the fact that one isocyanide dichloride the general formula
X-C-N = CCl,X-C-N = CCl,
worin X für Halogen, einen gegebenenfalls substituierten ungesättigten oder gesättigten Alkyl-, Aralkyl-, Aryl-, Alkoxy- oder Aroxyrest steht, mit der äquivalenten Menge einer wasserfreien starken iiäure, die an Sauerstoff gebundenen dissoziierbaren Wasserstoff enthält, im Temperaturbereich von etwa +10 bis etwa 150eC gegebenenfalls in Anwesenheit eines inerten Lösungsmittels umsetztwherein X stands for halogen, an optionally substituted unsaturated or saturated alkyl, aralkyl, aryl, alkoxy or aroxy radical, with the equivalent amount of an anhydrous strong iiic acid which contains dissociable hydrogen bonded to oxygen, in the temperature range from about +10 to about 150 ° C., optionally in the presence of an inert solvent
Als Alkylreste seien solche mit bis zu 18 (vorzugsweise bis zu 6) Kohlenstoffatomen genannt, welche bis zu 2 Doppelbindungen enthalten können. Die Alkylreste können als Substituenten Halogen (vorzugsweise Fluor, Chlor, Brom) ein- oder mehrfach tragen.As alkyl radicals those with up to 18 (preferably up to 6) carbon atoms may be mentioned, which have up to 2 May contain double bonds. The alkyl radicals can be halogen (preferably fluorine, Chlorine, bromine) one or more times.
Aralkylreste sind solche mit bis zu 12 Kohlenstoffatomen (Aryl—Naphtyl, Alkyl=Äthyl), vorzugsweise jedoch BenzyLAralkyl radicals are those with up to 12 carbon atoms (Aryl-naphthyl, alkyl = ethyl), but preferably BenzyL
Unter den Arylresten sind solche mit bis zu 10 Kohlenstoffatomen, vorzugsweise Phenyl, zu verstehen. Unter Aroxy sei vorzugsweise Phenoxy genanntThe aryl radicals are to be understood as meaning those with up to 10 carbon atoms, preferably phenyl. Aroxy is preferably phenoxy
Die Aralkyl- und Arylreste und der Phenoxyrest können durch Halogen (vorzugsweise Fluor, Chlor, Brom), niederes Alkyl, Alkoxy (G bis GiJl Nitro und -SOKDlsein.The aralkyl and aryl radicals and the phenoxy radical can be halogen (preferably fluorine, chlorine, bromine), lower alkyl, alkoxy (G to GiJl nitro and -SOKDl.
Alkoxyreste sind solche mit 1 bis 6 (vorzugsweise 1 bis 2) Kohlenstoffatomen, die auch verzweigt und durch Halogen (vorzugsweise Fluor, Chlor, Brom) substituiert sein können.Alkoxy radicals are those with 1 to 6 (preferably 1 to 2) carbon atoms, which are also branched and through Halogen (preferably fluorine, chlorine, bromine) can be substituted.
Als für das erfindungsgemäbe Verfahren verwendete Isocyanid-dichloride seien beispielhaft genannt:The isocyanide dichlorides used for the process according to the invention may be mentioned by way of example:
Acetyüsocyanid-dichlorid,
$ Chloracetylisocyanid-dichlorid,Acetyisocyanide dichloride,
$ Chloroacetyl isocyanide dichloride,
femer:
ίο Phenylacetylisocyanid-dichlorid,also:
ίο phenylacetyl isocyanide dichloride,
^Nitrophenylacetylisocyanid-dichlorid.^ Nitrophenylacetyl isocyanide dichloride.
4-Chlorphenylacetynsocyanid-dichlorid,4-chlorophenylacetynsocyanide dichloride,
3-NitrobenzoyIisocyanid-dichlorid, 2-,3-,4-ChIorbenzoylisocyanid-dichlorid,3-nitrobenzoyl isocyanide dichloride, 2-, 3-, 4-chlorobenzoyl isocyanide dichloride,
2-Chloräthoxycarbonyiisocyanid-dichIorid,2-chloroethoxycarbonyiisocyanide dichloride,
Methoxycarbonylisocyanid-dichlorid; jo weiterhin:Methoxycarbonyl isocyanide dichloride; jo continues:
chlorid
ortho-, meta- und para-Nitrophenylcarboxyisocya-chloride
ortho-, meta- and para-nitrophenylcarboxyisocya-
nid-dichlorid, ortho- und Paratolylcarboxyisocyanid-dichlorid.nid-dichloride, ortho- and paratolylcarboxyisocyanide-dichloride.
Als Säulen, die zur Umsetzung benutzt werden können, seien beispielsweise genannt: gegebenenfalls substituierte aliphatische und aromatische Sulfonsäuren, wie Methan- und Benzolsulfonsäure, Toluolsulfonsäure; aliphatische und aromatische Phosphonsäuren; starke Carbonsäuren, wie Trichlor- und Trifluoressigsäure; anorganische Säuren, wie Chlorsulfonsäure und Fluorsulfonsäure, insbesondere auch Halogenphosphorsäuren, wie Dichlorphosphorsäure.Examples of pillars that can be used for the conversion are: if appropriate substituted aliphatic and aromatic sulfonic acids, such as methane and benzenesulfonic acid, toluenesulfonic acid; aliphatic and aromatic phosphonic acids; strong carboxylic acids such as trichloroacetic and trifluoroacetic acid; inorganic acids such as chlorosulfonic acid and fluorosulfonic acid, in particular also halophosphoric acids, such as dichlorophosphoric acid.
Im allgemeinen werden äquimolare Mengen dieser Säuren bezogen auf Isocyanid-dichloride eingesetzt Das Verfahren der Erfindung sei an folgendem Reaktionsschema näher erläutert:In general, equimolar amounts of these will be used Acids based on isocyanide dichlorides used The process of the invention is based on the following Reaction scheme explained in more detail:
X-C-N = CCl, + YOHX-C-N = CCl, + YOH
-HCl-HCl
IlIl
X-C-N = C = O +YClX-C-N = C = O + YCl
Y bedeutet den Rest einer starken Säure. Die umgesetzte Säure wird nach dem erfindungsgemäßen Verfahren in das Säurechlorid überführt, das gegebe-Y means the remainder of a strong acid. The converted acid is according to the invention Process converted into the acid chloride, the given
nenfalls durch Umsetzung mit Wasser wieder in die Säure umgewandelt werden kann.If necessary, it can be converted back into the acid by reaction with water.
Im Gegensatz zur entsprechenden Reaktion mit Alkyl- oder Arylisocyanid-dichloriden darf die zur Umsetzung benutzte Säure im allgemeinen nicht in situIn contrast to the corresponding reaction with alkyl or aryl isocyanide dichlorides, the for Reaction generally did not use acid in situ
to aus Wasser und Säurechlorid hergestellt werden, da die entstehenden Isocyanate zum Teil extrem wasserempfindlich sind.to be made from water and acid chloride, since the The isocyanates produced are in some cases extremely sensitive to water.
Es ist im allgemeinen zweckmäßig, die Umsetzung ohne Lösungsmittel vorzunehmen. Man kann aber auch in Anwesenheit eines inerten Lösungsmittels, wie z. B. gegebenenfalls chlorierte aliphatische und aromatische Kohlenwasserstoffe wie Tetrachlorkohlenstoff, Chloroform, Benzol und Di- oder Trichlorbenzol, arbeiten.It is generally advantageous to carry out the reaction without a solvent. But you can also in the presence of an inert solvent, such as. B. optionally chlorinated aliphatic and aromatic Hydrocarbons such as carbon tetrachloride, chloroform, benzene and di- or trichlorobenzene work.
Die Reaktionstemperatur wird im aligemeinen zwischen +10 und 150°C (vorzugsweise etwa 20 bis etwa 100"C) insbesondere etwa +20 bis etwa +60"C gehalten. Anschließend wird der noch als Carbamidsäurecbtorid gebundene Chlorwasserstoff bei einer mögliebst hohen Sompftemperatur, gegebenenfalls mit Hufe eines trockenen Stickstoffstroms, Ober eine Kolonne ausgetrieben und das Isocyanat vom Säurechlorid durch Destillation abgetrenntThe reaction temperature is in the aligemeinen between +10 and 150 ° C (preferably about 20 to about 100 held "C) especially about +20 to about +60" C. The hydrogen chloride still bound as carbamic acid chloride is then expelled through a column at as high a sump temperature as possible, optionally with a stream of dry nitrogen, and the isocyanate is separated off from the acid chloride by distillation
Die nach dem erfindungsgemaßen Verfahren erhältli- ι ο chen Isocyanate sind zum Teil bekannt und teilweise auch neu und entsprechen der allgemeinen FormelSome of the isocyanates obtainable by the process according to the invention are known and some also new and correspond to the general formula
IlIl
X-C-N-C=OX-C-N-C = O
worin X die vorstehend genannte Bedeutung hatwherein X has the meaning given above
Sie werden direkt als SchädJingsbekimprongsmittel eingesetzt und können auch als wasserentziehendes Mittel bei speziellen Synthesen verwendet werden.They are used directly as a pest control agent and can also be used as a dehydrating agent Means to be used in special syntheses.
2294 g (1,43 Mol) N-Chlorcarbonylisocyanid-dichlorid werden vorgelegt und bei 200C 1374 g (1.43 MoI) Methyisulfonsäure so zugetropft, daß die Innentemperatur bis auf 50° C ansteigt Anschließend wird innerhalb etwa 5 Stunden mit langsam gesteigerter Sumpftemperatur der als Carbamidsäurechlorid gebundene Chlorwasserstoff fiber eine Kolonne ausgetrieben und das zurückbleibende N-Qüorcarbonylisocyanat vom Methylsulfochlorid destillativ getrennt Man erhält 106 g S («-70% der Theorie) N-Cnlorcarbonylisocyanat vom Siedepunkt 64°C/760 Torr.2294 g (1.43 mol) of N-Chlorcarbonylisocyanid dichloride are introduced and C 1374 g (1:43 mol) Methyisulfonsäure were added dropwise at 20 0, that the internal temperature up to 50 ° C increases Subsequently, within about 5 hours with slowly increased bottom temperature of the Hydrogen chloride bound as carbamic acid chloride is driven off through a column and the remaining N-carbonyl isocyanate is separated from the methyl sulfochloride by distillation.
208 g (1,34 Mol) N-Methoxicarbonylisocyanid-dichlorid werden wie im Beispiel 1 mit 134 g (!39 Mo!) wasserfreier Methyisulfonsäure umgesetzt und aufgearbeitet Man erhält 99 g (—73% der Theorie) N-MethoxicarbonyUsocyanat vom Siedepunkt 95 bis 97°C/760Torr.208 g (1.34 moles) of N-methoxycarbonyl isocyanide dichloride are as in example 1 with 134 g (! 39 Mo!) anhydrous methyl sulfonic acid reacted and worked up. 99 g (-73% of theory) of N-methoxycarbonyusocyanate are obtained from boiling point 95 to 97 ° C / 760 Torr.
1 Liter mit Wasser gesättigter Diäthyläther wird mit CaCb 12 Stunden getrocknet, filtriert und halbiert Etwa 50% der einen Hälfte wird über eine 30-cm-FÜllkörperkolonne destilliert In das Destillat wird Natriumdraht eingepreßt, wobei sich unter Hz-Entwicklung schon nach wenigen Minuten auf der zuerst blanken Metalloberfläche eine deutlich sichtbare Hydroxidschicht bildet1 liter of diethyl ether saturated with water is dried with CaCb for 12 hours, filtered and cut in half 50% of one half is over a 30 cm packed column distilled Sodium wire is pressed into the distillate, with the development of Hz already after a few minutes a clearly visible hydroxide layer appears on the initially bare metal surface forms
Die andere Hälfte des mit CaCb vorgetrockneten Äthers wird mit 5 ml (etwa 1%) Cl-CO-NCO versetzt und ebenfalls zu etwa 50% Ober eine 30-cm-FüUkörperkolonne destilliert Der in dieses Destillat eingepreßte Natriufndraht hat auch nach 48 Stunden noch eine unverändert reine metallisch glänzende Oberfläche.The other half of the ether pre-dried with CaCb is mixed with 5 ml (about 1%) Cl-CO-NCO and also to about 50% over a 30 cm column with columns distilled The sodium wire pressed into this distillate still has a wire after 48 hours unchanged pure metallic glossy surface.
Claims (1)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681768179 DE1768179C3 (en) | 1968-04-10 | Chlorocarbonyl isocyanate and process for making isocyanates | |
| CH379769A CH509271A (en) | 1968-04-10 | 1969-03-13 | Process for the preparation of acyl isocyanates |
| NL6905153A NL6905153A (en) | 1968-04-10 | 1969-04-02 | |
| GB1806869A GB1192900A (en) | 1968-04-10 | 1969-04-09 | Process for the Preparation of Isocyanates |
| BE731350D BE731350A (en) | 1968-04-10 | 1969-04-10 | |
| FR6911107A FR2006011A1 (en) | 1968-04-10 | 1969-04-10 | Preparation of insecticidal isocyanates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681768179 DE1768179C3 (en) | 1968-04-10 | Chlorocarbonyl isocyanate and process for making isocyanates |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1768179A1 DE1768179A1 (en) | 1971-11-18 |
| DE1768179B2 DE1768179B2 (en) | 1975-12-18 |
| DE1768179C3 true DE1768179C3 (en) | 1976-07-29 |
Family
ID=
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